Urea (multi)-(meth)acrylate (multi)-silane compositions and articles including the same

Cross-reference to related applications

The application requirements for all of the United States Provisional application filed 8 August 2012 61/681, 003, 61/681, 008, 61/681, 023, 61/681, 051 and 61/680, 995 interests, the disclosure of these Provisional applications is incorporated herein by reference the text.

Technical Field

The discloses involves the urea (multiple)-(meth) acrylic ester (multiple)-silane compound in the preparation of the preparation and the use of composite barrier assembly. More specifically, the invention relates to products and barrier film for multi-layer composite barrier component in the vapour deposition of the protective of the (co) polymer layer, the protective (co) polymer layer comprising at least one urea (multiple)-(meth) acrylic ester (multiple)-silane precursor compound reaction product.

Background Art

Inorganic or hybrid inorganic/organic layer has been used in electrical, packaging and decorative applications use in a film. These layer can provide the desired properties, such as mechanical strength, heat resistance, chemical resistance, wear resistance, moisture barrier, and oxygen barrier. Also has developed a high degree of transparency of the multi-layer barrier coating by water vapor in order to prevent the damage of the sensitive material. Moisture sensitive material can be the electronic components, such as organic, inorganic, and hybrid organic/inorganic semiconductor device. Multi-layer barrier coating can be deposited directly over a moisture-sensitive material, is deposited on the flexible transparent substrate or such as the (co) polymer film.

Multi-layer barrier coating can be prepared through various production method. These methods include liquid coating technology, such as solution coating, roller coating, dip-coating, spraying, spin-coating; and technical sides, such as chemical vapor deposition (CVD), plasma-enhanced chemical vapor deposition (PECVD), sputtering and for solid material vacuum thermal evaporation method. Is used in the multi-layer barrier coating of a method for producing multi-layer oxide coating, such as thin (co) dispersed polymer film protective layer of alumina or silicon oxide. Each oxide / (co) polymer film is often referred to as the "gaps", and alternate oxide / (co) polymer multi-layer structure may comprise a plurality of pairs of layers of the moisture and oxygen to provide the full protection. Such transparent multi-layer barrier coating and the method of the example may be found in for example United States Patent 5,440,446 (Shaw, and others), (, Shaw) 5,877,895, 6,010,751 (Shaw, and others), 7,018,713 (Padiyath and others) and 6,413,645 (Graff, and others).

Content of the invention

In one aspect, the present disclosure has described formula R_S-N (R⁵)-C (O)-N (H)-R_A of at least one urea (multiple)-(meth) acrylic ester (multiple)-silane compound composition of matter. R_S in formula-R¹-[ Si (Y_p) (R²)_3-p]_q of the group containing silane, wherein R¹ to multi-price Asia alkyl, arylene, aryl or yafang alkyl groups provide polyurea gel, states Asia alkyl, arylene, provide polyurea gel aryl or yafang alkyl group optionally contains one or more oxygen atom chain, each Y is hydrolysable group, R² is a monovalent alkyl or aryl groups; p is 1, 2 or 3, and for q 1-5. Furthermore, R_A formula R¹¹-(A)_n containing (meth) acryloyl group, wherein R¹¹ to multi-price Asia alkyl, arylene, aryl or yafang alkyl groups provide polyurea gel, states Asia alkyl, arylene, provide polyurea gel aryl or yafang alkyl group optionally contains one or more oxygen atom chain, in formula A X²-C (O)-C (R³) =CH₂ of the (meth) acryloyl group, wherein X² is-O, -S or –NR³, R³ is H or C₁-C₄, and n=1 to 5. R⁵ to H, C₁-C₆ alkyl or cycloalkyl or R_S, premise is that at least one of the following conditions is applicable: to n 2 to 5, R⁵ to R_S, or q is 2 to 5.

In the aforesaid embodiment in any one of, each of the hydrolysable group Y independently selected from alkoxy groups, acetate groups, aryloxy groups and halogen. In the specific illustrative embodiment, can hydrolyze at least some of the group Y in chlorine.

In another aspect, the present disclosure describes a kind of products, which comprises is selected from the (co) polymer film or substrate of the electronic device, the electronic device also includes the organic light-emitting device (OLED), an electrophoretic light-emitting device, a liquid crystal display device, thin film transistor, photovoltaic device, or their combination ; (a) based on an oxide layer on the polymer layer; and the protective oxide layer (co) polymer layer, wherein the protective (co) polymer layer comprises a as mentioned above of formula R_S-N (R⁵)-C (O)-N (H)-R_Afore-mentioned urea of (multiple)-(meth) acrylic ester (multiple)-silane precursor compounds in the reaction product of at least one kind.

In another aspect, the present disclosure describes a kind of products, which comprises is selected from the (co) polymer film or substrate of the electronic device, the electronic device also includes the organic light-emitting device (OLED), an electrophoretic light-emitting device, a liquid crystal display device, thin film transistor, photovoltaic device, or a combination thereof; a main surface of the substrate on the basis of the (co) polymer layer ; (a) based on an oxide layer on the polymer layer; and the protective oxide layer (co) polymer layer, wherein the protective (co) polymer layer formula R_S1-N (R⁴)-C (O)-N (H)-R_A1fore-mentioned urea of (multiple)-(meth) acrylic ester (multiple)-silane precursor compounds in the reaction product of at least one kind. R_S1 in formula-R^1d-Si (Y_p) (R²)_3-p of the group containing silane, wherein R^1d to two price Asia alkyl, arylene, aryl or yafang alkyl groups provide polyurea gel, states Asia alkyl, arylene, provide polyurea gel aryl or yafang alkyl group optionally contains one or more oxygen atom chain, each Y is hydrolysable group, R² is a monovalent alkyl or aryl groups, and for p 1, 2 or 3. Furthermore, R⁴ to H, C₁-C₆ alkyl or C₁-C₆ cycloalkyl. R_A1 formula R^11d-(A) containing (meth) acryloyl group, wherein R^11d to two price Asia alkyl, arylene, aryl or yafang alkyl groups provide polyurea gel, states Asia alkyl, arylene, provide polyurea gel aryl or yafang alkyl group optionally contains one or more oxygen atom chain, and for A formula X²-C (O)-C (R³) =CH₂ of the (meth) acryloyl group, further, wherein the X² is-O, -S or –NR³, and R³ is H or C₁-C₄.

The in any one of the aforesaid products, each of the hydrolysable group Y independently selected from alkoxy groups, acetate groups, aryloxy groups and halogen. In the aforesaid products some of the particular illustrative embodiment, can hydrolyze at least some of the group Y in chlorine.

In the aforesaid products of any one additional exemplary embodiment, the article also comprises the foundation for the (co) polymer layer of the protective oxide layer and polymer layer (a) a plurality of alternating layers. The disclosed some exemplary embodiments provide a composite barrier assembly, such as composite barrier film. Therefore, in the aforesaid products of any one of some exemplary embodiments, the substrate comprises a flexible transparent (co) polymer film, optionally wherein the base comprises polyethylene terephthalate (PET), polynaphthalic acid ethylene glycol ester (PEN), heat stabilized PET, heat stabilized PEN, polyoxymethylene, naphthalin from polyethylene, polyether-ether-ketone, fluorine (co) polymer, polycarbonate, polymethyl methacrylate, poly α-methyl styrene, polysulfone, polyphenylene oxide, polyether imide, polyether sulfone, polyamide-imide, polyimide, such as dimethyl amide, or their combination. In the aforesaid products of any one in other exemplary embodiments, basic (co) polymer layer comprises a (meth) acrylic ester smoothing layer.

In the aforesaid products in any one of the exemplary embodiments, the oxide layer comprises the following at least one of oxide, nitride, carbide or boride, the substance is selected from IIA, IIIA, IVA, VA, VIA, VIIA, IB or group IIB the atomic element, IIIB, IVB or VB metal, rare earth metal, or their combination or mixture. In the aforesaid products of any one of some exemplary embodiments, the product also comprises applied to the protective (co) polymer layer of oxide layer, optionally wherein the oxide layer comprises aluminum oxide.

In another aspect, the present disclosure has described selected from the group consisting of a photovoltaic device, solid-state light-emitting device, a display device, the combination of and the products of their use in the method of, as described above, of the composite membrane. An exemplary solid-state light-emitting device includes a semiconductor light-emitting diode (SLED, more commonly referred to as LED), organic light emitting diode (OLED) or polymer light-emitting diode (PLED). An exemplary display device includes a liquid crystal display, OLED display and quantum dot display.

In another aspect, the present disclosure described a method, the method comprises : (a) a main surface of the substrate is applied to the (co) polymer layer basis, (b) on the basis of the (co) polymer layer applied oxide layer, and (c) depositing protective on the oxide layer (co) polymer layer, wherein the protective (co) polymer layer containing (co) polymer, the (co) polymer as as previously the formula R_S-N (R⁵)-C (O)-N (H)-R_A or R_S1-N (R⁴)-C (O)-N (H)-R_A1fore-mentioned urea of (multiple)-(meth) acrylic ester (multiple)-silane precursors at least one kind of compound to form a reaction product. The substrate is selected from the (co) polymer film or electronic device, the electronic device also includes the organic light-emitting device (OLED), an electrophoretic light-emitting device, a liquid crystal display device, thin film transistor, photovoltaic device, or a combination thereof.

In this method in some of the exemplary embodiment, the at least one urea (multiple)-(meth) acrylic ester (multiple)-silane precursor compound undergoing chemical reaction in order to at least partially on the oxide layer (a) forms a protective polymer layer. Optionally, the chemical reaction is selected from the group consisting of free-radical polymerization reaction and hydrolyzing reaction. In the aforesaid method in any one of, each of the hydrolysable group Y independently selected from alkoxy groups, acetate groups, aryloxy groups and halogen. In the aforesaid products some of the particular illustrative embodiment, can hydrolyze at least some of the group Y in chlorine.

In the aforesaid method of any one of some particular illustrative embodiment, step (a) comprises (i) evaporation based (co) polymer precursor, the evaporation (ii) based (co) polymer precursor condensation on the substrate, the evaporation of solidified and (iii) based (co) polymer precursor in order to form the basic (co) polymer layer. In some such exemplary embodiments, basic (co) polymer precursors comprising (meth) acrylic ester monomer.

In the aforesaid method of any one of some particular illustrative embodiment, step (b) comprises the oxide deposition to the base (co) polymer layer in order to form the oxide layer. The use of sputter deposition, reactive sputtering, chemical vapor deposition, or a combination thereof to achieve deposition. In the aforesaid method of any one of some particular illustrative embodiment, step (b) comprises adding the inorganic silicon-aluminum oxide layer is applied to the basic (co) polymer layer. In the aforesaid method, in a further exemplary embodiment, the method further comprises sequentially repeating steps (b) and (c) to the base (co) polymer layer (a) forms a protective polymer layer, and a plurality of alternating layers of oxide.

In the aforesaid method of any one of an additional exemplary embodiment, step (c) also includes at least one of the following: co-evaporation from liquid mixture of at least one urea (multiple)-(meth) acrylic ester (multiple)-silane precursor compound and (meth) acrylic acid ester compound, or sequentially from the independent source of the evaporating the at least one urea (multiple)-(meth) acrylic ester (multiple)-silane precursor compound and (meth) acrylic acid ester compound. Optionally, the liquid mixture comprises no more than about 10 weight % urea (multiple)-(meth) acrylic ester (multiple)-silane precursor compounds. In such method the further exemplary embodiment, step (c) also includes at least one of the following in: urea (multiple)-(meth) acrylic ester (multiple)-silane precursor compound and (meth) acrylic acid ester compound co-condensation to the oxide layer, the oxide layer condensation urea or sequentially (multiple)-(meth) acrylic ester (multiple)-silane precursor compound and (meth) acrylic acid ester compound.

In the aforesaid method, in a further exemplary embodiment, causes the urea (multiple)-(meth) acrylic ester (multiple)-silane precursor compound and (meth) acrylic acid ester compound is formed on the oxide layer in the protective (co) polymer layer at least partially occur on the oxide layer.

The disclosed some exemplary embodiments provide a composite barrier assembly, product or barrier film, the application is for moisture-exposure exhibits improved moisture resistance. The disclosed illustrative embodiment can make it possible to form the barrier assembly, product or barrier films, they exhibit excellent mechanical properties such as elastic and flexible, and has low oxygen or water vapor transmission rate.

According to the disclosed barrier assembly or barrier films preferably illustrative embodiment of both the visible light and infrared light can be transmitted. According to the disclosed barrier assembly or barrier films are normally of the illustrative embodiment is also flexible. The disclosed barrier assembly according to an exemplary embodiment of a barrier film is generally not shown in the multi layer structure may be caused by thermal stress caused by shrinkage or a layered or crimped. This text the disclosed barrier assembly or barrier films the characteristics of the illustrative embodiment of the wet at a high temperature and even after aging are also maintained normally.

The SUMMARY of the present disclosure have been illustrative embodiment of various aspects and advantages of the. The above disclosure is not intended to describe the disclosed current certain exemplary embodiment example or each instantiated implementation of each embodiment. Subsequent Figures and specific embodiment more specifically examples disclosed herein use of some of the preferred embodiment of the principle.

Description of drawings

With photos into the in this specification and form a part of this specification, and together with the description to explain an exemplary embodiment of the present disclosure and the advantages of the principle.

Figure 1 is a schematic diagram, shown in in the product or film the illustrative moisture-resistant barrier assembly, the product or film according to the disclosed exemplary embodiment of the vapor deposition of a coating of adhesion promoting; and

Figure 2 is a schematic diagram, shown for the preparation according to the disclosed exemplary embodiment of the barrier films of the illustrative method and apparatus.

Similar to the Figure of the reference mark indicating similar element. The Figure herein are not to scale, and in the drawings, the size of the component is set to be shown that the characteristic of the selected.

Mode of execution

Glossary

Throughout the specification and claims certain terms used in the book although most of the well-known for people, but may still require some explanation. It should be understood, as used herein,

The word "a", "an" and "the" and "at least one" interchangeable, in order to represent one or more of the described element.

Through the coated products disclosed in the position of the various elements of the use of such as "top", "upper", "covering", "top", and "under" orientation word , we relative to the horizontally disposed, base-oriented note by the relative position of the elements. Not intended to the substrate or product during manufacture or after manufacture of the space should have any particular orientation.

Through the use of the term "coating" to describe the layer with respect to the the disclosed in the product or film of the barrier assembly of the position of the substrate or other elements, we refer to the layer on the top of a substrate or other element, but not necessarily be contiguous with the substrate or other element.

Through the use of the term " by the... Septations " to describe the (co) polymer layer relative to the position of the two inorganic barrier layer, we mean (co) polymer layer between the inorganic barrier layer, but not necessarily with any one of the inorganic barrier layer.

The term "barrier assembly", "barrier film" or "barrier layer" means that is designed to the vapor, gas or aromatic migration permeable component, film. Can get rid of the example of the gas and the vapor comprises oxygen and/or water vapor.

On the monomer, oligomer or compound the terminology "(meth) acrylate" meaning as with alcohol and acrylic acid or methacrylic acid to form the reaction product of a vinyl functional alkyl ester.

The term "polymer" or "(co) polymer" includes homopolymers and copolymers, and blends of miscible can be in the form of homopolymers or copolymers, for example, by co-extrusion or by including, for example, transesterification of the reaction. The term "copolymer" comprises a random copolymer of the two and a block copolymer.

The term "curing" refers to cause chemical change (for example, by the reaction of water consumption) in order to make the layer hardening or to increase their viscosity method.

The term "cross-linked" refers to the (co) polymer to make it through the covalent chemical bond (co) polymer link together in order to form the mesh (co) polymer of the (co) polymer, the covalent chemical bond usually by molecular or group of cross-linked. Cross-linked (co) polymer of the general characterized in that it is soluble, but in an appropriate solvent can be in the presence of the swelling.

The term "solidified (co) polymer" includes cross-linked and non-cross-linked of two (co) polymer.

Terminology "T_g" means in block form and is not during the assessment in the form of film, cured (co) polymer has a glass transition temperature. In the (co) polymer can only check the form of film under the condition of, block form T_g can usually be appropriate to evaluate the precision. Block forms T_g is determined by a process value will typically adoption of the following: use differential scanning calorimetric (DSC) assessment heat flow rate and temperature, in order to confirm the (co) polymer of the initial and segment movement can be said to be (co) polymer from the glass state into rubbery feel of the inflection point (change is usually two levels). Block forms T_g value measurement can also be used the modulus of the (co) polymer changes as a function of the frequency of temperature and vibration of a dynamic mechanical thermal analysis (DMTA) techniques to assess.

By using the term "visible light-permeable" support, layer, assembly or device, we means the carrier, layer, assembly or device on the visible part of the spectrum which the axial measurement with sets of at least about 20% of the average transmissivity T_vis.

The term "metal" includes pure metal (in other words, to element forms of metal, such as silver, gold, platinum) or metal alloy.

The term "gas phase coating" or "vapor deposition", for example, by the following manner to the coating applied to the substrate surface from the gaseous phase: the coating precursor material or coating material itself is evaporated and subsequently deposited on the surface of the substrate. An exemplary gas phase coating method including, for example, physical vapor deposition (PVD), chemical vapor deposition (CVD), and the combination of them.

Now will be described the disclosed with specific reference to the various exemplary embodiments. An exemplary embodiment of the present disclosure without departing from the nature and scope of the present disclosure under the condition of a plurality of modification and change. Therefore, it should be understood, the disclosed embodiment should not be limited to the following the illustrative embodiment, but by the claims and any equivalent restrictions shown in the control.

The determination of the problem to be solved

Flexible barrier assembly or film for its part of the intrusion of water vapor sensitive electronic device is desirable. Multi-layer barrier assembly or film can offer the advantages of better than glass, because it is flexible, light weight, durable, and enables low-cost continuous roller to roller processing.

For the production of multi-layer barrier assembly or film of each of the known method has a limitation. Chemical deposition method (CVD and PECVD) to form a gasification metal alkoxide precursor, when the adsorbed on the substrate, the precursor undergoing reaction in order to form the inorganic coating. These methods generally limited by the low deposition rate (and thereby causes the low line speed), the alcoholate use of precursors and the efficiency is low (alcoholate in the vapor coating in many not mixing). Often the CVD method also needs the 300-500 [...] substrate temperature in the high range, this may not be suitable for the (co) polymer substrate.

Vacuum method such as thermal evaporation of solid material (for example, resistive heating or electron beam heating) also provides low metal oxide deposition rate. The need for very uniform coating (for example, optical coating) roller extra wide of material application speaking, it is difficult to proportion thermal evaporation may need to be enlarged and the substrate is heated in order to obtain a quality coating. Furthermore, evaporation/sublimation method may need to be generally limited to small area in order to improve the coating quality of the ion-assisted.

Has also been the use of sputtering in order to form the metal oxide layer. Although barrier oxide layer used for forming the deposition of a sputtering method is generally higher energy, however, relates to deposition of the (meth) acrylate, usually with lower energy. Therefore, (methyl) acrylate layer is usually not provided with the lower layer (for example, inorganic barrier oxide sublayer) good bonding characteristics. In order to increase the protective (methyl) acrylate layer and the level of the adhesion of the barrier oxide, known thin oxide silicon Asia can be used for sputtering in this field. If silicon Asia oxide layer in the stack not included in, the protective (meth) acrylate to the barrier oxide is initial adhesion. silicon Asia oxide layer sputtering method to set accurate power and gas stream in order to maintain adhesion to the performance. The deposition method in the history vulnerable to the influence of the noise, thus cause the protective (meth) acrylate and of the change of low adhesion. Therefore it is desirable in the final barrier structure is the elimination of the need of silicon Asia oxide layer in order to enhance adhesion reliability and reduce the process complexity.

Even in the standard barrier stack "deposition" initial adhesion is acceptable, in exposed to the 85 [...] /85% relative humidity when the accelerated aging conditions (RH), sub-oxide and protective (meth) acrylic ester level oneself demonstrate weakening. The interlayer weakening can lead to product or film of the barrier assembly and its aimed at protecting the premature delamination of the device. Preferably, the multi-layer structure improving the initial adhesion and to maintain the level of the 85 and [...] 85% RH, the aging level of the adhesion of the under.

A solution of the problem is known as the particular element of the "adhesive" layer, the element such as chromium, zirconium, titanium, silicon, etc., as the element or in the presence of a small amount of oxygen in sputtering for depositing a material often single-layer or thin layer. Bonding layer element can then be formed with the base layer and the covering layer (oxide) ((co) polymer) chemical bond of the two.

The bonding layer is generally used in the vacuum coating industry, in order to realize the adhesion between different material layers. For deposit often need to finely tune the method for, in order to realize the appropriate layer concentration of atomic bonding layer. Method for vacuum coating is deposited in the impact of minor changes, such as vacuum pressure fluctuation, exhaust, and cross-contamination from other method, thereby causing the changes in the level of adhesion of the product. Furthermore, after the bonding layer when exposed to the water vapor are often not maintain their level of the initial adhesion. In the product or film of the barrier assembly more reliable in improving the adhesion of the solutions is desirable.

Problems discovered solutions

We have surprisingly found, further described below, comprising at least one urea (multiple)-(meth) acrylic ester (multiple)-silane precursor compound reaction product (co) polymer layer of the composite barrier assembly or film to improve product or film of multi-layer composite barrier component in adhesive force and moisture barrier properties. These multi-layer composite barrier assembly or to separate the film of the photovoltaic device, a display device, the light-emitting device and electronic device market as a glass packaging material in flexible substitute and has many applications.

In the disclosed exemplary embodiment, to the technical problems in the technical effects and solutions obtained through the following manner in order to obtain improved multi-layer composite barrier assembly or film: used to protect the (co) polymer layer is applied (for example, by vapor coating) in the product or film multi-layer composite barrier assembly in order to in some exemplary embodiment of the invention to achieve the following effect used in the method of chemical modification of the composition:

1) the chemical bond of the surface of the inorganic oxide and,

2) through the (co) polymerization of (meth) acrylic acid ester with the reliable chemical bond coating, and

3) modified molecular-keeping some of the physical characteristics (for example, boiling point, vapor pressure, etc.), so that they can be used with bulk (methyl) acrylate material is evaporated.

Multi-layer composite barrier assembly or film

Therefore, in an exemplary embodiment, is described in the product or film multi-layer composite barrier assembly, comprising a substrate, a main surface of the substrate on the basis of the polymer layer (co), (co) based oxide layer on the polymer layer; and the protective oxide layer (co) polymer layer, the protective (co) polymer layer include such as further described below, having the general formula R_A-NH-C (O)-N (R⁴)-R¹¹-[ O-C (O) NH-R_S]_n or R_S-NH-C (O)-N (R⁴)-R¹¹-[ O-C (O) NH-R_A]_n of at least one urea (multiple)-(meth) acrylic ester (multiple)-silane precursor compound reaction product. The substrate is selected from the (co) polymer film or electronic device, the electronic device also includes the organic light-emitting device (OLED), an electrophoretic light-emitting device, a liquid crystal display device, thin film transistor, photovoltaic device, or a combination thereof.

As explained further below, this type of material can be through having isocyanate functional group of the (meth) acrylic acid ester material and pure or solvent in the reaction of the amino silane compound synthesis of, and optionally a catalyst such as a tin compound used to accelerate the reaction.

To the attached drawing, Figure 1 is a schematic diagram of product or film 10 in the product component in an exemplary barrier assembly, the product or film 10 comprising a single layer of a moisture-resistant coating. Product or film 10 includes a barrier assembly in accordance with the following order of arrangement: the base 12 ; basic (co) polymer layer 14 ; oxide layer 16 ; such as described herein comprising at least one urea (multiple)-(meth) acrylic ester (multiple)-silane precursor compound protective of the reaction product (co) polymer layer 18 ; and the optional oxide layer 20. Oxide layer 16 and protective (co) polymer layer 18 to form the gaps together, and although only one layer is shown, but the film 10 can be included in a substrate 10 and the alternate oxide layer between the layer 16 and protective (co) polymer layer 18 additional dyads.

In certain exemplary embodiment, product or film composite barrier assembly on the basis of the (co) polymer layer comprises a oxide layer and protective (co) polymer layer of a plurality of alternating layers. Oxide layer and protective (co) polymer layer together form a "DYAD", and in some exemplary embodiment, product or film of the barrier assembly may include more than one layer, in the product or film to form a multi-layer barrier assembly. Product or film in the multi-layer barrier assembly in each of the protective oxide and/or (co) polymer layer (i.e., including more than one layer) can be the same or different. Optionally inorganic layer can be (it is preferably oxide layer) is applied to the plurality of alternating layers, or in pairs layer.

In some exemplary embodiment of the invention, comprising at least one urea (multiple)-(meth) acrylic ester (multiple)-silane precursor compound protective of the reaction product (co) polymer layer 18 improves the film 10 and the protective resistance to moisture of the (co) polymer layer 18 and the peel strength of the adhesion of the oxide layer, thus leading to the improvement of the barrier stack layer and the adhesion of the delamination resistance, as explained further below. The currently preferred for the product or film 10 in the material of the barrier assembly and also below further define in the embodiment.

The protective polymer layer

The present invention is described for use in composite barrier assembly or film (in other words, as barrier films) protective (co) in the polymer layer, the composite barrier assembly or film in the used as the packaging material, such as used for packaging electronic devices, can be used to reduce oxygen and/or water vapor-barrier penetration. Each protective (co) polymer layer includes in its manufacture for urea described herein (multiple)-(meth) acrylic ester (multiple)-silane precursor compound at least one of a composition of matter, to form a reaction product (co) polymer, such as further described below.

Therefore, in some exemplary embodiments, the present disclosure has described composite barrier assembly or film, the composite barrier assembly or film includes a substrate, a main surface of the substrate on the basis of the (co) polymer layer, based on the (co) polymer layer of the oxide layer, and the protective oxide layer (co) polymer layer, wherein the protective (co) polymer layer includes as further described herein below of formula R_S-N (R⁵)-C (O)-N (H)-R_Afore-mentioned urea of (multiple)-(meth) acrylic ester (multiple)-silane precursor compounds in the reaction product of at least one kind.

In other exemplary embodiments, is described in the product or film composite barrier assembly, the product or film includes a substrate, a main surface of the substrate on the basis of the (co) polymer layer, based on the (co) polymer layer of the oxide layer, and the protective oxide layer (co) polymer layer, wherein the protective (co) polymer layer formula R_S1-N (R⁴)-C (O)-N (H)-R_A1fore-mentioned urea of (multiple)-(meth) acrylic ester (multiple)-silane precursor compounds in the reaction product of at least one kind. R_S1 in formula-R^1d-Si (Y_p) (R²)_3-p of the group containing silane, wherein R^1d to two price Asia alkyl, arylene, aryl or yafang alkyl groups provide polyurea gel, states Asia alkyl, arylene, provide polyurea gel aryl or yafang alkyl group optionally contains one or more oxygen atom chain, each Y is hydrolysable group, R² is a monovalent alkyl or aryl groups, and for p 1, 2 or 3. Furthermore, R⁴ to H, C₁-C₆ alkyl or C₁-C₆ cycloalkyl. R_A1 formula R^11d-(A) containing (meth) acryloyl group, wherein R^11d to two price Asia alkyl, arylene, aryl or yafang alkyl groups provide polyurea gel, states Asia alkyl, arylene, provide polyurea gel aryl or yafang alkyl group optionally contains one or more oxygen atom chain, and for A formula X²-C (O)-C (R³) =CH₂ of the (meth) acryloyl group, further, wherein the X² is-O, -S or –NR³, and R³ is H or C₁-C₄.

The in any one of the aforesaid products, each of the hydrolysable group Y independently selected from alkoxy groups, acetate groups, aryloxy groups and halogen. In the aforesaid products some of the particular illustrative embodiment, can hydrolyze at least some of the group Y in chlorine.

Composite barrier assembly or barrier film material

The present disclosure describes the protective (co) polymer layer, the protective (co) polymer layer include such as further described below, having the general formula R_A-NH-C (O)-N (R⁴)-R¹¹-[ O-C (O) NH-R_S]_n or R_S-NH-C (O)-N (R⁴)-R¹¹-[ O-C (O) NH-R_A]_n of at least one urea (multiple)-carbamate (meth) acrylic ester-silane precursor compound reaction product. In addition to others, comprising at least one urea (multiple)-carbamate (meth) acrylic ester-silane precursor compounds of one or more of such reaction product (co) polymer layer may be used for improving the product or film in the interlaminar adhesion compound barrier assembly.

Urea (multiple)-(meth) acrylic ester (multiple)-silane precursor compound

The present disclosure also describes new composition of matter, said composition of matter comprising at least one of the following formula of urea (multiple)-(meth) acrylic ester (multiple)-silane compound: R_S-N (R⁵)-C (O)-N (H)-R_A. R_S in formula-R¹-[ Si (Y_p) (R²)_3-p]_q of the group containing silane, wherein R¹ to multi-price Asia alkyl, arylene, aryl or yafang alkyl groups provide polyurea gel, states Asia alkyl, arylene, provide polyurea gel aryl or yafang alkyl group optionally contains one or more oxygen atom chain, each Y is hydrolysable group, R² is a monovalent alkyl or aryl groups; p is 1, 2 or 3, and for q 1-5. Furthermore, R_A formula R¹¹-(A)_n containing (meth) acryloyl group, wherein R¹¹ to multi-price Asia alkyl, arylene, aryl or yafang alkyl groups provide polyurea gel, states Asia alkyl, arylene, provide polyurea gel aryl or yafang alkyl group optionally contains one or more oxygen atom chain, in formula A X²-C (O)-C (R³) =CH₂ of the (meth) acryloyl group, wherein X² is-O, -S or –NR³, R³ is H or C₁-C₄, and n=1 to 5. R⁵ to H, C₁-C₆ alkyl or cycloalkyl or R_S, premise is that at least one of the following conditions is applicable: to n 2 to 5, R⁵ to R_S, or q is 2 to 5.

In the aforesaid embodiment in any one of, each of the hydrolysable group Y independently selected from alkoxy groups, acetate groups, aryloxy groups and halogen. In the specific illustrative embodiment, can hydrolyze at least some of the group Y in chlorine.

As explained further below, urea (multiple)-(meth) acrylic ester (multiple)-silane composition can be through having an isocyanate functional group of the (meth) acrylic acid ester material and pure or solvent in the reaction of the amino silane compound synthesis of, and optionally a catalyst such as a tin compound used to accelerate the reaction.

these urea (multiple)-(meth) acrylic ester (multiple)-silane composition in some only include a silane group and only one (meth) acryloyl group, and is a following formula:

R_S1-N (R⁴)-C (O)-N (H)-R_A1     (1)

Wherein:

R_S1 the group containing silane of the following formula:

-R^1d-Si (Y_p) (R²)_3-p, wherein:

R^1d to two price Asia alkyl, arylene, aryl or yafang alkyl groups provide polyurea gel, states Asia alkyl, arylene, provide polyurea gel aryl or yafang alkyl group optionally contains one or more oxygen atom chain,

Y is a hydrolyzable group, the alkoxy group, acetic acid groups, aryloxy groups and halogen, in particular chlorine , and

R² is a monovalent alkyl or aryl groups, and

P is 1, 2 or 3;

R_A1 is a following formula containing (meth) acryloyl group:

R^11d-(A), wherein:

R^11d to two price Asia alkyl, arylene, aryl or yafang alkyl groups provide polyurea gel, states Asia alkyl, arylene, provide polyurea gel aryl or yafang alkyl group optionally contains one or more oxygen atom chain, and

For A formula X²-C (O)-C (R³) =CH₂ of the (meth) acryloyl group:

Wherein X² is-O, -S or –NR³, further, wherein R³ is H or C₁-C₄; and

R⁴ to H, C₁-C₆ alkyl or cycloalkyl.

Example natural urea (multiple)-(meth) acrylic ester (multiple)-silane composition of some of the in comprising two or more silane groups, and/or two or more (meth) acryloyl group, and have the following general formula:

R_S-N (R⁵)-C (O)-N (H)-R_A     (2)

Wherein:

R_S the group containing silane of the following formula:

-R¹-[ Si (Y_p) (R²)_3-p]_q

Wherein:

R¹ to multi-price Asia alkyl, arylene, aryl or yafang alkyl groups provide polyurea gel, states Asia alkyl, arylene, provide polyurea gel aryl or yafang alkyl group optionally contains one or more oxygen atom chain,

Y is a hydrolyzable group, the alkoxy group, acetic acid groups, aryloxy groups and halogen, in particular chlorine , and

R² is a monovalent alkyl or aryl groups; and

P is 1, 2 or 3,

For q 1-5

R_A is a following formula containing (meth) acryloyl group:

R¹¹-(A)_n, wherein:

R¹¹ to multi-price Asia alkyl, arylene, aryl or yafang alkyl groups provide polyurea gel, states Asia alkyl, arylene, provide polyurea gel aryl or yafang alkyl group optionally contains one or more oxygen atom chain,

For A formula X²-C (O)-C (R³) =CH₂ of the (meth) acryloyl group, wherein:

X² is-O, -S or –NR³, wherein R³ is H or C₁-C₄; and n=1 to 5 ; and

R⁵ to H, C₁-C₆ alkyl or cycloalkyl or R_S, premise is that at least one of the following conditions is applicable:

N is 2 to 5, R⁵ to R_S, or q is 2 to 5.

Some suitable single isocyanogen ester functional group of the (meth) acrylic acid ester material comprises 3-methyl acrylic isocyanate the root gathers the ethyl ester , 3-methyl-acrylic acid isocyanic the root gathers the ethyl ester and 1, 1-bis-(acryloxy methyl) ethyl isocyanate.

And suitable for binding the present disclosure the use of amino-silane can be a primary or secondary based silane. Can be used for the practice of the disclosed some pergam amino silane described in the United States Patent 4,378,250 (Treadway, and others, the full text of the way into this text by reference) and includes the ammonia ethyl triethoxy silane, β-aminoethyl trimethoxy silane, β-aminoethyl triethoxy silane, β-aminoethyl three butoxypolyethylene silane, silane three third oxygen radicals -amino ethyl β, α-aminoethyl trimethoxy silane, α-aminoethyl triethoxy silane, γ-aminopropyl trimethoxy-silane, γ-aminopropyl triethoxy silane, γ-aminopropyl three butoxypolyethylene silane, γ-aminopropyl- three third oxygen radicals silane, β-aminopropyl trimethoxysilane, β-aminopropyl triethoxy silane, silane three third oxygen radicals -aminopropyl β, β-aminopropyl three butoxypolyethylene silane, α-aminopropyl trimethoxy silane, α-aminopropyl triethoxy silane, α-aminopropyl three butoxypolyethylene silane and α-aminopropyl three third oxygen radicals silane.

Can be used for the practice of the disclosed silane includes some of the sec-N-methyl-aminopropyl trimethoxy silane, N-methyl-aminopropyl triethoxy silane, double (propyl-3-trimethoxysilane) amine, double (propyl-3-triethoxy silane) amine, N-butyl-aminopropyl trimethoxy silane, N-butyl aminopropyl triethoxy silane, N-cyclohexyl-aminopropyl trimethoxy silane, N-cyclohexyl ammonia methyl trimethoxy silane, N-cyclohexyl ammonia methyl triethoxy silane and N-cyclohexyl ammonia methyl diethoxy-mono-methyl silane.

Urea compound can be found in typical preparation procedures Polyurethanes:   and Chemistry Technology   , Saunders   and   Frisch, Interscience   Publishers (New   York, 1963 (Part   I) and (Part   II)   1964 (polyurethane: chemistry and technology, Saunders and Frisch, new York Interscience Publishers, 1963 years (I portion) and 1964 years (part II)).

Urea (multiple)-(meth) acrylic ester (multiple)-silane precursor compound of molecular weight in a certain range, under the condition of the vacuum process, sufficient vapor pressure can be effectively evaporated and then condensed into a thin liquid film. The molecular weight preferably less than approximately 2,000Da, more preferably smaller than 1,000Da, even more preferably less than 500Da.

Preferably, urea (multiple)-(meth) acrylic ester (multiple)-silane precursor compound in gas phase coating mixture is not more than 20 weight % (%wt.) exist; more preferably not more than vapor deposition mixture 19%, 18%, 17%, 16%, 15%, 14%, 13%, 12%, 11%, and even more preferably 10%, 9%, 8%, 7%, 6%, 5%, 4%, 3%, 2% or even 1% in weight.

Optionally inorganic layer can be (it is preferably oxide layer) is applied to the protective (co) polymer layer. The currently preferred inorganic layer comprises Si-al oxide or indium tin oxide of at least one.

Substrate

Substrate 12 is selected from the (co) polymer film or electronic device, the electronic device also includes the organic light-emitting device (OLED), an electrophoretic light-emitting device, a liquid crystal display device, thin film transistor, photovoltaic device, or a combination thereof.

Usually, electronic device substrate is wet-sensitive electronic device. Wet-sensitive electronic device may be, for example, organic, inorganic or hybrid organic/inorganic semiconductor device, including, for example, photovoltaic device, such as a copper-indium-gallium (b) selenium (CIGS) solar cell; a display device, such as organic light-emitting display (OLED), electrochromic display, electrophoretic display or liquid crystal display (LCD), such as quantum dot LCD display; or other OLED electroluminescent light-emitting solid-state light-emitting device, or a combination of them.

In some exemplary embodiments, substrate 12 can be a flexible, visible light permeable substrate, such as flexible light through the (co) polymer film. In one present preferred illustrative embodiment, the substrate is substantially transparent, and in the 550 nm can be has at least about 50%, 60%, 70%, 80%, 90% or even the highest least about 100% of the visible light transmittance.

Exemplary flexible light permeable thermoplastic polymer film and the substrate includes thermosetting film, the thermoplastic polymer film include, for example, polyester, polypropylene ester (for example, polymethyl methacrylate), polycarbonate, polypropylene, high or low density polyethylene, polysulfone, polyether sulfone, polyurethane, polyamide, polyvinyl butyral, polyvinyl chloride, fluoropolymer (such as polyvinylidene fluoride, ethylene-tetrafluoroethylene (ETFE) (co) polymer, tetrafluoroethylene (co) polymer, hexafluoro-propylene (co) polymer, polytetrafluoroethylene, and a copolymer of them), polyethylene sulfide, cyclic olefin (co) polymer, the thermosetting film such as epoxy resin, cellulose derivative, polyimide, polyimide benzocarbazoles Polystyrene [...] and Azole.

The current preferred polymeric film comprises a polyethylene terephthalate (PET), polynaphthalic acid ethylene glycol ester (PEN), heat stabilized PET, heat stabilized PEN, polyoxymethylene, naphthalin from polyethylene, polyetheretherketone, fluoropolymer, polycarbonate, polymethyl methacrylate, poly α-methyl styrene, polysulfone, polyphenylene oxide, polyether imide, polyether sulfone, polyamide-imide, polyimide, such as dimethyl amide, or their combination.

In some exemplary embodiments, the substrate can also be multi-layer optical film ("MOF"), such as in the United States Patent application Publication US   2004/0032658   A1 those described in. In one exemplary embodiment, the film can be prepared on the substrate of the PET.

The substrate thickness can be provided with a plurality of, for example, about 0.01 to about 1 mm. However, for example, when the need to be self-supporting article, the substrate may be of substantial thickness. Can also be the laminated or in other words will be made using a flexible substrate of the disclosed film bonding to a thick, non-flexible or flexible relatively small supplementary carrier to facilitate to make this kind of products.

Can use heat setting, annealing under tension or other techniques to heat-stabilized polymer film (co), when the (co) polymer film is not restricted, the technique will prevent shrinkage to a maximum temperature of at least thermal stability.

Based (co) polymer layer

To return to Figure 1, basic (co) polymer layer 14 can include thin film deposition is adapted to any of the (co) polymer. In one aspect, for example, basic (co) polymer layer 14 may be made from various precursor is formed, include, for example, acrylate or methyl acrylate (meth) acrylic ester monomer and/or oligomer, such as urethane (meth) acrylate, isobornyl (meth) acrylate, fifth heavenly stem four mellow five second quarter (meth) acrylate, epoxy (meth) acrylate, and styrene blend of epoxy (meth) acrylate, propane four di-trimethylolpropane (meth) acrylate, diethylene glycol di (meth) acrylate, 1, 3- butylene-glycol two (meth) acrylate, five (meth) acrylate, pentaerythritol tetra (meth) acrylate, (meth) acrylic acid ester triacrylate, ethoxylated (3) trimethylolpropane propane three (meth) acrylate, ethoxylated (3) trimethylolpropane (meth) acrylic acid ester propane three , alkoxyl three functional (meth) acrylate, dipropylene glycol (meth) acrylate, new pentamethylene glycol two (meth) acrylate, ethoxylated (4) bisphenol A two (meth) acrylate, cyclohexane dicarboxylic mellow two (meth) acrylate, isobornyl (meth) acrylic ester, cyclic (meth) acrylate, tri (2-hydroxy ethyl) isocynauric diethylene glycol dinitrate three (meth) acrylate, and acrylic acid ester by the formed and methyl acrylate (meth) acrylic acid ester compound (for example, oligomer or polymer). Preferably, basic (co) polymer precursors comprising (meth) acrylic ester monomer.

Based (co) polymer layer 14 can be formed by the following manner: the monomer or oligomer added to the substrate and the layer of the layer of cross-linking in order to in-situ to form a (co) polymer, for example, through a radiation cross-linked monomer flash and vapor deposition, electron beam apparatus using, for example, subsequently, UV light source, a discharge device or other suitable device to cross-linked. Cooling said substrate can be adopted to improve the coating efficiency.

Can also use conventional coating method such as roll coating (e.g., gravure roll coating) or spray coating (e.g., electrostatic spray coating) to the monomer or oligomer is applied to the substrate 12, then states crosses linking as noted above. Based (co) polymer layer 14 can also be applied to the solvent contained in the oligomer or (co) polymer of such polycrystalline silicon layer is formed in order to remove the solvent. Chemical vapor deposition (CVD) can also be used in some cases.

Preferably, basic (co) polymer layer 14 through the flash and the gas phase of the original deposit the subsequent cross-linking is formed is, for example, in the following documents: US Patent 4,696,719 (Bischoff), 4,722,515 (Ham), (such as Yializis) 4,842,893, (Yializis) 4,954,371, 5,018,048 (Shaw, and others), (, Shaw) 5,032,461, 5,097,800 (Shaw, and others), (, Shaw) 5,125,138, 5,440,446 (Shaw, and others), (such as Furuzawa) 5,547,908, (, Lyons) 6,045,864, 6,231,939 (Shaw, and others) and 6,214,422 (Yializis); PCT International Publication WO   00/26973 (delta V technology Company (Delta   Technologies   V, Inc.)); and D.G.Shaw M.G.Langlois, "A   New   Vapor   Deposition   Process   for   Webs   Coating   Polymer   Paper   and" (a kind of used for coating the web and the polymer web of the new vapor deposition method), 6th International vacuum coating Conference (6th   International   Conference   Coating   Vacuum) (1992); and D.G.Shaw M.G.Langlois, "  for   New A   Depositing   High   Acrylate   Speed   Thin   Process   Films   Vapor:   Update An" (used for vapor deposition acrylate thin film of new high-speed method: an updated version), vacuum coater association section 36 annual technical Proceedings (Society   of   Vacuum   Coaters   36th   Technical   Annual   Conference   Proceedings) (1993); and D.G.Shaw M.G.Langlois, "Use   of   Vapor   Deposited   Acrylate   Coatings   to   Improve   the   Film   Properties   Metallized   Barrier   of" (vapor deposition acrylate coating for improving of the metallized film the use of barrier properties), vacuum coater association section 37 annual technical Proceedings (Society   of   Vacuum   Coaters   37th   Technical   Annual   Conference   Proceedings) (1994); D.G.Shaw, M.Roehrig, and M.G.Langlois C.Sheehan, "Use   of   Evaporated   Acrylate   Coatings   to   Smooth   the   Surface   of   Substrates   Film   Polypropylene   Polyester   and" (evaporation acrylate coating for smooth polyester and polypropylene film the use of a surface of a substrate), the organization of the International radiation-curable (RadTech) (1996); J.Affinito, P.Martin, M.Gross, and C.Coronado E.Greenwell, "Vacuum   Deposited   Polymer/Metal   Application   Films   Optical   Multilayer   for" (for use in optical applications of vacuum-deposited polymer/metal multi-layer film), a thin film of solid material 270 (  Films   Solid Thin), 43-48 (1995); and J.D.Affinito, M.E.Gross, C.A.Coronado, G.L.Graff, and E.N.Greenwell P.M.Martin, "  Layers   Barrier   Transparent Polymer-Oxide" (polymer-oxide transparent barrier layer), vacuum coater association section 39 annual technical Proceedings (Society   of   Vacuum   Coaters   39th   Technical   Annual   Conference   Proceedings) (1996).

In some exemplary embodiments, basic (co) polymer layer 14 (and each of the oxide layer 16 and protective (co) polymer layer 18) and the smoothness and continuity of the adhesion of the substrate or layer can be enhanced by appropriately pre-processed. Suitable examples include of the programme of the pre-treatment of the appropriate reactive or non-reactive atmosphere (e.g., plasma, glow discharge, corona discharge, dielectric barrier discharge or atmospheric pressure discharge) in the presence of a discharge; chemical pre-treatment or flame pretreatment. These pre-treatment to the layer thereby the more acceptable the surface of subsequently applied (co) polymer (or inorganic) the formation of the layer. Plasma pre-treatment may be is particularly usable.

In some exemplary embodiments, can also be the substrate or the underlying layers on the top of the foundation for the (co) polymer layer 14 has different viburnitor independent adhesion to improve adhesion. For example, adhesion can be for the independent viburnitor (co) polymer layer, or a metal-containing layer, such as metal layer, the metal oxide layer, metal nitride or metal oxynitride layer. Adhesion promoting layer can have several nanometers (for example, 1 nm or 2 nm) to about 50 nm thickness, and can be more thick (if necessary).

(Co) polymer layer basis of the required chemical composition and thickness will partially depend on the nature of the substrate and surface topography features. The thickness preferably is sufficient to provide the follow-up of the oxide layer can be applied to the smooth, defect-free surface. For example, basic (co) polymer layer can have several nanometers (for example 2 nm or 3 nm) to about 5 microns thickness, and can be more thick (if necessary).

In another aspect, barrier assembly comprises is selected from the (co) polymer film and the substrate of the wet-sensitive device, and the barrier layer is arranged on the substrate or adjacent substrate. As further described below, barrier component can be directly deposited on the (co) polymer film substrate or on the base of the wet-sensitive device, this is a kind of is often referred to as the direct deposition or direct encapsulation method. Exemplary direct deposition method and barrier assembly or described in the United States Patent 5,654,084 (Affinito), (the Graff) 6,522,067, (the Graff) 6,548,912, 6,573,652 (Graff, and others) and 6,835,950 in (Brown and others).

In some exemplary embodiments, a flexible electronic device can be directly encapsulated by the methods described herein. For example, the device can be attached to flexible bears the weight of the substrate, and can make the mask deposition in order to protect the electrical connection from one or more of the inorganic layer, one or more of the (co) polymer layer, or one or more other layers of the impact of the in its during deposition. Can be in other places such as the disclosed the deposition form a multi-layer barrier assembly of one or more inorganic layer, one or more of the (co) polymer layer and one or more of the other layer, and then removing the mask, to thereby expose electrically connected.

In one exemplary direct deposition or is directly encapsulated embodiment, wet-sensitive device as the wet-sensitive electronic device. Wet-sensitive electronic device may be, for example, organic, inorganic or hybrid organic/inorganic semiconductor device, including, for example, photovoltaic device, such as a copper-indium-gallium (b) selenium (CIGS) solar cell; a display device, such as organic light-emitting display (OLED), electrochromic display, electrophoretic display or liquid crystal display (LCD), such as quantum dot LCD display; or other OLED electroluminescent light-emitting solid-state light-emitting device, or a combination of them.

Used for preparing the multi-layer barrier assembly and the appropriate transparent multi-layer barrier coating an appropriate method, for example, examples of U.S. patents can be seen (the Shaw) 5,440,446, (, Shaw) 5,877,895, 6,010,751 (Shaw, and others) and 7,018,713 (Padiyath and others). In a current preferred embodiment, product or film of the barrier assemblies may be similar to the United States Patent 5,440,446 (Shaw, and others) and 7,018,713 in (Padiyath and others) of the system through the chamber the roller is realroller the various layers is produced by deposition onto the substrate.

Current preferably, basic polymer layer 14 through the flash and the gas phase of the original deposit the subsequent cross-linking is formed is, for example, in the following documents: US Patent 4,696,719 (Bischoff), 4,722,515 (Ham), (such as Yializis) 4,842,893, (Yializis) 4,954,371, 5,018,048 (Shaw, and others), (, Shaw) 5,032,461, 5,097,800 (Shaw, and others), (, Shaw) 5,125,138, 5,440,446 (Shaw, and others), (such as Furuzawa) 5,547,908, (, Lyons) 6,045,864, 6,231,939 (Shaw, and others) and 6,214,422 (Yializis); and PCT International Publication WO   00/26973 (delta V technologies Corporation).

Oxide layer

Product or film for improved barrier assembly comprises at least one oxide layer 16. The oxide layer preferably comprises at least one of an inorganic material. Suitable inorganic materials include different atomic element oxide, nitride, carbide or boride. In contained in the oxide layer of the current preferred inorganic material includes IIA, IIIA, IVA, VA, VIA, VIIA, IB or group IIB the atomic element, IIIB, IVB or VB metal, rare earth metal, or their combined oxide, nitride, carbide or boride. In some particular exemplary embodiments, the inorganic layer (more preferably inorganic oxide layer) is applied to the upper surface of the protective (co) polymer layer. Preferably, oxide layer comprises Si-al oxide or indium-tin-oxide.

In some exemplary embodiments, the composition of the oxide layer in the thickness direction of the layer to change, i.e., gradient composition. In such an exemplary embodiment, oxide layer preferably comprises at least two kinds of inorganic material, and the two kinds of inorganic material in the ratio of the change in the entire thickness of the oxide coating. Two kinds of inorganic material to the ratio of the inorganic material is in the relative proportion of each kind. The ratio may be, for example, than the quality, volume ratio, concentration ratio, mol ratio, than the surface area of the, or the atomic ratio.

The obtained gradient of the oxide layer with a single-layered compared with which is a kind of improvement. When the vacuum deposition of a thin layer of protective (co) polymer when combined, can also realize optical characteristic and the additional beneficial effects. Can be made into the multi-layer gradient inorganic (co) polymer barrier stack so as to enhance barrier properties and optical characteristics.

Product or film of the barrier assemblies may be similar to the United States Patent 5,440,446 (Shaw, and others) and 7,018,713 in (Padiyath and others) of the system through the chamber the roller is realroller the various layers is produced by deposition onto the substrate. Layer deposition can be embedded, and the single-pass system. In some cases, product or film barrier component can be a plurality of times through the system, with a having a plurality of pairs of layers in the product or film forming a multi-layer barrier assembly.

1st and 2nd inorganic material can be a metal or non-metal atomic element, or a metal or non-metal atomic element of the combined oxide, nitride, carbide or boride. The so-called "metal or non-metal" atomic element, is selected from the periodic table of elements to IIA, IIIA, IVA, VA, VIA, VIIA, IB, or IIB atomic element of clan, IIIB, IVB, or VB metal, rare earth metal, or a combination thereof. Suitable inorganic materials include, for example, metal oxide, metal nitride, metal carbide, metal oxynitride, metal boron oxide, and a combination of them, such as silicon oxide, for example, silicon dioxide, alumina, for example, alumina, titanium oxide, such as titanium dioxide, indium oxide, tin oxide, indium-tin-oxide ("ITO"), tantalum oxide, zirconium oxide, niobium oxide, aluminum nitride, silicon nitride, boron nitride, aluminum oxynitride, silicon oxynitride, nitrogen, boron oxide, boron zirconium oxide , boron titamium oxide , and the combination of them. ITO each element is a correct choice of the components in the relative proportion of the special categories become conductive one example of ceramic material. Si-al oxide and indium-tin-oxide is the current preferred form the oxide layer 16 of the inorganic material.

For the purpose of clear representation, described in the following discussion the oxide layer 16 relates to oxide composition; however, it should be understood, the above composition may comprise oxide, nitride, carbide, boride, nitrogen oxides, such as analyzers-with any one of the in.

The oxide layer 16 in one of the embodiment, the inorganic material is silicon oxide 1st, and 2nd inorganic material is alumina. In this embodiment, the atomic ratio of silicon to aluminum of the change in the thickness of the oxide coating as a whole, for example, the surface of the oxide layer near 1st more than the aluminum of the silicon, with the distance from the surface of the 1st becomes gradually more aluminum than silicon. In one embodiment, the atomic ratio of silicon to aluminum from the surface of the 1st change monotonically with increased distance from a, i.e., from the 1st with the ratio of increase in a distance of the surface to increase or decrease, however, the ratio of the distance from the surface of the 1st and both increasing and decreasing. In another embodiment, the ratio is not monotonous increase or decrease, i.e., as the distance from the surface of the 1st, the ratio increases in the part of the 1st, 2nd, and in the reduced part. In this embodiment, with the increase in a distance of from the 1st surface, there can be several times the ratio of the increasing and decreasing, and the ratio is non-monotonic. The oxide layer 16 in the entire thickness of the, from one kind of oxide material to another kind of oxide material change of the concentration of the inorganic oxide to improve barrier properties, as measured by the water vapor transmission rate.

In addition to improved barrier characteristics, the gradient composition can be prepared into the improvement of the barrier properties with other unique simultaneous display of the optical characteristics. Layer composition to produce a change of gradient of the change of the refractive index of the corresponding by level. Can be selection of material, can make the refractive index changes from high to low, or vice versa. For example, from a high-refractive index to a low refractive index can be allowed to spread along one direction of the light energy easily penetrate layer, and of the light propagating in the opposite direction can be layer reflection. Refractive index change can be used for a design, in order to enhance the light-emitting device from the protection level extracting light. Furthermore, the refractive index change can be used for the light will all be caught and penetrate the device (such as a solar cell). Other optical structure can also be (such as a band-pass filter) in doping layer, at the same time improvement of the barrier properties.

In order to promote bonding of the silane and the oxide surface, may be advantageously in the new sputter deposited silicon dioxide (SiO₂) layer of silanol (Si-OH) to form hydroxyl group. The vacuum chamber means of the reservoired within the full control amount can be obtained, high enough in order to facilitate the forming of the surface concentration of Si-OH base, so as to increase the binding site. In monitoring the source and the residual gas under the condition of using water vapor, gas reservoired within the vacuum chamber can be controlled, in order to ensure the generation of adequate Si-OH base.

Used for preparing comprises a barrier assembly or barrier films of the products of the method

In other exemplary embodiments, the present disclosure describes such as used for the (co) polymer film substrate used for barrier films or on the electronic device on the substrate through deposition multi-layer composite barrier assembly and method for producing product, the method comprises : (a) a main surface of the substrate is applied to the (co) polymer layer basis, (b) on the basis of the (co) polymer layer applied oxide layer, and (c) depositing protective on the oxide layer (co) polymer layer, wherein the protective (co) polymer layer containing (co) polymer, the (co) polymer as as previously the formula R_S-N (R⁵)-C (O)-N (H)-R_A or R_S1-N (R⁴)-C (O)-N (H)-R_A1fore-mentioned urea of (multiple)-(meth) acrylic ester (multiple)-silane precursors at least one kind of compound to form a reaction product.

In this method in some of the exemplary embodiment, the at least one urea (multiple)-(meth) acrylic ester (multiple)-silane precursor compound undergoing chemical reaction in order to at least partially on the oxide layer (a) forms a protective polymer layer. Optionally, the chemical reaction is selected from the group consisting of free-radical polymerization reaction and hydrolyzing reaction. The in any one of the aforesaid products, each of the hydrolysable group Y independently selected from alkoxy groups, acetate groups, aryloxy groups and halogen. In the aforesaid products some of the particular illustrative embodiment, can hydrolyze at least some of the group Y in chlorine.

In other exemplary embodiments, the present disclosure describes such as used for the (co) polymer film substrate used for barrier films or on the electronic device on the substrate through deposition multi-layer composite barrier assembly and method for producing product, the method comprises : (a) the basic (co) polymer layer gas-phase deposition and solidification to the (co) polymer film on the main surface of the substrate ; (a) the basic (co) polymer layer gas-phase is deposited and solidified on the main surface of the substrate ; (b) the base (co) polymer layer vapor deposition oxide layer; and (c) the protective (co) polymer layer gas-phase deposition and solidification to the oxide layer, this protective (co) polymer layer containing (co) polymer, the (co) polymer as as previously the formula R_S-N (R⁵)-C (O)-N (H)-R_A or R_S1-N (R⁴)-C (O)-N (H)-R_A1fore-mentioned urea of (multiple)-(meth) acrylic ester (multiple)-silane precursors at least one kind of compound to form a reaction product.

Vapor deposition method is generally limited to the pumpability (with an acceptable viscosity of the liquid phase), can be atomized (form a liquid droplet), flash evaporation of the (under the vacuum condition the vapor pressure is high enough), can be condensed (vapor, molecular weight) and can be cross-linked in a vacuum (molecular weight range, reactive, functionality) composition.

Figure 2 is a schematic diagram of system 22, shown for preparing product or film 10 in the method of the separation of the assembly. System 22 is accommodated in an inert environment and includes for receiving and moving from the membrane 26 of the substrate 12 (Figure 1) of the freezing drum 24, thereby providing the barrier layer is formed on the moving web. Preferably, can use the optional nitrogen plasma processing unit 40 to the film 26 is subjected to a plasma treatment or pretreatment, in order to improve the (co) polymer layer 14 (Figure 1) and the substrate 12 (Figure 1) of adhesion. Evaporator 28 to the rotary drum 24 the membrane 26 to arrow 25 in the direction shown by applying the basis of the (co) polymer precursor, its by curing unit 30 in order to form the cured based (co) polymer layer 14 (Figure 1). Oxide sputtering unit 32 to the rotary drum 24 promote film 26 applied to the oxide in order to forming layer 16 (fig. 1).

For additional alternate oxide layer 16 and protective (co) polymer layer 18, drum 24 can be and-arrow 25 opposite reverse rotation, and then once again advance the film 26, in order to exert additional alternate based (co) polymer and the oxide layer, and the sub-processes can be directed against expectations, or to repeat many of the alternating layers. Once the basic (co) polymer and oxide completed, the drum 24 to further promote film, and evaporator 36 the oxide layer 16 deposition urea on (multiple)-(meth) acrylic ester (multiple)-silane compound (as described above), the reaction or cured in order to form the protective (co) polymer layer 18 (Figure 1). In some currently preferred embodiment, causes the urea (multiple)-(meth) acrylic ester (multiple)-silane by reaction of a compound of the oxide layer 16 is formed on the protective (co) polymer layer 18 at least partially in the oxide layer 16 on.

Optionally, additional use of the evaporator 34 to provide can be used for forming the protective (co) polymer layer 18 (Figure 1) of the other co-reactants or comonomer (for example, an additional protective (co) polymer compound). For additional alternate oxide layer 16 and protective (co) polymer layer 18, drum 24 can be and-arrow 25 opposite reverse rotation, and then once again advance the film 26, in order to exert additional alternate oxide layer 16 and protective (co) polymer layer 18, and the sub-processes can be directed against expectations or needs or DYAD many of the alternating layers is repeated.

Oxide layer 16 can be used with in the field of metal film such as sputtering (such as the cathode or planar magnetron sputtering), evaporating (such as resistance or electron beam evaporation), chemical vapor deposition, a technique such as electroplating. In one aspect, oxide layer 16 using sputtering (such as reactive sputtering) form. When the oxide layer through the conventional chemical vapor deposition method such as the lower energy art high-energy deposition technique, such as sputtering and form, has been observed that the enhanced barrier properties. Not bound by theory, it is believed that as the sputtering in the middle, is due to the enhanced property of the condensed substances reach the substrate has large kinetic energy, so as to lead to a lower drive ratio of the pores.

In some exemplary embodiments, with the inert and reactive gas (for example for argon and oxygen) in the presence of a gas atmosphere, sputtering deposition method can use the alternating current (AC) power supply of the power source of the polypeptide. Polypeptide AC power source is alternating the polarity of each of the, so as to as half of the AC cycle, a target adopts the cathode and another target adopts the anode. In the next cycle, the polarity of switching between the polypeptide. The conversion in order to set the frequency (example as promised 40kHz) generating, but can also use other frequency. The introduction of oxygen in the process without the admission as well as target composition on the base of the the surface of the oxide layer is formed on the two. During the sputtering of the dielectric oxide may be charged, thus cut off sputter deposition process. Polarity conversion can be and the surface material of the sputtering target, and can provide the uniformity of the deposited material and better control.

In further exemplary embodiment, is used for double-AC sputtering of each of the target can comprise a single metal or non-metal element, or a metal and/or a mixture of non-metallic elements. The most close to the mobile base part of the oxide layer using 1st 1st group of sputter deposition. Then the substrate moves close to the 2nd group of sputtering target, and using the 2nd group of sputtering target will be a layer of oxide deposited on the 1st 2nd part on the top of the part. Oxide layer along the whole of the change of direction of the thickness of a layer.

In an additional exemplary embodiment, in a inert and reactive gas (for example for argon and oxygen) in the presence of a gas atmosphere, sputtering deposition method can use the direct current (DC) power supply of the power source of the target. DC power source independent of the other power source to supply power to each of the targets (for example, pulse power). In this regard, each individual targets and corresponding material can be in different sputter power level, thereby to provide the composition of the entire layer thickness of the additional control. DC power source similar to the pulse in the frequency of the AC sputtering in the hand, thereby allowing for the types of reactive gas (for example oxygen) in the presence of control to the high speed sputtering. Pulse DC power source allows the polarity switching control, and can the surface material of the sputtering target, and can provide the uniformity of the deposited material and better control.

In one particular illustrative embodiment, control of the sputtering period can be improved through the use of elements of each target composition of the mixture or atoms, for example target can comprise a mixture of aluminum and silicon. In another embodiment, target in each of the relative proportions of elements can be different, in order to easy to provide through the atomic ratio of change in the oxide layer. In one embodiment, for example, 1st group of double-AC sputtering target can comprise silicon and aluminum of the 90/10 mixture, and 2nd group of double-AC sputtering target can comprise aluminum and silicon 75/25 mixture. In this embodiment, a layer of oxide can be used for part of the 1st 90% Si/10% Al target deposition, and a 2nd 75% Al/25% Si target deposition. The resulting oxide layer has a gradient composition, the gradient in the composition in the entire thickness of the inorganic layer from about 90% Si change to about 25% Si (and on the contrary, from about 10% Al to about 75% Al).

In a typical double-AC in the sputtering, a uniform oxide layer is formed, but the layer in a micron and nano-size defect, so that the uniform oxide layer by the barrier performance loss. These small scale defect inherent in one of the reasons is because the oxide growth of grain boundary structure, it then spread to the whole film thickness. Not bound by theory, it is believed that a number of effect to contribute to the improvement of the gradient composition described herein to separate the characteristic of the barrier member. One effect can be to make the gradient appearing in the area of mixed oxide more densification, and separating vapor by the densification of the oxide may be any path. Another effect can be by changing the composition of the oxide material, the formation of the grain boundary can be stopped, thereby causing the micro-structure of the film changes also through the thickness of the oxide coating. Another effect may be an oxide with another oxide concentration the concentration of increase gradually decreases through the thickness, to form a small scale so as to reduce the probability of the defect position. The reduction of the defect position can lead to water penetration with reduced transmittance of the coating.

In some exemplary embodiments, the exemplary film can be subjected to after-treatment, such as heat treatment, ultraviolet (UV) or vacuum UV (VUV) processing or plasma processing. The membrane can pass through the oven or in the coating equipment directly heating the membrane (for example, using an infrared heater or on a tumbler direct heating) to carry out heat treatment. For example, can be of from about 30 a to about [...] the 200 [...] , about 35 the [...] to about 150 the [...] or about 40 a to about [...] the 70 [...] the implementation of the temperature of the heat treatment.

Inorganic or hybrid membrane can be added in other functional layer of the film or coating includes more hard one or a plurality of optional layer. Optionally the upper most layer of the film of the protective layer is appropriate, such as the optional inorganic layer 20. If necessary, such as the roller spreads can be used (for example, gravure roll coating) or spray coating (e.g., electrostatic spray coating) conventional coating method of applying protective layer, then crosslinked using, for example, UV radiation. Also can be through like of the above monomer a flash evaporation, vapor deposition and cross-linked to form a protective layer. Volatile (meth) acrylate monomer is suitable for use in the protective layer of this kind. In a particular embodiment, the volatilization of the (meth) acrylate monomer.

Method for the use of barrier films

In another aspect, the present invention described the barrier film as described above is used for is selected from solid-state light-emitting device, a display device, the combination of and in their method of the products. An exemplary solid-state light-emitting device includes a semiconductor light-emitting diode (SLED, more commonly referred to as LED), organic light emitting diode (OLED) or polymer light-emitting diode (PLED). An exemplary display device includes a liquid crystal display, OLED display and quantum dot display.

An exemplary LED described in the United States Patent 8,129,205 in. An exemplary OLED described in the United States Patent 8,193,698 and 8,221,176 in. Illustrative PLED described in the United States Patent 7,943,062 in.

Unexpected results and advantages

The disclosed product or film of an exemplary barrier assembly in the display unit, the light-emitting and electronic device market as a glass packaging material in flexible substitute and has many applications and advantages. Therefore, the disclosed certain exemplary embodiments provide the product or film of the barrier assembly, they are used for wet barrier application exhibits a improved moisture resistance. In some exemplary embodiments, the barrier component can be on the base of the wet-sensitive device which is directly deposited, this is a kind of the package is often referred to as the direct method.

The wet-sensitive device may be, for example, organic, inorganic or hybrid organic/inorganic semiconductor device, including, for example, : photovoltaic device, such as CIGS; a display device, such as the OLED, electrochromic display device or electrophoretic display; or other OLED electroluminescent light-emitting solid-state light-emitting device, or other. Flexible electronic device can be directly packaged. For example, the device can be attached to flexible bears the weight of the substrate, and can be a deposition mask in order to prevent electric connection is subjected to the impact of the oxide layer deposition. Can be as mentioned above deposition based (co) polymer layer and the oxide layer, and then removing the mask, to thereby expose electrically connected.

The disclosed illustrative example of the method can make the can be formed in the product or film barrier assembly, they demonstrate excellent mechanical properties such as elastic and flexible, and has low oxygen or water vapor transmission rate. The barrier assembly has at least one inorganic or hybrid organic/oxide layer or may have additional inorganic or hybrid organic/oxide layer. In one embodiment, the disclosed barrier assembly can with the organic compound (for example, polymer (a)) of the inorganic or hybridization level alternately. In another embodiment, the barrier assembly can include inorganic or hybrid material and organic compound. Using the disclosed method for forming in the product or film of the barrier assemblies can have less than about 1cc/m²-days, less than about 0.5cc/m²-days or less than about 0.1cc/m²-days of oxygen transmission rate (OTR). Using the disclosed method for forming in the product or film of the barrier assemblies can have less than about 10cc/m²-days, less than about 5cc/m²-days or less than about 1cc/m²--day water vapor transmission rate (WVTR).

The barrier assembly according to the present disclosure (and more specifically, barrier films) preferably an exemplary embodiment of the visible light and infrared light through. As used herein the term "visible light and an infrared light permeable" may refer to, sets the spectrum the axial measurement of the visible and infrared part has at least about 75% (in some embodiments at least about 80, 85, 90, 92, 95, 97 or 98%)of the average transmittance. In some embodiments, can be visible light and infrared light through the barrier assembly in the 400 nm to 1400 nm average transmittance in the range of at least about 75% (in some embodiments at least about 80, 85, 90, 92, 95, 97 or 98%). Visible light and infrared light through the barrier assembly is capable of non-interference to the photovoltaic cell, for example, the absorption of the visible light and infrared light of those. In some embodiments, can be visible light and infrared light through the barrier assembly of the photovoltaic cell to the useful average transmittance in the wavelength range of at least about 75% (in some embodiments at least about 80, 85, 90, 92, 95, 97 or 98%).

In some exemplary barrier film embodiment, can be selected based on the refractive index and thickness of the 1st and 2nd (co) polymer film substrate, pressure-sensitive adhesive layer and a barrier assembly in order to enhance the visible light and infrared light transmittance

According to the disclosed exemplary barrier assembly and a barrier film which is usually flexible. The terminology used in the "flexible" means that can be formed in a roll. In some embodiments, the term "flexible" means a radius of curvature of at most about 7.6 centimeters (cm) (3 inch), in some embodiments up to 6.4 cm (2.5 inch), 5 cm (2 inches), 3.8 cm (1.5 inch) or 2.5 cm (1 inch) bending of the roll core. In some embodiments, flexible assembly of at least about 0.635 cm (1/4 inch), 1.3 cm (1/2 inch) or 1.9 cm (3/4 inch) radius of curvature of the bend.

According to the disclosed exemplary barrier assembly and the barrier film may be generally not shown in the multi layer structure caused by thermal stress or shrinkage of a layered or crimped. In this text, the Ronald   P.Swanson is to use cincinal 2006AWEB Proceedings (industrial metallization, coating and lamination, application web processing Society Proceedings 2006 (Association   of   Industrial   Metallizers, Coaters   and   Laminators, Applied   Proceedings2006   Handling   Web   Conference)) of the in "web curl measurement (  Curl Measurement   Web   of)" curly regulate in the measurement. According to this method, the measurable achieve resolution 0.25m^-1 curling of the of curvature. In some embodiments, the barrier assembly according to the present disclosure and the highest performance barrier film 7, 6, 5, 4 or 3m^-1 curly. According to the solid mechanics, the known curvature of the beam applied to the proportional to the bending moment. The size of the known bending stress proportional to the bending moment. According to these relations, relatively speaking, curling of the sample can be used to compare the residual stress. Barrier assembly and usually also the barrier film is cured on the substrate of the photovoltaic device and other commonly used EVA encapsulated agent exhibiting high peel adhesion. Disclosed herein the characteristics of the barrier assembly and barrier film even in high-temperature and wet after aging are also maintained normally.

An exemplary embodiment of the disclosure has been described in the above, and further by the following examples to explain in the following text, it should not in any way to these examples will be understood as limiting the scope of the present disclosure. On the contrary, it should be clearly understood, may take a variety of other embodiments, modified form and its equivalent, persons of skill in the art after reading the description herein, without deviating from the essence of the present disclosure and/or the the scope of the claim attached to the premise of books, these other embodiments, modified version of the obvious equivalents thereof.

Examples

To the following examples in this disclosure in the description of the illustrative embodiments within the scope of. Unless otherwise specified, all of the parts otherwise in the examples, percentages and ratios are by weight. Although, on the broad scope of the claims and of the value range of the parameter is the approximate, however, in particular embodiments, is the list of values of the report of the as accurately as possible. However, any of the values are inherently contain certain errors, these errors can be avoided not by the in the corresponding test measurement caused by presence in the standard deviation. The lowest degree, each of the numerical parameters equivalent is not intended to limit the principles of the application of the protection range, according to at least the effective value of the recorded digital and through the usual rounds up the law to explain each numerical parameter.

Material

In the embodiment using the following material, abbrebytions and tradenames:

Self- target 90% Si/10% Al Materion advanced chemical Company Albuquerque, new Mexico (Materion   Advanced   Chemicals, Inc., Albuquerque, nm).

ETFE film: to tradenames" ETFE " can be derived from plastic Company new Jersey wern city Saint Ge Ban performance (  Plastics   Performance St.Gobain) ethylene-tetrafluoroethylene film.

Table 1 lists the content for according to the above preparation (multiple) are (meth) acrylate (multiple) silane compound material:

Table 1 :

The materials used in examples

Unless otherwise indicated, otherwise the used solvent and other reagent are derived from the Wisconsin milwaukie of chemical Company [...] (Chemical   Company (Milwaukee, WI)).

Urea (multiple)-(meth) acrylic ester (multiple)-silane precursor compound synthesis

Preparation example 1

Of the stirring rod to a 250 ml round-bottom flask by adding 40g (0.117mol, 341 . 55MW) double (3-trimethoxy silyl propyl) amine (Dynasylan   1124) and via the constant pressure feeding funnel in the ice bath, the 18.17g (0.117mol) the root gathers the ethyl ester of isocyanic methacrylate (IEM) in about 25 minutes before adding. The removed ice bath, to continue to re-stirring 1 hour 15 minutes. At this moment, the sample obtained is subjected to a Fourier transform infrared (FTIR) spectroscopic analysis, wherein the sample is in 2265 cm^-1 isocyanic diethylene glycol dinitrate peak is not shown. Then separated as a product of the clarified oil:

Preparation example 2

In the water bath at the room temperature to the drying air and the overhead stirrer equipped with a 500 ml round-bottom flask by adding 58.50g (0.414mol) of isocyanato (meth) acrylic acid ethyl ester (IEA). Via the dropping funnel, the 141.53g (0.414mol) double (3-trimethoxy silyl-propyl) amine (Dynasylan   1124) in 1.5 hours by adding. At this moment, to obtain samples for FTIR, wherein the sample is in 2265 cm^-1 isocyanic diethylene glycol dinitrate peak is not shown. The matter through the proton Fourier transform nuclear magnetic resonance (NMR) characterization of:

Preparation example 3

Equipped with overhead stirrer to 250 ml three-necked round-bottom flask by adding 12.36g (0.0517mol, 239 . 23MW) of 1, 1-bis-(acryloxy methyl) ethyl isocyanate (BEI) and 176 microliters of a 10% of the MEK solution DBTDL (based on the total weight of the reactant 500 PPM). In the flask, the 35 in oil bath [...] , and will 17.64g (0.517mol, 341 . 55MW) double (3-trimethoxy silyl propyl) amine (Dynasylan   1124) through the dropping funnel in 1 hour in the reaction. completes the amine after the addition of approximately 10 minutes, to obtain samples for FTIR, wherein the sample is in 2265 cm^-1 isocyanic diethylene glycol dinitrate peak is not shown. Then separated as a product of the clarified oil:

Preparation example 4

In addition to the following aspects similar to the preparation example 3 experiments: the 12.85g (0.72mol, 179 . 29MW) ammonia propyl trimethoxy silane (  AMMO Dynasylan) and 17.15g (0.72mol) of 1, 1-bis-(acryloxy methyl) ethyl isocyanate (BEI) and 176 microliters of a 10% of the MEK solution DBTDL (500 PPM   DBTDL) in about 45 minutes the reaction to provide the product as an oil:

Preparation example 5

In addition to the following aspects similar to the preparation example 1 experiments: the 22.53g (0.0529mol, 425 . 71MW) double (3-triethoxy silyl propyl) amine (Dynasylan   1122) and 7.47g (0.0529mol) IEA in the presence of 35 microliters of a 10% of the MEK solution DBTDL (100 PPM   DBTDL) to provide reaction under the condition of the following product:

Preparation example 6

In addition to the following aspects similar to the preparation example 1 experiments: the 14.42g (0.065mol) ammonia propyl triethoxy silane (  AMMO Dynasylan) and 15.58g (0.065mol) BEI in the presence of the 176 microliters of a 10% of the MEK solution DBTDL (500 PPM   DBTDL) to provide reaction under the condition of the following product:

Preparation example 7

Equipped with overhead stirrer to the 200 ml flask add 20.0g (0.0836mol) of 1, 1-bis-(acryloxy methyl) ethyl isocyanate (BEI) and 250 microliters of a 10% DBTDL of, and then in the drying air and the the 55 [...] in the oil bath. Then via the dropping funnel in 20 minutes will 23.02g (0.0836mol) the N-cyclohexyl-triethoxy silyl methylamine (  XL Geniosil   926) to join. Allowing the mixture to reaction 1 hour. decadent oil then separated as to clarify the product, as follows. FTIR obtaining sample, wherein the sample is in 2265 cm^-1 isocyanic diethylene glycol dinitrate peak is not shown.

Preparation example 8

Of the stirring rod to a 250 ml round-bottom flask by adding 40g (0.223mol, 179 . 29MW) ammonia propyl trimethoxy silane (  AMMO Dynasylan) then placed in ice bath. Via the constant pressure feeding funnel, the 34.61g (0.223mol, 155 . 15MW) ethyl isocyanato methacrylate (IEM) in about 25 minutes before adding. Shift eliminates the ice-bath , continue stirring 1 hour 15 minutes, obtaining samples for FTIR at this moment, the 2265 cm^-1 isocyanic diethylene glycol dinitrate peak is not shown, and of a separation product of the clarified oil:

Preparation example 9

With the preparation example 8 preparation of similar manner, the 40g (0.170mol, 235 . 4MW) the N-(n-butyl)-3-aminopropyl trimethoxy silane (Dynasylan   1189) and 26.36g the (0.170mol) IEM reaction to provide the product as a clarified oil:

Preparation example 10

With the preparation example 8 preparation of similar manner, the 44.10g (0.199mol, 221 . 37MW) ammonia propyl triethoxy silane (  AMEO Dynasylan) and 30.90g (0.199mol) IEM of the clarified oil to provide as a reaction product of (the material will solidify under the ice-bath temperature):

Preparation example 11

With the preparation example 8 preparation of similar manner, the 41.61g (0.215mol, 221 . 37MW) the N-methyl-aminopropyl trimethoxy silane and 33.39g (0.215mol) IEM of the clarified oil to provide as a reaction product of:

Preparation example 12

With the preparation example 8 preparation of similar manner, the 16.79g (0.0936mol, 179 . 29MW) ammonia propyl trimethoxy silane and 13.21g (0.0936mol, 141 . 13MW) of the (meth) acrylic acid ethyl ester (IEA) reaction of isocyanato following urea product to provide:

Preparation example 13

With the preparation example 8 preparation of similar manner, the 18.76g (0.080mol, 235 . 4MW) the N-(n-butyl)-3-aminopropyl trimethoxy silane (Dynasylan   1189) and 11.25g (0.080mol) IEA of the reaction in order to provide the following product:

Preparation example 14

With the preparation example 8 preparation of similar manner, the 18.32g (0.0827mol) ammonia propyl triethoxy silane and 11.68g (0.0827mol) IEA of the reaction in order to provide the following product:

Preparation example 15

With the preparation example 8 preparation of similar manner, the 17.30g (0.090mol) the N-methyl-aminopropyl trimethoxy silane and 12.70g (0.090mol) IEA of the reaction in order to provide the following product:

Preparation example 16

To the 100 ml round-bottom flask by adding 10.16g (0.072mol) and IEA of 35 microliters of a 10% of the MEK solution DBTDL (100 PPM   DBTDL). Feeding the hopper by the 55 the [...] 10 minutes to add 19.84g (0.072mol, 275 . 46MW) the N-cyclohexyl-triethoxy silyl methylamine. Further reaction 0.5 hour later, does not show the FTIR analysis isocyanic diethylene glycol dinitrate peak , and separate the product:

Preparation example 17

With the preparation example 16 preparation of similar manner, the 10.81g (0.069mol) of the IEM the 55 [...] in the presence of under 100 PPM of the DBTDL 19.19g (0.069mol) the N-cyclohexyl-triethoxy silyl methylamine reaction in order to provide the following product:

Composite barrier assembly and barrier films preparation

Multi-layer composite barrier assembly and the barrier films in the examples of U.S. patents (such as Shaw) 5,440,446 and 7,018,713 (Padiyath and others) of the coater in a vacuum coating machine similar to preparation.

The comparative example below 18 and 25 and examples 19 to 24 relates to form an analog display or a light-emitting element package module, so that they stand in the design into an analog outdoor environment under the conditions of aging in the test, and then subjected to a peel adhesion test in order to confirm the above examples of the urea (multiple)-(meth) acrylic ester (multiple)-silane whether peeling adhesion can be effectively improved. First of all these examples show some of the common procedure.

Use as 3M   ADHESIVE   CLEAR   OPTICALLY   8172P (3M optical transparent adhesive 8172P) from Minnesota saintpaul the 3M Company (3M   Company, of   St.Paul, MN) commercially-available of 0.05 mm thick pressure-sensitive adhesive (PSA), the barrier film according to the following example of multi-layer composite of laminated to a barrier assembly New Jersey wern the two from ETFE high-performance plastic Company (St.Gobain   Performance   Plastics   of   Wayne, NJ) commercially-available of 0.05 mm thick ethylene-tetrafluoroethylene (ETFE) film. Then formed in each of the following examples as the material puts in of spacer lamination anti- 8656K61 santa Fe Springs from California Company McMaster-Carr (McMaster-Carr,   Springs Santa   Fe, CA) commercially-available coating 0.14 mm thick polytetrafluoroethylene (PTFE) on the top of the aluminum foil, wherein the 13 mm wide as the   LP01   Edge   SET   Tape SOLARGAIN [...] (SOLARGAIN edge sealing adhesive tape SET the   LP01 [...]) technology companies from Ohio soulen Truseal (Truseal   Inc.of   Technologies   Solon, OH) commercially-available drying edge sealing adhesive tape between the barrier sheet and the PTFE the periphery of the aluminum foil.

The 0.38 mm thick as from JURASOL [...] JuraFilms Company of Illinois (JuraFilms   Grove   of   Downer, IL) commercial purchase of additional and lamination anti- the packaging film of the back surface of the aluminum foil spacer material layer, wherein the packaging film is located between the barrier sheet and the aluminum foil. In the multi-part structure 150 the lower vacuum lamination [...] 12 minutes.

Test method

Aging test

In some of the above-mentioned laminated structure of the set condition of the 85 [...] and 85% relative humidity environmental chamber (RH) aging 250 hours, 500 hours, and in some cases the aging 1,000 hours.

T peel adhesion test

Not cut off from the surface of the PTFE and aging of aging of the barrier sheet material, and is divided into a 1.0 inch wide strip in order to use the ASTM   D1876-08T stripping method for adhesion testing. The sample by peeling tester (with Testworks   4 software the tradenames " INISIGHT   2SL the [...] from Minnesota Eden prarie MTS Company (MTS, Eden   Prarie, MN) commercially-available) to 10 inches/minute (25.4 cm/min) for peeling the peeling rate. (N/cm) recorded in Newtons/cm from the adhesion value is 1.27 cm to 15.1 cm measured value of the average value of the four strip. In the 85 [...] and 85% relative humidity 250 hours t is measured after peeling adhesion barrier sheet, and the 500 and/or 1000 hours is measured again post-exposure.

Example 18 (comparative example)

Without the use of this embodiment example 1 to 17 in the sense of coupling is comparative. The polyethylene terephthalate (PET) base film covered on the upper (methyl) acrylate planarizing layer, inorganic Si-al oxide (SiAlOx) barrier layer and the (meth) acrylic ester protective layer stack. Formed in each layer in the following manner:

((Meth) acrylic ester smoothing layer deposition)

The 305 meters long as XST   6642 from DuPont Company of Wilmington, Delaware (DuPont   of   Wilmington, DE) commercially-available of 0.127 mm thick × 366 mm wide PET film roll loading to rollerroller vacuum processing chamber to. Pumping on the chamber, the pressure drops to 1 × 10^-5 taintor. Web speed is kept at 4.8 meters/minute, maintaining at the same time the back of the membrane in the frozen to -10 the coating [...] contact with the tumbler. The film under the contact condition of the tumbler, to 0.02kW with nitrogen plasma power of plasma processing the film surface. And then the film surface coated with as SR-833S Exton, Pennsylvania the sartomer the United States from a limited liability Company (Sartomer   USA, LLC, Exton, Pa) commercially-available tricyclic decane diformic mellow two acrylate. More specifically, before the coating of the second acrylic ester in 20 millitorr pressure of the degassing under vacuum, is loaded into the pump, then to 1.33 ml/min flow rate pumped through to 60kHz the operation of the frequency of the ultrasonic atomizer is maintained at the 260 [...] in a heated evaporation chamber. The condensed vapor stream of the monomer on the surface of the film, and use in 7.0kV and 4mA the operation of the multi-filament electron beam cured cross-linked electron beam gun, in order to form the 720 nm (meth) acrylic acid of the rain.

(Inorganic Si-al oxide (SiAlOx) the deposition of the barrier layer)

The deposition of the (meth) acrylic ester of the still and under the situation of contacting with a rotating drum, immediately be sputter-deposited on layer SiAlOx coating (meth) acrylic ester of the top of the coiled material. The two alternating current (AC) power source is used for controlling the two pairs of cathode; wherein each cathode receiving two from Materion Corporation of Albuquerque, new Mexico (Materion   of   Albuquerque, nm) of the commercially-available 90% Si/10% Al target. In the process of the sputtering deposition, each of the voltage signal is used as the power source of the proportional-integral-differential control loop input, for maintaining a predetermined flow to oxygen flow of each of the cathode. AC power source using 5000 watts of power to the sputter target 90% Si/10% Al, the 3.5 millitorr of the sputtering pressure, gas mixture include 450sccm argon and 63sccm oxygen. This provides deposition in the above-mentioned (meth) acrylic acid on the ester goes against 30 nm thick SiAlOx layer.

((Methyl) acrylate deposition of the protective layer)

After the deposition of the film still SiAlOx layer after contact with the rotary drum, the same immediately 2nd the coiled material is coated on the (meth) acrylic ester and cross-linked protective layer, wherein the general use and smoothing layer deposition the same conditions, but with the following exception. Use in 7kV and 5mA the operation of the multi-filament electron-beam cured gun electron beam cross-linking. This in the layer 2 provided on the top of the 720 nm thick (meth) acrylic acid from the rain.

The (co) polymer substrate of the three-layer stack manifestations of the average spectral transmittance T_vis to 87% (the 400 nm and 700 between through the percentage of the determined average T), the value in 0° measured under an angle of incidence. membrane Kang from the Company of Minneapolis, Minnesota (MOCON, Inc, Minneapolis, MN) commercial purchase the MOCON 700 type WVTR test system in the 50 [...] and 100% relative humidity under (RH) ASTM   F-1249 measuring water vapor transmission rate (WVTR). Results of less than equipment 0.005g/m² /-day rate the lower limit of the detection.

The resulting three-layer barrier assembly for forming a rectangular general procedures above stated in the section of the structure for simulating the solar module. These analog solar module according to the aging test is subjected to accelerated aging, as described in the evaluation of the T peel adhesion. T peeling adhesion in the table below the results of the test 2 shown in.

Example 19

The polyethylene terephthalate (PET) base film covered on the upper (methyl) acrylate planarizing layer, inorganic Si-al oxide (SiAlOx) comprising the barrier layer and open the molecular (meth) acrylic ester protective layer stack. In addition to the following aspects, such as the comparison example 18 of each layer is formed in: the in the process of the formation of the protective layer, not to use 100% of the three ring decane diformic mellow two acrylate SR-833S, but using 97% by weight of the three ring decane diformic mellow two acrylate SR-833S and 3 weight % of the above-example 2 synthesis of a mixture of the compounds.

In the (co) polymer substrate of the three-layer stack manifestations of the average spectral transmittance T_vis to 87%, and lower than the WVTR 0.005g/m²/days, both of which are such that the comparison is an example 18 in carrying out the test. Then the resulting three-layer stack for forming a general procedures above stated in the section of the structure for simulating the solar module. These analog solar module according to the aging test is subjected to accelerated aging, as described in the evaluation of the T peel adhesion. T peeling adhesion in the table below the results of the test 2 shown in.

Example 20

The polyethylene terephthalate (PET) base film covered on the upper (methyl) acrylate planarizing layer, inorganic Si-al oxide (SiAlOx) comprising the barrier layer and open the molecular (meth) acrylic ester protective layer stack. In addition to the following aspects, such as the comparison example 18 of each layer is formed in: the in the process of the formation of the protective layer, not to use 100% of the three ring decane diformic mellow two acrylate SR-833S, but using 97% by weight of the three ring decane diformic mellow two acrylate SR-833S and 3% of the weight of the above preparation example 3 synthesis of a mixture of the compounds.

In the (co) polymer substrate of the three-layer stack manifestations of the average spectral transmittance T_vis to 87%, and lower than the WVTR 0.005g/m²/days, both of which are such that the comparison is an example 18 in carrying out the test. Then the resulting three-layer stack for forming a general procedures above stated in the section of the structure for simulating the solar module. These analog solar module according to the aging test is subjected to accelerated aging, as described in the evaluation of the T peel adhesion. T peeling adhesion in the table below the results of the test 2 shown in.

Example 21

The polyethylene terephthalate (PET) base film covered on the upper (methyl) acrylate planarizing layer, inorganic Si-al oxide (SiAlOx) comprising the barrier layer and open the molecular (meth) acrylic ester protective layer stack. In addition to the following aspects, such as the comparison example 18 of each layer is formed in: the in the process of the formation of the protective layer, not to use 100% of the three ring decane diformic mellow two acrylate SR-833S, but using 97% by weight of the three ring decane diformic mellow two acrylate SR-833S and 3% of the weight of the above example 4 synthesis of a mixture of the compounds.

In the (co) polymer substrate of the three-layer stack manifestations of the average spectral transmittance T_vis to 87%, and lower than the WVTR 0.005g/m²/days, both of which are such that the comparison is an example 18 in carrying out the test. Then the resulting three-layer stack for forming a general procedures above stated in the section of the structure for simulating the solar module. These analog solar module according to the aging test is subjected to accelerated aging, as described in the evaluation of the T peel adhesion. T peeling adhesion in the table below the results of the test 2 shown in.

Example 22

The polyethylene terephthalate (PET) base film covered on the upper (methyl) acrylate planarizing layer, inorganic Si-al oxide (SiAlOx) comprising the barrier layer and open the molecular (meth) acrylic ester protective layer stack. In addition to the following aspects, such as the comparison example 18 of each layer is formed in: the in the process of the formation of the protective layer, not to use 100% of the three ring decane diformic mellow two acrylate SR-833S, but using 97% by weight of the three ring decane diformic mellow two acrylate SR-833S and 3 weight % of the examples above 12 synthesis of a mixture of the compounds.

In the (co) polymer substrate of the three-layer stack manifestations of the average spectral transmittance T_vis to 87%, and lower than the WVTR 0.005g/m²/days, both of which are such that the comparison is an example 18 in carrying out the test. Then the resulting three-layer stack for forming a general procedures above stated in the section of the structure for simulating the solar module. These analog solar module according to the aging test is subjected to accelerated aging, as described in the evaluation of the T peel adhesion. T peeling adhesion in the table below the results of the test 2 shown in.

Example 23

The polyethylene terephthalate (PET) base film covered on the upper (methyl) acrylate planarizing layer, inorganic Si-al oxide (SiAlOx) comprising the barrier layer and open the molecular (meth) acrylic ester protective layer stack. In addition to the following aspects, such as the comparison example 18 of each layer is formed in: the in the process of the formation of the protective layer, not to use 100% of the three ring decane diformic mellow two acrylate SR-833S, but using 97% by weight of the three ring decane diformic mellow two acrylate SR-833S and 3 weight % of the above-example 13 synthesis of a mixture of the compounds.

In the (co) polymer substrate of the three-layer stack manifestations of the average spectral transmittance T_vis to 87%, and lower than the WVTR 0.005g/m²/days, both of which are such that the comparison is an example 18 in carrying out the test. Then the resulting three-layer stack for forming a general procedures above stated in the section of the structure for simulating the solar module. These analog solar module according to the aging test is subjected to accelerated aging, as described in the evaluation of the T peel adhesion. T peeling adhesion in the table below the results of the test 2 shown in.

Example 24

The polyethylene terephthalate (PET) base film covered on the upper (methyl) acrylate planarizing layer, inorganic Si-al oxide (SiAlOx) comprising the barrier layer and open the molecular (meth) acrylic ester protective layer stack. In addition to the following aspects, such as the comparison example 18 of each layer is formed in: the in the process of the formation of the protective layer, not to use 100% of the three ring decane diformic mellow two acrylate SR-833S, but using 97% by weight of the three ring decane diformic mellow two acrylate SR-833S and 3 weight % of the examples above 15 synthesis of a mixture of the compounds.

In the (co) polymer substrate of the three-layer stack manifestations of the average spectral transmittance T_vis to 87%, and lower than the WVTR 0.005g/m²/days, both of which are such that the comparison is an example 18 in carrying out the test. Then the resulting three-layer stack for forming a general procedures above stated in the section of the structure for simulating the solar module. These analog solar module according to the aging test is subjected to accelerated aging, as described in the evaluation of the T peel adhesion. T peeling adhesion in the table below the results of the test 2 shown in.

Example 25 ( comparative example)

The polyethylene terephthalate (PET) base film covered on the upper (methyl) acrylate planarizing layer, inorganic Si-al oxide (SiAlOx) comprising the barrier layer and open the molecular (meth) acrylic ester protective layer stack. In addition to the following aspects, such as the comparison example 18 of each layer is formed in: the in the process of the formation of the protective layer, not to use 100% of the three ring decane diformic mellow two acrylate SR-833S, but using 97% by weight of the three ring decane diformic mellow two acrylate SR-833S and 3% of the weight of N-n-butyl-aza -2, 2-dimethoxy silicon heterocyclic pentane (in order to product code 1932.4 from Pennsy Morrisville the gaies is special Company (Gelest, Morrisville, Pa) commercially-available) mixture.

In the (co) polymer substrate of the three-layer stack manifestations of the average spectral transmittance T_vis to 87%, and lower than the WVTR 0.005g/m²/days, both of which are such that the comparison is an example 18 in carrying out the test. Then the resulting three-layer stack for forming a general procedures above stated in the section of the structure for simulating the solar module. These analog solar module according to the aging test is subjected to accelerated aging, as described in the evaluation of the T peel adhesion. T peeling adhesion in the table below the results of the test 2 shown in.

Table 2 :

Example 18-25 the test result of the

Although the specification a detailed description of the certain exemplary embodiments, but should be understood, the of skill in the art after understanding the above-mentioned content, can be easily envisaged modification of the embodiment form, modified forms and equivalents. Therefore, it should be understood, the present invention should not be unduly limited to the illustrative embodiment shown above. Furthermore, all publications cited herein, the disclosure of the Patent application and Publication cited patents incorporated into the full text in this way, as concrete and individually pointed out that each individual Publication or Patent referenced herein to the extent of incorporating the same manner.

Various exemplary implementation described have been carried out actually zoom unrestrictedly. the example falls and other implementation of these embodiments in the following list of the disclosed embodiment and within the scope of the claim.