KR20090095638A - Resin composition and use thereof - Google Patents

Abstract

Disclosed is a resin composition which is composed of a styrene copolymer and a norbornene polymer, while having excellent compatibility and being free from phase separation. This resin composition can be easily formed into a film. Also disclosed are an optical film mainly composed of this resin composition and having excellent transparency, such an optical film further having reverse wavelength dispersion, and uses of such an optical film. Specifically disclosed is a resin composition characterized by containing a styrene copolymer (A) having a structural unit (1) represented by the formula (1) below and a structural unit (2) represented by the formula (2) below, and a norbornene polymer (B).

Description

Resin composition and its use {RESIN COMPOSITION AND USE THEREOF}

The present invention relates to a resin composition containing a styrene copolymer and a norbornene polymer and its use. Specifically, the present invention comprises a resin composition comprising a styrene copolymer and a norbornene-based polymer, having excellent transparency and suitable for the production of an optical film, a molded article and an optical film obtained from the resin composition, and this optical film. It relates to the used stretched film, polarizing plate, and liquid crystal display device.

Films, such as polycarbonate and polyester, which are conventionally used as optical films, have a large photoelastic coefficient, and thus have a problem in that retardation is expressed in transmitted light due to a slight change in stress or the like, resulting in a change in retardation. In addition, films such as triacetyl cellulose have low heat resistance and have problems such as absorption deformation.

Thermoplastic norbornene-based resins (cyclic olefin resins) have high glass transition temperature and light transmittance, and also exhibit low birefringence compared to conventional optical films due to their low anisotropy of refractive index. It is attracting attention as a transparent thermoplastic resin excellent in transparency and optical characteristics. And using these characteristics, for example, cyclic olefin resin in the field of optical materials, such as an optical lens, an optical fiber, transparent plastics base, electronic and optical materials, such as a low dielectric material, and sealing materials, such as an optical semiconductor sealing, etc. The application of this is under consideration.

The above-described properties of the cyclic olefin resin can improve the problems of the conventional resin even when viewed as a resin for an optical film. For this reason, a film containing a cyclic olefin resin has been proposed as various films for optics.

For example, Patent Documents 1 and 2 describe retardation plates using films of cyclic olefin resins. In addition, Patent Documents 3 to 5 describe using a film of cyclic olefin resin for a protective film of a polarizing plate. In addition, Patent Document 6 describes a substrate for a liquid crystal display device including a film of cyclic olefin resin.

In general, the retardation film has a function of providing retardation (birefringence) to transmitted light obtained by stretching orientation, and the characteristic that the absolute value of the retardation (birefringence) of transmitted light becomes smaller as the wavelength of transmitted light becomes longer (plus wavelength dispersion). In this case, it was very difficult to provide the transmitted light with a specific phase difference such as 1/4 wavelength in all of the visible light region (400 to 800 nm). In fact, in a wavelength range (400 to 800 nm) with a wide phase difference, a function as a quarter wavelength is required for a reflective or semi-transmissive liquid crystal display or an optical disk pickup. In addition, in the liquid crystal projector, a phase difference of 1/2 lambda is required, and in the optical film containing the conventional cyclic olefin resin, the film has to be laminated. The lamination of the film not only complicates the processes such as bonding, cutting, and bonding of the film, but also makes it difficult to reduce the thickness of the resulting optical film.

In order to solve this problem, the optical film which shows the characteristic that the absolute value of the phase difference of transmitted light becomes large as a wavelength becomes long wavelength, ie, reverse wavelength dispersion property is needed. As an optical film which shows this reverse wavelength dispersibility, in patent document 7 and patent document 8, the blend of retardation film, polycarbonate resin, and styrene resin containing specific cellulose acetate type resin is proposed. However, in the film containing the cellulose-based resin, there are problems in terms of changes in properties due to absorption, heat resistance, and the like. In the polycarbonate system, the glass transition temperature is high, and stretching at high temperatures is required. Because the photoelastic coefficient of is large, optical deformation due to stress occurs.

In addition, in the blend composition of styrene resin and cyclic cycloolefin resin, highly volatile solvents, such as methylene chloride, which have good film forming property at the time of film formation, cannot be used in most cases because phase separation occurs, and a specific solvent must be selected. . Therefore, the drying time of a solvent takes long, productivity fell extremely, and there existed a problem that it was difficult to obtain a film with high transparency easily.

For this reason, the appearance of the resin composition which can suppress phase separation and can obtain a transparent optical film easily, and the reverse film dispersibility which has the resin composition as a main component, and the optical film with high transparency was strongly desired.

Patent Document 1: Japanese Patent Application Laid-Open No. 5-2108

Patent Document 2: Japanese Patent Application Laid-Open No. 5-64865

Patent Document 3: Japanese Patent Application Laid-Open No. 5-212828

Patent Document 4: Japanese Patent Application Laid-Open No. 6-51117

Patent Document 5: Japanese Patent Application Laid-Open No. 7-77608

Patent Document 6: Japanese Patent Application Laid-Open No. 5-61026

Patent Document 7: Japanese Patent Application Laid-Open No. 2000-137116

Patent Document 8: Japanese Patent Application Laid-Open No. 2001-337222

[Initiation of invention]

[Problem to Solve Invention]

An object of the present invention is to provide a resin composition comprising a styrene copolymer and a norbornene-based polymer, which has excellent compatibility and is not phase separated, thereby providing a resin composition having excellent transparency and easy filming. Moreover, this invention makes it a subject to provide the optical film excellent in transparency which has this resin composition as a main component, the optical film which shows reverse wavelength dispersion, and its use.

[Means for solving the problem]

MEANS TO SOLVE THE PROBLEM This inventor earnestly examined in view of the said situation, As a result, the styrene copolymer which has a specific structural unit in a specific quantity, the resin composition containing a norbornene-type polymer, the optical film which has this resin composition as a main component, and its manufacturing method And it found that the said subject is solved by the use.

That is, this invention relates to the invention of the following [1]-[16].

[1] (A) A structural unit (1) represented by the following general formula (1) and a structural unit (2) represented by the following general formula (2), wherein the content of the structural unit (2) is 100 mol % Of Styrene copolymer of 0.1 to 50 mol%,

(B) A resin composition comprising a norbornene-based polymer.

(In formula (1) and formula (2), R represents a hydrogen atom or a methyl group, and in formula (2), R ⁰ represents a hydrogen atom; a halogen atom; an oxygen atom, a sulfur atom, a nitrogen atom, or a silicon atom). A substituted or unsubstituted hydrocarbon group having 1 to 30 carbon atoms, or a polar group).

[2] The resin composition according to [1], wherein the styrene copolymer (A) has a weight average molecular weight Mw of 30,000 to 1,000,000 measured by gel permeation chromatography (GPC).

[3] The resin composition according to [1], in which the styrene copolymer (A) has a yellowness (YI) of 10% by weight toluene solution measured using a colorimeter at 5.0 or less.

[4] After the styrene copolymer (A) polymerizes styrene and / or α-methylstyrene with the monomer (4) represented by the following general formula (4), in the structural unit derived from the monomer (4) -OR ¹⁴ group of the resin composition according to [1], characterized in that the paper obtained by a process comprising the step of converting a group -OH;

(In formula (4), R represents a hydrogen atom or a methyl group, R ⁰ represents a hydrogen atom; a halogen atom; a substituted or unsubstituted that may have a linking group containing an oxygen atom, a sulfur atom, a nitrogen atom, or a silicon atom. A hydrocarbon group having 1 to 30 carbon atoms or a polar group, and R ¹⁴ represents an acetyl group, t-butyl group, t-butoxycarbonyl group, -CH (OR ¹⁵ ) (R ¹⁶ ), or -SiR ¹⁵ ₃ group R ¹⁵ and R ¹⁶ each independently represent an alkyl group having 1 to 6 carbon atoms, and R ¹⁵ and R ¹⁶ , or R ¹⁵ may be bonded to each other to form a hetero ring having 2 to 12 carbon atoms). .

[5] The step of converting the -OR ¹⁴ group in the structural unit derived from the monomer (4) into the -OH group by the styrene copolymer (A) in the presence of an acid, and then adding a basic substance The resin composition as described in [4] obtained by the method including the process of making it react with the acid inside.

[6] The resin composition according to [1], wherein the norbornene-based polymer (B) is a (co) polymer having a structural unit derived from a monomer (6) represented by the following general formula (6).

(Wherein (6), a and b are independently 0 or 1, c and d are independently 0 to indicate a second ^{integer, R 4, R 5, R} 6, R 7, R 8, R 9 , R ¹⁰ , R ¹¹ , R ¹² , and R ¹³ each independently represent a hydrogen atom; a halogen atom; a substituted or unsubstituted carbon number that may have a linking group including an oxygen atom, a sulfur atom, a nitrogen atom, or a silicon atom A hydrocarbon group of 30 to 30; or a polar group, R ¹⁰ and R ¹¹ , or R ¹² and R ¹³ may be integrated to form a divalent hydrocarbon group, and R ¹⁰ or R ¹¹ and R ¹² or R ¹³ may be bonded to each other; Carbocycles or heterocycles (which may be monocyclic or may be condensed to form a polycyclic structure).

[7] The resin composition according to [1], in which the norbornene-based polymer (B) is a (co) polymer having a structural unit represented by the following general formula (i).

(In Formula (i), A ¹ to A ⁴ each independently represent a hydrogen atom; a halogen atom; the number of substituted or unsubstituted carbon atoms which may have a linking group including an oxygen atom, a sulfur atom, a nitrogen atom, or a silicon atom. A hydrocarbon group of 1 to 30; or a polar group, and at least one of A ¹ to A ⁴ is a group represented by-(CH ₂ ) _n COOA ⁵ (A ⁵ includes an oxygen atom, a sulfur atom, a nitrogen atom, or a silicon atom Is a substituted or unsubstituted hydrocarbon group having 1 to 30 carbon atoms, and n is 0 or an integer of 1 to 5)

[8] The norbornene-based polymer (B) has a structural unit represented by the general formula (i) as 10 to 70 mol% in 100 mol% of the total structural units of the norbornene-based polymer (B), The resin composition as described in [7].

[9] The composition ratio ((A) / (B)) of the styrene-based copolymer (A) and the norbornene-based polymer (B) is in the range of 5/95 to 70/30 by weight ratio, [ The resin composition as described in 1].

[10] A molded article comprising the resin composition according to [1] as a main component.

[11] The molded article according to [10], which is obtained by melt extrusion molding.

[12] An optical film containing the resin composition according to [1] as a main component.

[13] The optical film according to [12], which is obtained by forming a film by a casting method.

[14] The optical film according to [12], which is obtained by forming a film by an extrusion method.

[15] A stretched film obtained by heating and stretching the optical film according to [12].

[16] A polarizing plate comprising the optical film according to [12].

[17] A liquid crystal display device comprising the optical film according to [12].

[Effects of the Invention]

According to the present invention, even if a solvent such as methylene chloride used in film forming is used, phase separation can be suppressed, and thus it is preferable for optical film applications, and an optical film having excellent reverse wavelength dispersion and excellent transparency can be easily produced. A resin composition can be provided.

Moreover, according to this invention, by adjusting the content rate of each structural unit of the styrene-type copolymer contained in a resin composition, it shows the favorable compatibility also at the time of heating, and is excellent in the film composition which can maintain transparency even at high temperature. Can be provided.

Moreover, according to this invention, the resin composition which shows low birefringence can be provided by adjusting the composition ratio of a styrene-type copolymer and a norbornene-type polymer.

Moreover, the optical film obtained from the resin composition of this invention is useful also as a stretched film, the polarizing plate using the said stretched film, a liquid crystal display device, and an optical component.

1 shows the IR spectrum of the styrene polymer (1A) obtained in Synthesis Example 1. FIG.

2 shows the ¹³ C-NMR spectrum of the styrenic polymer (1A) obtained in Synthesis Example 1. FIG.

3 shows the IR spectrum of the styrenic polymer (4A) obtained in Synthesis Example 4. FIG.

4 shows the ¹³ C-NMR spectrum of the styrenic polymer (4A) obtained in Synthesis Example 4. FIG.

5 shows the IR spectrum of the styrenic polymer (5A) obtained in Synthesis Example 5. FIG.

FIG. 6 shows a ¹³ C-NMR spectrum of a styrenic polymer (5A) obtained in Synthesis Example 5. FIG.

7 shows a chart in a Tg measurement of the blend resin obtained in Example 10. FIG.

8 shows a chart in a Tg measurement of the blend resin obtained in Example 11. FIG.

Best Mode for Carrying Out the Invention

The resin composition according to the present invention contains a styrene copolymer (A) and a norbornene polymer (B). Hereinafter, these are demonstrated.

In addition, in this specification, a (co) polymer means a polymer or a copolymer.

<Styrene-based copolymer (A)>

The styrene-based copolymer (A) contained in the resin composition according to the present invention has a structural unit (1) represented by the following general formula (1) and a structural unit (2) represented by the following general formula (2).

In formula (1) and formula (2), R represents a hydrogen atom or a methyl group. In formula (2), R ⁰ is a hydrogen atom; Halogen atom; Substituted or unsubstituted C1-C30 hydrocarbon group which may have a coupling group containing an oxygen atom, a sulfur atom, a nitrogen atom, or a silicon atom; Or a polar group.

The content rate of the structural unit (2) is usually 0.1 to 50 mol%, preferably 0.2 to 40 mol%, and more preferably 1 to 20 mol% in 100 mol% of the total structural units. If it is in the said numerical range, both the styrene-type copolymer (A) and the norbornene-type polymer (B) which are contained in the resin composition which concerns on this invention exist in addition to the solvent which shows favorable solubility, and also phase-separates even at high temperature. Since transparency can be maintained, it is preferable.

In addition, the styrenic copolymer (A) may have a structural unit (3) represented by the following general formula (3).

In formula (3), R <^1> -R <^3> is respectively independently a hydrogen atom; Halogen atom; A substituted or unsubstituted hydrocarbon group having 1 to 30 carbon atoms which may have a linking group containing an oxygen atom, a sulfur atom, a nitrogen atom or a silicon atom; Or a polar group. In addition, R ¹ and R ² may be bonded to each other to form a carbocyclic ring or a heterocycle (these carbocyclic rings or heterocycles may have a monocyclic structure or other rings may condense to form a polycyclic structure).

In the formulas (1) to (3), examples of the halogen atom include a fluorine atom, a chlorine atom and a bromine atom.

As a hydrocarbon group of 1-30 carbon atoms, For example, Alkyl groups, such as a methyl group, an ethyl group, and a propyl group; Cycloalkyl groups such as cyclopentyl group and cyclohexyl group; Alkenyl groups, such as a vinyl group, an allyl group, and a propenyl group, etc. are mentioned.

In addition, the above-mentioned substituted or unsubstituted hydrocarbon group may be directly bonded to the ring structure, or may be bonded via a linkage. As the linking group, for example, a divalent hydrocarbon group having 1 to 10 carbon atoms (for example, an alkylene group represented by-(CH ₂ ) _m- (wherein m is an integer of 1 to 10)); Linking groups containing oxygen, nitrogen, sulfur or silicon (e.g., carbonyl group (-CO-), oxycarbonyl group (-0 (CO)-), carbonyloxy group (-CO0-), sulfone group (-SO ₂ -, Ether bond (-0-), thioether bond (-S-), imino group (-NH-), amide bond (-NHCO-, -CONH-), siloxane bond (-OSi (R)-( In formula, R is alkyl groups, such as methyl and ethyl)))), etc. are mentioned, The coupling group containing two or more may be sufficient.

Examples of the polar group include a hydroxyl group, an alkoxy group having 1 to 10 carbon atoms, a carbonyloxy group, an alkoxycarbonyl group, an aryloxycarbonyl group, a cyano group, an amide group, an imide group, a triorganosiloxy group, and triorganosilyl A group, an amino group, an acyl group, an alkoxy silyl group, a sulfonyl group, a carboxyl group, etc. are mentioned. More specifically, as said alkoxy group, For example, a methoxy group, an ethoxy group, etc .; As a carbonyloxy group, For example, Alkylcarbonyloxy groups, such as an acetoxy group and a propionyloxy group, and arylcarbonyloxy groups, such as a benzoyloxy group; As an alkoxycarbonyl group, For example, a methoxycarbonyl group, an ethoxycarbonyl group, etc .; As an aryloxycarbonyl group, For example, a phenoxycarbonyl group, a naphthyloxycarbonyl group, a fluorenyloxycarbonyl group, a biphenylyloxycarbonyl group, etc .; As a triorgano siloxy group, For example, a trimethyl siloxy group, a triethyl siloxy group, etc .; Examples of the triorganosilyl group include trimethylsilyl group and triethylsilyl group; As an amino group, Primary amino group; As an alkoxy silyl group, a trimethoxy silyl group, a triethoxy silyl group, etc. are mentioned, for example.

As a specific example of the monomer which derives the structural unit represented by General formula (3), (meth) acrylamide, (meth) acrylic acid and its derivative (s), maleic anhydride, maleimide, maleic acid and its derivative (s), fumaric acid and its derivative (s), p-methoxy styrene etc. are mentioned. Moreover, the styrene monomer represented by Formula (4), etc. are contained in the said monomer, such as the case where the structural unit derived from the styrene derivative represented by Formula (4) remains partially, without being converted into the deprotection reaction mentioned later. The content rate of the structural unit (3) is usually 20 mol% or less, preferably 15 mol% or less, and more preferably 10 mol% or less in 100 mol% of all the structural units.

As for the styrene copolymer (A) used for this invention, it is preferable that the logarithmic viscosity ((eta)) measured in 30 degreeC chlorobenzene solution (concentration 0.5 g / dL) is 0.1-3.0 dL / g. In addition, the weight average molecular weight Mw of polystyrene conversion measured by gel permeation chromatography (GPC) is usually 30,000 to 1,000,000, preferably 40,000 to 800,000, and more preferably 50,000 to 500,000. When molecular weight is too small, the strength of molded articles, such as a film obtained, may fall. When molecular weight is too big, solution viscosity may become high too much and productivity and workability of the resin composition used for this invention may deteriorate.

In addition, the molecular weight distribution (Mw / Mn) of the styrenic copolymer (A) is usually 1.0 to 10, preferably 1.2 to 5.0, and more preferably 1.2 to 4.0.

Moreover, as a styrene-type copolymer (A), what has little coloring, such as yellowing, and is excellent in transparency is preferable. Specifically, the yellowness (YI) of the 10% by weight toluene solution measured using a colorimeter is preferably 5.0 or less, more preferably 4.0 or less, and still more preferably 0.05 to 3.0. . In addition, the yellowness is usually colorless at 0.2.

[Method for producing styrene copolymer (A)]

The styrenic copolymer (A) used in the present invention may be obtained by directly copolymerizing styrene and / or α-methylstyrene and vinylphenols in which R ¹⁴ of the monomer (4) represented by the following general formula (4) is substituted with a hydrogen atom. There is a polymerization reaction between styrene and / or α-methylstyrene, the monomer (4) represented by the following general formula (4) and the monomer represented by the following general formula (5), if necessary, in the presence of a suitable polymerization initiator, a group -OR ¹⁴ in the structural unit of the monomer (4) derived may be prepared by a process comprising the step of converting a group -OH. It is preferable to use a radical polymerization initiator, an anionic polymerization catalyst, a coordination polymerization catalyst, a cationic polymerization catalyst, etc. as a polymerization initiator, and it is especially preferable to use a radical polymerization initiator.

In formula (4), R and R ⁰ have the same meaning as in formula (2). R ¹⁴ represents any of a group represented by an acetyl group, t-butyl group, t-butoxycarbonyl group, -CH (OR ¹⁵ ) (R ¹⁶ ), or -SiR ¹⁵ ₃ . R ¹⁵ and R ¹⁶ each independently represent an alkyl group having 1 to 6 carbon atoms, and R ¹⁵ and R ¹⁶ or R ¹⁵ may be bonded to each other to form a hetero ring having 2 to 12 carbon atoms.

As R and R ^{0, a} hydrogen atom is preferable. As R <^14> , an acetyl group and t-butyl group are especially preferable.

Further, the styrene and / or α-methylstyrene is preferably styrene only.

In the formula (5), R ¹ to R ³ is the same meaning as R ¹ to R ³ in the general formula (3).

In addition, the styrene-based copolymer (A) according to the present invention may be a styrene and / or α-methylstyrene, a monomer (4 ') represented by the following general formula (4'), and, if necessary, the general formula (5) It can manufacture suitably also by the process of copolymerizing the monomer shown. In this case, the styrene copolymer (A) used by this invention can be manufactured, without going through the conversion reaction process to -OH group mentioned later.

(In formula (4 '), R and R <^0> are the same as the definition in the said General formula (2).)

Each of these monomers can be preferably used in the same ratio as the desired content rate of each structural unit derived from each monomer.

<polymerization>

As a radical initiator used for a polymerization reaction, the well-known organic peroxide which generate | occur | produces a free radical, or an azobis type radical polymerization initiator can be used. Moreover, since the linearity of the styrene-type copolymer obtained may fall, the polyfunctional initiator or the initiator which is easy to produce a hydrogen release reaction is not preferable.

Examples of the organic peroxide include diacetyl peroxide, dibenzoyl peroxide, diisobutyroyl peroxide, di (2,4-dichlorobenzoyl) peroxide, di (3,5,5-trimethylhexanoyl) peroxide and diocta Diacyl peroxides such as noyl peroxide, dilauroyl peroxide, distearoyl peroxide, and bis {4- (m-toluyl) benzoyl} peroxide;

Ketone peroxides such as methyl ethyl ketone peroxide, cyclohexanone peroxide, methylcyclohexanone peroxide and acetylacetone peroxide;

Hydrogen peroxide, t-butylhydroperoxide, α-cumene hydroperoxide, p-mentane hydroperoxide, diisopropylbenzenehydroperoxide, 1,1,3,3-tetramethylbutylhydroperoxide, t-hexylhydro Hydroperoxides such as loperoxide;

Di-t-butylperoxide, dicumylperoxide, dilaurylperoxide, α, α'-bis (t-butylperoxy) diisopropylbenzene, 2,5-dimethyl-2,5-bis (t-butyl Dialkyl peroxides such as peroxy) hexane, t-butyl cumyl peroxide, 2,5-dimethyl-2,5-bis (t-butylperoxy) hexine-3;

t-butylperoxy acetate, t-butylperoxy pivalate, t-hexyl peroxy pivalate, 1,1,3,3-tetramethylbutylperoxy-2-ethylhexanoate, 2,5-dimethyl- 2,5-bis (2-ethylhexanoylperoxy) hexane, 1-cyclohexyl-1-methylethylperoxy-2-ethylhexanoate, t-hexylperoxy-2-ethylhexanoate, t- Butylperoxy-2-ethylhexanoate, t-butylperoxyisobutyrate, t-butylperoxymaleate, t-butylperoxy-3,5,5-trimethylhexanoate, t-butylperoxylau Late, 2,5-dimethyl-2,5-bis (m-toluoylperoxy) hexane, α, α'-bis (neodecanoylperoxy) diisopropylbenzene, cumylperoxy neodecanoate, 1 , 1,3,3-tetramethylbutylperoxy neodecanoate, 1-cyclohexyl-1-methylethylperoxy neodecanoate, t-hexyl peroxy neodecanoate, t-butylperoxy neodode Decanoate, t-butylperoxybenzoate, t-hexylperoxybene Ate, bis (t-butylperoxy) isophthalate, 2,5-dimethyl-2,5-bis (benzoylperoxy) hexane, t-butylperoxy-m-toluoylbenzoate, 3,3 ', 4 Peroxy esters such as 4′-tetra (t-butylperoxycarbonyl) benzophenone;

1,1-bis (t-hexylperoxy) 3,3,5-trimethylcyclohexane, 1,1-bis (t-hexylperoxy) cyclohexane, 1,1-bis (t-butylperoxy) 3 , 3,5-trimethylcyclohexane, 1,1-bis (t-butylperoxy) cyclohexane, 1,1-bis (t-butylperoxy) cyclododecane, 2,2-bis (t-butylper Peroxy ketals such as oxy) butane, n-butyl-4,4-bis (t-butylperoxy) pivalate and 2,2-bis (4,4-di-t-butylperoxycyclohexyl) propane ;

t-hexyl peroxy isopropyl monocarbonate, t-butyl peroxy isopropyl monocarbonate, t-butyl peroxy-2-ethylhexyl monocarbonate, t-butyl peroxy allyl monocarbonate, etc. Peroxy monocarbonates;

Di-sec-butylperoxydicarbonate, di-n-propylperoxydicarbonate, diisopropylperoxydicarbonate, bis (4-t-butylcyclohexyl) peroxydicarbonate, di-2 -Ethoxyethylperoxydicarbonate, di-2-ethylhexylperoxydicarbonate, di-2-methoxybutylperoxydicarbonate, di (3-methyl-3-methoxybutyl) peroxydica Peroxydicarbonates such as carbonate;

Although t-butyl trimethylsilyl peroxide etc. are mentioned, The organic peroxide used for this invention is not limited to these exemplary compounds.

Examples of azo radical polymerization initiators include azobisisobutyronitrile, azobisisovaleronitrile, 2,2'-azobis (4-methoxy-2,4-dimethylvaleronitrile), and 2,2'-azo. Bis (2,4-dimethylvaleronitrile), 2,2'-azobis (2-methylbutyronitrile), 1,1'-azobis (cyclohexane-1-carbonitrile), 2- (carba Moyl azo) isobutyronitrile, 2,2'-azobis [2-methyl-N- {1,1-bis (hydroxymethyl) -2-hydroxyethyl} propionamide], 2,2'-azo Bis [2-methyl-N- {2- (1-hydroxybutyl)} propionamide], 2,2'-azobis [2-methyl-N- (2-hydroxyethyl) -propionamide], 2 , 2'-azobis [N- (2-propenyl) -2-methylpropionamide], 2,2'-azobis (N-butyl-2-methylpropionamide), 2,2'-azobis (N-cyclohexyl-2-methylpropionamide), 2,2'-azobis [2- (5-methyl-2-imidazolin-2-yl) propane] dihydrochloride, 2,2'-azo Bis [2- (2-imidazolin-2-yl) pro ] Dihydrochloride, 2,2'-azobis [2- (2-imidazolin-2-yl) propane] disulfate dihydrate, 2,2'-azobis [2- (3,4,5] , 6-tetrahydropyrimidin-2-yl) propane] dihydrochloride, 2,2'-azobis [2- {1- (2-hydroxyethyl) -2-imidazolin-2-yl} propane ] Dihydrochloride, 2,2'-azobis [2- (2-imidazolin-2-yl) propane], 2,2'-azobis (2-methylpropionamidine) dihydrochloride, 2, 2'-azobis [N- (2-carboxyethyl) -2-methyl-propionamidine], 2,2'-azobis (2-methylpropionamide oxime), dimethyl-2,2'-azobisbutyrate , 4,4'-azobis (4-cyanopentanoic acid), 2,2'-azobis (2,4,4-trimethylpentane), and the like. Preferred initiators include 1,1'-azobis ( Cyclohexane-1-carbonitrile), 2- (carbamoylazo) isobutyronitrile, 2,2'-azobis (N-butyl-2-methylpropionamide), having a weight average molecular weight of 850 A styrene copolymer of a high molecular weight body of 00 or more is obtained. The azobis type radical polymerization initiator used for this invention is not limited to these exemplary compounds.

Examples of cationic polymerization initiators include brested acids such as hydrochloric acid, sulfuric acid, p-toluenesulfonic acid and phosphoric acid, boron trifluoride complexes, aluminum trichloride, ethyl aluminum dichloride, titanium tetrachloride, titanium tetraisopropoxide and tungsten chloride. Mountain.

As an anionic polymerization initiator, organic lithiums, such as butyl lithium and phenyl lithium, metal amides, such as lithium amide and sodium amide, Grignard reagent, such as ethyl magnesium bromide, and phenyl magnesium chloride, sodium methoxide, sodium ethoxide, etc. And metal alkoxides.

The use amount of these polymerization initiators is usually 0.01 to 5 mol%, preferably 0.03 to 3 mol%, more preferably 0.05 to 2 mol% in 100 mol% of the total monomers.

In addition, a catalyst may be used in the polymerization reaction of the styrene monomer. This catalyst is not specifically limited, For example, a well-known anionic polymerization catalyst, a coordination polymerization catalyst, a cationic polymerization catalyst, etc. are mentioned.

The polymerization reaction of the styrene monomers is conventionally performed in the presence of the polymerization initiator or catalyst, such as bulk polymerization, solution polymerization, precipitation polymerization, emulsion polymerization, suspension polymerization or bulk-suspension polymerization. It is performed by copolymerizing by a well-known method.

Although it will not specifically limit, if it melt | dissolves the said monomer and polymer as a solvent used at the time of performing solution polymerization, A hydrocarbon solvent, such as cyclohexane, and aromatic hydrocarbon solvents, such as toluene, are preferable. It is preferable that the usage-amount of a solvent is an amount of 0 to 3 times (weight ratio) with respect to the said styrene-based monomer whole quantity. When using radical polymerization, a chain transfer agent can also be added as needed in order to obtain the polymer which has a desired molecular weight. As a chain transfer agent, a conventionally well-known chain transfer agent can be used without a restriction | limiting, More specifically, the following can be enumerated. Dodecanethiol, mercaptoethanol, mercaptopropanol, mercaptoacetic acid, mercaptopropionic acid, and the like. These chain transfer agents may be used independently, or may mix and use multiple types.

The polymerization reaction time is usually 1 to 30 hours, preferably 3 to 20 hours, and the polymerization reaction temperature is not particularly limited because it depends on the type of radical initiator to be used, but is usually 40 to 180 ° C, preferably 50 to 120 ℃.

<Conversion reaction to OH group>

The styrene-based copolymer (A) used in the present invention can be obtained by polymerizing the styrene-based monomer, and then further converting the -OR ¹⁴ group in the structural unit derived from the monomer (4) to the -OH group. Thus, for example, R ¹⁴ of the styrene monomer represented by the formula (4) is released to form the structural unit represented by the formula (2) contained in the styrene copolymer (A).

As the conversion reaction, a method of converting to alcoholic or hydrolysis in the presence of an acid or a base, a method of heating and converting under acidic conditions, a method of converting by heating only, a method of converting using fluoride ions, and the like Although the preferable method which can be employ | adopted according to the structure of R <^14> in the said OR <^14> group differs from each other, in the presence of an acid, the group represented by -OR <^14> from the structural unit derived from monomer (4) is -OH group It is preferable to convert, and the method of converting into an alcoholic decomposition or hydrolysis in the presence of an acid, or the method of converting by heating under acidic conditions is preferably employed.

R ¹⁴ in the —OR ¹⁴ group may be bonded to an acetyl group (-COCH ₃ ), t-butoxycarbonyl group (-COO ^t Bu), silyl group (SiR ¹⁵ ₃ ), and an oxygen atom to form an acetal group In the case of the alkoxyalkyl group (-CH (OR ¹⁵ ) (R ¹⁶ )) which can be used, the method of hydrolyzing or an alcoholic decomposition under acidic conditions is employ | adopted preferably.

In the case where R ¹⁴ in the —OR ¹⁴ group is, for example, an acetyl group (-COCH ₃ ), a t-butoxycarbonyl group (-COO ^t Bu), or the like, a method of hydrolyzing or alcoholic decomposition under basic conditions is preferable. Is adopted.

As R <^14> in the said -OR <^14> group to which the method of heating and converting under acidic conditions or the method of converting only by heating is applicable, it is a t-butyl group ( ^-t Bu) and t-butoxy, for example. group (-COO ^t Bu) may be mentioned, can be given as R ¹⁴ that can be applied to a method for conversion using the fluoride ion silyl group (SiR ¹⁵ _3).

`` Hydrolysis and Alcohol Decomposition ''

Examples of the acid used for hydrolysis and dialcohol decomposition include carboxylic acids such as hydrogen halides such as hydrochloric acid and bromic acid, formic acid, oxalic acid, acetic acid and trifluoroacetic acid, sulfuric acid, p-toluenesulfonic acid, benzenesulfonic acid, methanesulfonic acid, Sulfonic acids such as trifluoromethanesulfonic acid, bronsted acids such as nitric acid, or phenols, heteropoly acids such as phosphotungstic acid, phosphomolybdic acid, solid acids such as zirconia sulfate, zeolite, ion exchange resin, polymer electrolyte, etc. And high molecular acids, and Lewis acids such as halogenated, alkylated and / or alkoxylated aluminum, titanium, tungsten, or boron compounds, and known immobilized Lewis acids. Among these acids, sulfuric acid is particularly preferably used. The amount of acid used is styrene monomer of the molar ratio with the amount of styrene monomer represented by the general formula (4), which is usually represented by acid / chemical formula (4) = 1/1000 to 1/1, preferably 1/300 to 1 / 5.

Examples of the base include potassium hydroxide, sodium hydroxide, lithium hydroxide, ammonium hydroxide, tetramethylammonium hydroxide, tetrabutylammonium hydroxide and the like. The usage-amount of a base requires the number-of-moles more than the number-of-moles of the styrene-type monomer represented by General formula (4), and the styrene type whose molar ratio with the usage-amount of the styrene-type monomer represented by general formula (4) is represented by base / chemical formula (4) Monomer = 1/1 to 5/1. In addition, it is necessary to neutralize with an acid after hydrolysis or after alcoholic decomposition. As an acid used for neutralization, the same acid as the said acid can be used. In the case of using a water-soluble base such as a metal hydroxide such as potassium hydroxide, sodium hydroxide, lithium hydroxide, or the like as a base, as a correlation transfer catalyst, quaternary ammonium salts, quaternary phosphonium salts, crown ethers, poly (oligo) ethylene Glycol etc. can also be used.

As reaction temperature, it is 0-180 degreeC normally, Preferably it is 30-150 degreeC, More preferably, it is 40-120 degreeC. As reaction time, it is 1 to 30 hours normally, Preferably it is 1 to 25 hours, More preferably, it is 1 to 20 hours. The reaction solvent is not particularly limited as long as the polymer before the conversion reaction and the polymer after the conversion reaction are dissolved, but is preferably the same solvent as the polymerization reaction. Moreover, as a usage-amount of a solvent, it is preferable that it is 1 to 5 times the weight of a solvent used for a polymerization reaction, and it is more preferable that it is 1 to 3 times the weight. As the addition amount of water or alcohol, preferably 1 to 30 moles per mole of the -OR ¹⁴ group, and more preferably from 1 to 20 moles per mole. The alcohol to be used is not particularly limited, but an alcohol having 1 to 4 carbon atoms is preferable.

`` Heating conversion reaction under acidic conditions ''

The same conditions as those exemplified in the above-mentioned `` hydrolysis and alcoholic decomposition '' can be applied to the acid and its addition amount, the reaction temperature, the reaction time, the solvent species, and the amount of solvent used for the heat conversion reaction under acidic conditions. . However, in this method, water or alcohol may or may not be added.

`` Neutralization after Conversion Reaction ''

In the production of the styrenic copolymer (A) used in the present invention, when the conversion reaction for converting the -OR ¹⁴ group to the OH group is performed using an acid or a base, at least the acid or base remaining in the system after the conversion reaction It may have a process of neutralizing a part with a base or an acid.

In the production of styrene-based copolymer (A), the case where the conversion reaction for converting -OR ¹⁴ groups -OH group in the structural unit of the monomer (4) derived in the presence of an acid is then added to a basic substance, It is preferable to carry out the step of reacting with the acid in the system. In addition, when a conversion reaction is performed in presence of a base, it is preferable to perform the process of adding an acidic substance next and making it react with the base in a system.

Or less, it performs the conversion reaction to convert -OR ¹⁴ groups -OH group in the structural unit of the monomer (4) derived in the presence of an acid, and subsequently described with respect to the case of the addition of a basic material, reacts with the acid in the system. Here, the acid in the system means an acid remaining in the system without being consumed in the conversion reaction among the acids used in the conversion reaction for converting the -OR ¹⁴ group to the -OH group.

As the basic substance, metal hydroxides, metal alkoxides, carboxylates, phenol salts, carbonates, amines and the like are preferably used. More preferably, the basic substances are metal hydroxides, metal alkoxides, carboxylates, As one or more types chosen from the group which consists of phenol salts, the large cation is any one of lithium, sodium, potassium, and calcium. These basic substances may be used alone or in combination of two or more thereof.

Specific examples of such a basic substance include metal hydroxides such as sodium hydroxide, potassium hydroxide, lithium hydroxide and calcium hydroxide; Metal alkoxides such as sodium methoxide, sodium ethoxide and sodium t-butoxide; Carboxylates such as sodium acetate, sodium propionate, sodium lactate, sodium 2-ethylhexanoate and sodium benzoate; Phenol salts such as sodium phenoxide; Carbonates, such as sodium carbonate, potassium carbonate, and sodium hydrogencarbonate, amines, such as a triethylamine and a pyridine, can be used. Any of these bases may be used alone or in combination of a plurality thereof. In terms of availability and price, sodium hydroxide, potassium hydroxide, lithium hydroxide, sodium methoxide, sodium acetate, sodium lactate, sodium benzoate, sodium carbonate and potassium carbonate This is preferred. Among them, sodium acetate, sodium lactate, sodium benzoate, sodium carbonate, potassium carbonate and the like are particularly preferable since the OH group is stably maintained even if the step of adding a weakly acidic substance described later is not performed.

The reaction temperature of the basic substance and the remaining acid is 15 to 100 ° C, preferably 20 to 90 ° C, more preferably 30 to 80 ° C. When the said reaction temperature range is exceeded, the color of a polymer may deteriorate. Moreover, reaction may not fully advance as it is less than the said reaction temperature range.

The reaction time is 5 to 120 minutes, preferably 10 to 100 minutes, more preferably 15 to 80 minutes. If it exceeds the said reaction time range, productivity will fall, and if it is less than the said reaction time range, reaction may not fully advance.

The amount of the basic substance to be added may be an amount in which the remaining acid is sufficiently neutralized, but the product A of the number of moles of acid used in the step of converting the group represented by -OR ¹⁴ to the -OH group, the valence of the acid, and the basic substance to be added It is preferable that the product B of the number of moles of and the valence of its base satisfies the following formula.

A≤B≤ [A × 3]

In addition, when the acidity of the conjugate acid is lower than the acidity of the phenol moiety contained in the polymer among the above-described basic substances, the -OH group converted from -OR ¹⁴ group in the structural unit derived from monomer (4) becomes unstable. Since there is a concern, it is preferable to add a weakly acidic substance having a higher acidity than the phenol moiety contained in the polymer at the same time or after using the base to make the reaction system weakly acidic. Examples of such weakly acidic substances include phenols such as phenol, nitrophenol, cyanophenol, and halogenated phenol; Carboxylic acids such as acetic acid, propionic acid, lactic acid, 2-ethylhexanoic acid and benzoic acid; Carbonic acid is mentioned, and acetic acid, lactic acid and benzoic acid are preferable from the price and compatibility with the reaction solution.

As reaction conditions, the same conditions as the reaction conditions when the base is added can be applied.

By making the inside of the reaction system weakly acidic, a styrene copolymer (A) having better color and excellent heat stability can be obtained.

≪Conversion reaction only by heating≫

In the case where R ¹⁴ in the OR ¹⁴ group represented by the formula (4) can be released by only thermal energy, the styrene copolymer (A) is thermally decomposed under a temperature condition that does not significantly exceed the temperature at which the polymer chain is decomposed. ) Can be obtained. This temperature is usually 100 to 350 ° C, preferably 120 to 300 ° C.

`` Conversion reaction using fluoride ions ''

As a reagent which can be used for the conversion reaction using a fluoride ion, tetramethylammonium fluoride, tetrabutylammonium fluoride, potassium fluoride, sodium fluoride, hydrogen fluoride, etc. are mentioned. As the amount of fluoride ions used, the molar ratio between the amount of fluoride ions and the amount of styrene monomer represented by the general formula (4) (a fluoride ion / styrene monomer represented by the formula (4)) is usually 1/1 to 5/1. , Preferably from 1/1 to 3/1.

<Tablet>

A styrene-type copolymer (A) is obtained by refine | purifying after the said conversion reaction. For purification, a conventionally known method can be used. For example, after diluting the obtained reactant solution with a good solvent such as toluene or tetrahydrofuran, methanol, water, or a mixed solution thereof is added, and the polymer is appropriately aggregated. The extraction process is mentioned. At the time of extraction treatment, the weight ratio (good solvent / polymer) of the good solvent amount and the polymer, which is the sum of the solvent used as the reaction solvent and the solvent added for dilution, is 0.5 / 1 to 6/1, preferably 0.7 / 1 to 4/1. The amount of the poor solvent such as methanol, water, or a mixed solution thereof used for extraction is 0.3 to 5, preferably 0.5 to 3, by weight ratio (poor solvent / good solvent). As extraction temperature, it is 40-120 degreeC normally, Preferably it is 50-100 degreeC.

After extraction as described above, the solution is cooled to separate the light and heavy layers, and the light layer is removed using a centrifuge or the like. After repeating these extraction operations 1 to 10 times, the heavy liquid is concentrated and deaerated by a desorber such as a divorati writer or a luther. The temperature at the time of desorption is 150-350 degreeC, Preferably it is 200-350 degreeC, and a vacuum degree is 0.1-50 mmHg, Preferably it is 1-40 mmHg. Moreover, it can also dilute before filtration and perform circulating filtration. In the case of a filtration, the pore size of a filter agent may be used individually by 1 type, and multiple filters with different pore sizes may be provided in steps. Moreover, it can also refine | purify by filtering the molten polymer after demolition. It is preferable that the pore size of the polymer filter at this time is 0.1-100 micrometers.

<Norbornene-based polymer (B)>

The norbornene-based polymer (B) contained in the resin composition according to the present invention is a (co) polymer having a structural unit derived from monomer (6) represented by the following general formula (6), and specifically, monomer (6) Ring-opening polymer of a monomer, a ring-opening copolymer of a monomer (6) with a copolymerizable monomer, or a hydrogenated substance thereof, or an addition (co) polymer comprising one or more monomers (6), and a monomer (6) And a vinyl compound-based addition type (co) polymer.

(Formula (6) of, a, and b are independently 0 or 1, c and d represents an integer of 0 to 2 ^{independently, R 4, R 5, R} 6, R 7, R 8, R ⁹ , R ¹⁰ , R ¹¹ , R ¹² , and R ¹³ each independently represent a hydrogen atom; a halogen atom; a substituted or unsubstituted carbon number that may have a linking group including an oxygen atom, a sulfur atom, a nitrogen atom, or a silicon atom Or a polar group, R ¹⁰ and R ¹¹ , or R ¹² and R ¹³ may be integrated to form a divalent hydrocarbon group, and R ¹⁰ or R ¹¹ and R ¹² or R ¹³ may be bonded to each other. To form a carbocyclic ring or heterocycle (these carbocycles or heterocycles may be monocyclic, or other rings may condense to form a polycyclic structure).

Examples of the halogen atom include a fluorine atom, a chlorine atom and a bromine atom.

As a hydrocarbon group of 1-30 carbon atoms, For example, Alkyl groups, such as a methyl group, an ethyl group, and a propyl group; Cycloalkyl groups such as cyclopentyl group and cyclohexyl group; Alkenyl groups, such as a vinyl group, an allyl group, and a propenyl group, etc. are mentioned.

In addition, the above-mentioned substituted or unsubstituted hydrocarbon group may be directly bonded to the ring structure, or may be bonded via a linking group. As the linking group, for example, a divalent hydrocarbon group having 1 to 10 carbon atoms (for example, an alkylene group represented by-(CH ₂ ) _m- (wherein m is an integer of 1 to 10)); Linking groups containing oxygen, nitrogen, sulfur or silicon (e.g., carbonyl group (-CO-), oxycarbonyl group (-0 (CO)-), carbonyloxy group (-CO0-), sulfone group (-SO ₂ -, Ether bond (-0-), thioether bond (-S-), imino group (-NH-), amide bond (-NHCO-, -CONH-), siloxane bond (-OSi (R)-( In formula, R is alkyl groups, such as methyl and ethyl)), etc. are mentioned, A coupling group containing two or more may be sufficient.

Examples of the polar group include a hydroxyl group, an alkoxy group having 1 to 10 carbon atoms, a carbonyloxy group, an alkoxycarbonyl group, an aryloxycarbonyl group, a cyano group, an amide group, an imide group, a triorganosiloxy group, and triorganosilyl A group, an amino group, an acyl group, an alkoxy silyl group, a sulfonyl group, a carboxyl group, etc. are mentioned. More specifically, as said alkoxy group, For example, a methoxy group, an ethoxy group, etc .; As a carbonyloxy group, For example, Alkylcarbonyloxy groups, such as an acetoxy group and a propionyloxy group, and arylcarbonyloxy groups, such as a benzoyloxy group; As an alkoxycarbonyl group, For example, a methoxycarbonyl group, an ethoxycarbonyl group, etc .; As an aryloxycarbonyl group, For example, a phenoxycarbonyl group, a naphthyloxycarbonyl group, a fluorenyloxycarbonyl group, a biphenylyloxycarbonyl group, etc .; As a triorgano siloxy group, For example, a trimethyl siloxy group, a triethyl siloxy group, etc .; Examples of the triorganosilyl group include trimethylsilyl group and triethylsilyl group; As an amino group, Primary amino group; As an alkoxy silyl group, a trimethoxy silyl group, a triethoxy silyl group, etc. are mentioned, for example.

As a specific example of the monomer (6) represented by the said General formula (6), the following compounds are mentioned.

Bicyclo [2.2.1] hept-2-ene,

Tricyclo [4.3.0.1 ^2,5 ] -3-decene,

Tricyclo [5.2.1.0 ^2,6 ] -deca-3,8-diene,

Tricyclo [4.4.0.1 ^2,5 ] -3-undecene,

Tetracyclo [4.4.0.1 ^2,5 .1 ^7,10 ] -3-dodecene,

^Pentacyclo [6.5.1.1 ^{3,6 2,7} .0 ^9,13 ] -4- ^pentadecene ,

Pentacyclo [7.4.0.1 ^2,5 .1 ^9,12 .0 ^8,13 ] -3- ^pentadecene ,

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

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

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

5-methyl-5-methoxycarbonylbicyclo [2.2.1] hept-2-ene,

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

8-methoxycarbonyltetracyclo [4.4.0.1 ^2,5 .1 ^7,10 ] -3-dodecene,

8-ethoxycarbonyltetracyclo [4.4.0.1 ^2,5 .1 ^7,10 ] -3-dodecene,

8-n-propoxycarbonyltetracyclo [4.4.0.1 ^2,5 .1 ^7,10 ] -3-dodecene,

8-isopropoxycarbonyltetracyclo [4.4.0.1 ^2,5 .1 ^7,10 ] -3-dodecene,

8-n-butoxycarbonyltetracyclo [4.4.0.1 ^2,5 .1 ^7,10 ] -3-dodecene,

8-phenoxycarbonyltetracyclo [4.4.0.1 ^2,5 .1 ^7,10 ] -3-dodecene,

8- (1-naphthoxy) carbonyltetracyclo [4.4.0.1 ^2,5 .1 ^7,10 ] -3-dodecene,

8- (2-naphthoxy) carbonyltetracyclo [4.4.0.1 ^2,5 .1 ^7,10 ] -3-dodecene,

8- <4-phenylphenoxy> carbonyltetracyclo [4.4.0.1 ^2,5 .1 ^7,10 ] -3-dodecene,

8-methyl-8-methoxycarbonyltetracyclo [4.4.0.1 ^2,5 .1 ^7,10 ] -3-dodecene,

8-methyl-8-ethoxycarbonyltetracyclo [4.4.0.1 ^2,5 .1 ^7,10 ] -3-dodecene,

8-methyl-8-n-propoxycarbonyltetracyclo [4.4.0.1 ^2,5 .1 ^7,10 ] -3-dodecene,

8-methyl-8-isopropoxycarbonyltetracyclo [4.4.0.1 ^2,5 .1 ^7,10 ] -3-dodecene,

8-methyl-8-n-butoxycarbonyltetracyclo [4.4.0.1 ^2,5 .1 ^7,10 ] -3-dodecene,

8-methyl-8-phenoxycarbonyltetracyclo [4.4.0.1 ^2,5 .1 ^7,10 ] -3-dodecene,

8-methyl-8- (1-naphthoxy) carbonyltetracyclo [4.4.0.1 ^2,5 .1 ^7,10 ] -3-dodecene,

8-methyl-8- (2-naphthoxy) carbonyltetracyclo [4.4.0.1 ^2,5 .1 ^7,10 ] -3-dodecene,

8-methyl-8- <4-phenylphenoxy> carbonyltetracyclo [4.4.0.1 ^2,5 .1 ^7,10 ] -3-dodecene,

Pentacyclo [8.4.0.1 ^2,5 .1 ^9,12 .0 ^8,13 ] -3-hexadecene,

Heptacyclo [8.7.0.1 ^3.6 .1 ^10,17 .1 ^12,15 .0 ^2,7 .0 ^11,16 ] -4-eicosene,

Heptacyclo [8.8.0.1 ^4.7 .1 ^11,18 .1 ^13,16 .0 ^3,8 .0 ^12,17 ] -5- ^heneicosene ,

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

8-ethylidenetetracyclo [4.4.0.1 ^2,5 .1 ^7,10 ] -3-dodecene,

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

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

8-phenyl-tetracyclo [4.4.0.1 ^2,5 .1 ^7,10] -3- dodecene,

5-n-butylbicyclo [2.2.1] hept-2-ene,

5-n-hexylbicyclo [2.2.1] hept-2-ene,

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

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

5-n-octylbicyclo [2.2.1] hept-2-ene,

5-n-decylbicyclo [2.2.1] hept-2-ene,

5-isopropylbicyclo [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-methylbicyclo [2.2.1] hept-2-ene,

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

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

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

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

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

5-tri-n-propoxysilylbicyclo [2.2.1] hept-2-ene,

5-tri-n-butoxysilylbicyclo [2.2.1] hept-2-ene,

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

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

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

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

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

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

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

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

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

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

5-methyl-5-trifluoromethylbicyclo [2.2.1] hept-2-ene,

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

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

8-fluorotetracyclo [4.4.0.1 ^2,5 .1 ^7,10 ] -3-dodecene,

8-fluoromethyltetracyclo [4.4.0.1 ^2,5 .1 ^7,10 ] -3-dodecene,

8-trifluoromethyltetracyclo [4.4.0.1 ^2,5 .1 ^7,10 ] -3-dodecene,

8,8-difluorotetracyclo [4.4.0.1 ^2,5 .1 ^7,10 ] -3-dodecene,

Spiro [fluorene-9,8'-tricyclo [4.3.0.1 ^2,5 ] [3] decene]

Etc. can be mentioned.

These compounds can be used as monomer (6) individually by 1 type or in combination of 2 or more types.

Heat resistance and moisture resistance of the resin composition and optical film from which the said specific monomer in which at least one of R <^10> -R <^13> in the said General formula (6) is a specific polar group represented by following General formula (I) are obtained among these monomers (6) It is preferable at the point that water-repellency maintains a favorable balance.

-(CH ₂ ) _n COOR ¹⁷ (I)

(Wherein n is usually 0 or an integer of 1 to 5, R ¹⁷ is a hydrocarbon group of 1 to 15 carbon atoms)

In the general formula (I), the smaller the value of n and the smaller the number of carbon atoms of R ^17, the higher the glass transition temperature of the resin composition obtained and the higher the heat resistance. That is, n is usually 0 or an integer of 1 to 5, preferably 0 or 1, and R ¹⁷ is usually a hydrocarbon group having 1 to 15 carbon atoms, preferably an alkyl group having 1 to 4 carbon atoms.

In addition, in the said General formula (6), the said monomer which the alkyl group couple | bonded with the carbon atom which the polar group represented by the said General formula (I) couple | bonded further has heat resistance and moisture resistance (water) resistance of the resin composition and optical film obtained. It is preferable at the point which maintains a good balance. It is preferable that carbon number of this alkyl group is 1-5, More preferably, it is 1-2, Especially preferably, it is 1.

Of these monomers (6), 8-methyl-8-methoxycarbonyltetracyclo [4.4.0.1 ^2,5 .1 ^7,10 ] -3-dodecene and 8-methyl-8-ethoxycarbonyltetracyclo [4.4.0.1 ^2,5 .1 ^7,10 ] -3-dodecene, 8-methyl-8-butoxycarbonyltetracyclo [4.4.0.1 ^2,5 .1 ^7,10 ] -3-dodecene, And 8-methyl-8-methoxycarbonyltetracyclo [4.4.0.1 ^2,5 .1 ^7,10 ] -3-dodecene and 5-methyl-5-methoxycarbonyl-bicyclo [2.2.1] hept Use with 2-ene is preferable at the point which the resin composition and optical film obtained are excellent in heat resistance, and especially 8-methyl-8-methoxycarbonyl tetracyclo [4.4.0.1 ^2,5 .1 ^7,10 ] -3-dodecene and 8-methyl-8-methoxycarbonyltetracyclo [4.4.0.1 ^2,5 .1 ^7,10 ] -3-dodecene and 5-methyl-5-methoxycarbonyl-bicyclo [ 2.2.1] Combination with hept-2-ene is preferable in that a norbornene-based polymer (B) having excellent compatibility with the styrene-based copolymer (A) is obtained.

Preferred examples of other monomers (6) represented by the general formula (6) include bicyclo [2.2.1] hept-2-ene and tricyclo [5.2.1.0 ^2,6 ] -deca-3,8-diene, 5 -Ethylidenebicyclo [2.2.1] hept-2-ene, 5-phenylbicyclo [2.2.1] hept-2-ene, 5-n-butylbicyclo [2.2.1] hept-2-ene , 5- ⁿ decylbicyclo [2.2.1] hept-2-ene, and the like.

[Opening (co) polymer]

As a norbornene-type polymer (B) obtained by ring-opening-polymerizing the monomer (6) mentioned above, the polymer which has a structural unit represented by following General formula (II) is mentioned, for example.

(In formula (II), a, b, c, d and R ⁴ to R ¹³ are the same as the definitions of a, b, c, d and R ⁴ to R ¹³ in the formula (6), respectively. Is a group represented by the formula: -CH = CH- or a group represented by the formula: -CH ₂ CH _2- , and plural X's are the same or different).

As a norbornene-type polymer (B) obtained by ring-opening-polymerizing the above-mentioned monomer (6), It is preferable that it is a (co) polymer which has a structural unit represented by following General formula (i) preferably.

(In Formula (i), A ¹ to A ⁴ each independently represent a hydrogen atom; a halogen atom; the number of substituted or unsubstituted carbon atoms which may have a linking group including an oxygen atom, a sulfur atom, a nitrogen atom, or a silicon atom. A hydrocarbon group of 1 to 30; or a polar group, and at least one of A ¹ to A ⁴ is a group represented by-(CH ₂ ) _n COOA ⁵ (A ⁵ includes an oxygen atom, a sulfur atom, a nitrogen atom, or a silicon atom A substituted or unsubstituted hydrocarbon group having 1 to 30 carbon atoms, and n is 0 or an integer of 1 to 5).

When the norbornene-based polymer (B) includes the structural unit represented by the above formula (i), the structural unit represented by the above formula (i) is contained in 100 mol% of all the structural units of the norbornene-based polymer (B). It is preferable to contain 5 mol% or more normally, Preferably it is 10-70 mol%, More preferably, it is 20-50 mol%.

The structural unit represented by the said general formula (i) is a structural unit preferably obtained by ring-opening-copolymerizing the monomer represented by the following general formula (i-a) in the said monomer (6), and hydrogenating.

In formula (ia), A <^1> -A <^4> is as defined in the said Formula (i).

As such a monomer (i-a), for example

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

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

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

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

5-benzyloxycarbonylbicyclo [2.2.1] hept-2-ene

Etc. can be mentioned. Preferred monomer is 5-methoxycarbonylbicyclo [2.2.1] hept-2-ene.

Such monomers (ia) are groups (groups having ester bonds) in which at least one of A ¹ to A ⁴ in formula (ia) is represented by-(CH ₂ ) _n COOA ⁵ , wherein-(CH ₂ ) _n COOR ⁵ It is preferable that another atom or group which couple | bonded with the carbon atom which the displayed group couple | bonds is an atom or group other than a hydrogen atom. Specifically, for example, A ¹ is a group represented by-(CH ₂ ) _n COOA ⁵ , and A ² is preferably a structural unit or an atom other than a hydrogen atom.

More preferably, as a monomer (i-a), the compound (i-a ') represented by a following formula is mentioned.

In formula (i-a '), A ⁵ represents a substituted or unsubstituted hydrocarbon group having 1 to 30 carbon atoms which may have a linking group containing an oxygen atom, a sulfur atom, a nitrogen atom or a silicon atom, and A ⁶ is a halogen atom ; A substituted or unsubstituted hydrocarbon group having 1 to 30 carbon atoms which may have a linking group containing an oxygen atom, a sulfur atom, a nitrogen atom or a silicon atom; Or a polar group. More preferably, A is a C1-C10 hydrocarbon group.

As such a monomer (1-a '), the following can be illustrated, for example.

5-methyl-5-methoxycarbonylbicyclo [2.2.1] hept-2-ene

5-methyl-5-ethoxycarbonylbicyclo [2.2.1] hept-2-ene

5-methyl-5-phenoxycarbonylbicyclo [2.2.1] hept-2-ene

In the monomer (6), at least one of c and d in the formula (6) is a non-zero compound, preferably a monomer in which at least one of c and d represents 1 (hereinafter also referred to as "multinuclear body"). ) And the monomer (i-a ') have low reactivity of the monomer (i-a'), so that the polymerization conversion rate is low, or a large amount of monomer (i-a ') remains in the reaction system at the end of the polymerization and the monomer There exists a possibility that the polymer chain derived only from (i-a ') may produce | generate. Since the polymer chain derived only from the monomer (i-a ') is difficult to advance the hydrogenation reaction mentioned later, it is preferable to suppress generation | occurrence | production of this polymer chain. As a method of solving this problem, the method of sequentially adding or continuously adding a polynuclear body and superposing | polymerizing is mentioned. Specifically, a method of sequentially adding or continuously adding a multinuclear body while batch polymerizing a part of the multinuclear body and the monomer (i-a '), a mixture of the polynuclear body and the monomer (i-a') from the start to the end of the reaction Successive addition or the method of continuous addition, etc. are mentioned. Copolymerization reactivity ratio can be calculated by the well-known method, the curve matching method by the Fineman-Ross method, or the integral formula by the Mayo-Lewis method (Otsu Ryuko-Otsu). Kinoshita Masayoshi Textbook, Chemical Drivers, Twelfth Person, Experimental Method of Polymer Synthesis, pp183-189]. Particularly preferred embodiments are as follows. The polynuclear body is 8-methyl-8-methoxycarbonyltetracyclo [4.4.0.1 ^2,5 .1 ^7,10 ] -3-dodecene and the monomer (i-a ') is 5-methoxycarbonylbicyclo [ 2.2.1] In the case of hept-2-ene, the copolymerizable reactivity ratio at 80 ° C. determined by the Fineman-Ross method was 8-methyl-8-methoxycarbonyltetracyclo [4.4.0.1 ^2,5 .1 ^{7 , 10} ] -3-dodecene is 1.0, and 5-methoxycarbonylbicyclo [2.2.1] hept-2-ene is 1.0. That is, since the polynuclear body is consumed at a rate 2.1 times higher than that of the monomer (i-a '), it is particularly preferable that the input composition is monomer (i-a'): polynuclear body = 1: 2.1 (mol%), As a preferable range, it is 1-4 mol of polynuclear bodies with respect to 1 mol of monomers (i-a '). It is preferable to add a polynuclear body to maintain the composition in this range from the beginning to the end of the reaction.

[Copolymerizable Monomer]

Although the said monomer (6) may carry out ring-opening-polymerization independently, you may further ring-open-polymerize the said monomer (6) and another copolymerizable monomer.

Specific examples of the copolymerizable monomer include cycloolefins such as cyclobutene, cyclopentene, cycloheptene, and cyclooctene. 4-20 are preferable and, as for carbon number of cycloolefin, 4-12 are more preferable.

In addition, the monomer in the presence of an unsaturated hydrocarbon-based polymer containing a carbon-carbon double bond in the main chain, such as polybutadiene, polyisoprene, styrene-butadiene copolymer, ethylene-non-conjugated diene copolymer, polynorbornene and the like You can also ring-open-polymerize (6). In this case, the ring-opening copolymer obtained and its hydrogenated copolymer are useful as raw materials of the resin composition having high impact resistance.

The said ring-opening polymer ((co) polymer which has a structural unit represented by Formula (II)) is 1 type of the said monomer (6) using a molecular weight modifier and the ring-opening polymerization solvent as needed in presence of a ring-opening polymerization catalyst. As mentioned above and if necessary, a copolymerizable monomer can be obtained by ring-opening (co) polymerizing by a conventionally well-known method.

In addition, when copolymerizing the said monomer (6) and the said copolymerizable monomer, the said monomer (6) is 50 weight% or more normally with respect to a total of 100 weight% of the said monomer (6) and the said copolymerizable monomer, Preferably 60 wt% or more, more preferably 70 wt% or more, and 100 wt% or less, 0 wt% or more, usually 50 wt% or less, preferably 40 wt% or less, more preferably 30 wt% of the copolymerizable monomer. It is preferable to copolymerize in the ratio of% or less.

As the ring-opening polymer used in the present invention, a homopolymer of the monomer (6) or a copolymer of two or more kinds of monomers (6) is most preferred.

<Opening (co) polymerization catalyst>

As the catalyst for ring-opening (co) polymerization used in the present invention, the catalyst described in Olefin Metathesis and Metathesis Polymerization (K.J.IVIN, J.C.MOL, Academic Press 1997) is preferably used.

As such a catalyst, for example, (a) one or more selected from compounds of W, Mo, Re, V and Ti, and (b) Li, Na, K, Mg, Ca, Zn, Cd, Hg, B, Al And metathesis polymerization catalysts composed of one or more combinations selected from those having at least one corresponding element-carbon bond or the element-hydrogen bond as compounds such as Si, Sn, and Pb. This catalyst may be added with additive (c) which will be described later in order to increase the activity of the catalyst. Moreover, the metathesis catalyst which contains the periodic table group 4-8 transition metal-carbene complex, metacyclocyclobutane complex, etc. which do not use the (d) cocatalyst as another catalyst is mentioned.

Representative examples of the compounds of W, Mo, Re, V and Ti suitable as the component (a) include WCl ₆ , MoCl ₅ , ReOCl ₃ , VOCl ₃ , TiCl ₄ and the like described in JP-A-240517 The compound can be mentioned.

Examples of the component (b) include nC ₄ H ₉ Li, (C ₂ H ₅ ) ₃ Al, (C ₂ H ₅ ) ₂ AlCl, (C ₂ H ₅ ) _1.5 AlCl _1.5 , (C ₂ H ₅ ) AlCl ₂ , The compound of Unexamined-Japanese-Patent No. 1-240517, such as methyl alumoxane and LiH, is mentioned.

As representative examples of the component (c) which is an additive, alcohols, aldehydes, ketones, amines and the like can be preferably used, and the compounds described in JP-A-240517 can be used.

Representative examples of the catalyst (d) include W (= N-2,6-C ₆ H ₃ iPr ₂ ) (= CHtBu) (OtBu) ₂ , Mo (= N-2,6-C ₆ H ₃ iPr ₂ ) (= CHtBu) (OtBu) ₂ , Ru (= CHCH = CPh ₂ ) (PPh ₃ ) ₂ Cl ₂ , Ru (= CHPh) (PC ₆ H ₁₁ ) ₂ Cl ₂ , and the like.

As the usage-amount of a metathesis catalyst, "(a) component: whole monomer" is usually 1: 500-in the molar ratio of the said (a) component and all the monomers (the total amount of monomer (6) and the other copolymerizable monomer, the same hereafter). It is preferable that it is the range which becomes 1: 500,000, Preferably it is the range which becomes 1: 1,000-1: 100,000. As for the ratio of (a) component and (b) component, it is preferable that "(a) :( b)" is 1: 1-1: 100 in the metal atomic ratio, Preferably it is the range of 1: 2-1: 50. . In addition, when the said (c) additive is added to this metathesis catalyst, the ratio of (a) component and (c) component has a molar ratio of "(c) :( a)" of 0.005: 1-15: 1, Preferably Is preferably in the range of 0.05: 1 to 7: 1. In addition, the usage-amount of catalyst (d) is a range in which "(d) component: whole monomer" is usually 1: 50-1: 100,000 by the molar ratio of (d) component and all monomers, Preferably it is 1: 100-1. The range is preferably 50,000.

<Molecular weight regulator>

Although adjustment of the molecular weight of a ring-opening (co) polymer can be performed also according to polymerization temperature, the kind of catalyst, and the kind of solvent, in this invention, it is preferable to adjust by coexisting a molecular weight modifier in a reaction system. Preferred molecular weight modifiers include, for example, α-olefins such as ethylene, propylene, 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, 1-nonene and 1-decene; Allyl compounds, such as styrene, such as styrene and vinyltoluene, allyl acetic acid, and allylbenzene, are mentioned, Among these, 1-butene, 1-hexene, and 1-octene are especially preferable. These molecular weight modifiers can be used individually or in mixture of 2 or more types. As a usage-amount of a molecular weight modifier, it is preferable that it is 0.001-0.6 mol, Preferably it is 0.02-0.5 mol with respect to 1 mol of all monomers provided for a ring-opening (co) polymerization reaction.

<Solvent for ring-opening (co) polymerization reaction>

As a solvent used for the ring-opening (co) polymerization reaction, that is, a solvent for dissolving a norbornene-based monomer, a metathesis catalyst and a molecular weight modifier, for example, hydrocarbons such as petroleum ether, pentane, hexane, heptane, octane, nonane and decane Ryu; Cyclic hydrocarbons such as cyclopentane, cyclohexane, methylcyclohexane, cycloheptane, cyclooctane, decalin and norbornane; Aromatic hydrocarbons such as benzene, toluene, xylene, ethylbenzene, cumene and chlorobenzene; Halogenated hydrocarbons such as dichloromethane, dichloroethane, chlorobutane, chloroform and tetrachloroethylene; Esters such as methyl acetate, ethyl acetate, n-butyl acetate, iso-butyl acetate, and methyl propionate; Ethers such as dibutyl ether, tetrahydrofuran, dimethoxyethane and dioxane; N, N-11 dimethylformamide, N, N-dimethylacetamide, N-methylpyrrolidone, etc. are mentioned, These can be used individually or in mixture. In this invention, an aromatic hydrocarbon is preferable in these.

As a usage-amount of a solvent, "solvent: all monomers (weight ratio)" is the quantity which is 0.5: 1-20: 1 normally, It is preferable that it is the quantity which becomes 0.5: 1-10: 1.

[Hydrogenation]

In the present invention, the norbornene-based polymer (B) may be produced only by the above-described ring-opening polymerization, but it is preferable to further hydrogenate the ring-opening polymer obtained by the ring-opening polymerization. In the ring-opening polymerization alone, the norbornene-based polymer obtained is in the state of an olefinically unsaturated group in which all X in the structural unit (II) represented by the general formula (II) are represented by the formula: -CH = CH-. The ring-opening polymer can be used as it is, but from the viewpoint of heat stability, it is preferable that the olefinically unsaturated group described above is hydrogenated in which X is converted to a group represented by -CH ₂ -CH _2- . However, the hydrogenated substance used in this invention means that the said olefinic unsaturated group was hydrogenated, and the aromatic ring of the side chain based on norbornene-type monomer is not hydrogenated substantially.

Moreover, as a ratio to hydrogenate, it is preferable that it is 90 mol% or more of X in the said structural unit (II), Preferably it is 95% or more, More preferably, it is 97% or more. Since the coloring and deterioration by heat can be suppressed so that the ratio to add hydrogen is high, it is preferable.

In this production method, the hydrogenation reaction needs to be carried out under the condition that the aromatic ring of the side chain based on the monomer (6) is not substantially hydrogenated. For this reason, it is usually preferable to add a hydrogenation catalyst to the solution of the ring-opening polymer, and act on this at normal pressure to 30 MPa, preferably 2 to 20 MPa, more preferably 3 to 18 MPa.

As a hydrogenation catalyst, what is used for the hydrogenation reaction of a normal olefinic compound can be used. As this hydrogenation catalyst, both a well-known heterogeneous catalyst and a homogeneous catalyst can be used. As a heterogeneous catalyst, the solid catalyst which carried noble metal catalyst substances, such as palladium, platinum, nickel, rhodium, ruthenium, on support | carriers, such as carbon, a silica, alumina, titania, is mentioned. As the homogeneous catalyst, nickel naphthenate / triethylaluminum, bis (acetylacetonato) nickel (II) / triethylaluminum, cobalt octate / n-butyllithium, titanocenedichloride / diethylaluminum monochloride, Rhodium acetate, chlorotris (triphenylphosphine) rhodium, dichlorotris (triphenylphosphine) ruthenium, chlorohydrocarbonyltris (triphenylphosphine) ruthenium, dichlorocarbonyltris (triphenylphosphine) ruthenium Can be. The form of the catalyst may be powder or granular. In addition, this hydrogenation reaction catalyst can also be used individually by 1 type or in combination of 2 or more type.

These hydrogenated catalysts need to be adjusted in amount so that the aromatic rings of the side chains based on the monomer (6) or other monomers are not substantially hydrogenated. Generally, "opening (co) polymer: hydrogenated catalyst (weight ratio ) Is preferably used in a ratio of 1: 1 × 10 ⁻⁶ to 1: 2.

As a purification method, the method similar to a styrene-type copolymer (A) can be employ | adopted.

[Additional (co) polymer]

In the present invention, in addition to the ring-opening (co) polymer and its hydrogenated polymer as the norbornene-based polymer (B), an addition-type (co) polymer comprising one or two or more of the monomers (6), and the monomer (6 ) And an unsaturated (co) polymer of an unsaturated double bond containing compound can be used. The addition type (co) polymer produced | generated by the (co) polymerization reaction of 1 type individually or 2 or more types of said monomers (6) can be obtained by a conventionally well-known method. In addition, the monomer (6) and the unsaturated double bond-containing compound are usually 50 to 90% by weight, preferably 60 to 90% by weight, more preferably 70 to the monomer (6) to 100% by weight of the total amount thereof. It is preferable to copolymerize the compound at 90 to 90% by weight, and the unsaturated double bond-containing compound at a ratio of usually 10 to 50% by weight, preferably 10 to 40% by weight, more preferably 10 to 30% by weight.

As said unsaturated double bond containing compound, C2-C12, Preferably 2 to 8 olefin type compounds, such as ethylene, propylene, butene, are mentioned, for example.

As a catalyst used for the copolymerization reaction of the said monomer (6) with an unsaturated double bond containing compound, the catalyst containing a vanadium compound and an organoaluminum compound is mentioned. As a vanadium compound, VO (OR) _a X _b or V (OR) _c X _d (where R is a hydrocarbon group, 0≤a≤3, 0≤b≤3, 2≤a + b≤3, 0≤c Vanadium compounds represented by ≦ 4, 0 ≦ d ≦ 4, 3 ≦ c + d ≦ 4), or electron donor adducts thereof. As electron donors, oxygen-containing electron donors such as alcohols, phenols, ketones, aldehydes, carboxylic acids, organic acids or esters of organic acids or inorganic acids, ethers, acid amides, acid anhydrides and alkoxysilanes, and nitrogen-containing electrons such as ammonia, amines, nitriles and isocyanates Donors and the like. Examples of the organoaluminum compound include at least one organoaluminum compound selected from compounds having at least one aluminum-carbon bond or aluminum-hydrogen bond. The ratio of the vanadium compound and the organoaluminum compound in the catalyst is usually 2 or more, preferably 2 to 50, particularly preferably 3 to 20, in terms of the ratio (Al / V) of the aluminum atoms to the vanadium atoms.

As a solvent used for the said copolymerization reaction, For example, hydrocarbons, such as a pentane, hexane, heptane, an octane, a nonane, a decane; Cyclic hydrocarbons such as cyclohexane and methylcyclohexane; Aromatic hydrocarbons, such as benzene, toluene, and xylene, and their halogen derivatives are mentioned. Among these, cyclohexane and methylcyclohexane are preferable.

As a purification method, the method similar to the said styrene-type copolymer (A) can be employ | adopted.

As for norbornene-type polymer (B) used for this invention, it is preferable that the logarithmic viscosity ((eta)) measured in 30 degreeC chlorobenzene solution (concentration 0.5 g / dL) is 0.3-2.0 dL / g. In addition, the number average molecular weight (Mn) of polystyrene conversion measured by gel permeation chromatography (GPC) of the norbornene-based polymer (B) is usually 1,000 to 500,000, preferably 3,000 to 300,000, more preferably 5,000 to 100,000. The weight average molecular weight (Mw) is usually 10,000 to 1,000,000, preferably 20,000 to 500,000, more preferably 30,000 to 200,000.

When molecular weight is too small, the intensity | strength of the molded article and film obtained may become low. When molecular weight is too big, solution viscosity may become high too much and productivity and workability of the resin composition used for this invention may deteriorate.

In addition, the molecular weight distribution (Mw / Mn) of the norbornene-based polymer (B) is usually from 1.5 to 10, preferably from 2 to 8, more preferably from 2 to 6.

The glass transition temperature (Tg) of the norbornene-based polymer (B) is usually 100 to 250 ° C, preferably 110 to 220 ° C, more preferably 115 to 200 ° C. If the Tg is too low, the heat deformation temperature is lowered, which may cause a problem in heat resistance, and there may be a problem that the change in optical properties due to the temperature of the obtained molded product or film increases. On the other hand, when Tg is too high, it is necessary to raise processing temperature, and a resin composition may thermally deteriorate by this.

<Resin composition and optical film>

The resin composition and the optical film according to the present invention have a composition ratio ((A) / (B)) of the styrene copolymer (A) and the norbornene polymer (B) in a weight ratio of styrene copolymer / norbornene polymer = 5/95 to 70/30, preferably 15/85 to 60/40, more preferably 20/80 to 50/50. When the compounding quantity of a styrene-type copolymer (A) exists in the said range, an optical film which has reverse wavelength dispersion can be obtained by extending | stretching after film forming. In addition, the strength of the film is also improved. When the compounding quantity of a styrene copolymer (A) is less than the said minimum, the stretched film obtained from a resin composition may not show reverse wavelength dispersion. Moreover, when the compounding quantity of a styrene copolymer (A) exceeds the said upper limit, the heat resistance of the resin composition and optical film obtained may fall, or the intensity | strength of an optical film may fall.

The resin composition and the optical film may further contain a hydrocarbon resin. Examples of the hydrocarbon resin, C ₅ resins, C ₉ resins, C ₅ series / C ₉ based mixed resin, cyclopentadiene-based resins, olefin / vinyl substituted copolymer-based resin, aromatic-based compounds, cyclopentadiene compound / vinyl substituted The copolymer system resin of an aromatic compound, the hydrogenated substance of these resin, the hydrogenated substance of vinyl substituted aromatic resin, etc. are mentioned. The content of the hydrocarbon resin is usually 0.01 to 50 parts by weight, preferably 0.1 to 25 parts by weight based on 100 parts by weight of the norbornene-based polymer (B).

In order to improve heat | fever deterioration resistance and light resistance, the antioxidant, ultraviolet absorber, etc. which are shown below can also be added to the said resin composition.

As antioxidant

2,6-di-t-butyl-4-methylphenol, 2,2'-dioxy-3,3'-di-t-butyl-5,5'-dimethyldiphenylmethane, tetrakis [methylene-3 -(3,5-di-t-butyl-4-hydroxyphenyl) propionate] methane, 1,1,3-tris (2-methyl-4-hydroxy-5-t-butylphenyl) butane, 1,3,5-trimethyl-2,4,6-tris (3,5-di-t-butyl-4-hydroxybenzyl) benzene, stearyl-β- (3,5-di-t-butyl- 4-hydroxyphenyl) propionate, 2,2'-dioxy-3,3'-di-t-butyl-5,5'-diethylphenylmethane, 3,9-bis [1,1-dimethyl -2- (β- (3-t-butyl-4-hydroxy-5-methylphenyl) propionyloxy) ethyl], 2,4,8,10-tetraoxaspiro [5.5] undecane, tris (2, 4-di-t-butylphenyl) phosphite, cyclic neopentanetetrabisbis (2,4-di-t-butylphenyl) phosphite, cyclic neopentanetetrabisbis (2,6-di-t- Butyl-4-methylphenyl) phosphite and 2,2-methylenebis (4,6-di-t-butylphenyl) octylphosphite.

As a ultraviolet absorber,

2,4-dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2- (2H-benzotriazol-2-yl) -4,6-bis (1-methyl-1-phenylethyl ) Phenol, 2- (2H-benzotriazol-2-yl) -4,6-di-tert-pentylphenol, 2-benzotriazol-2-yl-4,6-di-tert-butylphenol, 2 , 2'-methylenebis [4- (1,1,3,3-tetramethylbutyl) -6-[(2H-benzotriazol-2-yl) phenol]] and the like.

The amount of these additives added is usually 0.01 to 5 parts by weight, preferably 0.05 to 4 parts by weight with respect to 100 parts by weight of the present resin composition.

Moreover, additives, such as a lubricant, can also be added for the purpose of improving workability.

<Method for producing resin composition>

The resin composition which concerns on this invention can be obtained by the method of following (i)-(iii), for example.

(i) A method in which a styrene copolymer (A), a norbornene polymer (B) and an optional component are mixed using a twin screw extruder or a roll kneader.

(ii) A method in which a styrene copolymer (A) is added and mixed in a solution in which a norbornene-based polymer (B) is dissolved in a suitable solvent.

(iii) A method of mixing and dissolving a styrene copolymer (A) or a solution thereof and a norbornene-based polymer (B) or a solution thereof, and desolvating it using a diboratiwriter, a luder or the like.

As a solvent used at this time, the polymerization solvent used for manufacture of a styrene copolymer (A) or a norbornene-type polymer (B), and the general solvent used by the solvent casting method of an optical film can be used. Since the resin composition obtained by the said method contains a high molecular weight polymer, the optical film excellent in film strength can be obtained.

Furthermore, after introducing the resin composition solution obtained by said (ii), (iii) etc. into an extruder and removing the volatile matter in this resin composition solution in an extruder, it melt-extrusion shape mentioned later from die | dye in film shape or strand shape ( Hereinafter, also referred to simply as extrusion molding), a molded article or an optical film can be obtained.

<Method for producing optical film>

The optical film of this invention can be obtained by shape | molding the resin composition mentioned above to a film by melt-molding method, the solution casting method (solvent casting method), etc.

As the solvent casting method, for example, the resin composition according to the present invention described above is dissolved or dispersed in a solvent to form a liquid having a suitable concentration, poured onto a suitable carrier, or applied, and dried and then peeled from the carrier. A method is mentioned.

When dissolving or dispersing the resin composition according to the present invention in a solvent, the concentration of the resin composition is usually 1 to 90% by weight, preferably 5 to 50% by weight, more preferably 10 to 35% by weight. When the concentration of this resin is less than the above, it becomes difficult to secure the thickness of the film. Moreover, the problem that the surface smoothness of a film becomes difficult to obtain by foaming etc. accompanying solvent evaporation arises. On the other hand, when the concentration exceeds the above, the solution viscosity becomes too high, so that the thickness and the surface of the optical film obtained become difficult to be uniform.

In addition, the viscosity of the solution at room temperature is usually 1 to 1,000,000 (mPa · s), preferably 10 to 500,000 (mPa · s), more preferably 100 to 200,000 (mPa · s), particularly preferably 1,000 to 100,000 (mPa · s).

Examples of the solvent used herein include hydrocarbon solvents such as cyclohexane, cyclopentane and methylcyclohexane, aromatic solvents such as benzene, toluene and xylene, methyl cellosolve, ethyl cellosolve, and 1-methoxy-2-propanol. Ketone solvents such as cellosolve solvents, diacetone alcohol, acetone, cyclohexanone, methyl ethyl ketone, 4-methyl-2-pentanone, methyl isobutyl ketone, methyl lactate, methyl acetate, ethyl acetate, acetic acid Ester solvents such as butyl, halogen-containing solvents such as methylene chloride and chloroform, ether solvents such as tetrahydrofuran, dioxane, dimethoxyethane and 1,3-dioxolane, 1-butanol and 1-pentanol Alcohol solvents are mentioned.

Further, in addition to the SP value (solubility parameter) is usually 10 to 30 (MPa ^1/2), preferably from 10 to 25 (MPa ^1/2), more preferably from 15 to 25 (MPa ^1/2), in particular preferably it is achieved by a good optical film surface uniformity and optical properties using a solvent in the range of 17 to 20 (MPa ^1/2).

The said solvent can be used individually or in combination of 2 or more types. When using 2 or more types of solvents together, it is preferable to make the range of SP value as a mixture into the said range. At this time, when the SP value as a mixture may be obtained from the weight ratio, for example, in the case of a mixture of two, the weight fraction of each solvent, W _1, W _2, also referred to an SP value SP _1, SP ₂ mixture The SP value of a solvent can be calculated | required as the value computed by the following formula.

SP value = W ₁ SP ₁ + W ₁ SP ₂

In the production of the resin solution, the temperature when dissolving the thermoplastic resin composition according to the present invention in a solvent may be room temperature or high temperature. A uniform solution is obtained by stirring sufficiently. Moreover, when coloring as needed, coloring agents, such as dye and a pigment, can also be added suitably.

Moreover, in order to improve the surface smoothness of an optical film, you may add a leveling agent. As long as it is a general leveling agent, any can be used, For example, a fluorine-type nonionic surfactant, a special acrylic resin type leveling agent, a silicone type leveling agent, etc. can be used.

As a method for producing the optical film of the present invention by a solvent casting method, a polyester drum such as a metal drum, a steel belt, polyethylene terephthalate (PET) or polyethylene naphthalate (PEN), poly The method of apply | coating on base materials, such as a belt made from tetrafluoroethylene, drying and removing a solvent after that, and peeling a film from a base material is mentioned generally. Moreover, it can also manufacture by apply | coating a resin composition solution to a base material using means, such as spraying, a brush, roll spin coating, and immersion, drying and removing a solvent after that, and peeling a film from a base material. Moreover, thickness, surface smoothness, etc. can also be controlled by repetition of application | coating.

In addition, when using a polyester film as a base material, the surface-treated film can also be used. As the surface treatment method, a hydrophilic treatment method which is generally performed, for example, a method of laminating an acrylic resin or a sulfonate group-containing resin with a coating or a laminate, or a method of improving the hydrophilicity of the film surface by corona discharge treatment or the like Can be mentioned.

There is no restriction | limiting in particular about the drying (solvent removal) process of the said solvent casting method, It can carry out by the method generally used, for example, passing through a drying furnace through a number of rollers, and evaporating a solvent in a drying process. Since bubbles generate | occur | produce along with this, the characteristic of a film will fall remarkably, In order to avoid this, it is preferable to make a drying process into two or more steps, and to control the temperature or air volume in each process.

Moreover, the amount of residual solvent in an optical film is 10 weight% or less normally, Preferably it is 5 weight% or less, More preferably, it is 2 weight% or less, Especially preferably, it is 1 weight% or less. Here, when the amount of residual solvent is 10 weight% or more, when actually using this optical film, the dimensional change with time becomes large and it is unpreferable. Moreover, since Tg becomes low and heat resistance also falls by a residual solvent, it is unpreferable.

In addition, in order to perform the extending process mentioned later preferably, it may be necessary to adjust the said residual solvent amount suitably in the said range. Specifically, in order to stably and uniformly express the phase difference in the stretching orientation, the amount of the residual solvent is usually 10 to 0.1% by weight, preferably 5 to 0.1% by weight, more preferably 1 to 0.1% by weight. There is. By remaining a trace amount of solvent, the stretching process may be easy or the control of the phase difference may be easy.

The thickness of the optical film of the present invention is usually 0.1 to 3,000 μm, preferably 0.1 to 1,000 μm, more preferably 1 to 500 μm, and most preferably 5 to 300 μm. For thicknesses less than 0.1 μm, handling becomes substantially difficult. On the other hand, when it is 3,000 micrometers or more, it becomes difficult to wind up in roll shape.

The thickness distribution of the optical film of the present invention is usually within ± 20%, preferably within ± 10%, more preferably within ± 5%, particularly preferably within ± 3% of the average value. In addition, the variation in thickness per cm is usually 10% or less, preferably 5% or less, more preferably 1% or less, particularly preferably 0.5% or less. By performing such thickness control, it can be set as a homogeneous optical film and the phase difference unevenness of the transmitted light at the time of extending | stretching orientation can be prevented.

In the extrusion method, the resin is melted by an extruder, quantitatively supplied by a gear pump, the impurities are removed by filtration by a metal filter, molded into a film by a die, the film is cooled by using a drawer, The winding method by using is generally used.

As an extruder used for extrusion molding, all of single screw, twin screw, planetary type, a kneader, a Benbury mixer type, etc. can also be used, Preferably a single screw extruder is used. In addition, the screw shape of the extruder includes a vent type, a tip dulmadge type, a double flight type, a full flight type, a barrier type, and the like, and the compression type includes a slow compression type and a rapid compression type. Slow compression type or barrier type is preferred.

As for the gear pump used for metering, there are an internal lubrication method in which the resin returned from the downstream side between the gears enters the system, and an external lubrication method discharged to the outside. External lubrication is preferable. The cutting direction of the gear tooth of the gear pump is more preferable in terms of stabilization of metering than in the direction parallel to the axis.

Examples of the filter used for filtration of foreign substances include leaf disc type, candle filter type, leaf type, screen mesh, and the like. A leaf disc type that is relatively small in distribution of residence time and which can increase the filtration area is preferable. . Examples of the filter element include metal fiber sintering type, metal powder sintering type, metal fiber / powder lamination type and the like.

Examples of the shape of the center pole of the filter include an outflow type, a hexagonal column inner flow type, a circumferential inner flow type, and the like, and any shape can be selected as long as the retention portion is small.

The molten resin is discharged from the die, solidified in close contact with the cooling drum, and molded into a target film. It is essential to make the resin flow inside a die uniform about die shape, and in order to maintain the uniformity of the thickness of a film, it is essential that the pressure distribution inside a die near die exit is constant in the width direction. In addition, the flow rate of the resin in the width direction is almost constant, and it is essential to obtain a uniformity of thickness, in which the fine adjustment of the flow rate at the outlet of the die can be adjusted by the leaf opening degree. In order to satisfy the above conditions, the manifold shape is preferably a coat hanger type, and the straight manifold, fishtail type and the like are not preferable because the flow rate distribution in the width direction tends to occur.

In addition, in order to make the thickness distribution of the film uniform, it is important to make the temperature distribution at the die outlet constant in the width direction, and the temperature distribution is preferably ± 1 ° C or less, and more preferably ± 0.5 ° C. It is as follows. If temperature nonuniformity is generated in the width direction exceeding ± 1 ° C, a difference in melt viscosity of the resin may occur, resulting in thickness nonuniformity, stress distribution nonuniformity, and the like, and thus, phase difference nonuniformity tends to occur during the stretching operation. not.

The leaf opening amount (hereinafter referred to as "leaf gap") at the die exit is usually 0.3 to 1.5 mm, preferably 0.3 to 1.2 mm, and more preferably 0.35 to 1.0 mm. If the leaf gap is less than 0.3 mm, the resin pressure inside the die becomes too high and the resin tends to cause resin leakage at a place other than the leaf of the die, which is not preferable. On the other hand, when the leaf gap exceeds 1.5 mm, since the resin pressure of the die becomes difficult, the uniformity of the thickness in the width direction of the film is deteriorated, which is not preferable.

Examples of a method for tightly solidifying the film extruded from the die include a nip roll method, an electrostatic application method, an air knife method, a vacuum chamber method, a calender method, and the like, and an appropriate method is selected according to the thickness of the film and the application.

It is preferable that various surface treatments are performed also on the cooling roll surface for solidifying the film extruded from the die like the extruder cylinder, the inner surface of the die, and the like.

Examples of the material of the extruder (cylinder screw, etc.) and the die include stainless steel such as SCM-based steel and SUS, but are not limited thereto. In addition, the inner surface of the extruder cylinder, the die, and the surface of the extruder screw are coated with chromium, nickel, titanium, or the like, and TiN, TiAlN, TiCN, CrN, DLC (diamond-like carbon) by PVD (Physical Vapor Deposition) or the like. It is preferable to use a film having a film formed thereon or the like, a tungsten-based material such as WC, or a ceramic such as cement sprayed or a nitrided surface thereof. Such surface treatment is preferable in that a uniform melt state of the resin is obtained because the coefficient of friction with the resin is small.

As resin temperature (extruder cylinder temperature) at the time of manufacturing the optical film of this invention, it is 200-350 degreeC normally, Preferably it is 220-320 degreeC. If the resin temperature is less than 200 ° C, the resin composition cannot be melted uniformly. On the other hand, if the resin temperature is higher than 350 ° C, the resin composition is thermally deteriorated at the time of melting, making it difficult to manufacture a high quality film having excellent surface properties. Moreover, it is especially preferable that it is in the said temperature range and is temperature in the range of Tg + 120 degreeC-Tg + 160 degreeC with respect to the glass transition temperature (Tg) of a resin composition. For example, when Tg of a resin composition is 130 degreeC, especially preferable temperature range is 250 degreeC-290 degreeC in film manufacture. Since the resin composition of this invention can suppress the crystallization (cloudy) of a film even at the high temperature as mentioned above, and has excellent compatibility, extrusion molding property is favorable. As an index of the extrusion characteristics, the melt flow rate (MFR) at 260 ° C. of the resin composition to be used is 10 to 200 g / 10 minutes, preferably 15 to 150 g / 10 minutes, particularly preferably 30 to 120 g / 10 Minutes. The melt flow rate value is preferably constant throughout the resin composition, and the variation is preferably within ± 10%, particularly preferably within ± 5%. By making a melt flow rate constant, the pressure fluctuation at the time of extrusion process can be suppressed, and the film excellent in film thickness uniformity can be obtained.

The shear rate at the time of melt extrusion is usually 1 to 500 (1 / sec), preferably 2 to 350 (1 / sec), more preferably 5 to 200 (1 / sec). If the shear rate at the time of extrusion is less than 1 (1 / sec), the resin composition cannot be melted uniformly, so that an extruded film with a small thickness nonuniformity cannot be obtained. On the other hand, if the shear rate is greater than 500 (1 / sec), the shear force is too large. Resin and an additive may decompose | disassemble and deteriorate, and defects, such as foaming, a die line, and a deposit, may arise in the surface of an extruded film.

The thickness of the optical film of this invention is 10-800 micrometers normally, Preferably it is 20-500 micrometers, More preferably, it is 40-500 micrometers. In the case of a thickness of less than 10 μm, it may be difficult in the case of post-processing such as stretching processing due to lack of mechanical strength, etc. On the other hand, in the case of thickness exceeding 800 μm, it is difficult to produce a film having a uniform thickness or surface property. In addition, it may become difficult to wind up the obtained film.

The thickness distribution of the raw film of the present invention is usually within ± 5%, preferably within ± 3%, more preferably within ± 1% of the average value. When thickness distribution exceeds +/- 5%, retardation nonuniformity may arise easily when extending | stretching process is made into an optical film.

<Stretched film>

The stretched film which concerns on this invention can be obtained by further heat-stretching the optical film of this invention obtained by the said method, and can be used as a film which provides retardation to transmitted light. Specifically, it can manufacture by a well-known uniaxial stretching method, biaxial stretching method, and Z-axis stretching method. That is, the uniaxial stretching method by the tenter method, the compression stretching method between rolls, the longitudinal uniaxial stretching method using rolls with different circumferential speeds, or the biaxial stretching method which combined the horizontal uniaxial and longitudinal uniaxial methods, the stretching method by the inflation method, etc. Can be used.

In the case of the uniaxial stretching method, the stretching speed is usually 1 to 5,000% / min, preferably 50 to 1,000% / min, and more preferably 100 to 1,000% / min.

In the biaxial stretching method, stretching may be performed in two directions at the same time, or stretching may be performed in a direction different from the first stretching direction after uniaxial stretching. At this time, the angle of intersection of the two stretching axes for controlling the shape of the refractive index ellipsoid is not particularly limited because it is determined according to desired characteristics, but is usually in the range of 120 to 60 degrees. The stretching speed may be the same or different in each stretching direction, usually 1 to 5,000% / min, preferably 50 to 1,000% / min, more preferably 100 to 1,000% / min, particularly preferably 100 to 500% / min.

The stretching processing temperature is not particularly limited, but is usually Tg ± 30 ° C., preferably Tg, based on the glass transition temperature Tg of the resin composition containing the styrene-based polymer (A) and the norbornene-based polymer (B). ± 15 ° C, more preferably Tg-5 ° C to Tg + 15 ° C. By setting it in the said range, it becomes possible to suppress generation | occurrence | production of phase difference nonuniformity. In addition, in this specification, the glass transition temperature of a resin composition means the extrapolation glass transition start temperature calculated | required according to Japanese Industrial Standard K7121, and the resin composition of this invention is compatible with styrene type polymer (A) and norbornene type polymer (B). It is a value that can be measured because of its superiority. In addition, the resin composition of the present invention can suppress the decrease in the transmittance and the cloudiness of the film due to crystallization or phase separation of the film by controlling the content of each structural unit constituting the styrene-based copolymer (A) even in the stretching process at such a high temperature. Number, excellent compatibility is imparted, and heat drawing processability is good.

The draw ratio is not particularly limited since it is determined according to desired characteristics, but is usually 1.01 to 10 times, preferably 1.03 to 5 times, and more preferably 1.03 to 3 times. When the draw ratio is 10 times or more, control of the phase difference may be difficult.

Although the stretched film may be cooled as it is, it is preferable to maintain and heat set at least 10 seconds, preferably 30 seconds to 60 minutes, more preferably 1 minute to 60 minutes, under a temperature atmosphere of Tg-20 ° C to Tg. Do. Thereby, there exists little change of the phase difference of transmitted light with time, and a stable optical film is obtained.

The dimensional shrinkage ratio by heating of the optical film of the present invention which has not been subjected to stretching is usually 5% or less, preferably 3% or less, more preferably 1% or less, when heating at 100 ° C. is performed for 500 hours. Especially preferably, it is 0.5% or less.

Moreover, when the dimensional shrinkage rate by heating of the stretched film of this invention is performed at 100 degreeC for 500 hours, it is 10% or less normally, Preferably it is 5% or less, More preferably, it is 3% or less, Especially preferably, 1% or less.

In order to carry out dimensional shrinkage rate in the said range, in addition to the selection of the monomer (6) in this invention, or the selection of another copolymerizable monomer, it is also a powerful means to adjust the conditions of an extending method.

In the stretched film obtained as described above, molecules are oriented by stretching to impart retardation to transmitted light, and the retardation can be controlled by stretching ratio, stretching temperature, film thickness, or the like. For example, when the film thickness before extending | stretching is the same, since the absolute value of the phase difference of transmitted light tends to become large, the film with a big draw ratio is large, and the optical film which gives a desired phase difference to transmitted light can be obtained by changing draw ratio. On the other hand, when the draw ratio is the same, since the absolute value of the phase difference of transmitted light tends to increase as the thickness of the film before extending | stretching is thick, the optical film which gives a desired phase difference to transmitted light can be obtained by changing the thickness of the film before extending | stretching. Moreover, in the said extending | stretching process temperature range, since the absolute value of the phase difference of transmitted light tends to become large, so that extending | stretching temperature is low, the optical film which gives a desired phase difference to transmitted light by changing extending | stretching temperature can be obtained.

Although the value of the phase difference which a stretched film provides to transmitted light is determined according to the use, it does not specifically limit, When using for a wavelength plate of a liquid crystal display element, an electroluminescent display element, or a laser optical system, it is usually 1-10,000 nm. , Preferably 10 to 2,000 nm, more preferably 15 to 1,000 nm.

Moreover, it is preferable that the phase difference of the light which permeate | transmitted the stretched film is high uniformity, and the variation of the phase difference in wavelength 550nm is usually ± 20% or less, Preferably it is 10% or less, More preferably, it is ± 5% or less. . That is, the phase difference at a wavelength of 550 nm is usually ± 20% or less with respect to the average value, preferably 10% or less, and more preferably within the range of ± 5% or less. When the variation of the phase difference exceeds ± 20%, when used for a liquid crystal display element or the like, color unevenness may occur, and the performance of the display main body may deteriorate.

In addition, the optical film according to the present invention has a ratio (Re (650) / Re (450)) of retardation Re (650) at a wavelength of 650 nm and retardation Re (450) at a wavelength of 450 nm of 1.8 to 1, preferably Is preferably in the range of 1.7 to 1, more preferably 1.6 to 1. As an optical film which satisfies such a condition, when the phase difference at a certain wavelength? Is set to Re (λ), the value of Re (λ) / λ can be made substantially constant in the entire wavelength region of 400 to 800 nm. .

<Polarizing plate>

Not only are the optical films of this invention used independently, they can be bonded to a transparent substrate etc. and can be used as a polarizing plate. Moreover, a polarizing plate can be laminated | stacked and used for another film, a sheet, and a board | substrate. When laminating | stacking, an adhesive or an adhesive agent can be used. As these adhesives and adhesives, those excellent in transparency are preferable, and specific examples thereof include a natural rubber, a synthetic rubber, a vinyl acetate / vinyl chloride copolymer, a polyvinyl ether, an acryl-based, a modified polyolefin-based, and a curable pressure-sensitive adhesive in which a curing agent such as isocyanate is added thereto. And the adhesive for dry lamination, a synthetic rubber adhesive, an epoxy adhesive, etc. which mix a polyurethane resin solution and a polyisocyanate resin solution.

In addition, in order to improve the workability of laminating with another film sheet, a board | substrate, etc., the said polarizing plate can laminate an adhesive layer or an adhesive bond layer previously. When laminating | stacking, the adhesive or adhesive agent mentioned above can be used as an adhesive and an adhesive agent.

<Liquid Crystal Display, Other Optical Components>

The optical film of this invention can be used for a liquid crystal display device, and can improve the display characteristic of a liquid crystal display device. As a liquid crystal display device, various liquid crystal display devices, such as a mobile telephone, a digital information terminal, a page beep, a navigation, a vehicle-mounted liquid crystal display, a liquid crystal monitor, a light control panel, a display for OA equipment, and a display for AV equipment, are mentioned, for example. have.

Moreover, various optical components can be obtained by injection molding using the resin composition of this invention. Examples of the optical component include various special lenses such as conical lenses and spherical and cylindrical lenses, dielectric mirrors or gold mirrors, and wave plates.

Conventionally well-known methods can be used for injection molding. For example, the resin composition of the present invention is heated and kneaded in a heating cylinder to melt, and is injected from the heating cylinder under pressure into a mold. Then, it cools and solidifies in a metal mold | die, and extrudes with an extrusion apparatus and obtains a molded article. By changing the mold structure used, it can be set as the optical component which has a various shape. At this time, the melting temperature of the resin is preferably the same as the melting temperature at the time of the extrusion molding.

Hereinafter, although this invention is demonstrated further more concretely based on an Example, this invention is not limited to these Examples. In addition, in the following example and a comparative example, "part" and "%" mean "weight part" and "weight%" unless there is particular notice. In addition, room temperature is 25 degreeC. In addition, all the reagents were bubbled with dry nitrogen, dehydrated, and used as the water content of 1 ppm or less.

In the following Examples and Comparative Examples, various measurements and evaluations were performed as follows.

[Polymerization reaction rate]

The polymerization reaction solution weighed in an aluminum container is heated on a hot plate heated to 300 ° C until constant temperature, and after removing the residual monomer and the solvent, the remaining polymer weight is measured to compare with the theoretical amount of polymer production. The reaction rate was calculated | required from ratio.

[Polymer molecular structure]

Using a superconducting nuclear magnetic resonance absorption device (NMR, manufactured by Bruker, trade name: AVANCE500), ¹³ C-NMR was measured in deuterated chloroform, and copolymerization ratio and acetoxy group or butoxy group were converted into OH group. The conversion rate was calculated.

Infrared spectrometer (IR) was measured using FT / IR-420 by Nippon Bunko Corporation.

[Intrinsic viscosity, logarithmic viscosity]

A chlorobenzene solution having a concentration of 0.5 g / 100 ml was prepared and used as a sample, and measured using an wobeldeide viscometer under the condition of 30 ° C.

[Glass Transition Temperature (Tg)]

Using a differential scanning calorimeter (manufactured by Seiko Instruments, Inc., trade name: DSC6200), extrapolation glass transition start temperature (hereinafter, simply referred to as glass transition temperature (Tg)) was obtained according to Japanese Industrial Standard K7121.

[Weight Average Molecular Weight (Mw) and Molecular Weight Distribution (Mw / Mn)]

Gel permeation chromatography (Tosoh Co., Ltd. HLC-8220GPC, column: Tosoh Co., Ltd. guard column H _XL- H, TSK gel G7000H _XL , TSK gel GMH _XL 2, TSK gel G2000H _XL sequentially connected, solvent : Tetrahydrofuran, flow rate: 1 mL / min, sample concentration: 0.7-0.8 weight%, injection | pouring amount: 70 microliters, measurement temperature: 40 degreeC, a detector: RI (40 degreeC), a standard substance: TSK standard manufactured by Tosoh Corporation Polystyrene), and the weight average molecular weight (Mw) and molecular weight distribution (Mw / Mn) were measured. In addition, said Mn is a number average molecular weight.

[Phase difference evaluation]

A toluene or methylene chloride solution (concentration: 25%) of the ring-opening polymer was cast on a smooth glass plate, and then dried to obtain a colorless transparent film having a thickness of 50 to 200 µm and a residual solvent of 0.5 to 0.8%. Free-width uniaxial stretching or width limited uniaxial stretching was carried out 1.2 to 3.0 times at the temperature 5-10 degreeC higher than the glass transition temperature (Tg) of this film. In addition, the thickness, the draw ratio, and the extending | stretching method of a cast film are as each Example mentioned later and Table 1 mentioned. The phase difference of this stretched film was measured using the delay measuring machine (Oji Keisokukiki make, brand name: KOBRA 21DH).

[Polymer Blend Ratio in Resin Composition]

The resin composition was dissolved in tetrahydrofuran and gel permeation chromatograph equipment (HLC-8220GPC manufactured by Tosoh Corporation, Column: Guard Column H _XL- H, TSK gel G7000H _XL , TSK gel GMH _XL , TSK gel G2000H _XL sequentially connected, solvent: tetrahydrofuran, flow rate: 1 mL / min, sample concentration: 0.7 to 0.8% by weight, injection amount: 100 μL, measurement temperature: 40 ℃, detector: UV (254 nm) The blend ratio was calculated by quantifying the styrenic polymer in the resin composition from the area intensity of the spectrum obtained using

[Yellow Degree of Resin]

The C-light 2 ° visual permeation measurement was performed 3 times using SM color computer SM-7-CH by Suga Shijanki Co., Ltd., and the average value was calculated | required (a measurement sample: toluene solution 20 containing 10 weight% of resin). g, measuring cell: cylindrical glass cell with an internal diameter of 60 mm and a height of 30 mm).

[Yellow Degree of Film (YI)]

The YI value of the film with a film thickness of 100 micrometers was measured according to ASTMD1925 using SM Color Computer SM-7-CH by Suga Shikinki Corporation.

[Evaluation of Compatibility under Heating]

Using a Shinto type SFA-37 type heating & cooling two-stage molding machine manufactured by Shinto Kinzoku Kogyo Sho, a film having a thickness of about 100 μm was formed under heating at 280 to 300 ° C., and the haze of the film was measured. Evaluated.

[Presence or absence of insoluble matter in resin]

30 mg of the resin sample was dissolved in 5 mL of toluene, and the presence or absence of an insoluble matter was visually observed. A case of no insoluble matter was evaluated as A and a case of some insoluble matters as B.

[Solution filterability]

30 mg of the resin sample was dissolved in 5 mL of tetrahydrofuran, and the filterability was evaluated using a PTFE filter having a pore size of 0.45 µm and a diameter of 1 cm. A case where no blockage occurred and the whole amount was filtered was evaluated as A, and a case where blockage occurred and partial filtration was not evaluated as B.

Melt Flow Rate (MFR)

MFR was measured at 98 N load and 260 degreeC based on JISK7210.

[Total Light Transmittance (Haze)]

It was measured using a Haze meter HM-150 manufactured by Murakami Shikisai Kijutsu Genjijo Co., Ltd.

[Tear strength]

The tear strength of the film was measured according to JIS K6772.

[Point Defect Measurement]

The mixed resin of component A and component B was dehumidified and dried for 4 hours under nitrogen at a drying temperature of 100 ° C., and then the resin was introduced into an 800 kg stainless steel container in a clean room, and the pressure was 8 kPa. It was preserved daily. In addition, the said stainless steel container is internally replaced by the washing paper (Asahi Kasei Kogyo Co., Ltd. make; brand name "Bencourt") wetted with clean water through a 0.2 μm PVDF filter after replacing the internal air with dry nitrogen before introducing the resin. The one which removed a tendon etc. was used. Then, the resin was introduced into an extruder (GM-65 manufactured by GM Engineering Co., Ltd.), melted at 260 ° C., quantitatively delivered using a gear pump, and removed with a 5 μm leaf disc filter. Extrusion was performed from the T die heated by the aluminum injection heater set to 260 degreeC, and the resin film was obtained. This film was placed on 10 m ^{2 black paper} , and it was confirmed that the reflected light was unstable under a fluorescent lamp of 100 w. The part where reflected light was unstable was made into a point defect, and the part was marked. Thereafter, the film surface was observed with a 50x optical microscope, and the number of point defects having a diameter of 30 µm or more was counted.

[Phase Difference Measurement]

Retardation (delay) at a wavelength of 550 nm was measured using an automatic birefringence meter (KOBRA-21ADH, manufactured by Oji Scientific Instruments Co., Ltd.).

Production Example 1 Preparation of Styrene Copolymer (1A)

In a glass flask equipped with a stirrer, a condenser and a thermometer, 127.87 g (1.23 mol) of styrene, 22.13 g (0.136 mol) of p-acetoxystyrene, 75 g of toluene as a solvent, and 1,1'-azobis (cyclo) as a radical initiator Hexane-1-carbonitrile) 0.67 g (2.7 mmol) was added, heated to 90 ° C. and reacted for 15 hours. A part of this polymerization liquid was taken out and the reaction rate was 85%. Moreover, when molecular weight was measured, it was Mw = 129,935 and Mw / Mn = 2.00.

150 g of toluene was added and diluted in the obtained polymerization reaction solution, and 43.6 g (1.36 mol) of methanol and 1.338 g (0.0136 mol) of concentrated sulfuric acid, which were 1/100 equivalents of acetoxystyrene, were added and heated to 60 ° C. for 2 hours. Reacted. The obtained reaction solution was diluted with tetrahydrofuran and solidified in a large amount of methanol to recover and purify the polymer, and dried in a vacuum dryer at 80 ° C. for 2 days. The molecular weight and logarithmic viscosity of the obtained polymer were measured, respectively. Mw = 131,910 (Mw / Mn = 1.88), logarithmic viscosity η = 0.44 dL / g, and the yield were 80%. IR spectrum and ¹³ C-NMR spectrum of the polymer obtained in FIGS. 1 and 2 are shown, respectively. The copolymerization composition ratio determined by NMR was the same as the charged value, and the methanol decomposition rate was 99% or more. Thereafter, the obtained styrenic copolymer is 1A.

Preparation Example 2 Preparation of Styrene Copolymer (2A)

146.53 g (1.407 mol) of styrene, 3.47 g (0.0214 mol) of p-acetoxystyrene, 75 g of toluene as solvent, and 0.35 g (1.4) of 1,1'-azobis (cyclohexane-1-carbonitrile) as radical initiator The polymerization was carried out in the same manner as in Production Example 1, except that polymerization was carried out using mmol), and then a styrene copolymer was obtained by performing polymerization reaction, dissolution of alcohol, purification and drying. Mw = 199,200 (Mw / Mn = 1.96) of the obtained polymer, and the yield was 80%. Thereafter, the obtained styrene copolymer is 2A.

Preparation Example 3 Preparation of Styrene-Based Copolymer (3A)

117.66 g (1.13 mol) of styrene, 32.34 g (0.199 mol) of p-acetoxystyrene, 75 g of toluene as solvent, and 0.65 g (2.65) of 1,1'-azobis (cyclohexane-1-carbonitrile) as radical initiator The polymerization was carried out in the same manner as in Production Example 1, except that polymerization was carried out using mmol), and then a styrene copolymer was obtained by performing polymerization reaction, dissolution of alcohol, purification and drying. Mw of the obtained polymer was 120,553 (Mw / Mn = 1.97) and the yield was 80%. Thereafter, the obtained styrenic copolymer is 3A.

Preparation Example 4 Preparation of Styrene Copolymer (4A)

84.17 g (0.808 mol) of styrene, 15.83 g (0.0898 mol) of pt-butoxystyrene, 75 g of toluene as solvent, and 0.44 g (1.8) of 1,1'-azobis (cyclohexane-1-carbonitrile) as radical initiator The polymerization was carried out in the same manner as in Production Example 1, except that polymerization was carried out using mmol), and the polymerization reaction, conversion with an acid catalyst, purification, and drying were performed to obtain a styrene copolymer. Mw = 112,000 (Mw / Mn = 2.73) of the obtained polymer, and the yield was 80%. The IR spectrum and ¹³ C-NMR spectrum of the polymer obtained in FIGS. 3 and 4 are respectively shown. The copolymerization composition ratio calculated | required by NMR was the same as the input value, and conversion rate to OH group was 50%. Thereafter, the obtained styrenic copolymer is 4A.

Production Example 5 Preparation of Styrene Copolymer (5A)

78.44 g (0.753 mol) of styrene, 21.56 g (0.133 mol) of pt-butoxystyrene, 50 g of toluene as solvent, and 0.43 g (1.8% of 1,1'-azobis (cyclohexane-1-carbonitrile) as radical initiator The polymerization reaction was carried out in the same manner as in Production Example 1 except that the polymerization was carried out using mmol). Then, 50 g of toluene was added and diluted, 20 g of n-butanol and 0.26 g of sulfuric acid were added, and reaction was performed at 80 degreeC for 8 hours. Purification and drying were carried out in the same manner as in Production Example 1 to obtain a styrene copolymer. Mw of the obtained polymer was 219,000 (Mw / Mn = 2.45) and the yield was 85%. The IR spectrum and ¹³ C-NMR spectrum of the polymer obtained in FIGS. 5 and 6 are shown, respectively. The copolymerization composition ratio determined by NMR was the same as the charged value, and the conversion rate to the OH group was 99% or more. Thereafter, the obtained styrene copolymer is 5 A.

Production Example 6 Preparation of Styrene-Based Polymer (6A)

In a glass flask equipped with a stirrer, a condenser and a thermometer, 117.66 g (1.13 mol) of styrene, 32.34 g (0.199 mol) of p-acetoxystyrene, 75 g of toluene as solvent, and 1,1'-azobis (cyclo) as a radical initiator Hexane-1-carbonitrile) 0.65 g (2.65 mmol) was added, heated to 90 ° C and reacted for 15 hours. It was 85% when a part of this polymerization liquid was taken out and the reaction rate was measured.

150 g of toluene was added and diluted in the obtained polymerization reaction solution, 43.6 g (1.36 mol) of methanol and 1.338 g (0.0136 mol) of concentrated sulfuric acid were added, and it heated at 60 degreeC and made it react for 2 hours. The obtained reaction liquid was diluted with tetrahydrofuran and solidified in a large amount of methanol to recover and purify the polymer, and dried in a vacuum dryer at 80 ° C. for 2 days to obtain styrene polymer 6A. Obtained polymer 6A was Mw = 120,553 (Mw / Mn = 1.97) and the yield was 80%.

Production Example 7 Preparation of Styrene-Based Polymer (7A)

In a glass flask equipped with a stirrer, a condenser, and a thermometer, 392.3 g (3.766 mol) of styrene, 57.72 g (0.3275 mol) of p- ^t butoxystyrene, 211 g of toluene as a solvent, and 1,1'-azobis (as a radical initiator) 1.50 g (6.141 mmol) of cyclohexane-1-carbonitrile) were added, heated to 90 ° C., and reacted for 10 hours, followed by 0.50 g (2.047) of 1,1′-azobis (cyclohexane-1-carbonitrile) mmol) was further added and the reaction was further conducted at 90 ° C for 10 hours. It was 92% when a part of this polymerization liquid was taken out and the reaction rate was measured. Moreover, when molecular weight was measured, it was Mw = 126,700 and Mw / Mn = 2.00.

225 g of toluene was added and diluted in the obtained polymerization reaction solution, 90 g of methanol (diffusion agent of sulfuric acid) and 1.15 g (0.0117 mol) of concentrated sulfuric acid were added, and it heated at 60 degreeC and made it react for 8 hours. Then, 3.03 g (0.027 mol) of 50.5 weight% sodium lactate aqueous solution was added, and stirring was continued at 60 degreeC for 30 minutes. A small amount of the reaction solution was applied to a pH test paper (CS type manufactured by Whatman, Inc., 0.2 interval), and the pH was measured. The pH was 3.8.

After adding 449 g of toluene to this reaction liquid and mixing it uniformly, 899 g of methanol was added and extraction was performed at 60 degreeC for 1 hour. It was cooled to 30 DEG C or lower, left to stand for 1 hour, and separated into a lower layer solution containing a polymer and an upper layer solution containing almost no polymer. Only this upper solution was separated and removed. 440 g of toluene was added to the remaining lower layer solution, and the mixture was uniformly mixed. Then, 617 g of methanol was added, and extraction was again performed at 60 ° C for 1 hour. It was cooled to 30 DEG C or lower and left to stand for 1 hour to separate the lower layer solution containing the polymer and the upper layer solution containing almost no polymer. 440 g of toluene and 617 g of methanol were added, and the operation of separating and removing the upper layer after cooling still further was repeated twice to obtain a polymer solution containing polymer, toluene and methanol. When the polymer concentration in this polymer solution was measured, it was 30 weight%, and the yield computed from the obtained solution weight was 90%. As a result of drying and analyzing a part of this solution, the copolymer composition ratio calculated | required by Mw = 129,208, Mw / Mn = 1.90, Tg = 111 degreeC, and NMR was the same as preparation ratio, and the conversion rate of butoxy group to OH group was 98%.

In the same manner, 10 kg of a polymer solution (polymer concentration of 30% by weight) extracted and purified was prepared, and tetrakis [methylene-3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate was used as an antioxidant. ] 9 g of methane were added and mixed uniformly (hereinafter this resin solution is called doping 1). This solution was demelted and pelletized at 220 degreeC and 20 mmHg using the twin screw extruder of 50 mm (L / D = 13.2), and pellet-shaped resin 7A was obtained. As a result of analyzing the obtained resin pellet 7A, it was YI = 0.8, Mw = 119369, Mw / Mn = 1.98, Tg = 111 degreeC, and residual toluene = 900 ppm. Table 3 shows the results of evaluating the presence or absence of an insoluble matter in the resin 7A and the solution filterability.

Production Example 8 Preparation of Styrene-Based Polymer (8A)

225 g of toluene was added to and diluted in the toluene solution of the styrene / p- ^t butoxystyrene copolymer obtained in the same manner as in Preparation Example 7, followed by adding 90 g of methanol and 1.15 g (0.0117 mol) of concentrated sulfuric acid and heating to 60 ° C. And reacted for 8 hours. Thereafter, 39.3 g (0.0469 mol) of 5 wt% lithium hydroxide aqueous solution was added, and stirring was continued at 60 ° C for 30 minutes. A small amount of the reaction solution was applied to a pH test paper (CS type manufactured by Wattsman Co., Ltd., 0.2 interval) to measure pH. 5.267 g (0.0235 mol) of 50 wt% aqueous lactic acid solution was added to the reaction solution, and stirring was continued at 60 ° C for 30 minutes. A small amount of the reaction solution was applied to a pH test paper (CS type manufactured by Wattsman Co., Ltd., 0.2 interval) to measure pH. The yield obtained in the same manner as in Example was 91%.

Extraction and purification of the polymer solution obtained in the same manner as in Production Example 7 was carried out to obtain a polymer solution having a polymer concentration of 30% by weight. As a result of drying and analyzing a part of this solution, the copolymer composition ratio calculated | required by Mw = 130,050, Mw / Mn = 1.91, Tg = 111 degreeC, and NMR was the same as preparation ratio, and the conversion rate of butoxy group to OH group was 98%.

10 kg of a polymer solution (polymer concentration of 30% by weight) extracted and purified as described above was prepared, and tetrakis [methylene-3- (3,5-di-t-butyl-4-hydroxyphenyl) was used as an antioxidant. 9 g propionate] methane was added and mixed uniformly (hereinafter this resin solution is called dope 2). This solution was demelted and pelletized at 20 degreeC and 220 degreeC using the twin screw extruder of 50 mm (L / D = 13.2), and pellet-shaped resin 8A was obtained. As a result of analyzing the obtained resin pellet 8A, it was YI = 0.9, Mw = 120,000, Mw / Mn = 1.96, Tg = 111 degreeC, and residual toluene = 900 ppm. Table 3 shows the results of evaluating the presence or absence of an insoluble matter in the resin 8A and the solution filterability.

Preparation Example 9 Preparation of Styrene-Based Polymer (9A)

A polymer solution synthesized in the same manner as in Production Example 11 except for not using a base was pelletized by demelting at 20 ° C. at 20 ° C. using a twin screw extruder of 50 mmφ (L / D = 13.2) to obtain pellet 9A. . As a result of analyzing the obtained pellet 9A, an insoluble component was produced in the organic solvent, and an soluble part analysis was carried out and found to be YI = 5.8, Mw = 244,410, Mw / Mn = 3.62, Tg = 115 ° C and residual toluene = 1000 ppm. . Table 3 shows the results of evaluating the presence or absence of an insoluble matter in the obtained resin 9A and solution filterability.

Production Example 10 Preparation of Styrene-Based Polymer (10A)

In a glass flask equipped with a stirrer, a condenser and a thermometer, 340.8 g (3.275 mol) of styrene, 54.83 g (0.409 mol) of p-isopropenylphenol, 215 g of toluene as a solvent of 35.21 g (0.409 mol) methyl acrylate, and as a radical initiator 1.50 g (6.141 mmol) of 1,1'-azobis (cyclohexane-1-carbonitrile) was added, heated to 90 ° C, and reacted for 10 hours, followed by 1,1'-azobis (cyclohexane-1). -Carbonitrile) 0.50 g (2.047 mmol) was further added, and reaction was further performed at 90 degreeC for 10 hours. A part of this polymerization liquid was taken out and the reaction rate was measured and found to be 92%. Moreover, when molecular weight was measured, it was Mw = 57,000 and Mw / Mn = 2.00.

Preparation Example 11 Preparation of Norbornene-Based Polymer (1B)

100 g of 8-methoxycarbonyl-8-methyltetracyclo [4.4.0.1 ^2,5 .1 ^7,10 ] -3-dodecene represented by the following general formula (1a) as a monomer, 3.6 g of 1-hexene as a molecular weight regulator And 200 g of toluene were introduced into a nitrogen-substituted reaction vessel and heated to 80 ° C. 0.21 mL of toluene solution of triethylaluminum (0.6 mol / L) and 0.86 mL of methanol-modified WCl ₆ toluene solution (0.025 mol / L) were added to this, and the ring-opening polymer was obtained by making it react at 80 degreeC for 1 hour. Subsequently, 0.04 g of RuHCl (CO) [P (C ₆ H ₅ ) ₃ ] ₃ as a hydrogenation reaction catalyst was added to the obtained ring-opened polymer solution, and the hydrogen gas pressure was 9 to 10 MPa at a temperature of 160 to 165 ° C. The reaction was carried out for 3 hours. After completion of the reaction, the obtained product was precipitated in a large amount of methanol to obtain a hydrogenated product [glass transition temperature (Tg) = 167 ° C., weight average molecular weight (Mw) = 14.4 × 10 ⁴ , molecular weight distribution (Mw / Mn) = 5.0, Logarithmic viscosity 0.79 dL / g, yield 90 g (yield 90%)]. The hydrogenation rate of this hydrogenated substance calculated | required by NMR measurement was 99.0% or more. Then, the obtained ring-opening polymer hydrogenated substance is set to 1B.

Preparation Example 12 Preparation of Norbornene-Based Polymer (2B)

144 g of 8-methoxycarbonyl-8-methyltetracyclo [4.4.0.1 ^2,5 .1 ^7,10 ] -3-dodecene represented by the above formula (1a), the ratio represented by the following formula (2a) 6 g of cyclo [2.2.1] hept-2-ene, 14.4 g of 1-hexene as a molecular weight regulator, and 225 g of toluene were introduced into a reaction vessel substituted with nitrogen, and heated to 80 ° C. 0.34 mL of toluene solution of triethylaluminum (0.6 mol / L) and 1.37 mL of methanol-modified WCl ₆ toluene solution (0.025 mol / L) were added to this, and the ring-opening polymer was obtained by making it react at 80 degreeC for 1 hour. Subsequently, 0.06 g of RuHCl (CO) [P (C ₆ H ₅ ) ₃ ] _3, which is a hydrogenation reaction catalyst, was added to the obtained ring-opened polymer solution, and the hydrogen gas pressure was 9 to 10 MPa at a temperature of 160 to 165 ° C. The reaction was carried out for 3 hours. After completion of the reaction, the obtained product was precipitated in a large amount of methanol to obtain a hydrogenated product [glass transition temperature (Tg) = 154 ° C., weight average molecular weight (Mw) = 7.4 × 10 ⁴ , molecular weight distribution (Mw / Mn) = 4.2, Logarithmic viscosity 0.55 dL / g, yield 90 g (yield 90%)]. The hydrogenation rate of this hydrogenated substance calculated | required by NMR measurement was 99.0% or more. Then, the obtained ring-opened polymer hydrogenated substance is set to 2B.

Preparation Example 13 Preparation of Norbornene-Based Polymer (3B)

135 g of 8-methoxycarbonyl-8-methyltetracyclo [4.4.0.1 ^2,5 .1 ^7,10 ] -3-dodecene represented by the formula (1a), a tree represented by the following formula (3a) 15 g of cyclo [5.2.1.0 ^2.6 ] deca-3,8-diene, 20.5 g of 1-hexene as a molecular weight modifier, and 225 g of toluene were charged to a nitrogen-substituted reaction vessel and heated to 80 ° C. 0.34 mL of toluene solution of triethylaluminum (0.6 mol / L) and 1.39 mL of methanol-modified WCl ₆ toluene solution (0.025 mol / L) were added thereto, and a ring-opening polymer was obtained by reacting at 80 ° C for 1 hour. Subsequently, in the obtained ring-opened polymer solution, RuH (OCO-Ar-CH ₂ CH ₂ CH ₂ CH ₂ CH ₃ ) (CO) [P (C ₆ H ₅ ) ₃ ] ₂ as a hydrogenation reaction catalyst, wherein Ar is paraphenyl 0.06 g of a benzene group) was added, and after heating up at 90 degreeC, the hydrogen gas pressure was 9-10 MPa, and it heated up to 160-165 degreeC and made it react for 3 hours. After completion of the reaction, the obtained product was precipitated in a large amount of methanol to obtain a hydrogenated product [glass transition temperature (Tg) = 160 ° C., weight average molecular weight (Mw) = 4.4 × 10 ⁴ , molecular weight distribution (Mw / Mn) = 5.5, Logarithmic viscosity 0.41 dL / g, yield 90 g (yield 90%)]. The hydrogenation rate of this hydrogenated substance calculated | required by NMR measurement was 99.0% or more. Then, the obtained ring-opening polymer hydrogenated substance is set to 3B.

Preparation Example 14 Preparation of Norbornene-Based Polymer (4B)

8-methoxycarbonyl-8-methyltetracyclo [4.4.0.1 ^2,5 .1 ^7,10 ] -3-dodecene 12.46 Kg represented by the formula (1a), the ratio represented by the formula (2a) 0.14 Kg of cyclo [2.2.1] hept-2-ene, 1.4 Kg of tricyclo [5.2.1.0 ^2,6 ] deca-3,8-diene represented by the formula (3a), 1.214 Kg of 1-hexene as molecular weight regulator And 21 Kg of toluene were put into the reaction vessel which carried out the nitrogen substitution, and it heated at 80 degreeC. 37.7 mL of toluene solution of triethylaluminum (0.6 mol / L) and 131.44 mL of methanol-modified WCl ₆ toluene solution (0.025 mol / L) were added to this, and the ring-opening polymer was obtained by making it react at 80 degreeC for 1 hour. Subsequently, the obtained ring-opened polymer solution was diluted with 17.7 Kg of toluene, and RuH (OCO-Ar-CH ₂ CH ₂ CH ₂ CH ₂ CH ₃ ) (CO) [P (C ₆ H ₅ ) ₃ ] _{2 which was a} hydrogenation reaction catalyst. 4.69g of (wherein Ar represents a paraphenylene group) were added, and after heating up at 90 degreeC, hydrogen gas pressure was 9-10 MPa, and it heated up to 160-165 degreeC and made it react for 3 hours. After completion of the reaction, the obtained product was precipitated in a large amount of methanol to obtain a hydrogenated product [glass transition temperature (Tg) = 159 ° C, weight average molecular weight (Mw) = 8.8 x 10 ⁴ , molecular weight distribution (Mw / Mn) = 3.0, Logarithmic viscosity 0.65 dL / g, yield 13 Kg (yield 93%)]. The hydrogenation rate of this hydrogenated substance calculated | required by NMR measurement was 99.0% or more. Thereafter, the obtained ring-opening polymer hydrogenated substance is 4B.

Preparation Example 15 Preparation of Norbornene-Based Polymer (5B)

50 parts by weight of 8-methyl-8-carboxymethyltetracyclo [4.4.0.1 ^2,5 .1 ^7,10 ] -3-dodecene (hereinafter also referred to as "DNM") represented by the formula (1a), 25 parts by weight of 5-methyl-5-methoxycarbonylbicyclo [2.2.1] hept-2-ene (hereinafter also referred to as "NM") represented by the formula (4a), 150 parts by weight of toluene, 1-hexene 3.18 weight part was thrown in and heated up at 80 degreeC. 0.030 parts by weight of triethylaluminum and 0.0510 parts by weight of methanol-modified WCl ₆ (methanol: PhPOCl ₂ : WCl ₆ = 103: 630: 427 (weight ratio)) were added and the reaction was started. After 2 minutes, 25 parts by weight of DNM was added dropwise over 10 minutes, and further reacted for 1 hour. The conversion rates of NM and DNM were 52%, 61%, 96.2%, and 97.2% after the completion of the reaction, 2 minutes after the start of the reaction, respectively.

110 parts by weight of toluene and 0.0418 parts by weight of RuH (OCOPh-C ₅ H ₁₁ ) (CO) (PPh ₃ ) ₂ ruthenium hydrogenation catalyst were added, and hydrogen substitution was carried out three times to increase the pressure to 8 MPa. Then, the internal temperature of the reactor was raised to 160 ° C, the pressure was set at 10 MPa, and a hydrogenation reaction of 3 h was performed. According to ¹ H-NMR analysis after hydrogenation, it was 99.9% or more of hydrogenation rate.

After completion of the reaction, 100 parts by weight of toluene was added and diluted, and 3 parts by weight of distilled water, 0.72 parts by weight of lactic acid and 0.00214 parts by weight of hydrogen peroxide were added, followed by heating at 60 ° C. for 30 minutes. Then 234 parts by weight of methanol was added and heated to 60 ° C. for 30 minutes. After cooling to 25 ℃ it was separated into two layers. 333 parts by weight of the supernatant was removed, 202 parts by weight of toluene and 3 parts by weight of water were added, followed by heating at 60 ° C. for 30 minutes. Then 132 parts by weight of methanol was added and heated to 60 ° C. for 30 minutes. After cooling to 25 ° C., it was separated into two layers. Again, 333 parts by weight of the supernatant was removed, 202 parts by weight of toluene and 3 parts by weight of water were added, followed by heating at 60 ° C. for 30 minutes. Then 132 parts by weight of methanol was added and heated to 60 ° C. for 30 minutes. After cooling to 25 ° C., it was separated into two layers. Finally, after removing 333 parts by weight of the supernatant, the polymer solution of the lower layer was diluted to 20% of solid content concentration, and three-stage filtration of 2.0 µm, 1.0 µm and 0.2 µm was performed. This was dried and polymer 5B was obtained. Polymer yield = 92%, 10% toluene solution of YI = 0.31, η = 0.64, Mw = 101450, Mn = 36658, and Tg = 137 ° C.

Example 1

7 g of the polymer 1A obtained in Production Example 1 and 13 g of the polymer 1B obtained in Production Example 11 were dissolved in 200 g of methylene chloride, and the solution obtained by filtration under reduced pressure (filter: GA200 manufactured by Advantech Co., Ltd.) was made of smooth glass. Cast to the bath. After peeling this film from the bathtub, it dried in the vacuum dryer of 100 degreeC for 12 hours, and obtained the film of 145 micrometers in thickness. The logarithmic viscosity and glass transition temperature of the obtained composition (film) were measured, respectively, and the logarithmic viscosity η = 0.68 dL / g and Tg = 141 ° C. In addition, the haze of the film was 0.3.

This film was cut out to a width of 10 mm and a length of 70 mm, and stretched by a tensile tester (Model 5567 manufactured by Instron Corporation) equipped with a constant temperature layer to prepare a free width uniaxial stretched film. When extended | stretched twice at the rate of 220% / min at 146 degreeC, the maximum stress at the time of extending | stretching was 73 Kgf / cm <2>. The film thickness of the obtained film was 104 micrometers, and when retardation (Re) was measured, it was Re450 = 125 nm, Re550 = 141 nm, and Re650 = 149 nm. Where Re450, Re550 and Re650 represent phase differences Re at wavelengths 450, 550 and 650 nm, respectively. Further, the stretching direction is the x-axis, the axis orthogonal to the x-axis in the film plane, the thickness direction of the film is the z-axis (the direction orthogonal to both the x-axis and the y-axis), and the refractive index in each axis direction is n, respectively. _{In the case of x} , n _y , and n _z , the NZ coefficient represented by NZ = (n _x -n _z ) / (n _x -n _y ) was 1.

When compatibility evaluation under the heating of the resin composition film before extending | stretching was performed, transparency was maintained also under the heating of 280-300 degreeC, and haze after heat processing was 0.3. The results are shown in Table 1.

Example 2

A mixture film of 2.9 g of the polymer 2A obtained in Production Example 2 and 5.4 g of the polymer 1B obtained in Production Example 11 was cast in the same manner as in Example 1 to obtain a film having a thickness of 59 μm. It was Tg = 134 degreeC when the glass transition temperature of the obtained composition (film) was measured. In addition, the haze of the film was 0.3.

A free width uniaxial stretched film was produced in the same manner as in Example 1. When extended | stretched twice at the speed | rate of 220% / min at 142 degreeC, the maximum stress at the time of extending | stretching was 68 Kgf / cm <2>. The film thickness of the obtained film was 43 µm, and the retardation (Re) was measured to find Re450 = 62 nm, Re550 = 66 nm, and Re650 = 68 nm. In addition, the NZ coefficient was 1.

When compatibility evaluation under the heating of the resin composition film before extending | stretching was performed, micro phase separation was recognized under the heating of 280 degreeC, and haze = 50. The results are shown in Table 1.

Example 3

A mixture film of 2.9 g of the polymer 3A obtained in Production Example 3 and 5.4 g of the polymer 2B obtained in Production Example 12 was cast in the same manner as in Example 1 to obtain a film having a thickness of 100 µm and a haze of 0.3.

A free width uniaxial stretched film was produced in the same manner as in Example 1. When extended | stretched twice at the speed | rate of 220% / min at 135 degreeC, the maximum stress at the time of extending | stretching was 61 Kgf / cm <2>. The film thickness of the obtained film was 79 µm, and the retardation (Re) was measured to find Re450 = 80 nm, Re550 = 93 nm, and Re650 = 99 nm. In addition, the NZ coefficient was 1.

When compatibility evaluation under the heating of this resin composition film was performed, transparency was maintained also under the heating of 280-300 degreeC, and haze after heat processing was 0.3. The results are shown in Table 1.

Example 4

A mixture film of 2.9 g of the polymer 3A obtained in Production Example 3 and 5.4 g of the polymer 3B obtained in Production Example 13 was cast in the same manner as in Example 1 to obtain a film having a thickness of 91 μm and a haze of 0.3.

A free width uniaxial stretched film was produced in the same manner as in Example 1. When stretched at 1.9 times at 220% / min at 142 ° C, the maximum stress at the time of stretching was 89 Kgf / cm 2. The film thickness of the obtained film was 67 µm, and the retardation (Re) was measured to find Re450 = 72 nm, Re550 = 86 nm, and Re650 = 92 nm. In addition, the NZ coefficient was 1.

When compatibility evaluation under the heating of this resin composition film was performed, transparency was maintained also under the heating of 280-300 degreeC, and haze after heat processing was 0.3. The results are shown in Table 1.

Example 5

A mixture film of 2.9 g of the polymer 4A obtained in Production Example 4 and 5.4 g of the polymer 1B obtained in Production Example 11 was cast in the same manner as in Example 1 to obtain a film having a thickness of 90 µm and a haze of 0.3.

A free width uniaxial stretched film was produced in the same manner as in Example 1. When extended | stretched twice at the rate of 220% / min at 145 degreeC, the maximum stress at the time of extending | stretching was 60 Kgf / cm <2>. The film thickness of the obtained film was 65 micrometers, and when retardation (Re) was measured, it was Re450 = 77 nm, Re550 = 86 nm, and Re650 = 90 nm. In addition, the NZ coefficient was 1.

When compatibility evaluation under the heating of this resin composition film was performed, transparency was maintained also under the heating of 280 degreeC, and haze after heat processing was 0.3. The results are shown in Table 1.

Example 6

A mixture film of 2.9 g of the polymer 5A obtained in Production Example 5 and 5.4 g of the polymer 3B obtained in Production Example 13 was cast in the same manner as in Example 1 to obtain a film having a thickness of 92 µm and a haze of 0.3.

A free width uniaxial stretched film was produced in the same manner as in Example 1. When stretched at 1.9 times at a rate of 220% / min at 147 ° C, the maximum stress at the time of stretching was 35 Kgf / cm 2. The film thickness of the obtained film was 72 micrometers, and when retardation (Re) was measured, it was Re450 = 88 nm, Re550 = 96 nm, and Re650 = 101 nm. In addition, the NZ coefficient was 1.

When compatibility evaluation under the heating of this resin composition film was performed, transparency was maintained even under 300 degreeC heating, and haze after heat processing was 0.3. The results are shown in Table 1.

Example 7

A mixture film of 7 g of the polymer 5A obtained in Production Example 5 and 13 g of the polymer 4B obtained in Production Example 14 was cast in the same manner as in Example 1 to obtain a film having a thickness of 93 µm and a haze of 0.3.

A free width uniaxial stretched film was produced in the same manner as in Example 1. When extended | stretched 2.8 times at the rate of 220% / min at 147 degreeC, the maximum stress at the time of extending | stretching was 65 Kgf / cm <2>. The film thickness of the obtained film was 58 micrometers, and when retardation (Re) was measured, it was Re450 = 99 nm, Re550 = 111 nm, and Re650 = 118 nm. In addition, the NZ coefficient was 1.

When compatibility evaluation under the heating of this resin composition film was performed, transparency was maintained even under 300 degreeC heating, and haze after heat processing was 0.3. The results are shown in Table 1.

Example 8

A mixture film of 7 g of the polymer 5A obtained in Production Example 5 and 13 g of the polymer 4B obtained in Production Example 14 was cast into a film by the same method as in Example 1 to obtain a film having a thickness of 180 μm and a haze of 0.3.

The obtained film was cut out in 10 cm directions, and the width was confined at 2.4 times at a speed of 300% / min at 145 ° C using a hydraulic servo-type biaxial stretching test apparatus X6H-S manufactured by Toyo Seiki Seisakusho Co., Ltd. 1 Axial-stretched. The maximum stress at the time of stretching was 4 Kgf / cm 2. The film thickness of the obtained film was 75 µm, and the retardation (Re) was measured to find Re450 = 86 nm, Re550 = 95 nm, and Re650 = 99 nm. In addition, the NZ coefficient was 1.44. The results are shown in Table 1.

Example 9

A mixture film of 6.6 g of the polymer 5A obtained in Production Example 5 and 13.4 g of the polymer 4B obtained in Production Example 14 was cast to form a film by the same method as in Example 1 to obtain a film having a thickness of 189 μm and a haze of 0.3.

In the same manner as in Example 8, the obtained film was uniaxially stretched at a width of 147 ° C at 2.3 times. The maximum stress at the time of stretching was 3 Kgf / cm 2. The film thickness of the obtained film was 83 µm, and the retardation (Re) was measured to find Re450 = 98 nm, Re550 = 104 nm, and Re650 = 108 nm. In addition, the NZ coefficient was 1.38. The results are shown in Table 1.

[Examples 10 and 11]

Styrene copolymer 7A before desolvent obtained in Production Example 7 and norbornene-based resin 5B before desolvent obtained in Production Example 15 were used as the weight ratios of 6/14 (Example 10) and 9/11 (Example 11). It prepared by the ratio and adjusted solid content to 20%. Each polymer solution was filtered through a 0.2 μm pore size PTFE filter. Then, solvent removal was performed on condition of 260 degreeC and 1.0 torr, and the blend resin pellet was obtained through the 5 micrometer filter. The chart in the Tg measurement of Example 10 is shown in FIG. 7, and the chart in the Tg measurement of Example 11 is shown in FIG. In all, Tg derived from a homopolymer was lost, and a single peak was confirmed, and it was found that styrene-based copolymer 7A and norbornene-based resin 5B were commercialized in any composition. Tg in Example 10 was 128 degreeC, and Tg in Example 11 was 124 degreeC.

The composition of Example 10 was deposited at a rate of 10 m / min at 260 ° C. with a melt extrusion apparatus having a 5 μm polymer filter. As a result, the pressure difference before and after passing the filter was as low as 2 MPa and was 500 mm wide and 250 μm thick. Film was obtained. Haze = 0.3 and YI = 0.3, the coloring property was small and it was a transparent film. Since the film had a single peak of Tg = 128 ° C., it was found that the styrene copolymer 7A and the norbornene-based resin 5B did not separate even after film molding. This film was cut out to 10 cm x 10 cm, and the width | variement binding extending | stretching which does not change with the width | variety of the lateral direction being 10 cm was performed. Stretching conditions: Stretching temperature = 133 degreeC (Tg + 5 degreeC), extending | stretching speed = 300 mm / min, draw ratio of the longitudinal direction = 3.0 times. Membrane thickness after stretching = 80 μm. The phase differences of 550 nm and 650 nm were 140 nm and 145 nm, respectively, and the phase difference ratio (wavelength dispersibility) of 650 nm and 550 nm was 1.036. The birefringence of 550 nm and 650 nm was calculated from retardation / film thickness and was 0.00175 and 0.00181, respectively. Moreover, it was NZ coefficient = 1.025. The results are shown in Table 1.

In addition, a molded article having a thickness of 3 mm was prepared at 280 ° C using the composition of Example 11 and using an injection molding machine. It was found that the phase difference of the molded article was very small at a maximum of 2 nm, low birefringence, and low colorability at YI = 0.7.

Example 12

Styrene-based copolymer 10A synthesized in Production Example 10 and norbornene-based resin 5B before desolvent obtained in Production Example 15 were prepared and adjusted in a ratio of 6 g / 14 g, and casted into a film by the same method as in Example 1. A film of 190 µm and haze = 0.3 was obtained. The results are shown in Table 1.

Comparative Example 1

Cast film forming of the mixture with Polymer 1B obtained in Production Example 11 was carried out in the same manner as in Example 1 except that PS Japan Co., Ltd. manufactured polystyrene was used instead of Polymer 1A. As a result, a transparent film could not be obtained regardless of the solvent used.

Moreover, when compatibility evaluation was performed under heating, phase separation of the shape of the structure was observed at 280 ° C. The results are shown in Table 2.

Comparative Example 2

Cast film formation of the mixture with Polymer 1B obtained in Preparation Example 11 was carried out in the same manner as in Example 1 except that maleic anhydride / styrene copolymer (DYLARK232) manufactured by Nova Chemicals was used instead of cyclic polymer 1A. It was. As a result, when methylene chloride was used as a solvent, a transparent film could not be obtained. On the other hand, when toluene was used as the solvent, a transparent film could be obtained, but the drying rate was slow, which was not suitable for industrial production.

Moreover, when the compatibility evaluation of the cast film obtained using toluene was performed under heating, micro phase separation was observed at 280 degreeC.

Moreover, when commercialization by melt kneading using a twin screw extruder was examined, only a cloudy pellet was obtained at 290 degreeC. The results are shown in Table 2.

Comparative Example 3

A polymer was synthesized in the same manner as in Production Example 1 except that p-isopropenylphenol was used instead of acetoxy styrene. The molecular weight of the obtained polymer was Mw = 20,000 (Mw / Mn = 2.2) and the reaction rate was 57%. When the film was cast into a mixture of the obtained polymerized product and the polymer 1B obtained in Production Example 5, the strength of the film was low, and the characteristics could not be evaluated. The results are shown in Table 2.

[Comparative Example 4]

20 g of the polymer 1B obtained in Production Example 11 was cast into a film in the same manner as in Example 1 to obtain a film having a thickness of 140 µm and a haze of 0.3.

In the same manner as in Example 1, the obtained film was uniaxially stretched free at 2.0 times at 177 ° C. The maximum stress at the time of stretching was 40 Kgf / cm 2. The film thickness of the obtained film was 100 micrometers, and when retardation (Re) was measured, it was Re450 = 396 nm, Re550 = 388 nm, and Re650 = 384 nm. In addition, the NZ coefficient was 1. The results are shown in Table 2.

Example 13

5 Kg of the resin pellet 7A obtained in Production Example 7, 3 Kg of the polymer 5B obtained in Production Example 15, tetrakis [methylene-3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate ] 9 g of methane and 7 Kg of toluene were added and mixed uniformly. This blend resin solution was demelted and pelletized at 20 mmHg at 280 degreeC using the twin-screw extruder of 50 mm (L / D = 13.2), and the resin pellet 1 was obtained. The obtained pellet 1 was analyzed and found to be YI = 1.1, Mw = 132,000, Mw / Mn = 2.96, Tg = 136 ° C. and residual toluene = 1000 ppm. In addition, the evaluation result of the presence or absence of an insoluble matter in the obtained resin pellet 1 and solution filterability is shown in Table 3.

Example 14

A resin solution was prepared in the same manner as in Example 13 except that the resin pellet 8A obtained in Production Example 8 was used instead of the resin pellet 7A. This blend resin solution was demelted and pelletized at 20 mmHg at 280 degreeC using the twin-screw extruder of 50 mm (L / D = 13.2), and the resin pellet 2 was obtained. The obtained pellet 2 was analyzed and found to be YI = 1.0, Mw = 131,000, Mw / Mn = 2.86, Tg = 136 ° C. and residual toluene = 1000 ppm. In addition, the evaluation result of the presence or absence of an insoluble matter in the obtained resin pellet 2 and solution filterability are shown in Table 3.

Example 15

In Example 11, the resin solution was manufactured like Example 1 except having used the resin pellet 9A obtained by the manufacture example 9 instead of the resin pellet 7A. This blend resin solution was demelted and pelletized at 20 mmHg at 280 degreeC using the twin-screw extruder of 50 mm (L / D = 13.2), and the resin pellet 3 was obtained. The obtained pellet 3 was analyzed and found to be YI = 5.6, Mw = 150751, Mw / Mn = 3.66, Tg = 119 ° C. and residual toluene = 2890 ppm. In addition, the evaluation result of the presence or absence of an insoluble matter in the obtained resin pellet 3 and solution filterability are shown in Table 3.

The resin composition of this invention is excellent in compatibility, excellent in transparency, hard to be colored at the time of heating, and can also be set as the resin composition containing a styrene copolymer of high molecular weight. Since the resin composition of this invention can be used suitably for the shaping | molding use of various optical materials, and is excellent in film forming property, it can be used especially for an optical film use, and the optical film excellent in the strength can be obtained. Moreover, when extending | stretching the optical film obtained from the resin composition of this invention, since what is called reverse wavelength dispersibility which phase difference increases as incident light wavelength becomes long wavelength can also be expressed, it can be used for various liquid crystal display devices, polarizing plates, etc. Further, by adjusting the composition ratio of the styrene copolymer (A) and the norbornene-based polymer (B), it is possible to easily adjust the magnitude of the phase difference and the wavelength dispersibility, so that the optical component or the like for which low birefringence is required Can be used.

Claims (17)

(A) It has a structural unit (1) represented by following General formula (1), and a structural unit (2) represented by following General formula (2), and content rate of the said structural unit (2) is 0.1 in 100 mol% of all the structural units. Styrene copolymer which is from 50 mol%, (B) A resin composition comprising a norbornene-based polymer.

(In formula (1) and formula (2), R represents a hydrogen atom or a methyl group, and in formula (2), R ⁰ represents a hydrogen atom; a halogen atom; an oxygen atom, a sulfur atom, a nitrogen atom, or a silicon atom). A substituted or unsubstituted hydrocarbon group having 1 to 30 carbon atoms, or a polar group). The resin composition according to claim 1, wherein the styrene copolymer (A) has a weight average molecular weight Mw of 30,000 to 1,000,000 measured by gel permeation chromatography (GPC). The resin composition according to claim 1, wherein the styrene copolymer (A) has a yellowness (YI) of 5.0 wt% or less of a 10 wt% toluene solution measured using a colorimeter. The structure derived from the monomer (4) according to claim 1, wherein the styrene-based copolymer (A) polymerizes styrene and / or α-methylstyrene with the monomer (4) represented by the following general formula (4). resin composition, characterized in that is obtained by a process comprising the step of converting an -OH group -OR ¹⁴ in the unit.

(In formula (4), R represents a hydrogen atom or a methyl group, R ⁰ represents a hydrogen atom; a halogen atom; a substituted or unsubstituted that may have a linking group containing an oxygen atom, a sulfur atom, a nitrogen atom, or a silicon atom. A hydrocarbon group having 1 to 30 carbon atoms or a polar group, and R ¹⁴ represents an acetyl group, t-butyl group, t-butoxycarbonyl group, -CH (OR ¹⁵ ) (R ¹⁶ ), or -SiR ¹⁵ ₃ group R ¹⁵ and R ¹⁶ may each independently represent an alkyl group having 1 to 6 carbon atoms, and R ¹⁵ and R ¹⁶ , or R ¹⁵ may be bonded to each other to form a hetero ring having 2 to 12 carbon atoms; ). The process according to claim 4, wherein the styrene copolymer (A) converts the -OR ¹⁴ group in the structural unit derived from the monomer (4) in the presence of an acid, followed by a basic substance. The resin composition obtained by the method including the process of adding and making it react with the acid in a system. The resin composition according to claim 1, wherein the norbornene-based polymer (B) is a (co) polymer having a structural unit derived from a monomer (6) represented by the following general formula (6).

(Wherein (6), a and b are independently 0 or 1, c and d are independently 0 to indicate a second ^{integer, R 4, R 5, R} 6, R 7, R 8, R 9 , R ¹⁰ , R ¹¹ , R ¹² , and R ¹³ each independently represent a hydrogen atom; a halogen atom; a substituted or unsubstituted carbon number that may have a linking group including an oxygen atom, a sulfur atom, a nitrogen atom, or a silicon atom A hydrocarbon group of 30 to 30; or a polar group, R ¹⁰ and R ¹¹ , or R ¹² and R ¹³ may be integrated to form a divalent hydrocarbon group, and R ¹⁰ or R ¹¹ and R ¹² or R ¹³ may be bonded to each other; Carbocycles or heterocycles (which may be monocyclic or may be condensed to form a polycyclic structure). The resin composition according to claim 1, wherein the norbornene-based polymer (B) is a (co) polymer having a structural unit represented by the following general formula (i).

(In Formula (i), A ¹ to A ⁴ each independently represent a hydrogen atom; a halogen atom; the number of substituted or unsubstituted carbon atoms which may have a linking group including an oxygen atom, a sulfur atom, a nitrogen atom, or a silicon atom. A hydrocarbon group of 1 to 30; or a polar group, and at least one of A ¹ to A ⁴ is a group represented by-(CH ₂ ) _n COOA ⁵ (A ⁵ includes an oxygen atom, a sulfur atom, a nitrogen atom, or a silicon atom A substituted or unsubstituted hydrocarbon group having 1 to 30 carbon atoms, and n is 0 or an integer of 1 to 5). The norbornene-based polymer (B) has a structural unit represented by the general formula (i) as 10 to 70 mol% in 100 mol% of the total structural units of the norbornene-based polymer (B). Resin composition made into. The composition ratio ((A) / (B)) of the styrene-based copolymer (A) and the norbornene-based polymer (B) is in the range of 5/95 to 70/30 by weight. Resin composition. A molded article comprising the resin composition according to claim 1 as a main component. The molded article according to claim 10, which is obtained by melt extrusion molding. The optical film which has a resin composition of Claim 1 as a main component. The optical film of Claim 12 obtained by forming into a film by the casting method. The optical film of Claim 12 obtained by forming into a film by the extrusion method. The stretched film obtained by heat extending | stretching the optical film of Claim 12. The polarizing plate containing the optical film of Claim 12. The liquid crystal display device containing the optical film of Claim 12.

Images