Thermoplastic resin composition and optical films made therefrom

Mode of execution

The invention relates to a thermoplastic resin composition containing (A) Cyclomonoolefin polymer and (B) having a polar group of the vinyl polymer.

(A) Cyclomonoolefin polymer

As the used of this invention (A) Cyclomonoolefin polymer, the following can be cited (i)-(iv) of the polymer is shown.

(I) the following formula (I) of the monomer (the following also referred to as "specific monomer") of the ring-opening polymer,

(Ii) and a specific monomer ring-opening copolymer of a polymerizable monomer,

The above-mentioned (iii) (i) or (ii) ring-opening polymer of hydrogenation of the polymer,

(Iv) the above-mentioned (i) or (ii) ring-opening polymer is cyclized by the Friedel-crafts reaction of polymer obtained by the hydrogenation after,

(V) and the above-mentioned specific monomer compound of the unsaturated double bond of the unsaturated copolymer.

Wherein the ring-opening polymer preferably (iii) hydrogenation object.

(In the formula, s and t is independently 0 or 1, at least one of them is 1, n and m is independently 0-2 integer. R¹-R⁹ independently represent is selected from the group consisting of a hydrogen atom; a halogen atom; can be provided with oxygen atom, nitrogen atom, sulfur atom or silicon atom of the linking groups of the substituted or unsubstituted carbon atom number is 1-30 hydrocarbyl; and the group consisting of polar group of the atom or group, R⁷ and R⁸, and/or R⁹ and R¹⁰ can be integrated to form hydrocarbyl, R⁷ or R⁸, and R⁹ or R¹⁰ can also be combined with each other to form a carbocyclic or heterocyclic (these carbocyclic or heterocyclic rings can be monocyclic structure, can also be condensed with other ring to form a ring structure. ).

In the above-mentioned type, as a halogen atom, can be points out the fluorine atom, chlorine atom or bromine atom.

As the carbon atom number is 1-30 hydrocarbyl, can cite, for example, methyl, ethyl, n-propyl and other alkyl; cyclopentyl, cyclohexyl, cycloalkyl; vinyl, allyl, propenyl, alkenyl, and the like.

And, the above-mentioned substituted or unsubstituted hydrocarbyl not only can be directly combined with a ring structure, through the linking groups (linkage) can also be combined. As the linking groups, the carbon atom number is, for example, can be cited 1-10 the 2 monovalent hydrocarbyl (for example-(CH₂)_m-(in the formula, m is 1-10 integer) of the alkylidene); containing oxygen atom, nitrogen atom, sulfur atom or silicon atom linking groups (e.g., carbonyl (-CO-), carbonyl oxygen (-O (CO)-), sulfonyl (-SO₂-), ether bond (-O-), thioether bond (-S-), imino (-NH-), amide (-NHCO-, -CONH-), siloxane bond (-OSi (R)-(in the formula, R is methyl, ethyl, etc. alkyl)), and the like, can be containing 2 or more linking groups of these groups.

As polar group, such as hydroxy group can be cited, the carbon atom number is 1-10 alkoxy, acyloxy, alkoxycarbonyl, aryloxyacetic carbonyl, cyano, amido, imido, triorganosiloxy groups, three organic silyl, amino, acyl, alkoxy silyl, sulfonyl and carboxyl, and the like. More specifically, as the above-cited the alkoxyl may , for example, methoxy, ethoxy, and the like; as acyloxy can cite, for example, acetoxy, c acyloxy, acyloxy benzoate acyloxide and so on is fragrantalkane acyloxy and; as, for example, can be cited methoxycarbonyl alkoxy carbonyl, ethoxy carbonyl, etc.; as aryloxyacetic carbonyl can cite, for example, phenoxy carbonyl, naphthalene oxygen carbonyl, carbonyl [...] , biphenyltetrazole oxycarbonyl, and the like; as monosilane three organicthe oxygen radical may cite for example trimethyl siloxy, triethyl siloxy, and the like; as three organic silicyl can cite, for example, trimethyl silyl, triethyl silyl, etc.; can be cited as a primary amino group of amino, for example; as alkoxy silyl can cite such as trimethoxy silyl, triethoxy silyl, and the like.

< 特定单体 >

As the above-mentioned general formula (I) of the said specific example of a specific monomer, the following compounds can be cited.

Bicyclo [2.2.1] hept-2-ene,

Tricyclic [4.3.0 . 1^2,5]-3-decene,

Tricyclic [4.4.0 . 1^2,5]-3-undecene,

Tetracyclic [4.4.0 . 1^2,5. 1^7,10]-3- dodecylene ,

Wuhuan [6.5.1 . 1^3,6. 0^2,7. 0^9,13]-4- 15 alkene ,

Wuhuan [7.4.0 . 1^2,5. 1^9,12. 0^8,13]-3- 15 alkene ,

5-a bicyclic [2.2.1] hept-2-ene,

5-b dihydrogenmethylenebisphosphonate ring [2.2.1] hept-2-ene,

5- methoxy carbo- dihydrogenmethylenebisphosphonate ring [2.2.1] hept-2-ene,

5-methyl-5- methoxy carbo- dihydrogenmethylenebisphosphonate ring [2.2.1] hept-2-ene,

5-cyano-bicyclo [2.2.1] hept-2-ene,

8-methoxy carbonyl tetracyclic [4.4.0 . 1^2,5. 1^7,10]-3- dodecylene ,

8-ethoxy carbonyl tetracyclic [4.4.0 . 1^2,5. 1^7,10]-3- dodecylene ,

8-are propoxy carbonyl tetracyclic [4.4.0 . 1^2,5. 1^7,10]-3- dodecylene ,

8-isopropoxy carbonyl tetracyclic [4.4.0 . 1^2,5. 1^7,10]-3- dodecylene ,

8-positive butoxypolyethylene carbonyl tetracyclic [4.4.0 . 1^2,5. 1^7,10]-3- dodecylene ,

8-phenoxy carbonyl tetracyclic [4.4.0 . 1^2,5. 1^7,10]-3- dodecylene ,

8-(1-naphthoxy) carbonyl tetracyclic [4.4.0 . 1^2,5. 1^7,10]-3- dodecylene ,

8-(2-naphthoxy) carbonyl tetracyclic [4.4.0 . 1^2,5. 1^7,10]-3- dodecylene ,

8-< aodirenc4-phenyl phenoxy > carbonyl tetracyclic [4.4.0 . 1^2,5. 1^7,10]-3- dodecylene ,

8-methyl-8-methoxy carbonyl tetracyclic [4.4.0 . 1^2,5. 1^7,10]-3- dodecylene ,

8-methyl-8-ethoxy carbonyl tetracyclic [4.4.0 . 1^2,5. 1^7,10]-3- dodecylene ,

8-methyl-8-n-propoxy carbonyl tetracyclic [4.4.0 . 1^2,5. 1^7,10]-3- dodecylene ,

8-methyl-8-isopropoxy carbonyl tetracyclic [4.4.0 . 1^2,5. 1^7,10]-3- dodecylene ,

8-methyl-8-n-butoxy carbonyl tetracyclic [4.4.0 . 1^2,5. 1^7,10]-3- dodecylene ,

8-methyl-8-phenoxy carbonyl tetracyclic [4.4.0 . 1^2,5. 1^7,10]-3- dodecylene ,

8-methyl-8-(1-naphthoxy) carbonyl tetracyclic [4.4.0 . 1^2,5. 1^7,10]-3- dodecylene ,

8-methyl-8-(2-naphthoxy) carbonyl tetracyclic [4.4.0 . 1^2,5. 1^7,10]-3- dodecylene ,

8-methyl-8-< aodirenc4-phenyl phenoxy > carbonyl tetracyclic [4.4.0 . 1^2,5. 1^7,10]-3- dodecylene ,

Wuhuan [8.4.0 . 1^2,5. 1^9,12. 0^8,13]-3- 16 alkene ,

Seven ring [8.7.0 . 1^3,6. 1^10,17. 1^12,15. 0^2,7. 0^11,16]-4- 20 alkene ,

Seven ring [8.8.0 . 1^4,7. 1^11,18. 1^13,16. 0^3,8. 0^12,17]-5- two hendecenes ,

5-ethydene dihydrogenmethylenebisphosphonate ring [2.2.1] hept-2-ene,

8-ethylidine tetracyclic [4.4.0 . 1^2,5. 1^7,10]-3- dodecylene ,

5-phenyl-bicyclo [2.2.1] hept-2-ene,

5-phenyl-5-a bicyclic [2.2.1] hept-2-ene,

8-phenyl tetracyclic [4.4.0 . 1^2,5. 1^7,10]-3- dodecylene ,

5-n-butyl bicyclo [2.2.1] hept-2-ene,

5-is f dihydrogenmethylenebisphosphonate ring [2.2.1] hept-2-ene,

5-cyclohexyl-bicyclo [2.2.1] hept-2-ene,

5-(2-cyclohexenyl) bicyclo [2.2.1] hept-2-ene,

5- xin dihydrogenmethylenebisphosphonate ring [2.2.1] hept-2-ene,

5- last of the ten Heavenly Stems dihydrogenmethylenebisphosphonate ring [2.2.1] hept-2-ene,

5-isopropyl-bicyclo [2.2.1] hept-2-ene,

5-(1-naphthyl) bicyclo [2.2.1] hept-2-ene,

5-(2-naphthyl) bicyclo [2.2.1] hept-2-ene,

5-(2-naphthyl)-5-methyl-bicyclic [2.2.1] hept-2-ene,

5-(4-biphenyl) bicyclo [2.2.1] hept-2-ene,

5-(4-biphenyl)-5-methyl-bicyclic [2.2.1] hept-2-ene,

5-amino-a bicyclic [2.2.1] hept-2-ene,

5-trimethoxy silyl dihydrogenmethylenebisphosphonate ring [2.2.1] hept-2-ene,

5-triethoxy silyl dihydrogenmethylenebisphosphonate ring [2.2.1] hept-2-ene,

5-three propoxy a silane dihydrogenmethylenebisphosphonate ring [2.2.1] hept-2-ene,

5-three butoxypolyethylene a silane dihydrogenmethylenebisphosphonate ring [2.2.1] hept-2-ene,

5-chloromethyl dihydrogenmethylenebisphosphonate ring [2.2.1] hept-2-ene,

5-hydroxy-a bicyclic [2.2.1] hept-2-ene,

5-cyclohexenyl bicyclo [2.2.1] hept-2-ene,

5-fluorobicyclo [2.2.1] hept-2-ene,

5-difluoromethane dihydrogenmethylenebisphosphonate ring [2.2.1] hept-2-ene,

5-trifluro dihydrogenmethylenebisphosphonate ring [2.2.1] hept-2-ene,

5, 5-difluoro bis ring [2.2.1] hept-2-ene,

5, 6-difluoro bis ring [2.2.1] hept-2-ene,

5, 5-di (trifluoromethyl) bicyclo [2.2.1] hept-2-ene,

5, 6-b (trifluoromethyl) bicyclo [2.2.1] hept-2-ene,

5-methyl-5-trifluoromethyl-ring [2.2.1] hept-2-ene,

5, 5, 6-three fluorine pair ring [2.2.1] hept-2-ene,

5, 5, 6, 6-fluorobicyclo [2.2.1] hept-2-ene,

8-fluoro tetracyclic [4.4.0 . 1^2,5. 1^7,10]-3- dodecylene ,

8-fluoro methyl tetracyclic [4.4.0 . 1^2,5. 1^7,10]-3- dodecylene ,

8-trifluoromethyl tetracyclic [4.4.0 . 1^2,5. 1^7,10]-3- dodecylene ,

8, 8- two fluorine four links [4.4.0 . 1^2,5. 1^7,10]-3- dodecylene , and the like.

These compounds can be in order to separate 1 or 2 or more combination is used as the norbornene monomer (I).

In these specific monomer, above-mentioned formula (I) in R⁷-R¹⁰ in the following formula (III) at least one specific polar group of the above-mentioned specific monomer, from the thermoplastic resin composition and an optical film and heat resistance of the wet (water) sex maintain good balance considerations are preferred.

-(CH₂)_n COOR¹¹     (III)

(In the formula, n is usually 0 or 1-5 integer, R¹¹ the carbon atom number 1-15 hydrocarbyl. )

Above-mentioned formula (V) in, the smaller the value of n and R¹¹ the smaller carbon atoms, the resulting thermoplastic resin composition of the higher glass transition temperature, the heat resistance, from this point to consider is the preferred. That is, ideally, is usually n 0 or 1-5 integer, preferably 0 or 1, and R¹¹ is usually carbon atom number 1-15 hydrocarbyl, preferably the carbon atom number 1-3 alkyl.

Furthermore, in the above-mentioned formula (I) in, that in the above-mentioned type (III) bonding the polar group is further bonded to the carbon atom of the above-mentioned specific monomer having an alkyl group, the resulting thermoplastic resin composition from the and an optical film with good heat resistance and good wet (water) sex maintain good balance considerations are preferred. The alkyl carbon atom number is preferably 1-5, more preferably 1-2, especially preferably 1.

In such a specific monomer, 8-methyl-8-methoxy carbonyl tetracyclic (4.4.0 . 1^2,5. 1^7,10)-3- dodecylene , 8-methyl-8-ethoxy carbonyl tetracyclic (4.4.0 . 1^2,5. 1^7,10)-3- dodecylene , 8-methyl-8-butoxy carbonyl tetracyclic (4.4.0 . 1^2,5. 1^7,10)-3- dodecylene and 8-methyl-8-methoxy carbonyl tetracyclic (4.4.0 . 1^2,5. 1^7,10)-3- dodecylene and 5-methyl-5-methoxy-carbonyl-bicyclo [2.2.1] hept-2-ene of the resulting thermoplastic resin composition and the optical of excellent heat resistance is preferred. In particular 8-methyl-8-methoxy carbonyl tetracyclic (4.4.0 . 1^2,5. 1^7,10)-3- dodecylene and 5-methyl-5-methoxy-carbonyl-bicyclo [2.2.1] hept-2-ene of the vinyl polymer can be obtained (B) of excellent compatibility, can adjust the difference of the glass transition temperature of the olefin series polymer, from this context, to consider is preferred.

As such a specific monomer ring-opening polymerization of a cycloolefin polymer obtained, can be cited, for example, that having the following general formula (II) structural units of the polymer.

(In formula (II), R¹, R², R³, R⁴, R⁵, R⁶, R⁷, R⁸, R⁹, R¹⁰, m, n, s and t is respectively connected with the above-mentioned formula (I) are as defined in the. X in formula: formula of the group--CH=CH :-CH₂ CH₂-the group that, when there are a plurality of X, X is the same or different. ).

In the invention, preferably contain n=0 in the above-mentioned formula (II), m is 0 or 1, and R⁷-R¹⁰ at least one of in the formula-(CH₂)_p COOR¹² (in the formula, R¹² the carbon atom number 1-20 hydrocarbyl, for p 0-10 integer. ) Said structural unit of group of the polymer.

< 共聚性单体 >

The above-mentioned specific monomer ring-opening polymerization can be separate, and then also can make the above-mentioned specific monomer with other co-polymerized monomer ring-opening copolymerization.

As the above-mentioned co-polymerized monomer, in particular can cite cyclobutene, cyclopentene, cycloheptene, cyclooctene to perform such cycloolefin. Preferably the carbon atoms of cyclic olefins 4-20, more preferably 5-12. Furthermore, the above-mentioned specific monomer can be ring-opening polymerization of the polybutadiene, polyisoprene, styrene-butadiene copolymer, ethylene-non-conjugated diene copolymer, the polynorbornene backbone containing carbon-carbon double bonds in the unsaturated hydrocarbon is carried out in the presence of polymers and the like. Such a situation, the resulting ring-opening copolymer and its hydrogenation copolymer as the impact resistance of the thermoplastic resin composition of the raw material is useful.

< 开环聚合物 >

The above-mentioned ring-opening polymer (general formula (II)) in the presence of a catalyst for the ring-opening polymerization according to the need to use the molecular weight controlling agent and solvent for ring-opening polymerization, in order to in the past the the known method of the above-mentioned specific monomer and a monomer copolymerization according to the needs of use is obtained by ring-opening polymerization.

Furthermore, in the above-mentioned specific monomer and the above-mentioned co-polymerized monomer copolymerized occasions, is ideal, and the above-mentioned specific monomer to the above-mentioned polymerized monomer the sum of a total of 100 weight %, polymerization is carried out in the following proportion: the above-mentioned specific monomer is generally 50 weight % or more, preferably 60 weight % or more, more preferably 70 weight % or more, and less than 100 weight % ; the above-mentioned co-polymerized monomer is greater than 0% by weight, is generally 50 weight % or less, preferably 40 weight % or less, more preferably 30 weight % of the following.

As used in the ring-opening polymer of the present invention, most preferably a specific monomer homopolymers or 2 or more kinds of the specific monomer copolymer.

< 开环聚合催化剂 >

As used in the present invention the catalyst for ring-opening polymerization, it is preferred to use a Olefin   Polymerization   Metathesis   Metathesis and " (K.J.IVIN, J.C.MOL, Academic   Press 1997) recorded in the catalyst.

As this kind of catalyst, can be cited for example by (a) is selected from W, Mo, Re, V and Ti at least compound 1 compound, and (b) compound combined to form a double decomposition of the polymerization catalyst, said (b) as Li, Na, K, mg, Ca, Zn, Cd, Hg, B, Al, Si, Sn, such as compounds of Pb, from a device having at least one of the element-carbon bond or the element-hydrogen bond in compounds of a selection of at least one compound. For the catalyst, in order to improve the catalyst activity, the latter can be added to (c) additive. Furthermore, as other catalyst, can be cited using cocatalyst (d) by the periodic table of the 4 group -8 transition metal-carbene complex compound or metal cyclobutane coordination compound to form metathesis catalyst.

Suitable for use as the above-mentioned (a) component of the W, Mo, Re, compounds of Ti and V, its representative examples can be cited for example WCl₆, MoCl₅, ReOCl₃, VOCl₃, TiCl₄ in special Kaiping 1-240517 of recorded in the compound.

As the above-mentioned (b) component, can be cited for example n-C₄ H₉ Li, (C₂ H₅)₃ Al, (C₂ H₅)₂ AlCl, (C₂ H₅)_1.5 AlCl_1.5, (C₂ H₅) AlCl₂, methyl aluminoxane, the LiH special Kaiping 1-240517 of recorded in the compound.

As the above-mentioned additive (c) the representative examples of components, can be very effectively using alcohol, aldehyde, ketone, amine, etc., and can further use the extra Kaiping 1-240517 of a compound shown by the.

As the above-mentioned catalyst (d) the representative examples of, can cite W (=N-2, 6-C₆ H₃ iPr₂) (= CHtBu) (OtBu)₂, Mo (=N-2, 6-C₆ H₃ iPr₂) (=CHtBu) (OtBu)₂, Ru (=CHCH=CPh₂) (PPh₃)₂ Cl₂, Ru (=CHPh) (PC₆ H₁₁)₂ Cl₂, and the like.

As the amount of the metathesis catalyst, ideally, in order to the above-mentioned (a) component with all monomer (norbornene monomer (Im), (IIm) and other copolymerizable monomer. The following are the same) mole compared to idea of, "(a) ingredient: all monomer" is usually 1 the [...] 500 to 1 the [...] 500,000, preferably the 1 [...] 1,000 to 1 the [...] 100,000 range. The above-mentioned (a) component with (b) component is the ratio of the ideal, to metal atomic ratio idea , "(a) : (b)" is usually 1 the [...] 1 to 1 the [...] 100, is preferably the 1 [...] 2 to 1 the [...] 50 range. Furthermore, in the metathesis catalyst is added in the above-mentioned (c) in the case of additive, (a) component with (c) component is the ratio of the ideal, to mole compared to idea , "(c) : (a)" is usually 0.005 the [...] 1 to 15 the [...] 1, preferably 0.05 the [...] 1 to 7 the [...] 1 range. Furthermore, the catalyst (d) is the amount of the ideal, in order to (d) of the composition with the all monomer mole compared to idea , "(d) component: all monomer" is usually 1 the [...] 50 to 1 the [...] 100000, preferably the 1 [...] 100 to 1 the [...] 50000 range.

< 分子量调节剂 >

According to the polymerization temperature, the kind of the catalyst, the kind of the solvent is subjected to ring-opening (co) the regulation of the molecular weight of the polymers, however, in the invention, preferably by the molecular weight regulator in the reaction system to regulate the polymer molecular weight. As a molecular weight controlling agent, preferably using, for example, ethylene, propylene, 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, 1-nonen, 1-decene, α-olefinic; styrene, vinyl toluene, etc. styrene; allyl acetate, allyl, and the like of such allyl compound. Wherein the special preferably 1-butene, 1-hexene, 1-octene. These molecular weight modifiers can be used alone or 2 or more mixed for use. The molecular weight regulator is the amount of, relative to 1 mole of supply in split-ring of the (co) polymerization reaction all monomer, is usually 0.001-0.6 mole, preferably 0.02-0.5 mole.

< 开环(共)聚合反应用溶剂 >

As in the open loop (a) the solvent used in the polymerization reaction, i.e. dissolving norbornene monomers, metathesis catalyst and molecular weight regulator of the solvent, can be cited, for example, petroleum ether, pentane, hexane, heptane, octane, nonane, decane and other hydrocarbon; cyclopentane, cyclohexane, methyl cyclohexane, cyclohepta, cyclooctane, decalin , norbornane, ring hydrocarbon; benzene, toluene, xylene, ethylbenzene, cumene, chlorobenzene and other aromatic hydrocarbon; dichloromethane, dichloroethane, chlorobutane, chloroform, tetrachloroethylene, halogenated hydrocarbon; methyl acetate, ethyl acetate, n-butyl acetate, isobutyl acetate, esters such as methyl propionate; dibutyl ether , tetrahydrofuran, dimethoxyethane, 1, 4-dioxane, ethers; N, N-11 dimethyl formamide, N, N-dimethyl acetamide, N-methyl pyrrolidone, and the like. These solvents may be used alone or in mixed for use. For the present invention, the solvent is preferably aromatic hydrocarbon.

The amount of the solvent is usually the "solvent: the above-mentioned all monomer (weight ratio)" is the 0.5 [...] the 1-20 [...] 1 amount of, preferably 0.5 the [...] the 1-10 [...] 1.

< 加氢 >

In this invention, can be only through the above-mentioned ring-opening polymerization manufacturing (A) Cyclomonoolefin ring-opening polymer, but preferably the ring-opening polymers obtained by ring-opening polymerization to carry out further hydrogenation. Only when subjected to ring-opening polymerization, the obtained Cyclomonoolefin ring-opening polymer of the above-mentioned formula (II) in the unit structure is X a formula: of the--CH=CH alkene the state of the unsaturated group. The open-loop polymer can be directly used, but from the viewpoint of thermal stability-resistant, preferably the alkene unsaturated group is hydrogenation make the above-mentioned X into-CH₂-CH₂-hydrogenation of group of said object. Wherein the products of this invention of the above unsaturated group alkene by the material after hydrogenation, and Cyclomonoolefin monomer side chain of the aromatic ring is not basically of hydrogenation.

Furthermore, as hydrogenation proportion, ideally, in the above-mentioned structural unit (II) X of of 90 mol % or more is hydrogenation, preferably 95 mol % or more, more preferably 97 mole % or more. Hydrogenation of the higher the ratio, the more capable of inhibiting coloring and deterioration caused by temperature, therefore, it is preferred.

In the manufacturing method, it is necessary for the hydrogenation reaction of the monomer (I) of the side chain of the aromatic ring are carried out under hydrogenation conditions. Therefore, usually ideal is, in the above-mentioned ring-opening polymer of the hydrogenation catalyst added in the solution, to atmospheric pressure -30 MPa, preferably 2-20MPa, more preferably 3-18 MPa hydrogen in the solution, thereby carrying out a hydrogenation reaction.

As hydrogenation catalysts, can use a usual alkene compound of a catalyst for the hydrogenation reaction. As such hydrogenation catalyst, can use the well-known are not of a kind of catalyst and any one of a kind of catalyst. As a kind of catalyst, can be cited the palladium, platinum, nickel, rhodium, ruthenium and other noble metal catalyst material picul carries in the carbon , silicon oxide, aluminum oxide, titanium oxide, the resulting solid catalyst on the carrier. As a kind of catalyst, can cite cyclohexane carboxylic acid nickel/triethyl aluminum, b (acetylacetone) nickel/triethyl aluminum, caprylene acid cobalt/n-BuLi, aluminum two chlorine two luxuriant titanium / chlorine two , ethanoic acid rhodium , chlorine three (triphenylphosphine) rhodium, two chlorine three (triphenylphosphine) ruthenium, chlorine and hydrogen carbonyl three (triphenylphosphine) ruthenium, dichloroborane carbonyl three (triphenylphosphine) of the front panel. The shape of the catalyst can be powder also can be granular. Furthermore, these hydrogenation catalyst can be independently 1 can also use 2 or more kinds combined to use.

These hydrogenation catalyst, in order to make the specific monomer (I) or other monomer side chain of the aromatic ring of the not in fact, it is necessary to adjust the addition amount of the same, is usually ideal in order to ring-opening (co) polymer : (weight ratio) hydrogenation catalyst for 1      1 × 10^-6 -1      2 a ratio of.

< 加成型聚合物(饱和聚合物)>

In this invention, as the cycloolefin-based polymer (A), in addition to the above ring-opening polymer and its hydrogenation polymer, can use the above-mentioned specific monomer and containing unsaturated double bond of compound saturated copolymer. The above-mentioned specific monomer and containing unsaturated double bond of the compound is copolymerized in the following proportion: to their total of 100 weight %, the above-mentioned specific monomer is usually 50-90 weight %, preferably 60-90 weight %, more preferably 70-90 weight % ; containing unsaturated double bond of compound is usually 10-50 weight %, preferably 10-40 weight %, more preferably 10-30 weight %.

As the above-mentioned unsaturated double bond-containing compounds, can be cited such as ethylene, propylene, butene, etc. the carbon atom number is 2-12, preferably 2-8 olefin compound.

As the above-mentioned specific monomer and containing unsaturated double bond of the compound of the catalyst for copolymerization reaction, can be cited for example, vanadium compound and an organic aluminum compound to form the catalyst. As the vanadium compound, can cite VO (OR)_a X_b or V (OR)_c X_d (wherein R are hydrocarbyl, the 0   a≤ 3, the 0   b≤ 3, the 2 [...] a+b ≤ 3, the 0   c≤ 4, the 0   d≤ 4, the 3 [...] c+d ≤ 4) said vanadium compound, or their power supply subfield addition compound. As the electron donor, can be points out mellowly , phenol, ketone, aldehyde, carboxylic acid, organic acid or inorganic acid ester, ether, acid amide, anhydride, alkoxy silane, oxygen-containing electron donor; ammonia, amines, nitriles, isocyanates containing nitrogen such as the electron donor. As the above-mentioned organic aluminum compound, can cite from the at least one aluminum-carbon bond or an aluminum-hydrogen bond in compounds of a selection of at least 1 kind of organo-aluminum compound. The above-mentioned catalyst compounds and vanadium in the ratio of the organic aluminum compound to the ratio of the aluminum atom relative to the vanadium atom (Al/V) meter is usually 2 or more, preferably 2-50, especially preferably 3-20.

As the above solvent used in the copolymerization reaction, can be cited such as pentane, hexane, heptane, octane, nonane, decane and other hydrocarbon; cyclohexane, methyl cyclohexane, ring hydrocarbon; benzene, toluene, xylene and other aromatic hydrocarbons and halogenated derivatives thereof. Wherein preferably cyclohexane, methyl cyclohexane.

< 环烯烃系聚合物 >

The used of this invention (A) Cyclomonoolefin polymer preferably in the 30 [...] the chlorobenzene solution (concentration 0.5g/100 ml) inherent viscosity measured in [η_inh] to 0.2-5.0dl/g. And, (A) Cyclomonoolefin polymer to gel permeation chromatography (GPC) measurement of the polystyrene converted to number average molecular weight (Mn) is ideal, is usually 8000-1,000, 000, preferably 10000-800,000, more preferably 20,000-500,000, its weight average molecular weight (Mw) ideally, is usually 10,000-3,000,000, preferably 20,000-2,000,000, more preferably 30,000-100 million.

(A) the molecular weight of the cycloolefin polymer is too small, the resulting molded article and the strength of the film sometimes reduced. Molecular weight is too large, the increase in the solution viscosity is too high, the invention for the production of the thermoplastic resin composition is sometimes deterioration of the efficiency and workability.

Furthermore, (A) Cyclomonoolefin polymer molecular weight distribution is ideally (Mw/Mn), generally 1.5-10, preferably 2-8, more preferably 2-5.

(A) Cyclomonoolefin polymer has a glass transition temperature (the following also referred to as Tg) is usually 100-170 the [...] , is preferably the 110-160 [...] , more preferably the 115-160 [...]. Tg is too low, then the thermal deformation temperature is reduced, there is a possibility that the problems arising in heat resistance, and sometimes produce the resulting molded product, and the temperature of the film due to the change of the optical characteristics is increased. On the other hand, too high Tg, it is difficult to control and (B) Tg vinyl polymer than of the 50 [...].

(B) having a polar group of the vinyl polymer

The used of this invention (B) of the vinyl polymer, having a polar group thereof. As preferred polar groups, can cite hydroxy, an acid anhydride group (also includes acyl chloride), amido, carboxyl, and the like, in order to improve the (A) Cyclomonoolefin polymer intermiscibility, the special it is preferred to use a hydroxyl group, an acid anhydride group and amide-based.

And, (B) vinyl polymer is preferably from the aromatic vinyl monomer unit structure of the polymer.

< 乙烯基系单体 >

As to (B) vinyl polymer polar groups hydroxy monomer, can cite P-hydroxy styrene, α-methyl-P-hydroxy-styrene, 2-methyl-4-hydroxy styrene, 3, 4-di-hydroxy styrene, hydroxy styrene ; (meth) acrylic acid 2-hydroxy-ethyl ester, (meth) acrylic acid 3-hydroxy-propyl ester, (meth) acrylic acid hydroxy alkyl ester monomer. Wherein hydroxy styrene series monomer preferably in α-methyl-P-hydroxy-styrene, (meth) acrylic acid hydroxy alkyl ester monomer preferably (meth) acrylic acid 2-hydroxy-ethyl ester.

Furthermore, as a given (B) vinyl polymer polar groups an acid anhydride group-containing monomer, can cite maleic anhydride, citric acid, cis-1-cyclohexene -1, 2-dicarboxylic anhydride, 3-methyl-cis-1-cyclohexene -1, 2-dicarboxylic anhydride, 4-methyl-cis-1-cyclohexene -1, 2-dicarboxylic acid anhydride of an acid anhydride group-containing monomer such as; acryloyl chloride, methacryloyl chloride, and the like of the monomer containing acyl chloride. Wherein the monomer preferably contains anhydride, maleic anhydride is particularly preferred.

As to (B) vinyl polymer polar group of the amide monomer, can cite N-phenyl acrylamide, N-phenyl methyl acrylamide, N-(4-hydroxy phenyl) acrylamide, N-(4-hydroxy phenyl) methyl acrylamide, and the like.

And then, as the given (B) vinyl polymer carboxyl-group-containing monomer with a polar group, can cite acrylic acid, methacrylic acid, itaconic acid.

Can be the use of a separate or two or more kinds of used to impart the polar group-containing monomer as a copolymerization component.

Other than as the above-mentioned monomer, aromatic vinyl monomer specific example, can cite styrene; α-methyl styrene, β-methyl styrene, P-methyl styrene, alkyl-substituted styrene; 4-chlorobenzene ethylene, 4-bromophenylacetic ethylene, and other halogen-substituted styrene; vinyl benzyl alcohol; the methoxylphenylboronic ethylene, the-tert butoxypolyethylene styrene, meta-tert butoxypolyethylene styrene, alkoxy-substituted styrene; 3-vinyl benzoic acid, 4-vinyl benzoic acid, vinyl benzoic acid; 4-vinyl benzoic acid methyl ester, 4-vinyl benzoic acid ethyl ester, vinyl benzoic acid ester; 4-vinyl benzyl acetate; 4-acetoxy-styrene ; 2-butyl amide styrene, 2-methyl amide styrene, styrene-sulfonaide amide such as the styrenic; 3-aminostyrene, 4-aminostyrene, 2-isopropenyl aniline, vinyl benzyl dimethyl amine, amino vinyl; 3-nitrostyrolene, 4-nitrobenzene ethylene, nitrophenyl vinyl; 3-cyano-styrene, 4-cyano-styrene and other cyanopentanoyl styrene; vinyl phenyl acetonitrile; phenyl styrene and other aryl styrene. Can use more than two kinds of these monomer as a copolymerization component. Wherein by the industry in the easily obtained and cheap price aspects, preferably styrene, α-methyl styrene.

As to (B) vinyl polymer other structural unit of the monomer, can cite, for example, acrylonitrile, methacrylonitrile, vinyl cyanide monomer ; (meth) acrylate, ethyl (meth) acrylate, benzyl (meth) acrylate, phenyl (meth) acrylic acid, (meth) acrylic acid esters; N-phenyl maleimide, maleic acid imide monomer and the like. These monomer, a polymerizable the point of view of from preferably Carbonitride vinyl monomer.

As the synthetic (B) vinyl polymers are particularly preferably use the combination of the monomers, can cite styrene / α-methyl-P-hydroxy-styrene, styrene / α-methyl-P-hydroxy-styrene/acrylonitrile, styrene/maleic anhydride, styrene/maleic anhydride/acrylonitrile, styrene/N-phenyl acrylamide/acrylic acid, and the like.

< 自由基聚合引发剂 >

In the free radical the polymerization gathers cost of the used by the invention (B) vinyl polymer, can be used to generate free radical of the well known organic peroxide or azo doublebase of free-radical polymerization initiator.

As organic peroxide, can cite diacetyl peroxide, dibenzoyl peroxide, di-isobutene acyl peroxide, b (2, 4-dichlorobenzene formoxyl) peroxide, b (3, 5, 5-trimethyl oneself acyl group) peroxide, dioctanoyl peroxide, b laurel acyl peroxide, b stearyl acyl peroxide, b {4-( toluene acyl group between) benzoyl} peroxide, diacyl peroxide;

Butanone peroxide, cyclohexanone peroxide, methyl cyclohexanone peroxide, acetyl acetone peroxide and so on alkone peroxide;

Hydrogen peroxide, T-butyl hydrogen peroxide, cumene hydroperoxide-α, to menthane hydrogen peroxide, hydrogen peroxide diisopropylbenzene, 1, 1, 3, 3-tetramethyl-butyl hydroperoxide, hydrogen peroxide such as hydrogen peroxide uncle hexyl such;

Di-tert-butyl peroxide, bicumene superoxyde, b lauryl peroxide, α, α '-di (tert-butyl peroxide) second cumene, 2, 5-dimethyl -2, 5-di (T-butyl peroxide) hexane, T-butyl cumyl peroxide, 2, 5-dimethyl -2, 5-di (T-butyl peroxide) 3-hexynoic, dialkyl peroxide;

T-butyl peroxide acetate, T-butyl peroxide special fifth heavenly stem ester, uncle hexyl peroxidises special fifth heavenly stem ester, 1, 1, 3, 3-tetramethyl-butyl peroxide 2- ethyl caproate , 2, 5-dimethyl -2, 5-bis (2-ethyl-based oneself acyl group peroxidises) hexane, 1-cyclohexyl-1-methyl ethyl peroxidises 2- ethyl caproate , uncle hexyl peroxidises 2- ethyl caproate , tert-butyl peroxide 2- ethyl caproate , tert-butyl peroxide isobutyrat, tert-butyl peroxide maleic acid ester, tert-butyl peroxide 3, 5, 5-trimethyl base oneself ester, tert-butyl peroxide laurel ester, 2, 5-dimethyl -2, 5-bis (toluene between the acyl peroxide) hexane, α, α '-bis (new last of the ten Heavenly Stems acyl group peroxidises) second cumene, cumyl peroxidises new last of the ten Heavenly Stems ester, 1, 1, 3, 3-tetramethyl-butyl peroxidises new last of the ten Heavenly Stems ester, 1-cyclohexyl-1-methyl ethyl peroxidises new last of the ten Heavenly Stems ester, uncle hexyl peroxidises new last of the ten Heavenly Stems ester, tert-butyl peroxide new twelve ester, tert-butyl peroxide benzoate, uncle hexyl peroxidises benzoates, b (T-butyl peroxide) m-benzoate, 2, 5-dimethyl -2, 5-di (benzoyl peroxide) hexane, T-butyl peroxide between toluols Carbamoyl benzoates, 3, 3 the [...] , 4, 4 the [...] -tetra (T-butyl crosses the oxygen carbonyl) benzophenoneoxime, peroxidises tenuifoliae;

1, 1-b (uncle hexyl peroxidises) 3, 3, 5-trimethyl cyclohexane, 1, 1-bis (uncle hexyl peroxidises) cyclohexane, 1, 1-bis (T-butyl peroxide) 3, 3, 5-trimethyl cyclohexane, 1, 1-bis (T-butyl peroxide) cyclohexane, 1, 1-bis (T-butyl peroxide) ring-dodecane, 2, 2-di (tert-butyl peroxide) butane, 4, 4-bis (tert-butyl peroxide) pivalic acid is n-butyl, 2, 2-bis (4, 4-di-tert-butyl peroxide cyclohexyl) propane a the oxidation shrinks ketone;

uncle hexyl peroxidises isopropylacrylamides single carbon ester, tert-butyl peroxide isopropyl single carbon ester, tert-butyl peroxide 2-ethyl hexyl single carbon ester, tert-butyl group of the oxyalkylene propyl single carbon ester a oxidized list carbonic acid esters;

Di-sec-butyl peroxidises two-carbon ester, di-n-propyl peroxidises two-carbon ester, diisopropyl peroxidises two-carbon ester, b (4-tert-butyl cyclohexyl) peroxidises two-carbon ester, di-2-ethoxy ethyl peroxidises two-carbon ester, di-2-ethyl hexyl peroxidises two-carbon ester, bis-2-methoxy-butyl peroxidises two-carbon ester, b (3-methyl-3-methoxy-butyl) peroxide two-carbon ester, peroxidises two carbonic acid esters;

In addition can also points out uncle butyl trimethylsilyl peroxide, and the like, used for the present invention, the organic peroxide is not limited to these exemplified compounds.

As the azo doublebase series free radical polymerization initiator, can cite azo two different third nitrile , azo group two different fifth heavenly stem nitrile , 2, 2 the [...] -azo-di (4-methoxy -2, 4-dimethyl valeronitriles), 2, 2 the [...] -azo-di (2, 4-dimethyl valeronitriles), 2, 2 the [...] -azo-di (2-methyl butyronitrile), 1, 1 the-azo-di [...] (cyclohexane-1-a nitrile), 2-(carbamoyl azo) isobutanenitrile, 2, 2 the [...] -azo-di [2-methyl-N-{ 1, 1-di (hydroxy methyl)-2-hydroxy-ethyl} propionamide], 2, 2 the [...] -azo-di [2-methyl-N-{ 2-(1-hydroxybutyl)} propionamide], 2, 2 the [...] -azo-di [2-methyl-N-(2-hydroxy-ethyl)-propionamide], 2, 2 the-azo-di [...] [N-(2-propenyl)-2-propionamide], 2, 2 the-azo-di [...] (N-butyl-2-propionamide), 2, 2 the-azo-di [...] (N-cyclohexyl-2-propionamide), 2, 2 the [...] -azo-di [2-(5-methyl-2-imidazoline-2-yl) propane] dihydrochloride, 2, 2 the [...] -azo-di [2-(2-imidazoline-2-yl) propane] dihydrochloride, 2, 2 the [...] -azo-di [2-(2-imidazoline-2-yl) propane] b sulfate-dihydrate, 2, 2 the [...] -azo-di [2-(3, 4, 5, 6-tetrahydro-pyrimidin-2-yl) propane] dihydrochloride, 2, 2 the [...] -azo-di [2-(1-(2-hydroxy-ethyl)-2-imidazoline-2-yl) propane] dihydrochloride, 2, 2 the [...] -azo-di [2-(2-imidazoline-2-yl) propane], 2, 2 the [...] -azo-di (2- methyl third trunk) dihydrochloride, 2, 2 the-azo-di [...] [N-(2-carboxy-ethyl)-2-methyl-propion], 2, 2 the [...] -azo-di (2-methyl [...]), dimethyl 2, 2 the second butyrate [...] -azo, 4, 4 the [...] -azo-di (4-cyano valeric acid), 2, 2 the [...] -azo-di (2, 4, 4-trimethyl pentane), and the like, according to the present invention, azo doublebase is used for free-radical polymerization initiator is not limited to these exemplified compounds.

< 催化剂 >

In the above-mentioned vinyl monomers can be used in the copolymerization reaction catalyst. The catalyst is not subject to special limit, can cite, for example, known anionic polymerization catalyst, polymerization catalyst coordinating anion, such as cationic polymerization catalyst.

< 乙烯基系聚合物 >

The used of this invention (B) vinyl polymer is in the above-mentioned polymerization initiator, the presence of a catalyst by bulk polymerization, solution polymerization, precipitation polymerization, emulsion polymerization method, suspension polymerization or bulk-suspension polymerization in the past such as the well-known method of the above-mentioned vinyl monomers obtained by copolymerization.

The so-obtained (B) in the vinyl polymer, having a polar group is a structural unit derived from a monomer to polar group the proportion of the structural unit, relative to 100 weight % of the sum of all the structural unit is usually 1 weight %-40% by weight, is preferably 1-30 weight %, more preferably 2-20 weight %. The structure of having a polar group if the proportion of unit in the above-mentioned range, the compatibility, low water absorption are preferred. Furthermore, the aromatic vinyl monomer-derived structure is usually the proportion of unit 60 weight %-99 weight %, preferably 70-99 weight %, more preferably 80-98 weight %. The aromatic vinyl monomer derived if the proportion of unit structure in the above-mentioned range, with Cyclomonoolefin resin (A) compatibility is preferred.

For (B) vinyl polymer, preferably, determined by gel permeation chromatography (GPC) converted to polystyrene of the number average molecular weight (Mn) is usually 3,000-500,000, preferably 5,000-400,000, more preferably 10,000-250,000, weight average molecular weight is usually (Mw) 500-1,000, 000, preferably 5,000-800,000, more preferably 20,000-500,000. The above-mentioned (B) vinyl polymer molecular weight is too small, the more the strength of the film sometimes reduced. Molecular weight is too large, the excess increase in the solution viscosity is high, the present invention the thermoplastic resin composition is sometimes deterioration of production efficiency and workability.

Furthermore, the above-mentioned (B) the molecular weight distribution of the vinyl polymer is ideally (Mw/Mn), is usually 1.0-10, is preferably 1.2-5, more preferably 1.2-4.

(B) Cyclomonoolefin polymer has a glass transition temperature (Tg) is usually 75-140 the [...] , is preferably the 80-130 [...] , more preferably the 90-130 [...]. Tg is too low, the thermoplastic resin composition of lowering the Tg, it is possible the problems arising in heat resistance, and sometimes produce the resulting molded product, and the temperature of the film due to the change of the optical characteristics is increased. On the other hand, too high Tg, the strength of the tendency to have extremely reduced.

Thermoplastic resin composition

The invention refers to a thermoplastic resin composition containing the (A) Cyclomonoolefin polymer and (B) having a polar group of the vinyl polymer, the composition of the glass-transition temperature (Tg) of 100 the above [...] , preferably 110 the above [...].

If Tg is smaller than the 100 [...] , the bad heat resistance of the resulting optical film, in practical application, deformed, problems such as deterioration of the optical characteristic. Furthermore, in the present invention the thermoplastic resin composition and the Tg of the polymer obtained is the following: the use of differential scanning calorimeter (DSC) in the nitrogen atmosphere, the temperature rising speed: 20 the under the condition of [...] /minutes to be measured, to find the results of DSC curve of the time differential of temperature and the peak in the peak-temperature -20 the temperature of the DSC [...] the tangent of the curve corresponding to the intersection of the temperature as that of the Tg (refer to Figure 1).

Furthermore, the thermoplastic resin composition of the present invention, the above-mentioned polymer (A) and (B) than glass-transition temperature of the of the 50 [...] , preferably less than 45 the [...]. The difference of the Tg of the polymer if the the 50 [...] the above, it is possible when the optical film obtained by stretching treatment, the excessive increase in stress, tensile processing varying difficulties, when the temperature raising the stretch or cause the stretching orientation easing, so that the phase difference performance and reduce the optical characteristics such as wavelength dispersibility.

Composition ratio of the thermoplastic resin composition is not subject to special limited, but for the manufacture in the case of the use of the optical film, ideally, with respect to 100 parts by weight (A) Cyclomonoolefin polymer as 20-200 the proportion of parts by weight containing (B) having a polar group of the vinyl polymer, preferably 25-100 parts by weight, more preferably 30-80 parts by weight. (B) if the amount of the vinyl polymer in the above-mentioned range, the strength of the resin is preferred, if the use of such a thermoplastic resin composition, can be obtained the excellent phase difference of expression with the phase difference film. (B) vinyl polymer the amount of if lower than the above-mentioned lower limit, the resulting resin is applied the optical characteristic of the film sometimes significantly reduced, in addition, if the amount exceeds the above upper limit, not only intensity is reduced, but also used as the phase difference film in the case of the phase difference of is sometimes negative performance.

Furthermore, in the injection molded product of the thermoplastic resin composition in the case of used, relative to 100 parts by weight (A) Cyclomonoolefin polymer, (B) the proportion of the vinyl polymer is preferably an ideal 10-300 parts by weight, more preferably 30-150 parts by weight, particularly preferred 40-100 parts by weight.

The thermoplastic resin composition of the present invention in addition to containing the polymer (A) and polymer (B) outer, can be further includes the hydrocarbon resin. As the hydrocarbon resin, can cite C₅ series resin, C₉ series resin, C₅ series/C₉ series mixed resin, cyclopentadiene resin, olefin/vinyl substituted aromatic compound copolymer resin, cyclopentadiene based compound/vinyl substituted aromatic compound copolymer resin, products of these resin and vinyl substituted aromatic resin and the like products. Relative to 100 parts by weight (A) Cyclomonoolefin polymer, the content of the hydrocarbon resin is usually 0.01-50 parts by weight, preferably 0.1-25 parts by weight.

Furthermore, the thermoplastic resin composition of the present invention the use of various additives can be added in, as shown in, for example, the following may be added to the antioxidant, ultraviolet absorbers in order to improve the heat-resisting the degrading and light resistance.

Antioxidant:

Can cite: 2, 6-di-tert-butyl-4-methyl phenol, 2, 2 the [...] -dioxo -3, 3 the [...] -di-tert-butyl -5, the 5 [...] -dimethyl diphenylmethane, four [methylene-3-(3, 5-di-tert-butyl-4-hydroxy-phenyl) propionate] methane, 1, 1, 3-tris (2-methyl-4-hydroxy-5-tert-butyl-phenyl) butane, 1, 3, 5-trimethyl -2, 4, 6-tris (3, 5-di-tert-butyl-4-hydroxybenzy) phenyltheophylline, octadecyl-β-(3, 5-di-tert-butyl-4-hydroxy-phenyl) propionate, 2, 2 the [...] -dioxo -3, 3 the [...] -di-tert-butyl -5, 5 the- [...]two ethyl benzenes yl methane, 3, 9-bis [1, 1-dimethyl-2-(β-(3-tert-butyl-4-hydroxy-5-methyl phenyl) c acyloxy) ethyl], 2, 4, 8, 10- four oxygen spirals [5.5] undecane, three (2, 4-di-tert-butyl phenyl) phosphite, ring new pentane four dihydrogenmethylenebisphosphonate (2, 4-di-tert-butyl phenyl) phosphite, ring new pentane four dihydrogenmethylenebisphosphonate (2, 6-tert-butyl-4-methyl phenyl) phosphite, 2, 2-methylene-bis (4, 6-tert-butyl phenyl) phosphate ester octyl Asia.

Ultraviolet absorbent:

Can cite, 2, 4-dihydroxy benzophenone, 2-hydroxy-4-methoxy benzophenone, 2-(2H-benzotriazole-2-yl)-4, 6-bis (1-methyl-1-phenyl-ethyl) phenol, 2-(2H-benzotriazole-2-yl)-4, 6-di-tert-amyl phenol, 2-benzotriazole-2-yl -4, 6-di-tert-butyl phenol, 2, 2 the [...] -methanodi-(4-(1, 1, 3, 3-tetramethyl-butyl)-6-[ (2H-benzotriazole-2-yl) phenol]), and the like.

Relative to 100 parts by weight of the resin composition, these and the addition amount of the additive is usually 0.01-5 parts by weight, preferably 0.05-4 parts by weight.

Furthermore, in the present invention in the thermoplastic resin composition of the additive may also be added a lubricant and the like in order to improve the processability.

The thermoplastic resin composition of the present invention can be, for example, manufacturing by the following method:

(I) using dual-axis extruder or the roller mixing roll (A) Cyclomonoolefin polymer, (B) vinyl polymer and the process of mixing the optional ingredient,

(Ii) will (A) Cyclomonoolefin polymers to be dissolved in the appropriate solvent, is added in the resulting solution, mixed (B) vinyl polymer and optional ingredient method.

Optical film

Known forming method can be used to the above-mentioned the invention refers to a thermoplastic resin composition molding to manufacture the optical film of the present invention, such as the use of solvent casting, injection molding, compression molding, or extrusion forming method for the above-mentioned thermoplastic resin composition forming the film to make the optical film of the present invention.

As solvent casting of, for example, the following method can be cited: the above thermoplastic resin composition of the invention is dissolved or dispersed in the solvent in the liquid of the appropriate concentration, casting or coating on the appropriate carrier, after the drying thereof, stripping film from the carrier.

The invention the thermoplastic resin composition is dissolved or dispersed in a solvent, the concentration of the thermoplastic resin composition is usually 1-90 weight %, preferably 5-50 weight %, more preferably 10-35 weight %. If the concentration of the resin is lower than the above-mentioned concentration, it is difficult to ensure that the thickness of the film, and accompanied by evaporation of the solvent to generate air bubbles, it is easy to produce difficult to obtain smoothness on the surface of the film and the like. On the other hand, if the concentration is more than the above concentration, the excessive increase in the solution viscosity, the resulting optical used and the thickness of the film is difficult to achieve a uniform surface.

Furthermore, the degree of viscosity of the above-mentioned solution at room temperature is usually 1-1,000, 000 (MPa ·s), preferably 10-500,000 (MPa ·s), more preferably 100-200,000 (MPa ·s), especially preferably 1000-100,000 (MPa ·s).

As the solvent used here, can cite cyclohexane, cyclopentane, methyl cyclohexane, hydrocarbon solvents; benzene, toluene, xylene and other aromatic series solvent; methyl soluble lignocellulose, ethyl soluble lignocellulose, 1-methoxy-2-propanol as solvent dissolves the filament element ; diacetone alcohol, acetone, cyclohexanone, butanone, 4-methyl-2-pentanone, which implements methyl isobutyl ketone, etc. series solvent; methyl lactate, methyl acetate, ethyl acetate, butyl acetate, ester solvent; dichloromethane, chloroform, etc. the halogen-containing solvent; tetrahydrofuran, dioxa six-ring, dimethoxy ethane, oxa amylcyclo ferrous alloys, such as; 1-butanol, 1-pentanol, solvent alcohol series.

And, in addition to the above-mentioned solvent other than the use of SP value (solubility parameter) is usually 10-30 (MPa^1/2), preferably 10-25 (MPa^1/2), more preferably 15-25 (MPa^1/2), especially preferably 17-20 (MPa^1/2) if range of solvent, surface uniformity can be obtained and good optical characteristic of the optical film. Furthermore, the SP value of the solvent the     EDITTION   THIRD POLYMER HANDBOOK, VII/526 recorded in the data.

The above-mentioned solvent can be used alone and used or more than two kinds. With more than two and in the case of the solvent, preferably make the mixture in the range of values of SP in the above-mentioned range. At this moment, the SP value of the mixture can be determined from its weight ratio, the two, for example, in the case of mixtures of the solvents, the solvent of the weight fraction for W₁, W₂, and SP value is SP₁, SP₂ time, the mixed solvent as the SP value of the averaging of the following formula is calculated.

SP value = W₁ ·SP₁ + W₂ ·SP₂

The above-mentioned solvent under atmospheric pressure is usually the boiling point of the 100 [...] the following, is preferably 70 the [...] the following, especially preferred as the 45 [...] the following. If the boiling point is more than 100 the solvent [...] , after film-forming the drying time of the variable-length, sometimes poor production efficiency. And, the residual solvent in the film increased, in some cases optical characteristics such as expression of the deterioration of the phase difference.

In these solvents, in the low-boiling point of methylene chloride is preferably used in particular. Containing Cyclomonoolefin polymer and the vinyl polymer in the past that in the case of thermoplastic resin composition, if not used the solvent methylene chloride is dissolved, the dichloromethane evaporated after forming film, presence of the transparent film does not become the problem, however, the thermoplastic resin composition in the invention, even without using a phase solvent can also receive transparent film. The result, in the solvent casting method, drying temperature can be lower than in the past, can prevent octoix at the time of film formation.

In the modulation of the resin solution, the solvent used for dissolving the thermoplastic resin composition of the invention can be the temperature of the room temperature, also can be high temperature. Can be obtained by fully stirring is a solution. Furthermore, coloring is carried out according to need, also can be in the solution is suitable for adding dye, pigment, colorant.

Furthermore, in order to improve the smoothness of the surface of the film for optical use, leveling agent may be added. As long as the usual leveling agent, can use various flatting agent, such as fluorine-based non-ionic surface active agent can be cited, is the flatting agent special acrylic resin, silicone leveling agent, and the like.

As a solution casting method of the present invention manufacturing method of optical film, the following methods can be cited: the use of die head or applicator the above-mentioned solution coating the metal drum, steel, polyethylene terephthalate (PET) or polynaphthalic acid ethylene glycol ester (PEN) polyester film, such as, polytetrafluoroethylene with the substrate, subsequently, drying to remove the solvent, peeling a film from the substrate. Furthermore, use of a spraying, brushing, roller spin coat , dipping method, solution coating the resin composition on the substrate, subsequently, drying to remove the solvent, peeling a film from the substrate, it is also possible to manufacture optical film. Furthermore, by repeatedly coating can control the thickness of the film and surface smoothness and the like.

Furthermore, the use of polyester film used as the substrate, can use the surface-treated film. As the surface treatment method, usually can be cited of the hydrophilic processing method. The surface of the polyester film, for example, by coating or laminating acrylic resin or containing sulfonate-based resin, so as to of the stacked method, or by corona discharge treatment to improve the film surface hydrophilic method and the like. Furthermore, as a carrier, using, for example, on the metal drum, steel strip, such as bedding sand surface of the polyester film (sand mat) processing or extrusion processing and formed with a concavo-convex object, thus obtained membrane on the transfer surface of the concave-convex surface of the carrier, thereby, can make a film having a light diffusion function. Of course, the membrane directly implemented by processing the bedding sand, can also be given to the film light diffusion function.

With respect to the above-mentioned solution casting method (solvent removed) of the drying process, no special restrictions, can use a usual method, for example, can be utilized in the same by means of a plurality of optical method, and the like through the drying oven to implement, however, accompanied with the drying process will produce the bubble evaporation of solvent, the characteristics of the film significantly reduced, therefore, preferably set up the drying process 2 number of a plurality of procedures of above, in the process control of the temperature or air flow to avoid this question.

Furthermore, optical film is usually a residual solvent amount of 10 weight % or less, preferably 5 weight % or less, more preferably 2 weight % or less, especially preferably 1 weight % of the following. In this, if the residual solvent content of 10 weight % or more, then the actual use of the optical film, increase of the size of the change with time, is not preferred. Furthermore, the residual solvent to reduce the Tg, sometimes reduce the heat resistance, so is not preferred.

Furthermore, in order to better carry out the latter stretching processes, sometimes it is necessary to adjust the above-mentioned residual solvent amount is in the above-mentioned range. Specifically, in order to make the tensile oriented with a phase difference and a stable performance, sometimes control residual solvent amount is usually 10-0.1 weight %, preferably 5-0.1 weight %, more preferably 1-0.1 weight %. Through making the residual solvent as the trace, stretching processing sometimes becomes easy, or the phase difference of the control sometimes becomes easy.

For optical use of this invention the thickness of the film is usually 0.1-3,000 the  m, preferably 0.1-1,000 the  m, more preferably 1-500m, most preferably the 5-300  m. Thickness of less than 0.1 the when   m, in fact, it is difficult to dispose of film. On the other hand, the thickness of the the 3000 more than   m, is rolled into a tube-shape is difficult.

In the case of unstretched film, for optical use of the invention with respect to the distribution of the average thickness of the film is usually ± 20% or less, preferably ± 10% or less, more preferably ± 5% or less, especially preferably ± 3% to the inner. Furthermore, every 1 cm of the rate of change of the thickness of is, is usually 10% the following, is preferably 5% or less, more preferably 1% or less, especially preferably 0.5% the following. Through the implementation of the film thickness control, can be made into a homogeneous optical film, stretch oriented at the same time can prevent the non-uniform phase difference of the transmitted light.

Phase difference film

The optical film of the present invention also preferably the to the above-mentioned non-stretched optical film implementing stretching processing (stretch oriented processing) and get, the film having a phase difference (phase difference film).

Through the above-mentioned stretching processing, polymer formed into a film on the molecular chain of the rules orientation in a certain direction, shown by the function of the phase difference of the light transmission. In this, the so-called "rule-oriented" means that, by a melt extrusion method or in the casting of the usual high molecular compound (polymer) in the case of forming the film, although it is produced by the process of the membrane in the size of the of the impact of bending, but with the high-molecular compound molecule chain not and toward a specified direction to a random state is different, chain in membrane of macromolecule compound or uniaxial direction of the level of the double-axis direction or orientation of the rules in the direction of thickness. High-molecular compound, the degree of the orientation of the various rules, can be controlled by stretching conditions.

As the stretching processing method, in particular can be cited the known uniaxial stretching method or a biaxial stretching method. In other words, can be cited of the transverse uniaxial stretching method based on pulls a law , compressed between extension, the use of two different distance of the circumference of the longitudinal uniaxial stretching method, or combined horizontal single-axis and longitudinal uniaxial double-shaft extension, the extension and the like based on the blow molding method.

In use the uniaxial stretching method, stretching speed is usually 1-5,000% / minute, preferably 50-1,000% / minute, more preferably 100-1,000% / minute, especially preferably 100-500% / minute.

As the biaxial stretching method, can be cited in the interlaced 2 to stretch direction and at the same time the method of the uniaxial tensile after the initial tensile direction different from the direction in which the method of stretching. In these methods, the intersection of the two stretching axis angle according to a desired characteristic to determine, not subject to special limited, but is usually 120-60 degrees. Furthermore, in all stretching speed on the stretching direction may be identical or different, is usually 1-5,000% / minute, preferably 50-1,000% / minute, more preferably 100-1,000% / minute, especially preferably 100-500% / minute.

Processing in the drawing processing is not subject to special limit temperature, an optical film for the (thermoplastic resin composition) is the glass transition temperature, Tg, is ideal to the processing temperature, it is usually the Tg-Tg + 30 [...] , is preferably the Tg-Tg + 20 [...] , more preferably the Tg-Tg + 10 [...]. If the stretching temperature in the above-mentioned range, the phase difference of the high-performance, and can inhibit the occurrence of uneven the phase difference, and the control of the index ellipsoid becomes easy, therefore, is preferred.

According to the stretching ratio to the various characteristic to determine the phase difference and the like, not subject to special limited, but is usually 1.01-10 times, preferably 1.03-5 times, more preferably 1.03-3 times.

The present invention in the case of thermoplastic resin composition, because the temperature in the vicinity of the Tg can be to carry out stretching processing, therefore, even if low magnification stretching can also be applied to the film of high stress, high phase difference can be obtained. Furthermore, if it is the stretching ratio is relatively small, the transparency can be readily fabricated, without deflection optical axis of the phase difference film. Furthermore, if the stretching ratio is too large, then the phase difference and the optical axis of the control sometimes becomes difficult.

As the film can be stretched to obtain directly in the cooling at room temperature, but preferably in the Tg-100 [...] -Tg level under the environment of the temperature of at least 10 seconds, preferably 30 seconds to 60 minutes, more preferably 1 minute -60 minutes in order to carry on heat-curable, the following cooling to room temperature, thereby, the phase of the transmitted light can be obtained with a small variation of the difference of time, a stable characteristic of the phase difference of the phase difference film.

Such as the phase difference film by stretching, so that the molecular orientation, thereby giving the transmitted light phase difference, but can be adjusted before stretching magnification or control the thickness of the membrane of the absolute value of the phase difference. For example, even if the thickness of the is expandered the membrane the same as before, the greater the stretching ratio of the phase difference of the absolute value of the transmitted light with increased tendency, therefore, through changing the stretching ratio, the transmission light can be obtained to give the phase difference of the phase difference film. Furthermore, even if the same stretching ratio, before the greater the thickness of the membrane, to the absolute value of the phase difference of light transmission with increased tendency, therefore, through changing the thickness of the membrane before, the transmission light can be obtained to give the phase difference of the phase difference film.

As described above in the phase difference film, phase difference given to transmitted light of the value of the determined on the basis of the its use, the decision is not unity, but for the liquid crystal display element, an electroluminescent display element or laser learning system occasions wave length board , ideally is usually 1-10, 000 nm, preferably 10-2, 000 nm, more preferably 15-1, 000 nm.

Furthermore, the phase of light through the membrane preferably its equality is high, specifically, the wavelength is 550 nm light is usually a deviation of ± 20% or less, preferably 10% or less, more preferably ± 5% the following. The deviation of the phase difference is more than ± 20% in the case of the range, when used for liquid crystal display element or the like, sometimes generating a stain, display the question of performance degradation of the of the main body.

Furthermore, from the membrane through the phase of light, the wavelength of transmission light difference along with different. The invention of the phase difference film preferably has a positive wavelength dispersion. In particular, at a wavelength of 400 nm, 550 nm, 800 nm are respectively set as the delay value Re₄₀₀, Re₅₅₀, Re₈₀₀ time, ideally, the relationship between the value is preferably Re₄₀₀ <Re₅₅₀ <Re₈₀₀, wavelength 550 nm Re a phase difference of (550) and a wavelength 400 nm Re a phase difference of (400) than [Re (400/Re (550)] to 1.0-0.1, preferably 0.9-0.3, more preferably 0.9-0.5, and the phase difference Re (550) and wavelength 800 nm Re a phase difference of (800) than [Re (800/Re (550)] is 1.5-1.0, preferably 1.5-1.1, more preferably 1.5-1.2. To meet such a condition the phase difference film, a phase difference of a certain wavelength is λ the Re (λ), can make the 400-800nm in the entire wavelength region of the substantially constant Re (λ)/ λ.

If the control in 400-800nm the entire wavelength region of the Re (λ)/ λ value is the mean value ± 30% or less, preferably ± 20% or less, more preferably ± 10% or less, can be obtained in the entire wavelength region, for example, the phase difference or 1/4 λ of the broad band of 1/2 λ λ plate. In other words, in the 400-800 nm the entire wavelength region of the above-mentioned Re (λ)/ λ value of 0.15-0.40, preferably 0.16-0.35, more preferably 0.16-0.30 case, film in the whole wavelength region having a circular polarized light and linearly polarized light of the function of the 1/4 λ plate, and, similarly, the value of the above-mentioned Re (λ)/ λ 0.35-0.65, preferably 0.45-0.60, more preferably 0.45-0.55 in the case of the, film has in the entire wavelength region of the linear polarization plane of polarisation rotating 90 degrees the function of 1/2 λ plate, therefore, it is very useful.

The invention the phase difference film, the optical film can be independently 1 or 2 using the laminated sheet of the above, or the use of the transparent substrate, and the like. Furthermore, can also be stacked in other film, sheet, on the base plate.

In the case of the laminated film, and the like, can use the adhesive and adhesive. As the adhesive and the adhesive, preferably use of the excellent transparency, specific examples can be cited of natural rubber, synthetic rubber, vinyl acetate/vinyl chloride copolymer, polyvinylether, acrylic resin, such as modified polyolefin resin adhesive; in having a hydroxyl group, amino group, such as the above-mentioned resin compound containing isocyanate group with the curing agent such as a curable adhesive; the polyurethane dry laminating adhesive, synthetic rubber-based adhesive, such as epoxy adhesive.

Furthermore, in order to improve and the other film, sheet, the operation performance of the laminated substrate, etc., may be pre-in the above-mentioned phase difference film, an adhesive layer or adhesive layer. In the laminated adhesive layer or in the case of layer, as the adhesive and the adhesive can use the above-mentioned adhesive or adhesive.

The optical film of the invention phase difference film can be used for mobile phone, digital information terminal, a wireless paging system, navigation, vehicle-mounted liquid crystal display device, liquid crystal monitor, adjusts the worn out fur woman with no pubic hair , display for office automation equipment, such as audio-visual apparatus display for each kind of liquid crystal display element, an electroluminescent display anti-reflection plate or a touch panel, and the like. Furthermore, also can be used as the CD, CD-R, MD, MO, DVD recording-reproducing device for an optical disc such as the use of wavelength plate.

Embodiment

The following, specific example based on the implementation of the invention, but the invention is not limited by these examples. Furthermore, the following embodiment and comparative embodiment, in addition to the special description, "parts" and " %" represents "parts by weight" and "weight %". Furthermore, in the following embodiment, in the comparison example, the following various measuring and evaluation.

Molecular weight determination (Mw, Mw/Mn)

The use of gel permeation chromatograph (GPC, Tosoh Corporation systems, tradenames: HLC-8020, four chromatographic column: Tosoh Corporation systems, tradenames: TSK   gel   G7000HxL, TSK   gel GMHxL, TSK   gel   GMHxL, TSK   gel   G2000xL), to tetrahydrofuran (THF) as the solvent measured is converted into a weight average molecular weight of polystyrene (Mw/Mn) (Mw) and molecular weight distribution. Furthermore, Mn is the number average molecular weight.

Glass transition temperature (Tg)

Using Seiko   Instruments society system differential scanning calorimeter (DSC), in a nitrogen atmosphere, a temperature rise speed is per minute the 20 [...] determining the condition of the, differential time to find the results of DSC curve (DDSC curve) temperature and the peak in the peak-temperature -20 the temperature of the DSC [...] the tangent of the curve corresponding to the intersection of the temperature as that of the Tg. Figure 1 shown in the mode of the method for calculating map Tg.

Residual solvent

In the sample is dissolved in methylene chloride, the obtained solution is GC-7A Shimadzu seisakusho production for gas-phase chromatographic device analysis.

The whole light transmittance, haze

Xinhua   Instruments   Test use of Suga HGM-2DP type fog instrument determination.

The phase difference and through the light wavelength dispersibility

With the constant temperature trough of a tensile testing machine (Instron society system , MODEL5567-type), the glass transition temperature to + 10 [...] the resulting film to maintain the temperature of the 5 minutes, then uniaxial stretching. In order to set the stretching magnification is 2 times to perform the stretching. For the obtained stretched film, using Oji measuring machine society KOBRA-21ADH of production, and KOBRA-CCD of determining the phase difference of the transmitted light.

< gathers the precedent aodirenc 1>

The 20g following formula (A) of said 8-methoxy carbonyl-8-methyl tetracyclic [4.4.0 . 1^2,5. 1^7,10]-3- dodecylene , 5.0g following formula (B) of the said 5-methoxy carbonyl-5-a bicyclic [2.2.1.] hept-2-ene, 1.2g molecular weight regulator 1-hexene and 86.3g after nitrogen toluene added in replacement of the reaction vessel, and heating to the 80 [...]. Adding 0.15 ml triethyl aluminum (0.61 mol/L) of toluene solution, 0.47 ml methanol modified WCl₆ toluene solution (0.025 mol/L), for the 80 [...] reaction 3 hours, thereby obtaining the polymer. Secondly, the resulting ring-opening copolymer solution in the autoclave, and then adding 86.3g toluene. With respect to the monomer addition level is added 2500 PPM hydrogenation catalyst RuHCl (CO) [P (C₆ H₅)]₃, the hydrogen gas pressure is set to a 9-10MPa, for 160-165 the reaction [...] 3 hours. After the reaction, the precipitate in a large amount of methanol solution, hydrogenation object obtained. The hydrogenation product of ring-opening polymer (resin (A1)) of the Tg=147 [...] , weight average molecular weight (Mw) =11.5 × 10⁴, molecular weight distribution (Mw/Mn)=3.21.

< gathers the precedent aodirenc 2>

The 50g above-mentioned type (A) of said 8-methoxy carbonyl-8-methyl tetracyclic [4.4.0 . 1^2,5. 1^7,10]-3- dodecylene , 2.3g molecular weight regulator 1-hexene and 100g after nitrogen toluene added in replacement of the reaction vessel, and heating to the 80 [...]. Adding 0.09 ml triethyl aluminum (0.6 mol/L) of toluene solution, 0.29 ml methanol modified WCl₆ toluene solution (0.025 mol/L), for the 80 [...] reaction 3 hours, thereby obtaining the polymer. Secondly, the resulting ring-opening copolymer solution in the autoclave, and then adding 100g toluene. With respect to the monomer addition level is added 2500 PPM hydrogenation catalyst RuHCl (CO) [P (C₆ H₅)]₃, the hydrogen gas pressure is set to a 9-10MPa, for 160-165 the reaction [...] 3 hours. After the reaction, the precipitate in a large amount of methanol solution, hydrogenation object obtained. The hydrogenation product of ring-opening polymer (resin (A2)) of the Tg=167 [...] , weight average molecular weight (Mw) =13.49 × 10⁴, molecular weight distribution (Mw/Mn)=3.06.

< gathers the precedent aodirenc 3>

Added in the reaction container 101 ml styrene, 4.5g α-methyl-P-hydroxy styrene, 5.0 ml acrylonitrile, 0.6131g   2, the 2 [...] -azo-di (2, 4-dimethyl valeronitriles) (and optical reagent: V-65). Nitrogen it with nitrogen to 10 minutes, for the 55 [...] reaction 7 hours. After the reaction, the precipitate in a large amount of methanol, to obtain styrene / α-methyl-P-hydroxy-styrene/acrylonitrile copolymer. The resulting vinyl polymer (resin (B1) of the Tg=110 [...] , weight average molecular weight (Mw) =7.27 × 10⁴, molecular weight distribution (Mw/Mn)=1.81.

Embodiment 1

The gathers the precedent 1 the obtained resin (A1) and synthetic example 3 the obtained resin (B1) to 67 parts by weight/33 parts by weight of dissolved in dichloromethane in the ratio of, the solid component concentration to 20 weight % of the solution. Using the solution obtained by solvent casting is thick the 90  m, solvent residue 0.2% the following transparent casting film (PF1). The resultant film, to determine glass transition temperature (Tg), as a result, can be known, the glass transition temperature of the 129 [...] , measuring peak is unimodal, polymer compatible to each other. Furthermore, test the total light transmittance and haze. Results shown in table 1.

Embodiment 2, comparative example 1, 2

In addition to table 1 of the types shown, other than resin of the mixing ratio, with the embodiment 1 to operate the same, to obtain a casting film. The appearance of the resulting membrane observation, and use this film measuring Tg, the film thickness, total light transmittance and haze. And as a result, shown in table 1.

Furthermore, resin (B2) is styrene-maleic anhydride copolymer (NOVAChemical Xinhua production, DYLARKD232), the Tg=118 [...] , weight average molecular weight (Mw) =20.74 × 10⁴, molecular weight distribution (Mw/Mn)=1.99.

[Table 1]

Embodiment 3, 4 and comparative example 2

The use of embodiments 1, 2 and comparative example 1 to obtain the membrane to a stretching treatment of, the two kinds of different stretching ratio films, the evaluation of the same. Results shown in table 2. Furthermore, the resulting phase difference film, tensile stress during the comparison of expression with the phase difference shown in Figure 2. From table 2 and Figure 2 can be known, for the films of this invention, at low stress at the same time keeping the wavelength dispersibility, expression of phase difference can be improved.

[Table 2]

Re: phase difference (nm), d: the film thickness (µm)

Embodiment 5

In order to evaluate the above-mentioned embodiment 4 shown in the phase difference (Re) through the uniaxially stretching the 137-140 nm (PR-4) the direction of conveyance of the characteristic, will adopt the ASV mode TFT liquid crystal of low [...] sharp Corporation system of a liquid crystal panel of the liquid crystal television (LC-13B1-S) attached to the front of the observer side of the polarizer and a phase difference film peeling, in the stripping position of the stripping of a polarizing plate and stretched film obtained by the embodiment (PR-4), make it liquid crystal unit side, wherein when the original set up with the sticking of the same light transmission axis of the polarizer.

Can confirm, (PR-4) with the stretched film of a liquid crystal television set azimuth angle of 45 degrees, the polar angle 60 degrees direction, dark state color few, good contrast, excellent visibility.

Comparative example 3

Using TAC (three b acyl cellulose) stretched film (phase difference in the (Re) 137-140nm) replace the embodiment 4 (PR-4) of the stretched film, in addition, with the embodiment 5 the same on the liquid crystal television, can confirm, azimuth 45 degrees, the polar angle 60 degrees direction, dark color, contrast is low.