Adhesive laminate

Technical Field

The present invention relates to a member for bonding to the structure needed for the installation of the excellent adhesion between the adhesion of the laminate.

Background Art

In order to achieve light-weighted, and to improve security in the morphology of the glass is not possible using, has been actively utilize the transparent thermoplastic resin as a glass substitute attempt. In particular polycarbonate resin utilizing impact resistance, transparency, light , processability is used for characteristics such as the use of multiple aspects.

For example, in Patent document 1 for the automobile in the window glass, the sunroof, construction machinery in the window glass and the like, the purpose of use, made the following structure, in other words, the surface of the polycarbonate of a part or the whole colored layers are stacked in this order, by the primer layer of the acrylic resin layer, formed by organic silicone resin and a hard coating of adhesive a joint and to the metal structure.

However, in Patent document 1 the laminated body, the laminated body large scale , because the impact of the polycarbonate of linear expansion becomes large, the stress generated in the bonded portion, taking into account the long-term outdoor use in the case of adverse situation exists the problem of adhesion.

Furthermore, because the above-mentioned problem of bonding of the laminated body, and bonding the same size compared with the glass, by thickening the thickness of the adhesive needs to relax stress, therefore, in that it is part of the design of the special design.

On the other hand, even if it is under the condition of a small laminated body, such as the window glass of the vehicle when in use, in order to ensure that under vibration during the operation the gleyness, in the past to 6 mm above the thickness of the adhesive (reference valeant literature 1).

Therefore, there is an urgent desired without thickening the thickness of the adhesive layer used for under the condition that is bonded to the structural components needed for the installation of the excellent adhesion between the adhesion of the laminate.

Literature of the prior art

Patent literature

Patent literature 1: Japanese opens especially 2006-255928, the

Valeant literature

Valeant literature 1 :   and Adhesives   Sealants:   Knowledge General,   Techniques Application,   Techniques   Curing New (Elsevier   Ltd   Science, 2006) of 385 page Figure27

Content of the invention

The purpose of this invention to provide one kind is used for bonding parts to the structure needed for the installation of the excellent adhesion between the adhesion of the laminate.

Repeated in-depth study of the inventors, as a result to identify the transparent substrate layer (layer A), hard coating (B layer), nien used primer layer (layer C) and an elastic adhesive layer (D layer) are sequentially laminated, in laminate adhesion between, through the use of specific components B layer, having a specific use, and has a specific thickness of the elastic modulus of the pressing layer C, having a specific use of the thickness of layer D, thus even in the adhesive part of the substrate material layer and the structural member under the condition of high stress is generated, the expansion body also can be with the same small glass windows of the thickness of the adhesive, the adhesion is good, thereby completing the present invention.

In other words, the invention relates to laminate adhesion between, the structural parts used for adhesive mounting, comprising:

(A) by the melt extrusion of the thermoplastic resin layer a (layer A),

(B) use of a colloidal silica and/or alkoxy silane hydrolysis condensates does not include the solvent relative to the total weight to 10% by weight of more than to form a hard coating agent hard coating (B layer),

(C) nien used primer layer (layer C), and

(D) an elastic adhesive layer (D layer);

In laminate for above sticks ,

(I) layer-A D layer are sequentially laminated,

(Ii) C layer is a primer containing silane coupling agent is formed, its thickness is 1-20 the  m, and load 800 the nano-indentation method is under   N determining the use of the pressing in the elastic modulus is 500-4000MPa,

The thickness of the layer of (iii) D (Y) is 0.9-14 mm.

Laminate adhesion between of the present invention is bonded to the structural member, with the frame, of expansion of the thickness of the adhesive in the same situation the adhesion is good.

Description of drawings

Figure 1 is diagram of embodiment 1-7 and comparative example 1-5 in the laminate, and stress test is made.

Figure 2 is diagram of the laminate seen from above.

Figure 3 is graph of observed from the side surfaces of the laminate.

Figure 4 is plan of embodiment 9-17 and comparative example 6-9 in the laminate, and stress test is made.

Figure 5 is graph of the observation from above, having light-shielding layer of the laminate.

Figure 6 is graph of embodiment 19-23 and comparative example 10-12 in the laminate, and stress test is made.

Symbol description

11:a base material layer (A layer)

11 (a): polycarbonate resin layer

11 (b): an acrylic resin layer

12: hard coating (B layer)

12p: hard coating (primer) layer

12t: hard coating (top) layer

13: primer layer adhesion between (C layer)

14 : (D layer) adhesive layer

15: the light shielding layer (E layer)

31 : (A layer) sound deadening function

32: light shielding layer (E layer)

33: hard coating (B layer)

34: primer layer adhesion between (C layer)

35 : (D layer) adhesive layer

36: adherend

37: acrylic resin (A layer)

1: two-color molded product body (sheet and frame part of the integrated molding)

2: platelet (using 1.5 mm of the thickness of the fan-shaped gate forming, thickness 4 mm)

3: frame part (thickness 2 mm)

4: gate of the needle the frame part (4 is, diameter 1.4 mm)

5: the width of the longitudinal direction of the frame part (40 mm)

6: the transverse width of the frame part (40 mm)

7: the width of the above-mentioned molded article (200 mm)

8: the length of the above-mentioned molded product (300 mm)

Mode of execution

The following, detailed description of the invention.

<粘接用 底漆层 : C 层>

Adhesion between the primer layer (layer C) primer containing silane coupling agent is formed, its thickness is 1-20 the  m, and load 800 the nano-indentation method is under   N determining the use of the pressing in the elastic modulus is 500-4000MPa.

C to the thickness of the layer of the 1-20  m, is preferably the 2-10  m. If more than the lower limit of thickness, to obtain good cementability is, if the upper-limit or lower, to a minimum of necessary primer to obtain good adhesion between the amount of the adhesive.

C layer load 800 the nano-indentation method is under   N determining the use of the pressing in the elastic modulus is 500-4000MPa, preferably 1000-3500MPa. If the elastic modulus of more than the lower limit, the adherend to obtain the full reactive, if the upper-limit or lower, sufficient to expect the effect of stress relaxation.

Pressed into the determination of the modulus of elasticity is substantially as follows, in other words, a hard coating layer on the substrate is in the 50 spreads the cloth to stick   m primer for the thickness of the left and right, at a temperature of 23 the [...] and relative humidity 50% of the cured under the environment, the use of slicer of the cured section cutting, the smooth section is, for the section, near the center of the film thickness to be measured. The sample coated with the above-mentioned primer, Berkovich indenter using a (α: 65.03°)nano-indentation device, pressed into the elastic modulus determined. Application of the above-mentioned determination in the following conditions: in order to 20.4mgf/sec applying load of the load speed, will be of the maximum load of 800 the keep   N 1 seconds later, with the same load speed for unloading. As is suitable for the above-mentioned determination device, for example, can utilize ELIONIX Corporation systems, produces the commodity name ENT-2100 Ultramicro indentation hardness tester.

(Primer composition)

C layer comprising a silane coupling agent to form a primer composition. C layer to the hard coating layer is preferably (B layer) and an elastic adhesive layer (layer D) has good in the gleyness of any.

An elastic adhesive layer (layer D) when using polyurethane adhesive, primer composition preferably comprises at the same time to contain a silicone component reactive good alkoxy silyl and the reactive polyurethane adhesive of isocyanate groups of the compound. The above-mentioned compound alkoxy silyl directly with the hard coating (B layer), or lie between and the other containing an alkoxysilyl group with condensation key of the hydrolysis of the compound (B layer) hard coating firmly bonding.

As a primer composition containing silane coupling agent and the other, preferably the latter modified silane, more preferably instantiated with respect to the epoxy silane 1 mol to 0.1-1 mole ratio of reaction of the amino silane modified silane. Furthermore, as the above-mentioned epoxy silane, particularly preferred γ-glycidoxy propyl trimethoxy silane, as the above-mentioned amino-silane, particularly preferred N-(β-aminoethyl)-γ-amino propyl trimethoxy silane and N-(β-aminoethyl)-γ-amino propyl methyl dimethoxy silane.

On the other hand, compound isocyanic acid ester group can be directly bonded with the polyurethane adhesive, or lie between the other containing alcohol such as OH-based compound containing the isocyanate group of the reactive groups of the compounds are directly bonded. Therefore, at the same time containing alkoxy silyl and isocyanate based compounds can the hard coating is connected via a chemical bond with the polyurethane adhesive, is thus preferred.

Adhesion between the primer (C layer) having a specific elastic modulus, thus with a high applied for easing the stress of the prior art the characteristics of the laminate. In order to meet the above-mentioned characteristic, a primer for optimal sticks (C layer) cross-linked structure is not too dense. From this point of view, the above at the same time containing alkoxy silyl and isocyanate based compound is preferably any one of the reactive functional group from branched structure and of the structure of the separation point.

More specifically, as a preferred form, can be instantiated it has a chain structure with the polyisocyanate compounds of γ-mercapto propyl trimethoxy silane, such as isocyanate group containing a group reactive with the reaction product of a silane coupling agent (the following, referred to as "silane-modified polyisocyanate"). In the above-mentioned reaction, adjust the polyisocyanate composition the ratio of the silane compound, many of the residual isocyanate groups.

It has a chain structure as the polyisocyanate compounds, such as can be instantiated trimethylolpropane adduct of a polyol with a diisocyanate compound modified body, the TDI of HDI isocyanurate modified product, isocyanurate modified product of HDI, IPDI isocyanurate of HDI with modified body of the and IPDI isocyanurate modified body and the like. Should be note, the diisocyanate compound is shown as the following abbreviations.

In other words, as the above-mentioned diisocyanate compounds, can be instantiated

(1) toluene diisocyanate (commonly referred to as "TDI". Including 2, 4-TDI and 2, 6-TDI), diphenyl methane diisocyanate (referred to as "MDI", including 4, 4 the [...] -MDI, 2, 4 the [...] -MDI and 2, the 2 [...] -MDI), 1, 5-naphthalene diisocyanate, 1, 4-naphthalene diisocyanate, P-phenylene diisocyanate, phenylene diisocyanate between, phenylenedic jaya methyl diisocyanate (referred to as "XDI", including o-XDI, and m-XDI p-XDI), tetramethyl benzene dimethylene diisocyanate (referred to as "TMXDI"), 4, 4 the [...] -diphenyl ether diisocyanate, 2-nitro-biphenyl -4, 4 the [...] -diisocyanate, 2, 2 the [...] -diphenyl propane -4, the 4 [...] -diisocyanate, 3, 3 the [...] -dimethyl diphenylmethane -4, 4 the [...] -diisocyanate, 4, 4 the diisocyanate and-diphenyl propane [...] 3, 3 the [...] -dimethoxy-biphenyl -4, 4 the aromatic diisocyanate such as [...] -diisocyanate;

(2) four methylene diisocyanate, hexamethylene diisocyanate (referred to as "HDI"), 2-methyl -1, 5-pentane diisocyanate, 3-methyl -1, 5-pentane diisocyanate, lysine diisocyanate and trimethyl hexamethylene diisocyanate (referred to as "TMDI", including 2, 2, 4-TMDI and 2, 4, 4-TMDI) aliphatic diisocyanate such as;

(3) isophorone diisocyanate (referred to as "IPDI"), hydrogenation of toluene diisocyanate, hydrogenated diphenyl methane diisocyanate (referred to as "H₁₂ MDI"), hydrogenation of dimethylene diisocyanate (referred to as "H₆ XDI"), hydrogenated tetramethylbenzene dimethylene diisocyanate and cyclohexyl diisocyanate and so on fat ring type diisocyanate.

As mentioned above, from the relaxing stress considerations, require molecular kinetic, on the other hand, from the holding strength considerations, require a straight structure, therefore, the above-mentioned the gathers the isocyanic acid ester compound preferably instantiates polyol with an aromatic diisocyanate and/or alicyclic diisocyanate adduct modified body , and HDI with an aromatic diisocyanate and/or alicyclic diisocyanate isocyanurate modified product, adduct of the former particularly preferred. As a more preferred polyols, such as trimethylolpropane illustration, particularly preferably has the equivalent alcohol OH-based universal trimethylolpropane. Furthermore, as the diisocyanate compound, is good weather resisteant alicyclic diisocyanate, is thus preferred, particularly preferred H₆ XDI, IPDI and H₁₂ MDI.

Should be note, silane-modified polyisocyanate can also be utilized by the reaction with a diol poly isocyanate compound after quantizing high molecules, making the above-mentioned polyisocyanate and reactive silane coupling agent reaction of the silane-modified polyisocyanate. As the above-mentioned glycol, preferably instantiates ethylene glycol, 1, 4-butanediol, 1, 6-hexanediol, Ganong alcohol and 2, 2, 4-trimethyl -1, 3-pentanediol, 2-ethyl -1, 3-hexanediol, 2, 2-diethyl -1, 3-propanediol and 2-n-butyl-2-ethyl -1, 3-propylene glycol, and the like.

Primer composition in a solvent for coating, in addition, can also contain other silane coupling agent, other solidification ingredient, catalyst, drying agent, the resin component and the carbon black, and other compounds.

Other supplementary to the silane coupling agent of the silane-modified polyisocyanate compounds, and the firm the gleyness of the hard coating. The above-mentioned silane coupling agent is preferably the isocyanate group with active, therefore, preferably contains alcohol OH base, amino, imino, mercapto group and epoxy group as a functional group.

As a specific example of the above-mentioned silane coupling agent, as epoxy silane, for example, can be cited γ-glycidoxy propyl trimethoxy silane, γ-glycidoxy propyl methyl dimethoxy silane, 3, 4-epoxy cyclohexyl ethyl trimethoxy silane and 3, 4-epoxy cyclohexyl-ethyl methyl dimethoxy silane, and the like, as amino silane, for example can be cited amino methyl triethoxy silane, N-(β-aminoethyl) amino methyl trimethoxy silane, amino methyl diethoxy silane, N-(β-aminoethyl) methyl three butoxypolyethylene silane, γ-amino propyl triethoxy silane, γ-amino propyl methyl diethoxy silane, γ-amino-isobutyl trimethoxysilane, N-bis (β-hydroxyethyl)-γ-amino propyl triethoxy silane, N-(β-aminoethyl)-γ-amino propyl trimethoxy silane, N-(β-aminoethyl)-γ-amino propyl methyl dimethoxy silane and N-(β-aminoethyl)-γ-amino-β-methyl propyl trimethoxy silane, and the like, as a mercapto silane, for example can be cited γ-mercapto propyl methyl dimethoxy silane, γ-mercapto propyl trimethoxy silane, γ-mercapto propyl methyl diethoxy silane, γ-mercapto propyl triethoxy silane, γ-mercapto propyl ethyl dimethoxy silane, γ-mercapto propyl ethyl diethoxy silane, γ-mercapto propyl dimethyl-methoxy silane, γ-mercapto propyl methyl diethoxy silane, β-mercapto ethyl methyl dimethoxy silane, β-mercapto ethyl trimethoxy silane and β-mercapto ethyl triethoxy silane, and the like. Furthermore, as containing alcohol OH-based silane coupling agent, preferably instantiated to the above-mentioned epoxy silane 1 mol to 0.1-1 mol of the ratio of the above-mentioned amino-silane, mercapto silane with the activity of the epoxy group of the functional group of the silane compound modified silane.

As other solidification ingredient, can be cited various diisocyanate compounds and gathers the isocyanic acid ester compound. The above-mentioned solidified with the component facilitates good cementability polyurethane adhesive, on the other hand, it also become a limiting of the coating after the open time (open   time) of the important factors, therefore, the time to be increased the degree of freedom of the above-mentioned open in the use of the preferably does not contain. As other curing ingredients, in addition to the above-mentioned illustration, the isocyanate compound, as three different cyanate compound, can also be instantiated triphenyl methane -4, 4, 4-tri-isocyanate and three (the phenyl isocyanates) thiophosphate, and the like, the combination with other curing component, particularly preferably three (the phenyl isocyanates) thiophosphate.

As the resin component, can be instantiated polyester polyurethane resin, acrylic resin, epoxy resin, phenoxy resin, polycarbonate resin and vinyl chloride resin and the like. As mentioned above, the open time should be increased in the degree of freedom of the use of, preferably acrylic resin and epoxy resin, particularly preferred mixture of epoxy resin and acrylic resin. By using the above-mentioned mixture, the open time can be 1 months or more, more preferably 2 months or more. From the viewpoint of the chemical reaction, there is no limit on the open time, if other important factors considered by the pollution caused by, decomposition impacts, the lipid is 6 months following, more preferably at least 4 months of use of the following. On the other hand, does not need to be the above-mentioned uses, the considerations from the intensity excellent, preferably polyester polyurethane resin.

The above-mentioned epoxy resin of epoxy equivalent is preferably 1000-10000, more preferably 1000-5000. Furthermore, the molecular weight of the acrylic resin, based on standard polystyrene conversion assay method of GPC number average molecular weight of preferably 1000-100000, more preferably 5000-80000.

Should be note, the above-mentioned resin composition also can be through its modified, copolymerized processing method and form and contain alcohol OH base, in the form of an alkoxysilyl group, in particular to be able to use the degree of freedom to be increased the use of open time. The above-mentioned forms more preferably instantiated with these functional acrylic resin, for example, recorded with example the Japanese opens especially 2001-064470 of communiques, in the present invention can also be properly used.

From the dispersivity and other considerations, primer composition of the carbon black is preferably in acidic carbon black. As the acidic carbon black, its pH value is preferably 2.5-4 range. Furthermore, the particle size preferably utilize the 10-30nm range, an average particle diameter can also be of different 2 or more mixed for use.

As the catalyst, dibutyl tin lauric acid can be instantiated February, three bitter bismith , 2-ethyl hexanoic acid salt such as zinc and cobalt metal salt and N-methyl morpholine and N, N '-dimethyl piperazine and so on uncles amines, particularly preferably contains a metal salt. As a desiccant, can be instantiated synthetic zeolite, natural zeolites and molecular sieves, and the like, can be the appropriate use of its fine aperture is 3-10 heydon the scope of the desiccant. As other additives, for example, as stabilizer, can be instantiated malonic acid diethyl ester. Furthermore, as a solvent, can be instantiated methyl ethyl ketone, ethyl acetate, butyl acetate, cellosolve acetate, mineral oil, toluene, xylene, dimethylacetamide, acetone, hexane, dichloromethane, tetrahydrofuran, ethyl ether and the second alkane and so on. The above-mentioned solvent can be mixed 2 using above. Furthermore, in the above-mentioned compound and pentane, hexane, heptane, and octane, the carbon atom number 5-12 a saturated hydrocarbon compound. The above-mentioned solvent, preferably methyl ethyl ketone, ethyl acetate and butyl acetate, using ethyl acetate as a main component is particularly preferred. Usually the use level of the solvent relative to the total of the above-mentioned solid ingredient 100 part by weight as 100-1000 the left and right parts by weight, more preferably 200-700 parts by weight.

Primer composition in the proportion of the above-mentioned various components, the solid components of the solvent containing the same 100% in weight, silane-modified polyisocyanate is preferably 10-45 weight %, more preferably 12-30 weight %, other silane coupling agent is preferably 0-60 weight %, more preferably 10-35 weight %, the resin component is preferably 5-35 weight %, more preferably 20-30 weight % (should be note, the request for open time degree of freedom of application, epoxy resin is preferably 3-15 weight %), the carbon black is preferably 10-40 weight %, more preferably 20-35 weight %, and the catalyst is preferably 0.01-5% by weight, more preferably 0.05-3 weight %.

Adhesion between the primer layer (layer C) primer coating using various coating compositions, usually at room temperature to its drying and form. As a coating method, for example, can use the brushes spreads the law , spraying, bar coating method, blade coating method for coating and specification small amount products, and the like.

As preferred examples of the primer composition, can cite glass with a primer GP-402 (Sunstar   Engineering Corporation systems), G HAMATITE glass primer (MS-90) (YOKOHAMA   RUBBER Corporation systems) and the like.

<硬 涂层 : B 层>

Hard coating (B layer) formed using hard coating agent. In the hard coating agent colloidal silica and/or the content of the alkoxysilane hydrolysis condensate does not include the solvent relative to the total weight of 10 weight % or more, preferably 13% or more by weight, more preferably 15 weight %. If more than the lower limit, in the hard coating layer on the (B layer) for forms sticks the primer layer (layer C), to obtain excellent adhesive property. Furthermore, in the hard coating agent of the colloidal silica content is preferably 60% by weight the following. If colloidal silicon dioxide in the hard coating agent exceeds the upper limit, it is difficult to form a hard coating (B layer).

The hard coating agent in the organic silicon resin hard coating material, in the organic resin hard coating agent mixed organic solvent dispersed colloidal silicon dioxide to obtain.

Organic silicon resin hard coating material is formed with siloxane cured resin layer of the material, for example, can be cited to equivalent to 3 functional siloxane unit of the compound (such as three alkoxy silane compound) as a main component part of the hydrolysis condensate of a compound, preferably also contain equivalent to 4 functional siloxane unit of the compound (such as tetra alkoxy silane compound) partial hydrolysis condensate of, and in further in these compounds fill the colloidal silicon dioxide, metal oxide particles such as hydrolysis condensate of the part. Organic silicon resin hard coating material can also contain 2 functional siloxane unit and 1 functional siloxane unit. In these hard coating agent containing condensation reaction of the alcohol (alkoxy silane the situation of partial hydrolysis condensate), and the like, also can be dissolved or dispersed in any organic solvent, water, or a mixture of them. The purpose of as the organic solvent, can cite lower fatty acid alcohol, polyol and its ether , esters, etc.. Should be note, the surface state in order to get the smooth, hard coating can be added in various surface active agent, for example, siloxane, fluoro fundamental series surface active agents and the like.

As an organic resin hard coating material, for example, can be cited a melamine resin, polyurethane resin, alkyd resin, acrylic resin or multi-functional acrylic resin and the like. Here as a multi-functional acrylic resin, can cite polyol acrylate, polyester acrylate, urethane acrylate, epoxy acrylate, acrylic ester, a phosphazene resin.

And, the formation of a hard coating (B layer) of a resin can contain light stabilizer, ultraviolet ray absorbent and catalyst, heat · light polymerization initiator, a polymerization inhibitor, an antifoaming agent, leveling agent, tackifier, antiprecipitant, against class hangs the medicinal preparation , flame retardant, inorganic pigment with machine · · dye various additives and of the auxiliary agent.

As a coating method, can be used as the coating of the substrate on the basis of the shape of the shaped body of the appropriate selection of coating method, dimension, the class spreads the law , spraying, spin coating method, methods such as specification small amount products.

Hard coating (layer B) solidification method, preferably by selected from ionizing radiation irradiation, infrared irradiation, microwave irradiation, high-temperature vapor is exposed to the open air, heating of at least 1 kind of method to carry on.

Ionizing radiation means electromagnetic wave or a charged particle beam in the solidification reaction of the coating can cause the quantum of the energy of the ionizing radiation, usually using an ultraviolet (UV) or electron beam (EB), in addition, can also use the X-ray, electromagnetic wave such as γ-ray, α-ray, such as to strand charged particle beam.

The infrared irradiation causes the curing of the applied with the electromagnetic wave in the form of vibration energy in a short time so as to suppress local heating caused by the temperature rise of the substrate and cured, is thus preferred. If the use of laser, can also be reduced by using the normal infrared light beam diameter.

Microwave irradiation of the microwave by resonance, and the vibration of the matrix, to the matrix can be in the heat transfer of the heating, is thus preferred.

These cured method, the time required from the cured and considerations of the cost of equipment, particularly preferred of the ionizing radiation irradiation causes the solidification.

The preferred thickness of the hard coating the 1-30  m, more preferably the 2-20  m, further preferably the 3-10  m. If more than the lower limit, the wear resistance of the substrate is, if the upper-limit or lower, it is not easy to produce, does not have excellent adhesiveness with the substrate, thus preferred.

<弹性 粘接剂 层 : D 层>

D in the present invention the composition of the layer of an elastic adhesive preferably utilize the polyurethane adhesive. The polyurethane adhesive, moisture-curable one-component polyurethane adhesive and double-component polyurethane adhesive can be used, the moisture-curable one-component polyurethane adhesive excellent production efficiency, therefore, is particularly preferred.

Moisture-curable one-component polyurethane adhesive is generally used in a compound containing isocyanate groups, the isocyanate groups, in particular polyurethane prepolymer (the following, referred to as the tail end of the NCO prepolymer) as a main component, with the plasticizer, filler, catalyst and any other compound. Other compounds to the composition to impart the desired characteristics of the for the purpose such as, for example, include polyisocyanate compounds and γ-mercapto propyl trimethoxy silane, such as dense mixture of the silane coupling agent, and the like, used to impart heat-resistant adhesive (meth) acrylic acid ester copolymer and light for imparting damping · · sex of the sound insulation property of the foaming agent, such as micro-hollow ball. Here, the content of the NCO prepolymer of the polyurethane adhesive composition usually in total preferably in 15-50 weight %, more preferably in 20-45 weight %, further preferably in 30-45 selected in the range of weight %. As a polyurethane adhesive composition of the representative examples of preferably in the form of, preferably instantiates YOKOHAMA WS-222   RUBBER Corporation systems Corporation   Engineering and Sunstar Penguin   Seal# 560 of the window frame for mounting the various adhesive.

The thickness of the layer of D (Y) is 0.9-14 mm the following. Preferably A layer form the above-mentioned length of the long sides of the substrate is set as X (mm), D layer will be formed is set as Y (mm) of the thickness of the bond, X and Y satisfy the following formula (1)-(3).

0.9 the   Y <6     (0 <X <300 time)   (1)

3 × 10^-3 X≤Y <6     (300     X≤ 1500 time)   (2)

3 × 10^-3 X≤Y <(16/3) × 10^-3 X-2     (1500 <X≤ 3000 time)   (3)

If more than the lower limit of the thickness of the adhesive, is fully gleyness is, therefore, preferably, if the upper-limit or lower, the weight of the adhesive is small, low cost, with few restrictions of the design, therefore, preferred. Here, (1)-(3) type of the value of the upper limit according to the generic document 1.

<透光 基材层 : A 层>

The light transmission layer (A layer) by the melt extrusion of a thermoplastic resin.

(Thermoplastic resin)

Thermoplastic resin can be cited polyethylene, polyolefin resin such as polypropylene, poly-dicyclopentadiene, amorphous polyolefin resin, polycarbonate resin, acrylic resin such as polymethyl methacrylate, polyethylene terephthalate, polybutylene terephthalate, poly (2, 6-naphthalate), polyester resin, polystyrene, polyarylate, polyether sulfone, polyether-ether-ketone, polyimide, phenolic resin, urea resin and the like. Wherein preferably have excellent clarity of a polycarbonate resin, an acrylic resin such as polymethyl methacrylate, polyethylene terephthalate, polybutylene terephthalate, poly (2, 6-naphthalate), polyester resin, polystyrene, polypropylene, polyarylate, polyethersulfone. Furthermore, more preferably has high impact strength polycarbonate resin.

Polycarbonate resin in addition other than bisphenol A type polycarbonate, can also be a polymerized other dihydric phenols of the high heat resistance or low water absorption of the polycarbonate resin, use of the aliphatic glycol polymerization, and a high heat resistance of the polycarbonate resin. Polycarbonate resin can be manufactured by any manufacturing method, interfacial polycondensation usually uses a $the end-capping reagent of the phenol. The polycarbonate resin may also be 3 functional phenol is polymerized branched polycarbonate resin, can also be that the aliphatic dicarboxylic acid, aromatic dicarboxylic acid or divalent aliphatic or copolymerized the fat link race is mellow copolymerized polycarbonate. If the viscosity average molecular weight of polycarbonate resin 13000-40000 range, can be used for a wide range of fields. If having a viscosity average molecular weight of less than 20000, excellent fluidity is, even if the window with the resin in the vehicle, also can be suitable for complex shapes, large-scale resin molded article (such as the back door window), if having a viscosity average molecular weight of 20000 or more, the strength is excellent, is suitable for all vehicle resin window. As of the preferred use of this invention with the resin in the window of the vehicle, to choose the molded article is required to be matched with the target molecular weight. Because of this invention of the resin plate is thick, therefore, even if the relatively high molecular weight, is formed in the deformation of the acceptable limits. To consider from versatility, the upper limit of the viscosity average molecular weight is more preferably a 35000, further preferably 30000.

Should be note, above sticks average molecular weight is used as a polycarbonate resin as a whole can be satisfied, including through molecular weight different 2 or more kinds of the mixture meet the above-mentioned range. In particular, having a viscosity average molecular weight of more than 50000 (more preferably 80000 more, further preferably 100000 or more) of the polycarbonate at the time of mixing in the melt is advantageous entropy elasticity. For example, in the invention the injection inhibiting effect. The higher the molecular weight of polycarbonate entropy elasticity caused by the effect of the improvement of the more prominent, utility on the upper limit of the molecular weight is 200 million, preferably 30 million, more preferably at least 20 million. If combined with the above-mentioned polycarbonate resin 0.5-20 weight %, preferably 1-10 weight %, the moldability is not the special damage the effect of the specified circumstances.

Having a viscosity average molecular weight of polycarbonate resin (M) in methylene chloride by 100 ml polycarbonate resin dissolved in 0.7g of the solution in the 20 the viscosity obtained [...] (η_sp), the specific viscosity (η_sp) into the following formula to derive the. Detailed content of polycarbonate resin, for example, in Japan recorded opens especially 2002-129003 in its Bulletin.

η_sp/c= + 0.45 ײ c (wherein is an intrinsic viscosity)

[η] =1.23 × 10^-4 M^0.83

C=0.7

As the use of other dihydric phenol is polymerized high heat resistance or low water absorption of the specific example of polycarbonate resin, preferably instantiates the following material.

(1) in the polycarbonate dihydric phenol ingredient 100 in mol %, 4, 4 the [...] -(metaphenylene benzyl two different propylidenes) two phenol (hereinafter referred to as "BPM") component is 20-80 mol % (more preferably 40-75 mol %, further preferably 45-65 mol %), and 9, 9-bis (4-hydroxy-3-methyl phenyl) fluorene (hereinafter referred to as "BCF") component is 20-80 mol % (more preferably 25-60 mol %, further preferably 35-55 mol %)copolymerized polycarbonate.

(2) in the polycarbonate dihydric phenol ingredient 100 in mol %, is divided into a bisphenol A 10-95 mol % (more preferably 50-90 mol %, further preferably 60-85 mol %), and to the BCF 5-90 mol % (more preferably 10-50 mol %, further preferably 15-40 mol %)copolymerized polycarbonate.

(3) the polycarbonate of the dihydric phenol ingredient 100 in mol %, to the BPM 20-80 mol % (more preferably 40-75 mol %, further preferably 45-65 mol %), and 1, 1-bis (4-hydroxy phenyl)-3, 3, 5-trimethyl cyclohexane into divided into 20-80 mol % (more preferably 25-60 mol %, further preferably 35-55 mol %)copolymerized polycarbonate.

(4) in the polycarbonate dihydric phenol ingredient 100 in mol %, 2, 2-bis (4-hydroxy-3-methyl phenyl) propane (hereinafter referred to as "double-toxicarol C") component is 40-90 mol % (more preferably 50-80 mol %), is divided into a and bisphenol A 10-60 mol % (more preferably 20-50 mol %)copolymerized polycarbonate.

On the other hand, as the use of aliphatic diol is polymerized high heat resistance of the specific example of polycarbonate resin, of polycarbonate can be cited the aliphatic diol for different sorbitol , isomannide, polycarbonate different Ai Du Chun. Wherein from the manufacturing is easy, to consider excellent heat resistance, particularly preferred isosorbide (1, 4 ; 3, 6-anhydro-D-sorbitiol).

These special polycarbonate can be used alone, also can be appropriately mixed 2 the above. Furthermore, these may also be of polycarbonate with bisphenol A-type polycarbonate mixed for use.

On these special manufacturing method for polycarbonate and characteristics, for example, in Japan detail extra Kaiping 6-172508 of communiques, Japan extra Kaiping 8-27370 of communiques, Japan opens especially 2001-55435 of Japan and opens especially 2002-117580 in its Bulletin, and the like.

The above-mentioned thermoplastic resin without prejudice to the scope of the above-mentioned transparency, can contain various additives known in the past. As the above-mentioned additive, for example, can be instantiated heat stabilizer, antioxidant, ultraviolet absorber, light stabilizer, colorant, mold-releasing agent, glide medicinal preparation , an infrared ray absorber, light diffusing agent, fluorescent brightening agent, antistatic agent, flame retardant, flame retardant auxiliary agent, plasticizer, reinforced filling material, impact modifier, photocatalyst system such as photo-induced-blushing and anti-fouling agent. Should be note, heat stabilizer, antioxidant, ultraviolet absorber, light stabilizer, a coloring agent and the release agent and the like can be matched with the above-mentioned thermoplastic resin in the past known in a proper amount.

(Co-extrusion)

Light-transmitting substrate can include (A layer) is formed by co-extrusion a plurality of layers. Preferably A layer comprises a polycarbonate resin layer (A1 layer).

Preferably A layer comprises acrylic resin (A2 layer). Acrylic resin (A2 layer) and hard coating (B layer) the interface of the high sealing force, and to obtain excellent weather resistance, is thus preferred.

Acrylic resin (A2 layer) preferably in linear expansion coefficient of the 100-130 the average value of the range is counted [...] 3 × 10^-5 -80 × 10^-5/K, more preferably 3 × 10^-5 -60 × 10^-5/K, preferably further 3 × 10^-5 -50 × 10^-5/K. If the average value of the upper limit of the following, the process and the environment of use in the subsequent A2 layer and the hard coating (layer B) small difference in expansion, can prevent the A2 layer deformed or cracked and B crackle.

Acrylic resin (A2 layer) preferably contains the ultraviolet ray absorbent or the ultraviolet absorbent group is fixed. Ultraviolet absorbent due to improve weatherability, and preferably, wherein the preferred optical decomposition speed is slow, durability excellent benzocarbazoles triazole department ultraviolet absorber or triazine. Wherein more preferably the triazine-based ultraviolet absorbent.

As a benzotriazole-based ultraviolet absorber, for example, can be cited of 2-(2-hydroxy-5-methyl phenyl) benzotriazole, 2-(2-hydroxy-5- uncle octyl phenyl) benzotriazole, 2-(2-hydroxy -3, 5-dicumylphenyl phenyl) phenyl-benzotriazole, 2-(2-hydroxy-3-tert-butyl-5-methyl-phenyl)-5-chlorobenzo triazole, 2, 2 the [...] -methylene-bis [4-(1, 1, 3, 3-tetramethyl-butyl)-6-(2N-benzotriazole-2-yl) phenol], 2-(2-hydroxy -3, 5-di-tert-butyl phenyl) benzotriazole, 2-(2-hydroxy -3, 5-di-tert-butyl phenyl)-5-chloro-benzotriazole, 2-(2-hydroxy -3, 5-di-tert-amyl phenyl) benzotriazole, 2-(2-hydroxy-5- uncle octyl phenyl) benzotriazole, 2-(2-hydroxy-5-tert-butyl phenyl) benzotriazole, 2-(2-hydroxy-4-octoxy phenyl) benzotriazole, 2, 2 the [...] -methylene-bis (4-cumyl-6-benzo triazole phenyl), 2, 2 the the- [...]asian benzene dihydrogenmethylenebisphosphonate (1, 3-benzodioxan Hydrochlorothizide-4-one), 2-[ 2-hydroxy-3-(3, 4, 5, 6-tetrahydrophthalic acid imide methyl)-5-methyl phenyl] benzotriazole.

As the triazine series ultraviolet absorbent, specifically, can cite 2-(4, 6-diphenyl -1, 3, 5-triazin-2-yl)-5-[ (hexyl) oxy]-phenol, 2-(4, 6-bis (2, 4-dimethyl phenyl)-1, 3, 5-triazin-2-yl)-5-[ (octyl) oxy]-phenol.

These benzotriazole series or triazine-based ultraviolet absorbers can be used alone or to 2 in the form of a mixture of the above. The acrylic resin contains the amount of the ultraviolet absorber relative to the acrylic resin 100 parts by weight, preferably 0.3-35 parts by weight, more preferably 1-25 parts by weight, further preferably 2-15 parts by weight.

By using co-extrusion in polycarbonate resin layer (A1 layer) is formed on the surface of the acrylic resin such as polymethyl methacrylate (A2 layer) of the layer a, polycarbonate resin layer (A1 layer) and hard coating (B layer) interface sealing force is high, high weatherability, is thus preferred.

Furthermore, the excellent impact resistance, environmental load is small starting, by a co-extrusion is preferably used in polycarbonate resin layer (A1 layer) formed on the surface layer of the dihydroxy compound such as isosorbide-containing layer formed of the polycarbonate resin of the layer.

(A1 and A2 method of laminating of layer)

In polycarbonate resin layer (A1 layer) acrylic resin layer is laminated on the (A2 layer), preferably as a co-extrusion process.

Co-extrusion method using an extrusion device. A general by the extrusion of a polycarbonate resin substrate a main extruder and will form of acrylic resin extrusion coating 1 or 2 more than one sub-extrusion device, usually sub-extrusion machine adopts the main extruder small extruder.

The main extruder is usually the temperature condition of the 230-310 [...] , is preferably the 240-300 [...] , in addition, sub-extruder is usually the temperature condition of the 200-300 [...] , is preferably the 210-290 [...]. As coated 2 the above method of the molten resin, can be used (feed   block) mode for remnants , multi-manifold such as the well-known method. At this time, in the feeding head is introduced into the molten resin of the sheet material forming the mold die T, after the molded into a sheet form, into the surface of each mirror treatment (high), forming stack rubber (bank). The sheet forming material through the forming roll to mirror finish in the course of processing and cooling, forming a laminated plate. Furthermore, under the condition of a plurality of branch pipe mold , in the in-mold laminated molten resin into a sheet in the inside of the mould, by using shaping surface finish processing and cooling, forming a laminated plate. The temperature of the mould, it is usually the 220-300 [...] , is preferably the 230-290 [...] , as the temperature of the forming roll, it is usually the 90-190 [...] , is preferably the 100-180 [...]. Rollers can be contacted each other appropriate use of vertical or horizontal roller.

Obtained by co-extrusion of a polycarbonate resin layer (A1 layer) and acrylic resin (A2 layer) is preferably the total of the thickness of 1 mm -20 mm, more preferably 1 mm -18 mm, particularly preferably 1 mm -15 mm. If more than the lower limit, relative to the deflection of the load from the outside becomes small, dimension stability is excellent, is thus preferred, if the upper-limit or lower, can not hindering the thin, light-weighted, no deformation observed to the outside, is thus preferred.

Furthermore, obtained by co-extrusion of a polycarbonate resin layer (A1 layer) and acrylic resin (A2 layer) preferably thickness ratio of A1 layer/A2 layer = 200-4, more preferably 100-9. If the thickness ratio of the upper-limit or lower, the A2 layer containing ultraviolet radiation absorbents have sufficient weather resistance, so as to obtain excellent scratch resistance, is thus preferred, if more than the lower limit, the polycarbonate resin and thermosetting resin having a Vicat softening temperature of the thermosetting film formed between the thermoplastic resin is not susceptible to the softening deformation of, is thus preferred.

(The shape of the transparent substrate)

The light transmission layer (A layer) is preferably the length of the long sides 150-3000mm, more preferably 300-2500mm. If more than the lower limit length of the long side, the upper limit of the following, in order to meet the above-mentioned formula (1)-(3) the thickness of the adhesive of the rigid structure of the good bonding of the gleyness of the installation, is thus preferred. In this invention use in the substrate layer of the sheet is of the long side of the machine in an outer peripheral portion of the longest side.

Light transmission layer thickness of (A layer) is preferably 1-9mm. The lower limit of the above-mentioned thickness is more preferably 2 mm, further preferably 3 mm. The upper limit of the above-mentioned thickness is more preferably 8 mm, further preferably 7 mm.

A layer is made by co-extrusion using acrylic resin surface layer of the layer a, the thickness of the acrylic resin layer is preferably the 10-300  m, more preferably the 20-200  m. If more than the lower limit, it can control the thickness of the acrylic resin layer is, therefore, preferably, if the upper-limit or lower, it can inhibit reduction of impact properties, is thus preferred.

The light transmission layer (A layer) is preferably the maximum projection area 200-60000cm², more preferably 1000-40000cm².

Furthermore, the light transmission layer (A layer) may have a curved surface, with the degree in bending of the said radius of curvature (mm), preferably 500-30000mm, more preferably 1000-25000mm, further preferably 1500-10000mm range.

The above-mentioned such a large-scale substrate of the curved surface of the relatively slow and can give full play to the substrate by piercing of the present invention the effect of the stress resistance.

<遮光层 : E 层>

The laminate of this invention with B A layer between layer can have a screen printing layer or two-color molded resin layer as the light shielding layer (frame part, E layer). The above-mentioned light shielding layer in the glass assembling (glazing) formed in the peripheral part, in the periphery of the with-walled formed in the function of an adhesive and a structural member. Shading part is preferably formed of a substrate 1 side (for example, inside the vehicle) and 2 (for example, the outer side of the vehicle) side of the 1 surface (in this case formed in the section 1 side).

Shading of the coating of the ink, the color of the molded article and at the same time forming, and other to form. The above-mentioned bonding method can use the adhesive (moisture-curable, reactive, such as light-curable and pressure sensitive) welding and (direct, ultrasonic welding and laser welding, and the like) and other bonding method. The above-mentioned connector can utilize the coating with adhesive ability of the method and of the main body in the method of use of double-sided adhesive tape of any method.

(Coating of the ink)

For ink when the coating to form a shading part, can use various ink. As mentioned above, according to the forming position of the shading part, different characteristic required for, taking into account the above-mentioned various aspects to the selected ink. From the affinity of polycarbonate, the resistance of the hard and hot forming coating liquid of the following considerations, preferably the following substances as an ink binder, i.e., vinyl chloride-vinyl acetate copolymer resin, acrylic resin, polycarbonate resin, polyester elastomer, acrylic polyol isocyanate gathers mellowly by a two-component polyurethane resin of the polyester polyol and isocyanate gathers mellowly a two-component polyurethane resin. Ink binder can be used singly or mixed 2 the above. Wherein more preferably two-component polyurethane resin, particularly preferred isocyanate gathers mellowly by the acrylic polyol a two-component polyurethane resin.

For ink when the coating to form a shading part, as the above-mentioned forming method, can use various printing method, such as spraying and brushing various method. Printing method without particular limitation, can be the known method of the catenary or bending of the flat plate of the printing sheet surface. For example, can be instantiated jet printing, offset printing, flexographic printing, intaglio printing, screen printing and ink jet printing method, which may most preferably using screen printing.

(Two-color molded)

Through the molded product of the two-color molding, to form a shading part of the joint, and the like, the molding can be performed by a variety of plastic (including high-molecular alloy material), fiber reinforced plastic, mineral reinforced plastic and fiber-reinforced composite material (is composed of a glass fiber, aramid fiber, ceramic fiber and carbon fiber of the FRP, SMC and composite materials such as RTM) form. The above-mentioned molded article can utilize aluminum alloy and steel (steel plate), metal parts such as magnesium alloy and titanium alloy, other wood and the like and to strengthen the rigid part, in addition, can be through the gas-assisted forming, foaming molding to melt. The fiber-reinforced plastic by the injection molding, can be utilized for SVG connection based on the level.

The light shielding layer (E layer) formed by the latter resin composition. The light shielding layer (layer E) and the light transmission layer (A layer) of a part of the stress can be combined with, more preferably the light transmission layer (layer A) of the circumference (periphery) of the total binding. In other words, the light shielding layer (E layer) is more preferably in the form of the light-transmitting layer (layer A) of the peripheral portion of the molded body of the frame. Furthermore, preferably, in a light transmission layer (A layer) of the area of the 10-90% range of the light shielding layer (layer E) and the light transmission layer (layer A) binding. More preferred is the above-mentioned range 20-80%, further preferably 30-70%.

Furthermore, the light shielding layer (E layer) can be a transparent substrate layer (A layer) of the two surfaces of the lateral or in combination, more preferably the combination of the single surface.

The light transmission layer (layer A) and a light shield layer (layer E) than the thickness of the (A layer/E layer) is preferably 0.1-10 range, more preferably 0.5-5 range, further preferably 0.8-4 range. Furthermore, as the light shielding layer (layer E) the absolute value of the thickness of, preferably 0.1-10 mm range, more preferably 0.5-5 mm range, further preferably 1-3mm range. For the above-mentioned ratio and the thickness of the light transmission layer (layer A) bending deformation caused by the thermal expansion of the full binding to, as a result the frame part of the resin composition to obtain good long-term characteristics.

The light shielding layer (E layer) can be through the use of various methods to manufacture the resin composition. As the above-mentioned manufacturing method, in particular, can be instantiated injection molding, extrusion molding, compression molding, rotary molding, and blow molding, injection molding being particularly preferred. Furthermore, the above-mentioned molded body can also be 2 time processing.

(Light shielding layer of the resin)

A light shielding layer used in the present invention the resin preferably of a high rigidity (high bending elastic modulus), high-toughness (high elongation at break, high impact strength), flow properties, the resin of excellent heat resistance. Them from heat resistance, flow properties, impact-resistant, rigid considerations, more preferably aromatic polycarbonate 50-90 parts by weight, styrene resin 10-50 parts by weight, of inorganic filling material 0-50 parts by weight of the range. If the styrene resin is more than the upper limit, the heat resistance is reduced, if the lower limit of the following, the fluidity is insufficient. Furthermore, considering from heat resistance, the resin composition of the frame part is preferably not containing olefin.

Styrene resin is an aromatic vinyl monomer to polymer, or according to the requirements can be selected from aromatic vinyl monomer copolymerized with the other monomers in the polymer and rubber at least 1 kind a copolymer obtained by copolymerization (the following sometimes referred to as "styrene polymer") of the resin, the resin can be a plurality of polymer or copolymer mixture. Furthermore, the above-mentioned styrene-based resin is a copolymer containing at least 20% of the weight of the copolymer of an aromatic vinyl monomer.

The light shielding layer may contain a resin composition for bonded with the latter a compatilizer of different types of polymer such as a copolymer ingredient of the chain. In containing a styrene polymer or aromatic polycarbonate as its segment in the copolymer, each segment are respectively reflected styrene-based resin and the composition proportion of the aromatic polycarbonate resin. This is because of the consideration of the above copolymer ingredient of most of the segments with their respective properties of the polymer.

As the styrene resin of the aromatic vinyl monomer (the following, sometimes referred to as "aromatic vinyl compound"), can cite styrene, α-methyl styrene, O-methyl styrene, P-methyl styrene, vinyl xylene, ethyl styrene, dimethyl styrene, P-tert-butyl styrene, vinylnaphthaline, methoxylphenylboronic ethylene, single-bromophenylacetic ethylene, two bromophenylacetic ethylene, fluorobenzene ethylene, such as tribromostyrene, preferably styrene, α-methyl styrene, particularly preferably styrene.

As the aromatic vinyl monomer copolymerized monomer, can be preferably cited Carbonitride vinyl compound and (meth) acrylic acid ester compound. As Carbonitride vinyl compound, can cite acrylonitrile, methacrylonitrile and the like, special preferably acrylonitrile.

As the (meth) acrylic acid ester compound, in particular, can be cited (meth) acrylic acid methyl ester, (meth) acrylic acid ethyl ester, (meth) acrylic acid propyl ester, isopropyl ester (meth) acrylic acid, (meth) acrylic acid n-butyl, amyl ester of (meth) acrylic acid, (meth) acrylic acid own ester, octyl (meth) acrylic acid, (meth) acrylic acid 2-ethyl hexyl acrylate, cyclohexyl (meth) acrylic acid, (meth) acrylic acid dodecyl ester, eighteen alkyl (meth) acrylate, phenyl (meth) acrylic acid, (meth) acrylic acid ester, and the like. Should be note (meth) acrylate of said representations comprises a methyl acrylate and acrylic ester, (meth) acrylic ester of said representations comprises a methyl acrylate and acrylic acid ester. As a particularly preferred (meth) acrylic acid ester compound, can cite methyl methacrylate.

As Carbonitride vinyl compound and (meth) acrylic acid ester compound other than the aromatic vinyl compound can be copolymerized with other vinyl monomer, can cite methyl acrylic acid containing epoxy group such as glycidyl ester of methacrylic acid ester, maleimide, N-methyl maleimide, phenyl maleimide, and the like-N maleimide-series monomer, acrylic acid, methacrylic acid, maleic acid, maleic anhydride, phthalic acid, itaconic acid, α, β-unsaturated carboxylic acid and its acid anhydride.

With the above-mentioned aromatic vinyl monomer may be copolymerized with the monomer of the monomer of the proportion of the total of the two 100% in weight, of the aromatic vinyl monomer 50-95 weight % (preferably 65-85 weight %), and the copolymerizable monomer is 5-50 weight % (preferably 15-35 weight %). The above copolymerizable monomer, preferably Carbonitride vinyl compound and (meth) acrylic acid ester compound, particularly preferred Carbonitride vinyl compound. In other words, styrene resin preferably containing Carbonitride vinyl compound as the copolymerization component of the copolymer resin. A more preferred aromatic vinyl monomer that is copolymerized with the composition substantially only by Carbonitride vinyl compound (in particular acrylonitrile) a copolymer of the form of the styrene resin. In particular in the styrene resin as the aromatic vinyl monomer can be copolymerized with a mixture of the composition of the copolymer, preferably the above-mentioned arbitrary types of copolymer are containing Carbonitride vinyl compound as the copolymerization component of the copolymer, further preferably the aromatic vinyl monomer copolymerized ingredient substantially only by Carbonitride vinyl compound a (in particular acrylonitrile) copolymer.

Furthermore, used in the present invention can be a styrene resin in its manufacturing by using the metallocene catalyst as a catalyst, such as syndiotactic polystyrene with stereo-regularity of the styrene resin. Furthermore, depending on the circumstances, can be through the anion active polymerization, free radical active polymerization method such as the narrow molecular weight distribution polymer, copolymer, block copolymer, and three-dimensional regularity of the high polymer, copolymer. Furthermore, the copolymer of the styrene resin, using a large molecular monomer for the control of the polymer, such as comb-like structure according to the grade of various molecules of the precise control of the various copolymers is well known. As the styrene resin, these can be used to carry out the known precise control of the copolymer.

Styrene resin, containing a rubber component of polymer specific example of styrene resin, polystyrene resin, for example, can be cited, MS resin, resin and AS SMA resin and the like. Should be note, here represent main MS resin is a methyl methacrylate and styrene copolymer resin, resin AS that a mainly composed of acrylonitrile and styrene copolymer resin, said SMA resin is mainly composed of a styrene and maleic anhydride copolymer resin (MA).

As the above-mentioned of the rubber component of polymer containing styrene resin, preferably resin and AS MS resin, particularly preferred resin AS. In this invention means the AS resin is vinyl cyanide compound and aromatic vinyl compound copolymer and a thermoplastic copolymer. The above-mentioned Carbonitride vinyl compound one of the examples as mentioned above, preferably with the use of the acrylonitrile. Furthermore, aromatic vinyl compound one of the examples also as noted above, preferably styrene, α-methyl styrene, the styrene is preferably used. AS in the resin as the proportion of each ingredient is, in order to to 100% of the weight of the, Carbonitride vinyl compound (in particular acrylonitrile) to 5-50 weight %, preferably 15-35 weight %, aromatic vinyl compound (especially styrene) to 95-50 weight %, preferably 85-65 weight %. Furthermore, these vinyl compounds can be copolymerized with the above-mentioned other compounds can be copolymerized. These other compounds containing AS in the proportion of the resin component is preferably 15 weight % of the following. Furthermore, used in the reaction initiator, chain transfer agent, and the like can be used according to the needs of the various substances known in prior art.

The above-mentioned AS resin can be prepared by bulk polymerization, suspension polymerization, emulsion polymerization method for manufacturing any of the, is preferably made by bulk polymerization. Furthermore, co-poly method can be a segment of the copolymer, or the copolymer can be formed by a plurality of. Furthermore, the above-mentioned AS resin has a weight average molecular weight based on GPC measurement according to the standard polysterol, preferably 40000-200000. The above-mentioned lower limit more preferably 50000, further preferably 70000. Furthermore, the upper limit is more preferably 160000, further preferably 150000.

Styrene resin preferably containing copolymer (the following sometimes referred to as "rubber co-polystyrene polymer") styrene resin, the copolymer is at least in the bonding rubber polymer containing an aromatic vinyl monomer unit as the constitutional units of the polymer. The reason was that contains the above-mentioned rubber co-polystyrene polymer styrene resin in the broad composition range play a good toughness, practicability-rich, co-containing rubber and when the polystyrene polymer styrene resin, only the more significant the effect of C ingredient of the invention. As with rubber polymer bonding polymer, as described above can be cited the homopolymer of an aromatic vinyl compound and the aromatic vinyl compound is copolymerized with the compound can be a copolymer of the monomer. Aromatic vinyl compound and the content of the copolymerized monomer, preferably in the form of, and the composition proportion of the aromatic vinyl compounds such as mentioned above.

The above-mentioned rubber polymer has no particular limitation, the glass transition temperature refers to the 10 the following [...] , preferably -10 the following [...] , more preferably -30 the polymer following [...]. Furthermore, rubber polymer is cross-linked rubber particles, the particle size thereof to heavy particle size meter preferably 0.05-5 the  m, more preferably 0.1-1.5 the  m, further preferably 0.1-0.8 the  m. If it is in the above-mentioned range, it can realize more excellent impact resistance.

As the rubber polymer, can cite diene rubber (polybutadiene, polyisoprene, styrene · butadiene random copolymer and block copolymer, acrylonitrile · butadiene copolymer, acrylic acid alkyl acrylate or alkyl methacrylate and butadiene copolymer, butadiene · isoprene copolymer), olefin rubber (ethylene and α-olefin copolymer, ethylene and unsaturated carboxylic acid ester copolymer, ethylene and aliphatic vinyl ester copolymer), acrylic rubber (for example n-butyl acrylate, poly (acrylic acid 2-ethylhexyl) and butyl acrylate and acrylic acid 2-ethyl hexyl ester copolymer) and organic silicon rubber (such as polyorganosiloxane rubber, the polyorganosiloxane rubber component and the poly (meth) acrylate rubber component to form the IPN-shaped rubber; that is, with 2 a rubber ingredient can not be separated are interwoven into the structure of the rubber and by the organopolysiloxane rubber component and polyisobutylene rubber component to form the IPN-type rubber and the like) and other, wherein preferably diene rubber, olefin rubber and acrylic rubber.

The diene rubber further description. As the styrene-based resin for use in rubber polymer of a diene rubber, can be used, for example, polybutadiene, polyisoprene and styrene · butadiene copolymer a glass transition temperature of 10 the rubber of the following [...] , its proportion in the styrene resin is preferably 5-80 weight %, more preferably 8-70 weight %, further preferably 10-50 weight %, especially preferably 12-40 weight %. The rubber particle size is preferably 0.05-5 the  m, more preferably 0.1-1.5 the  m, especially preferably 0.1-0.8 the  m. The above-mentioned rubber the distribution of particle size of the rubber and is of the single distribution with 2 peak of the plurality of peaks of the above rubber can be used, in addition, the morphology of the rubber particles can be on the single-phase rubber, also can be through the periphery of the rubber particle containing inner phase (occlude) with sausage ([...]) and the rubber structure.

Further to explain the olefin rubber. As the styrene resin used in the rubber polymer of olefin rubber, can cite ethylene and α-olefin copolymer (for example, ethylene · propylene random copolymers and block copolymers, ethylene · butene random copolymers and block copolymers, etc.), ethylene and unsaturated carboxylic acid ester copolymer (such as ethylene · methyl acrylate copolymer and ethylene copolymer of butyl acrylate ·), a copolymer of ethylene with aliphatic vinyl ester (for example, ethylene vinyl acetate copolymer, ·), ethylene and propylene with non-conjugated diene ternary polymer (for example, ethylene · · hexadiene copolymer of propylene) and the like. Olefin rubber is preferably in the form of ethylene and α-olefin copolymer and from ethylene, α-olefin and the isomerization of nonconjugated polyene copolymer of, from the obtained to consider cross-linked structure, the special are preferably made of ethylene, α-olefin and the isomerization of nonconjugated polyene copolymer of. Here, α-olefin carbon atom number 3-60, preferably 3-30, more preferably 3-20. Should be note, these copolymers comprising the conjugated diene compound to be obtained by copolymerization of the (hydrogenated) copolymer obtained by hydrogenation of the copolymer. As obtained by the above-mentioned hydrogenation of the rubber, hydrogenation can be instantiated by the polybutadiene to produce polyethylene unit, generated by the polyisoprene hydrogenation of the poly (ethylene-propylene) unit and the like.

Olefin rubber also includes cross-linked and non-cross-linked of arbitrary rubber polymer, considered from the impact resistance, more preferably crossing linking oak glial polymer. The above-mentioned circumstances, the cross-linking ratio preferably hot toluene insolubles content is 30 weight % or more, further preferably 50 weight % or more.

Furthermore, olefin rubber can also be formed by 2 or more kinds of mixture. For example can be instantiated ethylene and α-olefin copolymer, in and by ethylene, α-olefin and copolymers of isomerization of nonconjugated polyene a containing selected from the low molecular weight polyethylene, low-molecular-weight ethylene ·α-olefin copolymer, the unsaturated carboxylic acid-modified low-molecular-weight polyethylene and unsaturated carboxylic acid-modified low-molecular-weight ethylene ·α-olefin copolymer at least 1 kind of the rubber polymer.

As the above-mentioned α-olefin compound, for example can be instantiated propylene, 1-butene, 1-pentene, 1-hexene, 3-methyl-1-butene, 3-methyl-1-pentene, 3-ethyl-1-pentene, 4-methyl-1-pentene, 4-methyl-1-hexene, 4, 4-dimethyl-1-hexene, 4, 4-dimethyl-1-pentene, 4-ethyl-1-hexene, 3-ethyl-1-hexene, 1-octene, 1-decene, 1- dodecylene , 1- tetradecene , 1- 16 alkene , 1- octadecene , 1- 20 alkene , and the like. Wherein preferably propylene, 1-butene, 1-hexene and 1-octene, further preferably propylene.

As a non-conjugated polyene compounds, for example, can be instantiated 1, 4-hexadiene, 5-ethylidene-2-norbornene, bicyclo pentadiene, 5-vinyl norbornene, 6, 7-dimethyl-4-ethylidene -1, 6-octadiene, 6, 7-dimethyl-4-ethylidene -1, 6- ninth stem two alkene , 7-methyl-6-propyl-4-ethylidene -1, 6-octadiene, 8-methyl-4-ethylidene -1, 7- ninth stem two alkene , 7, 8-dimethyl-4-ethylidene -1, 7- ninth stem two alkene , 7, 8-dimethyl-4-ethylidene -1, 7- ninth stem two alkene , 9-methyl-4-ethylidene -1, 8- decadiene-D and 8, 9-dimethyl-4-ethylidene -1, 8- decadiene-D , and the like.

Ethylene and α-olefin copolymer and from ethylene, α-olefin and copolymers of isomerization of nonconjugated polyene a, ethylene and α-olefin molar ratio of (ethylene / α-olefin) preferably 40/60-95/5 range, more preferably 60/40-92/8 range, further preferably 65/35-90/10 range. The above-mentioned range by satisfying, to obtain good impact resistance.

Furthermore, ethylene and α-olefin copolymer and from ethylene, α-olefin and copolymers of isomerization of nonconjugated polyene a, the same preferably whose iodine valence 5-40 range, more preferably 10-30 range, further preferably 10-20 range.

Furthermore, by ethylene, α-olefin and the isomerization of nonconjugated polyene copolymer of the synthetic linear polymer according to the need for cross-linking treatment. The above-mentioned cross-linking treatment use of the ionizing radiation of the radiation treatment, use of organic peroxides in past heat place disposition of the cross-linking treatment method known. The above-mentioned cross-linking of the rubber polymer is used for the rubber substrate of the graft copolymerization.

Ethylene and α-olefin copolymer and from ethylene, α-olefin and the isomerization of nonconjugated polyene copolymer usually use of a Ziegler-type catalyst manufacturing. As other catalysts, can be instantiated metallocene compound and organic-combination of compound.

On the other hand, the conjugated diene compound polymer to make hydrogenation of ethylene and α-olefin copolymer is, the conjugated diene compound polymer composite material commonly used to manufacture plasma polymerization catalyst, the hydrogenation treatment of the subsequent manufacturing of rubber polymer or rubber co-polystyrene polymer. For example, the polymer of the SEPS, · synthetic styrene-isoprene-styrene block copolymer after ·, to hydrogenation process.

As a conjugated diene compound, can cite butadiene, isoprene, and the like. Further preferably can cite polyisoprene, polybutadiene, and isoprene and butadiene copolymer. Copolymer under the condition of, as its shape, it is also able to select random copolymer, block copolymer and a tapered copolymer of arbitrary shape.

The conjugated diene compound polymer produced by hydrogenation of ethylene with α-olefins of the molecular weight of the copolymer is not limited, a number average molecular weight of preferably 10000-200000 range. Number average molecular weight of more preferably 15000-150000. In the above-mentioned range, further impart good molding processability.

The conjugated diene compound polymer containing the hydrogenation of ethylene and α-olefin copolymer unit of the block copolymer in the manufacture of catalyst of, coupling agent, co-catalyst, polymerization method and solvent, etc., can be appropriate to use the known method.

Further explanation to the acrylic rubber. As the styrene resin rubber polymer of the acrylic rubber used in the (meth) acrylic acid alkyl ester monomer, alkyl carbon atom number is preferably 2-20. Specifically, for example, as an alkyl carbon atom number 2-5 of the (meth) acrylic acid alkyl ester (hereinafter referred to as "C2-C5 acrylate"), can cite ethyl acrylate, n-propyl acrylate, n-butyl acrylate, acrylic acid 4-hydroxy-n-butyl and the like. Furthermore, for example, as an alkyl carbon atom number 6-20 of the (meth) acrylic acid alkyl ester (hereinafter referred to as "C6-C20 acrylate"), can cite acrylic acid 2-ethyl hexyl acrylate, acrylic acid ethoxy group second gradeoxygen radical ethyl ester , methoxy three propylene glycol acrylate, methyl acrylic acid own ester, methyl acrylic acid 2-ethyl hexyl acrylate, lauryl methacrylate, methyl acrylic acid tridecane ester, methyl acrylic acid stearin ester , and the like. As the above-mentioned C2-C5 acrylate, preferably n-butyl acrylate. On the other hand, as the C6-C20 acrylate, preferably acrylic acid 2-ethyl hexyl acrylate, acrylic acid ethoxy group second gradeoxygen radical ethyl ester , methoxy three propylene glycol acrylate, lauryl methacrylate, methyl acrylic acid ester and methyl acrylic acid stearin estertridecane , from heat resistance, impact resistance considerations, particularly preferred acrylic acid 2-ethyl hexyl acrylate. Wherein the preferred acrylic acid is n-butyl. The reason was that of n-butyl acrylate the balance of the heat resistance and impact resistance is excellent, can be more widely use, can be easily obtained, therefore the industry.

The above (meth) acrylic acid alkyl ester monomer can be used alone, and can also be 2 or more use. In the case of, the particularly preferred C2-C5 acrylate and C6-C20 acrylate and use. The above-mentioned and that can further improve the heat resistance and impact resistance of course. In the case of the above, in addition to the 2 the composition of the above method of copolymerization outside at the same time, can also be cited as a polymerization of the monomer obtained in the above-mentioned polymer in the impregnated other monomer to conduct polymerization method and the respective monomers are respectively after polymerization and method for mixing them. Particularly preferred monomer impregnation of the polymer in the method. Furthermore, more preferably the rubber the glass transition temperature of the matrix obtained DSC differential curve in the bimodal behavior.

Furthermore, acrylic rubber can be through the multi-functional (meth) acrylic acid alkyl ester with the above (meth) acrylic acid alkyl ester monomer is polymerized and together get more preferably of the rubber elasticity. Here, as the polyfunctional (meth) acrylate, allyl methacrylate can be cited, for example, ethylene glycol dimethacrylate, propylene glycol dimethacrylate, 1, 3-butanediol dimethacrylate, 1, 4-butanediol dimethacrylate, divinyl benzene, and the like and cyanogen uric acid three alkene propyl esterisocyanuric acid three alkene propyl ester. They can be the combination of 2 or more kinds. As the above-mentioned multi-functional (meth) acrylic acid alkyl ester, preferably methyl acrylic acid allyl ester, such as cyanogen uric acid three alkene propyl ester , more preferably methyl acrylic acid allyl ester. Furthermore, the above-mentioned multi-functional (meth) acrylic acid alkyl ester in the rubber polymer is preferably 0.1-20 weight %, more preferably 0.2-3% by weight, further preferably 0.3-2.5 weight %.

Furthermore, the lack of use in the above-mentioned acrylic rubber latex, the water-soluble monomer, the preferred modulation emulsion polymerization for manufacturing. As the above-mentioned manufacturing method, the latex micronized device, can cite the shearing force produced by the high-speed rotation the latex microparticulated the homogenizing mixer, the high-pressure generator to generate characteristics of the latex and homogenizer microparticulated by utilizing porous filter the microparticulated of the latex. Containing rubber of the present invention co-polystyrene polymer in the styrene-based resin, as the aromatic vinyl monomer can be copolymerized with other monomer, the above-mentioned substance can be used, through the graft copolymerization, block copolymerization of a variety of known method such as the rubber polymer obtained by copolymerizing. Method for copolymerization is not particularly limited, preferably graft copolymerization, block copolymerization, from can impart good impact resistance, taking into account toughness, particularly preferred graft copolymerization.

The above-described rubber as containing a polystyrene polymer styrene resin, may, for example, be cited styrene · butadiene · styrene copolymer resin (SBS resin), hydrogenated styrene · butadiene · styrene copolymer resin (hydrogenated SBS resin), hydrogenated styrene-isoprene-styrene copolymer resin · · (SEPS resin), acrylonitrile · butadiene · styrene copolymer resin (ABS resin), methacrylic acid methyl ester · butadiene · styrene copolymer resin (MBS resin), methacrylic acid methyl ester · · · butadiene acrylonitrile styrene copolymer resin (MABS resin), acrylonitrile acrylic rubber · · styrene copolymer resin (ASA resin), acrylonitrile · ethylene propylene rubber · styrene copolymer resin (AES resin) or their mixture. Styrene resin of the present invention usually by the rubber co-polystyrene polymer and not with the rubber polymer bonding styrene polymer sold and used in the form of a mixture. Here not with the rubber polymer bonding styrene polymer can be in the rubber polymer bonding reaction of the free component and the bonding of the polymer obtained by the polymerization of any one of the in the ingredient, most of the usual market styrene resin (especially graft copolymer styrene resin) also often includes the above-mentioned optional ingredient is well known. On the other hand, the additional polymer obtained by the polymerization may also be components of the resin composition of the present invention is the composition of the mixture.

Rubber as containing a polystyrene polymer styrene resin, preferably SBS resin or ABS resin, MBS resin, ASA resin, AES resin, more preferably ABS resin, AES resin, ASA resin, AES resin and particularly preferred ASA resin. In the AES resin and ASA resin in the past of inorganic filling material with the aromatic polycarbonate resin, the impact resistance thereof as a component of the effect of the acid-modified polyolefin wax and so on sometimes small. The above reasons are not yet clear, however, that the acid-modified polyolefin waxes with the AES resin, ASA resin compatibility, the inorganic filling material of the coated effect may not fully. In other words, because the usual acid-modified polyolefin waxes and aromatic polycarbonate resin of poor compatibility, therefore, in melting, mixing and the like, if the wax present in the polycarbonate resin of inorganic filling material contact, the coated inorganic filling material to the way around, on the other hand, the ASA resin, AES resin, good compatibility, so the above-mentioned coated role may not be easy to produce.

ABS resin, ASA resin, AES resin and, with respect to the aromatic vinyl compound and Carbonitride vinyl compounds total of 100 weight %, aromatic vinyl compound is preferably 95-50 weight %, more preferably 90-60 weight %, further preferably 85-65 weight %. On the other hand, Carbonitride vinyl compound is preferably 5-50 weight %, more preferably 10-40 weight %, further preferably 15-35 weight %. Furthermore, the above-mentioned part of the graft component, can also be mixed for use (methyl) methacrylate, ethyl acrylate, maleic anhydride, maleic acid imide such as substituted N, containing their proportion in the resin composition is preferably 15 weight % of the following. The ABS resin, AES resin, ASA resin, used in the reaction initiator, chain transfer agent, emulsifier, and the like can be used according to the needs of the various substances known in prior art.

Inorganic filling material is not particularly limited, preferred cite ceramic fiber, slag fiber, asbestos, wollastonite, hard rankinite, potassium titanate whisker, aluminum borate whisker, boron whisker , such as basic magnesium sulfate whisker fibrous filling material or talc, mica, hydrotalcite plate of inorganic filling material. These fibrous and placoid inorganic filling material can also be coated with different types of material. As different types of material, representative is a metal, alloy, metal oxide, and the like.

The above-mentioned fibrous and placoid in the inorganic filling material, from a high-rigid, high-toughness (cantilever beam impact characteristics, surface impact resistance), appearance, size stability considerations, preferably wollastonite, various whisker (especially synthetic whisker), metal fiber, talc and mica, etc., more preferably wollastonite, synthetic whisker, talc and mica. Furthermore, from the layer of HC to consider adhesiveness, wollastonite particularly preferred. As synthetic whisker, preferably instantiates potassium titanate whisker, aluminum borate whisker, zinc oxide whisker, basic magnesium sulfate whisker and hard rankinite, and the like.

<结构 部件>

The installation of the invention is adhesion between the structure of the laminated structure (structure) or the parts of the structure, other objects or shoulder part of the load support member, for example, the main body of the can be instantiated conveying device, affixed to the above-mentioned main body of the panel module and is arranged on the above-mentioned various such as a window frame of the main body. The above-mentioned conveying device comprises an automobile, truck, train, airplane, ship, two-wheel motorcycle, bicycle and car seat and construction equipment and tractors and other. The structure as the structural member, such as building, outdoor arena, gymnasium, arcade, shed, greenhouse and houses and other buildings, sound insulation wall, wind-proof wall and road facilities such as snow fence, signs, billboards and outdoor large-sized monitor display devices, such as solar power generating device and the power generating device, and the like.

In this invention the glass assembly combination of the invention is means adhesion between the laminated structure and become a part of the combination. As the structural member, can be instantiated by the metal, glass, ceramic, ceramic composite materials, fiber-reinforced plastic, fiber-reinforced composite material (is composed of a glass fiber, aramid fiber, ceramic fiber and carbon fiber of the FRP, SMC and composite materials such as RTM) and forming part of the wood and the like. As the metal part, can be instantiated steel (steel plate) and consists of an aluminum alloy, magnesium alloy and forming a part of the titanium alloy, and the like.

Embodiment

Embodiment 1-8, comparative example 1-5

(I) evaluation item

Primer (I-A) nien connection based on nano-indentation method is of pressed into the elastic modulus of the

The use of fully impregnated with wiping paper BEMCOT primer solution of the polycarbonate substrate spreads the cloth to stick a hard coating layer for connecting the primer, one week after curing, cutting profiles by a slicer, the resulting smooth profile implementation of the determination of the modulus of elasticity is pressed in. Primer layer is about the thickness of the adhesion between the 50  m. Primer film thickness of the above-mentioned determination in the implementation of the central portion. Utilizing nano-indentation method is pressed into the elastic modulus is determined for the thickness of the primer layers refers sticks the 50   m the value of at.

The determination of the modulus of elasticity is pressed in on as follows, in other words, using Ultramicro indentation hardness tester (ELIONIX Corporation systems, product name ENT-2100) in the surface portion of the primer layer of the press testing. The press-head Berkovich (α: 65.03 °), to 20.4mgf/sec applying load of the load speed, will be of the maximum load of 800 the keep   N 1 seconds later, with the same load speed for unloading. The results are shown in table 1.

[Table 1]

(I-B) hand stripping cementability evaluation

(I-B-i) assay preparation

As shown in Figure 1, in the substrate for the BEMCOT hard coating is formed on the 70 mm × 50 mm for the laminate spreads the cloth to stick primer, to the bottom edge of the 8 mm height 12 mm triangular strip coating (bead) of the moisture-curable polyurethane series adhesive. Primer coating by using the same connection has sticks to evaluation of the laminate of the height of the thickness of the bond, in the 23 [...] , 50% RH a week curing under the environment of the its solidification.

(I-B-ii) stress test

As shown in Figure 1, in (I-B-i) made of the test piece is fixed on the stress test fixture, in another laminated body side impose 1-6mm displacement, in the 40 [...] , 100% RH groove of constant temperature and humidity preservation 500hr and in 70 the stored in the oven [...] 500hr. After the preservation, the test piece is removed from the clamp, the adhesive thickness is 2 mm in the test piece of the border of the cutting plate on the lower side of the adhesive, the adhesive thickness is 2 mm test piece other than the test piece, the thickness of the adhesive from the plate is 3 mm of the cutting position, enable the hand stripping cementability test.

Applying a stress test is according to the above-mentioned displacement of the valeant literature 1 of in 392 page of formula (9), will be used for this type of polycarbonate resin which are calculated. In other words, application

ΔI=I₀ × Δα×ΔT=I₀ × 58 × 10^-6 × 70      4 × I₀ (mm).

Here I₀ length of the long sides of the base material (m), the coefficient of linear expansion of the steel to Δα: 12 × 10^-6 × K^-1 the coefficient of linear expansion of the resin with polycarbonate: 70 × 10^-6 × K^-1 difference between the coefficients of linear expansion, and imitate the valeant literature 1, the said   T assumed that in the 20 [...] -90 the temperature difference used under [...] the 70 [...]. Furthermore, if the valeant literature 1 stated, because the usual glass and is bonded the two of the fitting end is freely movable, so that the displacement of the adhesive to its 1/2. Therefore, it is assumed that the displacement of the adhesive part can be calculated for "2 × I₀ (mm)". Calculated by the above-mentioned calculation of the length of the long sides of the substrate layer with the assumption that the relationship between the displacement amount of the displayed in table 2 (small points the following-rounding).

[Table 2]

(I-B-iii) hand stripping cementability test

In hand stripping cementability test, tensile adhesive side of the edge of the cutting tool used to trace on the adhering interface moment, the adhesive of the damage area of 100% as the condition of 100. 80 that the situation of the damage area of adhesive 80%, of the area of the interface 20%. Coherencies damage area is preferably 75% or more, more preferably 100%.

(II) manufacture of the substrate layer

(II-1) polycarbonate resin-A1 of manufacturing

The following raw materials in accordance with the record, the polycarbonate resin-A1 a description of the manufacturing method. The high-speed mixer for 9.5 parts by weight of a PC, 0.08 parts by weight of a VPG, 0.02 parts by weight of a SA, 0.03 parts by weight of PEPQ, 0.05 parts by weight of a IRGN, 0.32 parts by weight of a UV1577 and 1 × 10^-4 BL uniformly mixed parts by weight. Relative to the above-mentioned mixture 0.0001 parts by weight, V-type mixer is used for mixing 90 parts by weight of a PC, for the supply of premix of the extruder.

The premixture supply extruder. The diameter of the screw extruding machine is used in the double-shaft extruder 77 mm φ (Corporation Japan the system steel makes : TEX77CHT (fully engaged, rotating in the same direction, 2, screw)). The extruder, from the screw root is observed about L/D 8-11 with the part of the tightener by a positive feed of the tightener and instead enters to the mixing region composed of the combination of, in a subsequent about L/D 16-17 of the feed part has a mixing region of a kneading discs. Furthermore, the extruder after the mixing region in the latter half with L/D to 0.5 of the length of the threaded area to instead enters. In L/D about 18.5-20 is provided with a part of the 1 exhaust outlets. Extrusion conditions for output 320 kg/h, a rotation speed of a screw the vacuum degree of the exhaust port 160rpm and 3kPa. Furthermore, extrusion temperature is from the section 1 supply port 230 the die head part to [...] 280 the phased [...] a rising temperature.

The tow is extruded from a die is cooled in the specialists, through the granulator is cut to form particles. The particles in the newly cut off 10 seconds through the vibrating sieve-portion , thus doing enough the cut in the long particle and curve of the material removed can be removed.

(II-2) acrylic resin-A2 of manufacturing

As a commercial acrylic resin using the Mitsubishi   Rayon systems ACRYPET   VH001.

(III) sheet manufacturing molded

(III-1) coextruded slice (A-1) manufacturing

Are respectively make the above-mentioned polycarbonate resin material-A1 and the above-mentioned acrylic resin material-A2 in the uniaxial extruder melt, for the use of laminated remnants law 2 layer and a setting temperature 290 the extrusion die head T of [...] , the sheets will receive the roller cold mirror-finishing of the polycarbonate resin and an acrylic resin layer of the single-side lamination, lamination body is made. Their respective extrusion temperature is from the section 1 supply port of the 280 [...] , the 220 to the die part [...] the 290 [...] , 240 the phased [...] a rising temperature. Furthermore, the width of the sheet is made of a length of 270 mm × 2000 mm, the total thickness is 3 mm, the use of acrylic resin and the thickness of a layer of the 100  m. The obtained sheet is cut into 70 mm × 50 mm size, made test piece.

(III-2) (A-2) single slice of manufacturing

Of the 4 axis parallel control mechanism of the injection press-molding can be large-sized forming machine (Corporation name machine seisakusho systems: MDIP2100, the maximum clamping force 33540kN)-A1 the above-mentioned resin material injection press-molding the particles, a thickness of 5 mm, length × width is 1000 mm × 600 mm sheet molded article. The obtained sheet is cut into 70 mm × 50 mm size, made test piece.

(IV) used in the preparation of the coating of the hard coating

(IV-1) organic silicon resin hard coating material (T-1) preparation of

In the water-dispersed colloidal silica dispersion (catalyst chemical industrial Corporation systems Cataloid   SN-30, the solid component concentration of 30 weight %): 100 parts by weight of concentrated hydrochloric acid is added in (12M): 0.1 parts by weight and fully stirred. The dispersed cooling to the 10 [...] , to the dropping methyl trimethoxy silane: 161 parts by weight. Dropwise methyl trimethoxysilane later, immediately because the reaction heat begin to rise in the temperature of the liquid mixture, after a few minutes from the start of heating up to the 60 [...]. Reach the 60 after [...] , is cooled in the ice water bath, side slowly reducing the temperature of the reaction solution. The temperature of the reaction liquid reached the 35 [...] stage, maintaining the temperature stirring 5 hours, is mixed as a curing catalyst in which the 45% choline methanol solution: 0.8 parts by weight, of the acetic acid as a pH regulator: 4.9 parts by weight, solution coating (α) obtained.

In the above-mentioned coating solution (α) 209 IPA138 in parts by weight to parts by weight and stirred, to obtain coating paint T-1.

Colloidal silicon dioxide and alkoxy silane ratio of a hydrolytic condensation to 99 weight %.

(IV-2) pigmentum the ester is hard ultraviolet-curable acrylic acid (T-2) preparation of

The multi-functional acrylate oligomer (new Nakamura chemical Corporation systems U-15HA) 100 parts, phenyl-1-hydroxy- cyclohexyl alkone (BASF Corporation systems Irgacure184) 5 parts, 1-methoxy-2-propanol 250 parts, 2-propanol 100 parts, organic solvent dispersed colloidal silica (Nissan chemical industrial Corporation systems IPA-ST solid content concentration 30%)150 parts mixed, obtained pigmentum the ester is hard ultraviolet-curable acrylic acid (I-2).

Colloidal silicon dioxide and alkoxy silane hydrolysis condensation product is the ratio of 30 weight %.

(IV-3) pigmentum the ester is hard ultraviolet-curable acrylic acid (T-3) preparation of

The multi-functional acrylate oligomer (new Nakamura chemical Corporation systems U-15HA) 100 parts, phenyl-1-hydroxy- cyclohexyl alkone (BASF Corporation systems Irgacure184) 5 parts, 1-methoxy-2-propanol 250 parts, 2-propanol 100 parts, organic solvent dispersed colloidal silica (Nissan chemical industrial Corporation systems IPA-ST solid content concentration 30%)38.9 parts mixed, obtained pigmentum the ester is hard ultraviolet-curable acrylic acid (T-3).

Colloidal silicon dioxide and alkoxy silane ratio of a hydrolytic condensation to 10 weight %.

(IV-4) pigmentum the ester is hard ultraviolet-curable acrylic acid (T-4) preparation of

The multi-functional acrylate oligomer (new Nakamura chemical Corporation systems U-15HA) 100 parts, phenyl-1-hydroxy- cyclohexyl alkone (BASF Corporation systems Irgacure184) 5 parts, 1-methoxy-2-propanol 250 parts, 2-propanol 100 parts, organic solvent dispersed colloidal silica (Nissan chemical industrial Corporation systems IPA-ST solid content concentration 30%)18.4 parts mixed, obtained pigmentum the ester is hard ultraviolet-curable acrylic acid (T-4).

Colloidal silicon dioxide and alkoxy silane hydrolysis condensation product is the ratio of 5 weight %.

(IV-5) melamine resin hard coating material (T-5) preparation of

The methylated methylol melamine [Nihon   Cytec Cymel   Industries Corporation systems   301] 100 parts, 1, 6-hexylene glycol 70 parts, maleic acid 5 parts, isopropanol 150 parts, isobutyl alcohol 320 parts, ethylene glycol n-butyl ether to 25 parts mixed, the melamine resin (T-5) hard coating agent.

Colloidal silicon dioxide and alkoxy silane hydrolysis condensates in the proportion of 0 weight %.

Embodiment 1-2, comparative example 1

In the above-mentioned dimension for (II)-(III) in the substrate layer (A-1) is made on the in order to thermoset the film thickness is 5 the way and coating of   m in (IV) hard coating agent made of (T-1), in 25 the stewing [...] 20 minutes later, in 130 the thermosetting the [...] 60 minutes.

The use of containing γ-mercapto propyl trimethoxy silane with poly-isocyanate is the reaction product of a silane-modified polyisocyanate and other silane coupling agent, acrylic resin and epoxy resin, and the like and has 1 months or more long-term open time behavior of the glass with a primer GP-402 (Sunstar   Engineering Corporation systems) as primer adhesion between, the use of moisture-curable one-component polyurethane adhesive in other words Penguin   Seal# 560 (Sunstar   Engineering Corporation systems) as an elastic adhesive, manufacturing of the laminate. Primer adhesion between the coating of the primer through the use of full impregnation solution twists gently BEMCOT after implementation of wiping paper. The adhesive thickness is 2 mm -8 mm of the range. To implement the above-mentioned laminate (I-B) said hand stripping cementability evaluation. The results are shown in table 3.

Embodiment 3

The primer for the spreading sticks after the 23 [...] , 50% RH keep the environment 3 months later, of the coating of the polyurethane adhesive, in addition, with the embodiment 1 of the above-mentioned implementation of the condition of the same completely (I-B) said hand stripping cementability evaluation. With 1 months or more long-term open time behavior of the glass with a primer GP-402 under the condition of, after the primer for the spreading sticks , in the 23 [...] , 50% RH keep the environment 3 months later, for polyurethane adhesive coating, and the connection obtained after the spreading sticks primer polyurethane adhesive coated embodiment 1, almost the same result. The results are shown in table 3.

Embodiment 4

In the above-mentioned dimension for (II)-(III) in the substrate layer (A-1) is made on the in order to thermoset the film thickness is 5 the way and coating of   m in (IV) hard coating agent made of (T-1), in 25 the stewing [...] 20 minutes later, in 130 the thermosetting the [...] 60 minutes.

The use of containing γ-mercapto propyl trimethoxy silane with poly-isocyanate is the reaction product of a silane-modified polyisocyanate and a polyester polyurethane resin, and the like and with not 1 months or more of the long-term open time characteristic G HAMATITE glass primer (MS-90) (YOKOHAMA   RUBBER   Corporation systems) as primer adhesion between, the use of moisture-curable one-component polyurethane adhesive in other words WS-222 (YOKOHAMA   RUBBER Corporation systems) as an elastic adhesive, manufacturing of the laminate. To the obtained laminated body is solidified in a week after the ripening of the 90 [...] , 24hr processing, then the implementation of the above-mentioned (I-B) said hand stripping cementability evaluation. The results are shown in table 3.

Comparative example 2

In the above-mentioned dimension for (II)-(III) in the substrate layer (A-1) is made on the in order to thermoset the film thickness is 5 the way and coating of   m in (IV) hard coating agent made of (T-1), in 25 the stewing [...] 20 minutes later, in 130 the thermosetting the [...] 60 minutes.

The isocyanate-modified polyethylene containing silanes with ester but 1 months or more of the long-term open time characteristic G HAMATITE glass primer (PC-3) (YOKOHAMA   RUBBER Corporation systems) as primer adhesion between, the use of moisture-curable one-component polyurethane adhesive in other words WS-222 (YOKOHAMA   RUBBER Corporation systems) as an elastic adhesive, the implementation of the above-mentioned (I-B) said hand stripping cementability evaluation. The results are shown in table 3.

Comparative example 3

In the above-mentioned dimension for (II)-(III) in the substrate layer (A-1) is made on the in order to thermoset the film thickness is 5 the way and coating of   m in (IV) hard coating agent made of (T-1), in 25 the stewing [...] 20 minutes later, in 130 the thermosetting the [...] 60 minutes.

Does not have to use 1 months or more long-term open time behavior primer 35 (  MSI Sunrise Corporation systems) as primer adhesion between, the use of moisture-curable one-component polyurethane adhesive that is, SR   U-90W   Seal (  MSI Sunrise Corporation systems) as an elastic adhesive, the implementation of the above-mentioned (I-B) said hand stripping cementability evaluation. The results are shown in table 3.

Embodiment 5

In the above-mentioned dimension for (II)-(III) in (A-1) layer made of ultraviolet cured on the film thickness is 5 the way and coating of   m in (IV) hard coating agent made of (T-2), in 25 the stewing [...] 1 minutes, in 80 the stewing [...] 1 minutes later, in order to accumulate the high-pressure mercury lamp for the illumination of 600mJ/cm² way of curing the ultraviolet ray is irradiated, in addition, with the embodiment 1 of the above-mentioned implementation of the condition of the same completely (I-B) said hand stripping cementability evaluation. The results are shown in table 3.

Embodiment 6

In the above-mentioned dimension for (II)-(III) in (A-1) layer made of ultraviolet cured on the film thickness is 5 the way and coating of   m in (IV) hard coating agent made of (T-3), in 25 the stewing [...] 1 minutes, in 80 the stewing [...] 1 minutes later, in order to accumulate the high-pressure mercury lamp for the illumination of 600mJ/cm² way of curing the ultraviolet ray is irradiated, in addition, with the embodiment 1 of the above-mentioned implementation of the condition of the same completely (I-B) said hand stripping cementability evaluation. The results are shown in table 3.

Embodiment 7

In the above-mentioned dimension for (II)-(III) in (A-2) layer made of ultraviolet cured on the film thickness is 5 the way and coating of   m in (IV) hard coating agent made of (T-2), in 25 the stewing [...] 1 minutes, in 80 the stewing [...] 1 minutes later, in order to accumulate the high-pressure mercury lamp for the illumination of 600mJ/cm² way of curing the ultraviolet ray is irradiated, in addition, with the embodiment 1 of the above-mentioned implementation of the condition of the same completely (I-B) said hand stripping cementability evaluation. The results are shown in table 3.

Comparative example 4

In the above-mentioned dimension for (II)-(III) in (A-1) layer made of ultraviolet cured on the film thickness is 5 the way and coating of   m in (IV) hard coating agent made of (T-4), in 25 the stewing [...] 1 minutes, in 80 the stewing [...] 1 minutes later, in order to accumulate the high-pressure mercury lamp for the illumination of 600mJ/cm² way of curing the ultraviolet ray is irradiated, in addition, with the embodiment 1 of the above-mentioned implementation of the condition of the same completely (I-B) said hand stripping cementability evaluation. The results are shown in table 3.

Comparative example 5

In the above-mentioned dimension for (II)-(III) in the substrate layer (A-1) is made on the in order to thermoset the film thickness is 5 the way and coating of   m in (IV) hard coating agent made of (T-5), in 25 the stewing [...] 20 minutes later, in the 120 [...] make it thermosetting 60 minutes, in addition, with the embodiment 1 of the above-mentioned implementation of the condition of the same completely (I-B) said hand stripping cementability evaluation. The results are shown in table 3.

Embodiment 8

Are respectively make the above-mentioned (I) the manufacturing in A1 of a polycarbonate resin and A2 of acrylic resin in the uniaxial extruder melt, for laminated remnants law 2 layer by the set temperature the 290 [...] of the extrusion die head T, the obtained sheet molded article cooling, in polycarbonate resin layer is made of single-sided laminated with an acrylic resin layer of the glass assembling sheet molded article. Their respective extrusion temperature is from the section 1 supply port of the 280 [...] , the 220 to the die part [...] the 290 [...] , 240 the phased [...] a rising temperature. Furthermore, the width of the pieces forming is made of length 1000 mm × 1000 mm, the total thickness is 3 mm, the use of acrylic resin and the thickness of a layer of the 100  m.

The sheet molding is masked by a part of the transparent processing, approximately the outer periphery 160 mm is formed at the width of about 20 the   m of the thickness of the light shielding layer. The above-mentioned light shielding layer, using POS: by the acrylic polyol to isocyanate gathers mellowly a polyurethane resin adhesive of two-component ink (silk stamp POS 911 ink: 100 parts by weight, 210 curing agent: 5 parts by weight and P-003 solvent: 23 parts by weight of the homogenate (raw material is Teikoku ink Corporation systems) as the ink, after the formation of the spray gun, for 20 minutes after air-drying, in 90 the to [...] 60 minutes of treatment, so that the ink curing. Thereafter, the masking is removed, the sheet is formed with a light shielding layer molded article. According to the-like, the use of the robot for coating the obtained using the class spreads the law respectively to face of the film thickness after thermosetting to 4 the manner of   m (IV) coating the above-mentioned embodiment is made of an ultraviolet-curable acrylic acid in pigmentum the ester is hard of (T-2), after air-drying, of the 130 [...] , 60 minutes of heat treatment, so that the its solidification.

Like peripheral end of the molded article, with a thickness of 8 the coated glass with a primer GP-402   m (Sunstar   Engineering Corporation systems), in order to become width 12 mm height 15 mm triangular shape of an elastic adhesive coated Penguin   Seal# 560 (Sunstar   Engineering Corporation systems). In with a thickness of 8 the main primer coated with   m M HAMATITE (RC-50E) (YOKOHAMA   RUBBER Corporation systems) in the frame of the stainless steel to polyurethane adhesive has a thickness of 6 mm is coated with a gluing in a manner of the above-mentioned polyurethane adhesive sheet molded article. The stainless steel frame is arranged on the same and adjust the above-mentioned thickness of the thickness of the spacer. Therewith will be used for the bonding of the 23 [...] , 50% RH carried out under the condition of 1 week after the maturation process, together with the frame is put together with 70 the hot air drying furnace for [...] , implementation of 1000 hours of processing. The adhesive completely does not fall off, adhesive for a is fixed.

Embodiment 9-18, comparative example 6-9

(I) evaluation item

Primer (I-A) nien connection based on nano-indentation method is pressed into the elastic modulus of the

The use of fully impregnated with wiping paper BEMCOT primer solution of the polycarbonate substrate spreads the cloth to stick a hard coating layer for connecting the primer, one week after curing, cutting and by a slicer section of the obtained pressed into a smooth profile implementation of the determination of the elastic modulus. Primer layer is about the thickness of the adhesion between the 50  m. Primer film thickness of the above-mentioned determination in the implementation of the central portion. In this invention of utilizing nano-indentation method is pressed into the elastic modulus is measured for the thickness of the primer layers refers sticks 50 the value of   m.

The determination of the elastic modulus of the press by using the super micro indentation hardness tester (ELIONIX Corporation systems, product name ENT-2100) in the surface portion of the primer layer of the press testing. The press-head Berkovich (α: 65.03 °), to 20.4mgf/sec applying load of the load speed, will be of the maximum load of 800 the keep   N 1 seconds later, with the same load speed for unloading. The results are shown in table 4.

[Table 4]

(I-B) hand stripping cementability evaluation

(I-B-i) assay preparation

As shown in Figure 4, used for a base layer BEMCOT is formed on the hard coat layer 70 mm × 50 mm for spreads the cloth to stick laminate body of the primer, to the bottom edge of the 8 mm height 12 mm triangular strip coating moisture-curable polyurethane series adhesive. has sticks primer coating by using the same connection to the evaluation of the thickness of the as the height of the adhesive 8 mm, in the 23 [...] , 50% RH a week curing under the environment of the its solidification. Furthermore, the thickness of the adhesives to 6 mm, similarly made assay.

(I-B-ii) stress test

As shown in Figure 4, in (I-B-i) made of the test piece is fixed on the stress test fixture, in another laminated body side impose 1-4mm displacement, in 70 the stored in the oven [...] 500hr. After the preservation test piece is removed from the clamp, the distance between the adhesive thickness of the plate is 3 mm of the cutting position, enable the hand stripping cementability test.

Applying a stress test is according to the above-mentioned displacement of the valeant literature 1 of in 392 page of formula (9), will be used for this type of polycarbonate resin which are calculated. In other words, application

ΔI=I₀ × Δα×ΔT=I₀ × 58 × 10^-6 × 70      4 × I₀ (mm)

Here I₀ length of the long sides of the base material (m), the coefficient of linear expansion of the steel to Δα: 12 × 10^-6 × K^-1 the coefficient of linear expansion of the resin with polycarbonate: 70 × 10^-6 × K^-1 difference between the coefficients of linear expansion, and imitate the valeant literature 1, the said   T assumed that in the 20 [...] -90 the temperature difference used under [...] the 70 [...]. Furthermore, if the valeant literature 1 recorded, because the usual glass and is bonded the two of the fitting end is freely movable, so that the displacement of the adhesive to its 1/2. Therefore, it is assumed that the displacement of the adhesive part can be calculated as "2 × I₀ (mm)". According to the above-mentioned calculating calculates the length of the long sides of the substrate layer with the assumption that the relationship between the displacement amount of the displayed in table 5 (small points the following-rounding).

[Table 5]

(I-B-iii) hand stripping cementability test

In hand stripping cementability test, tensile adhesive side of the edge of the cutting tool used to trace on the adhering interface moment, the adhesive of the damage area of 100% as the condition of 100. 80 that the situation of the damage area of adhesive 80%, of the area of the interface 20%. Coherencies damage area is preferably 75% or more, most preferably 100%.

(II-1) polycarbonate resin-A1 of manufacturing

The following raw materials in accordance with the record, the polycarbonate resin-A1 a description of the manufacturing method. The high-speed mixer for 9.5 parts by weight of a PC, 0.08 parts by weight of a VPG, 0.02 parts by weight of a SA, 0.03 parts by weight of PEPQ, 0.05 parts by weight of a IRGN, 0.32 parts by weight of a UV1577 and 1 × 10^-4 BL uniformly mixed parts by weight. Relative to the above-mentioned mixture 10.0001 parts by weight, V-type mixer is used for mixing 90 parts by weight of a PC, for the supply of premix of the extruder.

The premixture supply extruder. The diameter of the screw extruder is a of the double-shaft extruder 77 mm φ (Corporation Japan the system steel makes : TEX77CHT (fully engaged, rotating in the same direction, 2, screw)). The extruder screw is observed from the root of about L/D 8-11 with the part of the tightener by a positive feed of the tightener and instead enters to the mixing region composed of the combination of, in a subsequent about L/D 16-17 of the feed part has a mixing region of a kneading discs. Furthermore, the extruder after the mixing region in the latter half with L/D to 0.5 of the length of the threaded area to instead enters. In L/D about 18.5-20 is provided with a part of the 1 exhaust outlets. Extrusion conditions are output 320 kg/h, a rotation speed of a screw the vacuum degree of the exhaust port 160rpm and 3kPa. Furthermore, extrusion temperature is from the section 1 supply port 230 the die head part to [...] 280 the phased [...] a rising temperature.

The tow is extruded from a die is cooled in the specialists, through the granulator is cut to form particles. The particles in the newly cut off 10 seconds through the vibrating sieve-portion , thus doing enough the cut in the long particle and curve of the material removed can be removed.

(II-2) polycarbonate resin-A2 of manufacturing

Recorded in accordance with the following raw material, polycarbonate resin-A2 to a description of the manufacturing method. The high-speed mixer for 4.25 parts by weight of the PC1, 0.1 parts by weight of a VPG, 0.02 parts by weight of a SA, 0.03 parts by weight of PEPQ, 0.05 parts by weight of a IRGN, 0.3 parts by weight of a UV1577, 0.25 parts by weight of a YMDS and 5 parts by weight of a cm are evenly mixed. For the above-mentioned mixture V-shaped mixer 10 parts by weight and 90 parts by weight of a PC are evenly mixed, for the supply of premix of the extruder, in addition, with the above-mentioned resin material-A1 of manufacturing the same, to obtain a granular resin material-A2.

Should be note, the above-mentioned use of raw materials is as follows.

PC1: bisphenol a and phosgene A with interfacial polycondensation legal manufacture having a viscosity average molecular weight of 23700 polycarbonate resin powder (Teijin chemical Corporation systems:   L-1250WP PANLITE (tradenames))

VPG: pentaerythritol and aliphatic carboxylic acid (with stearic acid and palmitic acid as a main component) full of (Cognis   Japan Corporation systems:   VPG861 Loxiol)

SA: fatty acid partial ester (RIKEN   VITAMIN Corporation systems: RIKEMAL   S-100A)

PEPQ: phosphinates heat stabilizer (BASF corporate:   P-EPQ Irgafos)

IRGN: hindered phenolic antioxidant (BASF corporate: Irganox1076)

UV1577: 2-(4, 6-diphenyl -1, 3, 5-triazin-2-yl)-5-[ (hexyl) oxy] phenol (BASF corporate: Tinuvin1577)

Cm: the above-mentioned high-speed mixer for PC: 4.99489 weight, NB5856T: 0.00313 weight, R8370: 0.00071 parts by weight and R8370: 0.00127 parts by weight and uniformly mixing a colorant master batch. Here NB5856T said black dye (Orient   Chemical   BLACK5856T   Industries Corporation systems NUBIAN), R8350 and R8370 that red dye (with the chemical industrial Corporation systems PLAST   Red   8350 and PLAST   R_e d   8370).

YMDS: by the organic dispersion resin and as an inorganic infrared ray absorber Cs_0.33 WO₃ (an average particle size of 5 nm) form, the content of the inorganic infrared ray absorber is about 23% of the weight of the infrared shielding agent a (Sumitomo metal mining Corporation systems YMDS-874)

(III-1) used for the frame part resin composition (light shielding layer)-E1 of manufacturing

Recorded in accordance with the following raw material, the frame material-E1 a description of the manufacturing method. The V-type mixer with 75 parts by weight of the PC2, 12 parts by weight of the ABS1, 3 parts by weight of a MB, 10 parts by weight of a WRN1, 0.1 parts by weight of a M, 0.8 parts by weight of a CB are evenly mixed. The resulting mixture is supplied to the screw diameter of 30 mm φ exhaust double-shaft extruder (Kobe, KTX-30 the system steel makes) of section of the root of the screw rod 1 supplying, and a die temperature of the cartridge: the 260 [...] , the rotational speed of the screw: 180rpm, discharge amount: 15 kg/H, the exhaust vacuum degree: 3000 Pa carried out under the conditions of extrusion, the tow. Furthermore, the tow is cooled in the specialists, granulating machine to cut-off, a granular resin material by E1.

(III-2) used for the frame part resin composition (light shielding layer)-E2 of manufacturing

Recorded in accordance with the following raw material, the frame material-E2 a description of the manufacturing method. The V-shaped mixer for 65 parts by weight of the PC2, 30 weight parts of ABS2, 5 parts by weight of a MB, 0.3 parts by weight of a E, 0.3 parts by weight of a UV701, 0.8 parts by weight of a CB are evenly mixed. The resulting mixture is supplied to the screw diameter of 30 mm φ exhaust double-shaft extruder (Kobe, KTX-30 the system steel makes) of section of the root of the screw rod 1 supplying, and a die temperature of the cartridge: the 260 [...] , the rotational speed of the screw: 180rpm, discharge amount: 15 kg/H, the exhaust vacuum degree: 3000 Pa carried out under the conditions of extrusion, the tow. Furthermore, the tow is cooled in the specialists, granulating machine to cut-off, a granular resin material by E2.

(III-3) used for the frame part resin composition (light shielding layer)-E3 of manufacturing

Recorded in accordance with the following raw material, the frame material-E3 a description of the manufacturing method. The V-shaped mixer for 60 parts by weight of a PC3, 25 parts by weight of the PET, 3 parts by weight of a PBT, 10 parts by weight of a WRN2, 3 parts by weight of a MB, 0.6 parts by weight of a DC, 0.2 parts by weight of a PEP, 0.02 parts by weight of a M, 0.3 parts by weight of a UV701, 0.8 parts by weight of a CB are evenly mixed. The resulting mixture is supplied to the screw diameter of 30 mm φ exhaust double-shaft extruder (Kobe, KTX-30 the system steel makes) of section of the root of the screw rod 1 supplying, and a die temperature of the cartridge: the 270 [...] , the rotational speed of the screw: 180rpm, discharge amount: 15 kg/H, the exhaust vacuum degree: 3000 Pa carried out under the conditions of extrusion, the tow. Furthermore, the tow is cooled in the specialists, granulating machine to cut-off, to obtain a granular resin material E3.

(III-4) used for the frame part of the (light shielding layer) resin composition-E4 of manufacturing

Recorded in accordance with the following raw material, the frame material-E4 to explain the manufacturing method. The V-type mixer with 75 parts by weight of the PC2, 12 parts by weight of the ABS1, 3 parts by weight of a MB, 10 parts by weight of a TALC, 0.1 parts by weight of a M, 0.8 parts by weight of a CB are evenly mixed. The resulting mixture is supplied to the screw diameter of 30 mm φ exhaust double-shaft extruder (Kobe, KTX-30 the system steel makes) of section of the root of the screw rod 1 supplying, and a die temperature of the cartridge: the 260 [...] , the rotational speed of the screw: 180rpm, discharge amount: 15 kg/H, vacuum exhaust port: 3000 Pa carried out under the conditions of extrusion, the tow. Furthermore, the tow is cooled in the specialists, granulating machine to cut-off, a granular resin material by E4.

Should be note, the above-mentioned use of raw materials is as follows.

PC2: bisphenol a and phosgene A with interfacial polycondensation legitimate is made having a viscosity average molecular weight of 22400 polycarbonate resin powder (Teijin chemical Corporation systems:   L-1225WP PANLITE)

PC3: bisphenol a and phosgene A with interfacial polycondensation legitimate is made having a viscosity average molecular weight of 19700 polycarbonate resin powder (Teijin chemical Corporation systems:   L-1225WX PANLITE)

ABS1: butadiene rubber component is approximately 18 weight %, weight average rubber particle size is 0.8 the  m, ABS polymerization utilizes the body is made of resin (Japan A corporate & L:AT-05)

ABS2: ABS resin (Japan A & L Corporation systems UT-61 (tradenames), free AS polymer component is about 80 weight % and ABS polymer ingredient (acetone insoluble gel component) about 20 weight %, butadiene rubber ingredient about 14 weight %, weight average rubber particle size of 0.56 the  m, utilizes the body to polymerization manufacturing)

PET: Ge series catalyst of use for the IV is 0.52 polyethylene terephthalate (person system imperialists: TR-MB).

PBT: IV to 0.875 the polybutylene terephthalate (corporate   Polymer WinTech: 500FP)

MB: does not contain styrene rubber polymer -2 (Rohm   and   Haas Company system: PARALOID   EXL-2602, core is polybutadiene about 80 weight %, the shell is methyl methacrylate and ethyl acrylate graft copolymer, heavy particle size of 0.23 the  m)

WRN1: an average particle diameter of 5 the wollastonite of   m (corporate   MATEC KINSEI: SH-1250)

WRN2: average particle size is 4 the wollastonite   m (NYCO corporate: NYGLOS4)

TALC: compressed powder talc (corporate the forest turns into :   HS-T0.8 Upn)

E: lignite ester (Clariant   Japan corporate:   E Licowax)

PEP: double (2, 4-di-tert-butyl phenyl) phosphite ester fifth heavenly stem four mellow two quarter (ADEKA corporate: ADK   PEP-24G   STAB)

M: methyl phosphate (Daihachi chemical industry Company system: TMP)

DC: Mitsubishi chemical Corporation system DIACARNA   30 (1-olefin · maleic anhydride copolymer and a 1-olefin mixture)

UV701: 2-(2 the [...] hydroxy-5-methyl phenyl) benzotriazole (SHIPRO   KASEI systems)

CB: carbon black (the valley formation industrial corporate: RB961S)

(IV) two-color molded product production

The above-mentioned hot-air drier cycle for (II) and (III) in the particles obtained in the 110 [...] drying 6 hours later, the forming machine through the can-color molding (Japanese fine resin industries systems FN8000-36ATN) is as shown in Figure 5 is composed of a polycarbonate resin and the frame of the two-color molded article a (the transparent part of the area of the 56% combined with the frame). The obtained molded article of the polycarbonate resin and frame part are cut into 70 mm × 50 mm size, made test piece.

(V) used for the primer layer of the coating of the hard coating preparation

(V-1) acrylic acid copolymer resin (bp1) preparation of

The reflux cooler and a stirring device and the nitrogen replacement of the flask in adding and mixing methyl ethyl acrylate (hereinafter referred to as EMA) 85.6 weight, methyl acrylic acid cyclohexyl ester (hereinafter referred to as CHMA) 16.8 parts by weight, methyl acrylic acid 2-hydroxy-ethyl ester (hereinafter referred to as HEMA) 13.0 parts by weight, LA-82 (rising sun electrification industrial Corporation the system contains with a hindered amine light stabilizing group of the methyl acrylate; 1, 2, 2, 6, 6-pentamethyl-4-piperidinyl-methyl acrylate) 12.0 parts by weight, 1-methoxy-2-propanol (hereinafter referred to as PGM) 191.1 parts by weight. Nitrogen in mixture 15 minutes after the deoxidation, in the nitrogen gas stream temperature to under the 70 [...] , adding azobisisobutyronitrile (hereinafter referred to as AIBN) 0.33 parts by weight, in the gas stream in the presence of nitrogen, in the 70 the stirring [...] 5 hours to enable its reaction. Adding AIBN: 0.08 parts by weight and increasing the temperature to 80 the [...] , reaction 3 hours, the non-volatile component concentration is 39.7% by weight of the acrylic copolymer solution.

(V-2) acrylic acid copolymer resin (bp2) preparation of

In addition to to EMA: 74.2 weight, CHMA: 33.7 outside parts by weight, and bp1 similarly to, the non-volatile component concentration by 39.6 weight % acrylic acid copolymer solution.

(V-3) acrylic acid copolymer resin (bp3) preparation of

The reflux cooler and a stirring device is added in the flask mixed methyl isobutyl ketone (hereinafter referred to as MIBK): 443.4 parts by weight, 2-[ 4-[ (2-hydroxy-3-(2 the [...] -ethyl) hexyl) oxy]-2-hydroxy-phenyl]-4, 6-bis (2, 4-dimethyl phenyl)-1, 3, 5-triazine (corporate   Chemicals   Specialty TINUVIN405 Ciba) 350.3 parts by weight, methyl acrylic acid 2-isocyanate base ethyl ester : 93.1 weight and heated to 80 the [...]. Furthermore, by adding February dibutyl tin lauric acid : 0.1 parts by weight, at which temperature the stirring 30 minutes, the non-volatile component concentration is 49.5% of the 2-methacryloxy ethyl Carbamic 1-[ 3-hydroxy-4-{ 4, 6-bis (2, 4-dimethyl phenyl)-1, 3, 5-triazin-2-yl} phenyl phenoxy]-3-(2-ethyl hexyl oxy)-2-propyl ester (following, abbreviated as MOI-405) solution.

Next, the reflux cooler and a stirring device and flask of the nitrogen replacement of the additional mixing in EMA: 58.6 parts by weight, CHMA: 33.7 weight, HEMA: 13.0 parts by weight, the above-mentioned MOI-T405: 53.9 parts by weight, LA-82: 35.9 weight, PGM: 241.2 parts by weight. The mixture of nitrogen 15 minutes after being air, in a nitrogen gas stream temperature to under the 70 [...] , adding AIBN: 0.33 parts by weight, in the gas stream in the presence of nitrogen, in the 70 the stirring [...] 5 hours, to enable its reaction. And then, by adding AIBN: 0.08 parts by weight and increasing the temperature to 80 the [...] , reaction 3 hours, the non-volatile component concentration by 39.6 weight % acrylic acid copolymer solution.

(V-4) acrylic resin primer coating preparation (Bp1, Bp2)

In the above-mentioned bp1 and bp2 solution of acrylic copolymer resin 100 parts by weight of added in MIBK: 66.4 parts by weight, 2-butanol (hereinafter referred to as 2-BuOH): 33.2 weight, PGM: 106.4 and mixing parts by weight, relative to the acrylic resin solution of hydroxy-acrylic acid copolymer in 1 equivalent of the isocyanate group of 1.0 equivalent of adding way of VESTANAT   B1358/100 (Degussa   Japan Corporation the system inlays of this polyisocyanate compound): 9.8 parts by weight, adding TINUVIN   400 (Ciba   Specialty   Chemicals corporate triazine-based ultraviolet absorbent) 4.2 parts by weight and TINUVIN   479 (Ciba   Specialty   Chemicals corporate triazine-based ultraviolet absorbent) 1.1 parts by weight, APZ-6633 (Toray   Dow   Corning Corporation systems silane coupling agent hydrolysis condensate of the ethanol solution; solid ingredient 5 weight %): 9.5 parts by weight, the second new decanoic acid dimethyl base tin : 0.015 and the weight of the 25 [...] stirring 1 hour, to obtain acrylic resin primer coating (Bp1 and Bp2).

(V-5) acrylic resin primer coating preparation (Bp3)

In the above-mentioned bp3 acrylic acid copolymer solution of 100 parts by weight of added in MIBK: 65.4 parts by weight, 2-BuOH: 32.7 parts by weight, PGM: 65.8 and mixing parts by weight, relative to the acrylic acid copolymer solution of hydroxy-acrylic acid copolymer in 1 equivalent of the isocyanate group of 1.0 equivalent of adding way of VESTANAT   B1358/100: 7.6 parts by weight, then adding APZ6633: 13.7 parts by weight, the second new decanoic acid dimethyl base tin : 0.07 parts by weight and in the 25 [...] stirring 1 hour, to obtain acrylic resin primer coating (Bp3).

(VI) is used for coating of the top layer of the hard coating preparation

(VI-1) spreads hardly (Bt1) preparation of the coating

In the water-dispersed colloidal silica dispersion (catalyst chemical industrial Corporation systems Cataloid   SN-30, the solid component concentration of 30 weight %): 100 parts by weight of concentrated hydrochloric acid is added in (12M): 0.1 parts by weight and fully stirred. The dispersed cooling to the 10 [...] , to the dropping methyl trimethoxy silane: 161 parts by weight. From the dropping after methyl trimethoxysilane, due to the reaction heat immediately to begin to rise in the temperature of the liquid mixture, after a few minutes from the start of heating to 60 the [...]. Reach the 60 after [...] , side of the cooling side in the ice slowly reduce the temperature of the reaction solution. The temperature of the reaction liquid reached the 35 [...] stage, maintaining the temperature stirring 5 hours, is mixed as a curing catalyst in which the 45% choline methanol solution: 0.8 parts by weight, of the acetic acid as a pH regulator: 4.9 parts by weight, solution coating (α) obtained.

In the above-mentioned coating (α) 209 of the stock solution of isopropanol is added in parts by weight (hereinafter referred to as IPA) 138 parts by weight and stirred, to obtain (Bt1) coating.

Colloidal silicon dioxide and alkoxy silane ratio of a hydrolytic condensation to 99 weight %.

(VI-2) spreads hardly (Bt2) preparation of the coating

The cerium oxide slurry stirring (C.I.KASEI Corporation systems, NanoTek slurry CEANB, solid component concentration 15 weight %): 5.5 parts by weight of IPA to dropping of the: 112.1 for dilution by weight. -side further stirring the above-mentioned diluted slurry side dropwise the above-mentioned coating solution (α): 209 parts by weight, obtained (Bt2) coating.

Colloidal silicon dioxide and alkoxy silane hydrolysis condensation ratio of a to 97 weight %.

Embodiment 9-17, comparative example 6-9

The (II)-(IV) in the above-mentioned coated preforms made in the two-color forming stacked substrate through the film thickness is after thermosetting 4-10 the way and coating of about   m (V) is made in the acrylic resin primer coating (Bp1-Bp3), in 25 the stewing [...] 20 minutes later, in 130 the thermosetting [...] 60 minutes, discharge cold 40 minutes later, a streaming coated with the film thickness is a thermoset 2-5 the way and coating of about   m (VI) coating spreads hardly made in the (Bt1, Bt2), in 25 the stewing [...] 20 minutes later, in 130 the thermosetting the [...] 60 minutes. The obtained hard coat processing on the substrate in table 6 recorded in the combined coating C1: glass with a primer (  Engineering Corporation systems GP-402 Sunstar), C2:G HAMATITE glass primer (  RUBBER Corporation systems MS-90 YOKOHAMA), C3:G HAMATITE glass primer (PC-3) (YOKOHAMA   RUBBER Corporation systems), C4: primer 35 (  MSI Sunrise Corporation systems), C5: not the main body of a silane coupling agent-containing primer G HAMATITE (  RUBBER Corporation systems RC-50E YOKOHAMA) as primer adhesion between, according to table 6 combination of the recorded in D1: moisture-curable one-component polyurethane adhesive Penguin   Seal# 560 (Sunstar   Engineering Corporation systems), E2:WS-222 (YOKOHAMA   RUBBER Corporation systems) as an elastic adhesive, made Figure 4 is shown a test piece after solidifying the maturing of the week, in granting displacement 1-6mm carried out under the state of the 70 [...] , 500hr processed, is recorded in the above-mentioned implementation (I-B-iii) hand stripping cementability evaluation. The results are shown in table 6.

Embodiment 18

Circulation pattern for the above-mentioned hot air drying machine made of (II) and (III) in A1 and B1 of the particles in the 20 the drying [...] 6 hours later, can be used for machine-color molding (Japanese fine resin industries systems FN8000-36ATN) get Figure 5 is shown by a polycarbonate resin layer and its frame of part a (light shielding layer) of the two-color molded article (the transparent part of the area of the 56% combined with the frame). The two-color molded article coated preforms of the obtained polycarbonate resin layer and the frame after thermosetting component layers to the film thickness is 5 the manner of coating the above-mentioned left and right   m (V) is made in the acrylic resin primer coating Bp2, in 25 the stewing [...] 20 minutes later, in 130 the thermosetting [...] 60 minutes, discharge cold 40 minutes later, after thermosetting of a streaming coated with the film thickness is of the 4 left and right   m in the manner of coating (VI) coating spreads hardly Bt1, in 25 the stewing [...] 20 minutes later, in 130 the thermosetting the [...] 60 minutes.

Peripheral end of the obtained molded product, with a thickness of 8 the coated glass with a primer GP-402   m (Sunstar   Engineering Corporation systems), in order to become width 12 mm height 15 mm triangular shape of an elastic adhesive coated Penguin   Seal# 560 (Sunstar   Engineering Corporation systems). In with a thickness of 8 the main primer coating   m M HAMATITE (RC-50E) (YOKOHAMA   RUBBER Corporation systems) and a frame made of stainless steel, the thickness of the polyurethane adhesive to 6 mm is coated with a gluing in a manner of the above-mentioned polyurethane adhesive sheet molded article. The stainless steel frame is arranged on the same and adjust the above-mentioned thickness of the thickness of the spacer. Therewith will be used for the bonding of the 23 [...] , 50% RH maturation process the condition of 1 week later, together with the frame is put together with 70 the hot air drying furnace for [...] , implementation of 1000 hours of processing. The adhesive completely does not fall off, adhesive for a is fixed.

Embodiment 19-23, comparative example 10-12

(I) evaluation item

Primer (I-A) nien connection based on nano-indentation method is pressed into the elastic modulus of the

The use of fully impregnated with wiping paper BEMCOT primer solution on the polycarbonate substrate spreads the cloth to stick primer for the hard coating, curing after a week, the cutting profiles by a slicer, the implementation of the smooth surface of the pressed into the determination of the elastic modulus. Primer layer is about the thickness of the adhesion between the 50  m. Primer film thickness of the above-mentioned determination in the implementation of the central portion. Utilizing nano-indentation method is pressed into the elastic modulus is determined for the thickness of the primer layers refers sticks the 50   m the value of at.

The determination of the elastic modulus of the press by using the super micro indentation hardness tester (ELIONIX Corporation systems, product name ENT-2100) in the surface portion of the primer layer of the press testing. The press-head Berkovich (α: 65.03 °), to 20.4mgf/sec applying load of the load speed, will be the 800 as   N the maximum load to maintain 1 seconds later, with the same load speed for unloading. The results are shown in table 7.

[Table 7]

(I-B) hand stripping cementability evaluation

(I-B-i) assay preparation

BEMCOT on the substrate layer for forming a hard coating of a 70 mm × 50 mm for spreads the cloth to stick laminate body of the primer, to the bottom edge of the 8 mm height 12 mm triangular strip coating moisture-curable polyurethane series adhesive. has sticks primer coating by using the same connection to the laminate of the thickness of the adhesive as the height of the evaluation, in the 23 [...] , 50% RH a week curing solidified under the environment.

(I-B-ii) stress test

As shown in Figure 6, in (I-B-i) made of the test piece is fixed on the stress test fixture, in another laminated body side impose 1-6mm displacement, in the 40 [...] 100% RH groove of constant temperature and humidity preservation 500hr. The above-mentioned after keeping the test piece is removed from the fixture, the upper part of the adhesive thickness is the distance of the plate is 3 mm of the cutting position, enable the hand stripping cementability test.

Applying a stress test in accordance with the displacement of the above-mentioned generic literature 1 in 392 page of formula (9), will be used for this type of polycarbonate resin which are calculated. In other words, application

ΔI=I₀ × Δα×ΔT=I₀ × 58 × 10^-6 × 70      4 × I₀.

Here I₀ length of the long sides of the base material (m), the coefficient of linear expansion of the steel to Δα: 12 × 10-6 × K-1 the coefficient of linear expansion of a polycarbonate resin: 70 × 10-6 × K-1 difference between the coefficients of linear expansion, and imitate the valeant literature 1, the assumed that in said   T 20-90 the temperature difference used under [...] the 70 [...]. Furthermore, if the valeant literature 1 stated, because the usual glass and is bonded the two ends of the assembly can be freely movable, so that the displacement of the adhesive to its 1/2. Therefore, it is assumed that the displacement of the adhesive part is calculated as 2 × I0 (mm). The calculated according to the above-mentioned calculation of the length of the long side of the substrate layer with the assumption that the relationship between the displacement amount of the displayed in table 8 (small points the following-rounding).

[Table 8]

(I-B-iii) hand stripping cementability test

In hand stripping cementability test, tensile adhesive side of the edge of the cutting tool used to trace on the adhering interface moment, the adhesive of the damage area of 100% of the recorded 100. 80 that the situation of the damage area of adhesive 80%, of the area of the interface 20%. Coherencies damage area is preferably 75% or more, more preferably 100%.

(II) manufacture of the substrate layer

(II-1-i) (Aa1) polycarbonate resin

The use of through the conventional method by the interface polymerization process the bisphenol-a and phosgene A having a viscosity average molecular weight obtained by polymerizing 23900 namely emperor person the polycarbonate resin powder formation Corporation systems PANLITE   L-1250WP.

(II-1-ii) hotwired absorbent polycarbonate resin (Aa2)

In the conventional method by using the bisphenol-a by the interface polymerization and phosgene A having a viscosity average molecular weight obtained by polymerizing 23900 in the polycarbonate resin powder of a HOTLINE absorbers emperor person formation Corporation systems PANLITE   AM-1125ZV.

(II-2) (Ab) thermoplastic resin

Embodiment and comparative example of the thermoplastic resin used in the following, the abbreviation is shown. Furthermore, according to the ISO   306B-50, test load to 50N, temperature rise speed 50 the respective [...] /h measurement of the Vicat softening temperature are reproduced in table 9. Thermoplastic resin relative to 100 parts by weight, the amount of the UV absorbent 2 parts by weight. Should be note, the ultraviolet absorbent ADK   LA-31   STAB (ADEKA Corporation systems).

HT121:   HT121 ALTUGLAS ARKEMA corporate

980N: Asahi   Kasei   Chemicals systems 980N

PM120N: Asahi   Kasei PM120N   Chemicals systems

Sheet extrusion manufacturing of a total of (III)

The form the above-mentioned polycarbonate resin of (Aa layer) (II-1) and (II-2) of the polycarbonate resin layer in the diameter of the screw 40 mm uniaxial extruder melt, in addition, to form the above-mentioned thermoplastic resin layer (layer Ab) of the thermoplastic resin in the diameter of the screw 30 mm uniaxial extruder melt, for the laminated remnants law 2 layer, a setting temperature 280 the extrusion die head T of [...] , the obtained sheet in the mirror-finishing the cooling roller, in polycarbonate resin sheet of the obtained single-sided laminated with table 1 the thermoplastic resin layer of the resin laminate. Should be note, Ab Aa layer and the thickness of the layer of the layer Aa Ab ratio of the thickness of the layer of the table 9 is shown.

(IV) used for thermosetting film preparation of the coating of the

(IV-1) organosilicon resin coating (B-1) preparation of

In the water-dispersed colloidal silica dispersion (catalyst chemical industrial Corporation systems Cataloid   SN-30, the solid component concentration of 30 weight %): 100 parts by weight of concentrated hydrochloric acid is added in (12M): 0.1 parts by weight and fully stirred. The dispersed cooling to the 10 [...] , to the dropping methyl trimethoxy silane: 161 parts by weight. Dropwise methyl trimethoxysilane later, immediately because the reaction heat begin to rise in the temperature of the liquid mixture, after a few minutes from the start of heating to 60 the [...]. Reach the 60 after [...] , one side of the cooling side in the ice slowly reduce the temperature of the reaction solution. In the reaction solution of the temperature of the 35 [...] stage, maintaining the temperature stirring 5 hours, is mixed as a curing catalyst in which the 45% choline methanol solution: 0.7 parts by weight, of the acetic acid as a pH regulator: 4.9 parts by weight, solution coating (α) obtained.

While stirring the cerium oxide slurry (C.I.KASEI Corporation systems, NanoTek slurry CEANB, solid component concentration 15 weight %): 7.2 to the dropping of the weight 2-propanol: 100 parts by weight for dilution. While further stirring the above-mentioned diluting the slurry material dropping one side of the stock solution of the above-mentioned coating (α): 264 parts by weight, after the end of the dropping, then dropwise ethyl acetate: 311 parts. Finally for the purpose of leveling and the like to, adding SH28PA (Toray   Dow   Corning Corporation systems): 0.55 parts by weight, is composed of organic siloxane resin (B-1) coating. Through dynamic light scattering method (use electronic Corporation systems FPAR-1000 big tomb) measuring, coating (B-1) in the cerium oxide particles of an average particle diameter of 45 nm. Should be note, in the above-mentioned (B-1) solidification in the organic siloxane composition, relative to the from colloidal silicon dioxide and methyl trimethoxysilane derivative organic silicone resin component: 100 parts by weight, the proportion of the cerium oxide particles to 1 parts by weight.

(IV-2) organosilicon resin coating (B-2) preparation of

Dilution solvent is not matched with the isopropanol to ethyl acetate and 391 parts by weight, in addition, with the (IV-1) organosilicon resin coating (B-2) to equally to the preparation of, organic silicone resin is formed (B-2) coating.

(IV-3) acrylic resin paint (B-3) preparation of

Using direct Nippon   LT   Paint systems Superlac   Neo as acrylic resin paint (B-3).

(IV-4) melamine resin paint (B-4) preparation of

The reflux cooler and the mixing device and the flask is added in nitrogen replacement of a mixed methyl ethyl acrylate: 62.8 parts by weight, methyl acrylic acid cyclohexyl ester: 50.5 parts by weight, methyl acrylic acid hydroxy ethyl ester: 13.0 parts by weight, 1-methoxy-2-propanol: 192.6 parts by weight. The mixture of nitrogen 15 minutes after being air, in a nitrogen gas stream temperature to under the 70 [...] , adding AIBN1: 1.3 parts by weight, in the gas stream in the presence of nitrogen, in the 70 the stirring [...] 5 hours to enable its reaction. Adding AIBN2: 0.7 parts by weight and increasing the temperature to 80 the [...] , reaction 3 hours, the non-volatile component concentration is 40.0 weight % acrylic acid copolymer solution (β).

Relative to the methylated methylol melamine (Nihon   Cytec Cymel   Industries Corporation systems   301): 100 parts adding acrylic acid copolymer solution (β): 20 parts by weight, as the cross-linking agent of 1, 6-hexylene glycol: 70 parts by weight, of maleic acid as curing agent: 5 parts by weight, as the solvent of isopropanol: 150 parts, isobutyl alcohol: 320 parts, ethylene glycol monobutyl ether: 25 and mixing, to obtain melamine resin paint (B-4).

Using the above-mentioned (II), in (III) of the polycarbonate resin and the above-mentioned for thermoplastic resin manufactured by the method of (IV) a total recorded in sheet extrusion. The total of the thermoplastic resin sheet extrusion (Ab layer) contains ultraviolet absorption dose and polycarbonate resin layer (layer Aa) with a thermoplastic resin layer (layer Ab) of their respective thickness are reproduced in table 9.

The the class spreads the law for co-extrusion of the coating-on-a-chip in thermoset coating made of (IV), in 25 the stewing [...] 15 minutes later, thermosetting 1 hour while the laminated thermosetting film layer (layer B), made of polycarbonate resin laminate. Thermosetting coating will be used and the thickness of the layer of thermosetting temperature and B are reproduced in table 9. The obtained hard coat processing on the substrate in table 9 recorded in the combined coating C1: glass with a primer (  Engineering Corporation systems GP-402 Sunstar), C2: HAMATITE glass with a primer (  RUBBER Corporation systems MS-90 YOKOHAMA), C3: primer 35 (  MSI Sunrise Corporation systems) as primer adhesion between, the use of D1: moisture-curable one-component polyurethane adhesive   Seal# 560 Penguin (Sunstar   Engineering Corporation systems), D2:WS-222 (YOKOHAMA   RUBBER Corporation systems) as an elastic adhesive, made Figure 6 shown in a test piece, of a week after curing, the displacement 1-6mm carried out under the state of the 70 [...] , 500hr processed, is recorded in the above-mentioned implementation (I-B-iii) hand stripping cementability evaluation. The results are shown in table 9.

Laminate adhesion between of the present invention is bonded to the structural member at the time of installation, the expansion body can be with the same small glass windows of an elastic adhesive layer (layer D) to obtain good cementability the thickness of the. Furthermore, adhesion between laminated body of this invention even when a larger size, can also be without increasing the thickness of the adhesive layer under the condition of installation is bonded to the structural member.

Industrial availability

Adhesion between of the present invention can be suitable for laminate glass of the fitting for vehicle, such as a rear door window, sunroof, vehicle roof panel, the top of the detachable, window reflector, turn signal lens (including the cover), indoor lamp lens (including the cover) and the display with the front panel.

Furthermore, adhesion between of the present invention can also be used for overlay of window glass of the construction machinery, building, such as window glass of the housing and of the greenhouse, the roof of the garage and such as arcade of the use of wide range.