JP2009227868A - Resin composition and film - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To adjust a Rth (retardation in the thickness direction) value of an unoriented norbornene compound addition polymer film and to materialize the various Re (retardation) or Rth values only by uniaxial orientation of the film. <P>SOLUTION: A resin composition comprises the norbornene compound addition polymer (A) having the repeating unit shown by general formula (1) (wherein R<SP>1</SP>, R<SP>2</SP>, R<SP>3</SP>and R<SP>4</SP>are each a hydrogen atom or a functional substituent independently) and a vinyl polymer (B) having a hydroxyl group. <P>COPYRIGHT: (C)2010,JPO&INPIT

Description

  The present invention relates to a resin composition and a film using the resin composition (in particular, various functional films such as a retardation film, a viewing angle widening film, an antireflection film used for a plasma display, and a polarizing plate protective film).

  A film of norbornene-based addition polymer (hereinafter also referred to as norbornene-based polymer) obtained by vinyl polymerization of norbornene-based compound has a thickness direction retardation (Rth) in an unstretched state (not stretched) due to its unique structure. It has the characteristic that it is high (for example, refer patent document 1). When this is uniaxially stretched, retardation (Re) is developed, and Re and Rth in a region applicable to a VA (vertical alignment) liquid crystal display device can be developed (for example, see Patent Document 2).

  On the other hand, specific Re and Rth values are determined by the display. When the norbornene-based polymer film is uniaxially stretched as described above, it is possible to reach the target Re, but in this case, Rth automatically becomes a predetermined value. That is, Re and Rth can be close to the target area, but may not necessarily be unique values suitable for each display.

  Therefore, it is preferable to adjust the Rth value of the unstretched norbornene-based addition polymer film and to express various Re and Rth only by uniaxial stretching, but such a technique is not known.

A technique is known in which a vinyl polymer is added to a norbornene-based ring-opening polymerization hydrogenated product to change the wavelength dispersion of the film (see, for example, Patent Document 3). However, in this technique, it is essential to stretch the film at a high magnification of about 100% in order to develop wavelength dispersion. That is, it can be said that the effect of the addition of the vinyl polymer in this patent document is very small in an unstretched film or a low magnification stretched film (up to about 30%). Further, this patent document does not mention a norbornene addition polymer as a cyclic olefin polymer.
JP 2005-539275 A Special table 2007-534010 gazette International Publication No. 06/070820 Pamphlet

  An object of the present invention is to adjust the value of Rth of an unstretched norbornene-based addition polymer film, and to provide Re and Rth to various values only by uniaxial stretching. That is, it is to easily and freely control the values of Re and Rth of the norbornene polymer.

  The present inventor attempted to reduce Rth from the original norbornene polymer film by adding an organic material to the norbornene polymer, and examined the organic material in various ways. As a result, it has been found that a resin having a certain molecular weight and having a hydroxyl group is compatible with the norbornene-based polymer, which gives a transparent film, and Rth can be reduced, leading to the present invention.

Means for solving the above problems are as follows.
1. A resin composition comprising a norbornene polymer (A) having a repeating unit represented by the following general formula (1) and a vinyl polymer (B) having a hydroxyl group.

(In the general formula (1), R ¹ , R ² , R ³ and R ⁴ are each independently a hydrogen atom or — (CH ₂ ) _m —OC (O) —R ″, — (CH ₂ ) _{m. -OH, - (CH 2) m} -C (O) -OH, - (CH 2) m -C (O) OR '', - (CH 2) m -OR '', - (CH 2) m - A functional substituent selected from the group consisting of OC (O) OR ″, — (CH ₂ ) _m —C (O) R ″, — (CH ₂ ) _m —O— (CH ₂ ) _m —OH; Wherein m is independently 0 to 10, R ″ represents a linear or branched alkyl group having 1 to 10 carbon atoms, and R ¹ and R ⁴ are bonded to each other. Together with the ring carbon atoms can form an anhydride or dicarboximide group, provided that at least one of R ^{1 to} R ⁴ is a functional substituent.)
2. 2. The resin composition according to 1 above, wherein the vinyl polymer (B) having a hydroxyl group is a polymer having a repeating unit represented by the following general formula (2).

(In General Formula (2), R _{1 to} R ₃ each independently represent a hydrogen atom; a halogen atom; an oxygen atom, a sulfur atom, a nitrogen atom or a silicon atom, which may have a linking group, An unsubstituted hydrocarbon group having 1 to 30 carbon atoms; or a polar group, and n is 0 or a positive integer.)
3. 3. The resin composition as described in 2 above, wherein the vinyl polymer (B) having a hydroxyl group is a polymer further having at least one repeating unit selected from the following general formulas (3) and (4).

(In General Formulas (3) and (4), R _{4 to} R ₇ may each independently have a linking group containing 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, and all R _{5 s} may be the same atom or group or different from each other.
4). 4. The resin composition according to 3 above, wherein the vinyl polymer (B) having a hydroxyl group is a polymer having each repeating unit of the following general formula (5).

(In the general formula (5), R _{1 to} R ₇ are each independently a hydrogen atom; a halogen atom; an oxygen atom, a sulfur atom, a nitrogen atom or a silicon atom, which may have a linking group, An unsubstituted hydrocarbon group having 1 to 30 carbon atoms; or a polar group, and all R _{5 s} may be the same or different from each other, and n may be 0 or positive X, y and z represent the molar ratio of each repeating unit when x + y + z = 100 mol%, and 1 <x <20 and 40 <y <99 are satisfied.)
5. The resin composition according to any one of 1 to 4 above, wherein the vinyl polymer (B) having a hydroxyl group has a weight average molecular weight of 1000 to 50000 and a number average molecular weight of 500 to 25000.
6). 6. The resin composition according to 4 or 5 above, wherein R ₇ in the general formula (5) is COOR ″ (R ″ is an alkyl group having 1 to 4 carbon atoms).
7). 7. The resin composition according to any one of 1 to 6 above, wherein the norbornene polymer (A) contains 50 to 100 mol% of a repeating unit represented by the general formula (1).
8). One of R ¹ , R ² , R ³ and R ^{4 in} the general formula (1) is —CH ₂ —OC (O) —R ″ (R ″ is the same as described above) or —C (O) OR. 8. The resin composition according to any one of 1 to 7 above, wherein R is the same as described above, and the remaining three are hydrogen atoms.
9. The resin according to any one of 1 to 8 above, wherein a mass mixing ratio (A / B) of the vinyl polymer (B) having a hydroxyl group and the norbornene polymer (A) is 99/1 to 50/50. Composition.
10. The film which consists of a resin composition in any one of said 1-9.

  Hereinafter, embodiments of the present invention will be described in detail. In the present specification, “to” is used to mean that the numerical values described before and after it are included as a lower limit value and an upper limit value.

[Norbornene polymer (A)]
In the present invention, the norbornene polymer is defined as a homopolymer obtained by addition polymerization of one kind of norbornene compound or a copolymer obtained by addition polymerization of two or more kinds of norbornene compounds.

  The norbornene polymer (A) in the present invention has a repeating unit represented by the following general formula (1).

In the general formula (1), R ¹ , R ² , R ³ and R ⁴ are each independently a hydrogen atom or — (CH ₂ ) _m —OC (O) —R ″, — (CH ₂ ) _m —. OH, — (CH ₂ ) _m —C (O) —OH, — (CH ₂ ) _m —C (O) OR ″, — (CH ₂ ) _m —OR ″, — (CH ₂ ) _m —OC A functional substituent selected from the group consisting of (O) OR ″, — (CH ₂ ) _m —C (O) R ″, — (CH ₂ ) _m —O— (CH ₂ ) _m —OH Where m is independently 0-10, R ″ represents linear or branched (C ₁ -C ₁₀ ) alkyl, and R ¹ and R ⁴ are the ring member carbons to which they are attached. Together with the atoms, an anhydride or dicarboximide group can be formed. However, at least one of R ^{1 to} R ⁴ is a functional substituent.

The monomer for obtaining the repeating unit represented by the general formula (1) can be obtained by Diels-Alder reaction between cyclopentadiene and the corresponding olefin. Therefore, from the viewpoint of the versatility of the corresponding olefin, the functional substituents are — (CH ₂ ) _m —OC (O) —R ″, — (CH ₂ ) _m —OH, — (CH ₂ ) _m —. C (O) —OH, — (CH ₂ ) _m —C (O) OR ″, and — (CH ₂ ) _m —OR ″ are preferred. Furthermore, from the viewpoint of monomer polysynthesis, — (CH ₂ ) _m —OC (O) —R ″, — (CH ₂ ) _m —C (O) OR ″, — (CH ₂ ) _m —OR ′ ′ Is more preferable, and — (CH ₂ ) _m —OC (O) —R ″ and — (CH ₂ ) _m —C (O) OR ″ are most preferable.

  m and R ″ preferably have a small carbon number from the viewpoint of reducing the photoelasticity of the film, but are preferably large from the viewpoint of lowering the glass transition point of the polymer. Considering both points, R ″ preferably has 1 to 6 carbon atoms, more preferably 1 to 3, and most preferably 1 or 2. m is preferably 1 to 5, more preferably 1 to 3, and most preferably 1 to 2.

  There are two types of stereochemistry of functional substituents, endoexo, which may be used alone or in a mixture. In the Diels-Alder reaction described above, it is common that the end body is a mixture of main products, and this may be used as it is.

  Specific examples of the repeating unit represented by the general formula (1) are shown below, but the present invention is not limited thereto.

  The norbornene polymer (A) includes the skeleton of the general formula (1), but may include one or more other norbornene compounds. In this case, the skeleton of the general formula (1) is preferably contained in an amount of 50 to 100 mol%, more preferably 60 to 100 mol%, and most preferably 80 to 100 mol%.

  Although the preferable compound of the norbornene-type polymer (A) of this invention is illustrated below, this invention is not limited to these. In addition, the numerical value of the upper right of () shows the ratio of copolymerization.

  The norbornene-based polymer (A) of the present invention preferably has a polystyrene-equivalent number average molecular weight of 10,000 to 1,000,000 as measured by gel permeation chromatography using tetrahydrofuran as a solvent. It is more preferable that it is 1,000-500,000. The weight average molecular weight in terms of polystyrene is preferably 15,000 to 1,500,000, more preferably 70,000 to 700,000. When the number average molecular weight in terms of polystyrene is 10,000 or more and the weight average molecular weight is 15,000 or more, the fracture strength tends to be more preferable, the number average molecular weight in terms of polystyrene is 1,000,000 or less, and the weight average molecular weight. If it is 1,500,000 or less, the molding processability as a sheet tends to be improved, and when it is used as a cast film or the like, the solution viscosity becomes low and tends to be easy to handle. The molecular weight distribution (weight average molecular weight / number average molecular weight) is preferably 1.1 to 5.0, more preferably 1.1 to 4.0, and still more preferably 1.1 to 3.5. By setting the molecular weight distribution of the norbornene-based polymer within the above range, the norbornene-based polymer solution (dope) is likely to be uniform, and a good film can be easily produced.

  The norbornene polymer (A) of the present invention can be obtained by the following polymerization method using a monomer corresponding to the general formula (1) and, if necessary, other norbornene monomers.

[Pd (CH ₃ CN) ₄ ] [BF ₄ ] ₂ , di-μ-chloro-bis- (6-methoxybicyclo [2.2.1] hept-2-ene-endo-5σ, 2π) as a polymerization catalyst -Pd (hereinafter abbreviated as "I") and methylalumoxane (MAO), I and AgBF ₄ , I and AgSbF ₆ , [(η ³ -allyl) PdCl] ₂ and AgSbF ₆ , [(η ³ -allyl) PdCl] ₂ and AgBF ₄ , [(η ³ -crotyl) Pd (cyclooctadiene)] [PF ₆ ], [(η ³ -allyl) Pd (η ⁵ -cyclopentadienyl)] ₂ and tricyclohexylphosphine Dimethylanilinium tetrakispentafluorophenylborate or trityltetrakispentafluorophenylborate, palladium bisacetylacetonate, tricyclohexylphosphine and dimethyla Nilinium tetrakispentafluorophenylborate, palladium acetate and tricyclohexylphosphine and dimethylanilinium tetrakispentafluorophenylborate, [(η ³ -allyl) PdCl] ₂ and tricyclohexylphosphine and tributylallyltin or allylmagnesium chloride and dimethylanilinium Tetrakispentafluorophenylborate, [(η ⁵ -cyclopentadienyl) Ni (methyl) (triphenylphosphine)] and trispentafluorophenylborane, [(η ³ -crotyl) Ni (cyclooctadiene)] [B ( (CF ₃ ) ₂ C ₆ H ₄ ) ₄ ], [NiBr (NPMe ₃ )] ₄ and MAO, Ni (octoate) ₂ and MAO, Ni (octoate) ₂ and B (C ₆ F ₅ ) ₃ and AlEt ₃ , Ni (Oct Ate) ₂ and [Ph ₃ C] [B (C ₆ F ₅ ) ₄ ], Ali-Bu ₃ , Co (neodecanoate) and a cation complex or cation of Ni, Pd, Co or the like of Group 8 of the periodic table such as MAO It is obtained by homopolymerizing or copolymerizing monomers in a solvent at a temperature of 20 to 150 ° C. using a catalyst for forming a complex.
The monomer can be allowed to react in the reaction vessel from the beginning, or a method of gradually feeding the monomer can be employed.
Solvents include cycloaliphatic hydrocarbon solvents such as cyclohexane, cyclopentane and methylcyclopentane; aliphatic hydrocarbon solvents such as pentane, hexane, heptane and octane; aromatic hydrocarbon solvents such as toluene, benzene and xylene; dichloromethane Halogenated hydrocarbon solvents such as 1,2-dichloroethylene and chlorobenzene; polar solvents such as ethyl acetate, butyl acetate, γ-butyrolactone, propylene glycol dimethyl ether and nitromethane.
Other synthesis methods include Macromolecules, 1996, 29, 2755, Macromolecules, 2002, 35, 8969, International Patent Publication No. 04/007564, International Patent Publication No. 04/050726, International Patent The methods described in the pamphlets of Publication No. 06/004376, International Patent Publication No. 06/031067, International Patent Publication No. 06/013759, and International Patent Publication No. 06/046611 are also preferably used.

  Further, the norbornene-based polymer obtained by the above polymerization method can be further converted by a polymer reaction.

[Vinyl polymer containing hydroxyl group (B)]
The vinyl polymer (B) containing a hydroxyl group used in the present invention is a polymer having a structural unit represented by the following general formula (2). Further, the following general formulas (3) and (4) A copolymer having at least one structural unit selected from:

In the formula, each of R _{1 to} R ₇ independently represents a hydrogen atom; a halogen atom; a substituted or unsubstituted carbon atom which may have a linking group containing an oxygen atom, a sulfur atom, a nitrogen atom or a silicon atom. A hydrocarbon group of 1 to 30; or a polar group. R ₅ may all be the same atom or group, or may be different atoms or groups. n is 0 or a positive integer.
Examples of the halogen atom include a fluorine atom, a chlorine atom, and a bromine atom.

Examples of the hydrocarbon group having 1 to 30 carbon atoms include alkyl groups such as methyl group, ethyl group, and propyl group; cycloalkyl groups such as cyclopentyl group and cyclohexyl group; vinyl group, allyl group, propenyl group, and the like. An alkylidene group such as an ethylidene group or a propylidene group; an aryl group such as a phenyl group, a naphthyl group or an anthracenyl group; a formula: — (CH ₂ ) _m —R ′ (wherein R ′ represents the cycloalkyl group or The aryl group and m is an integer of 1 to 10, for example, an aralkyl group such as a benzyl group and a 2-phenylethyl group; and the like. A hydrogen atom bonded to a carbon atom in these groups may be substituted with, for example, a halogen atom such as fluorine, chlorine or bromine; a phenylsulfonyl group; a cyano group or the like.

In addition, the substituted or unsubstituted hydrocarbon group may be directly bonded to the ring structure, or may be bonded via a linking group (linkagc). 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)); A linking group containing an oxygen atom, nitrogen atom, sulfur atom or silicon atom (for example, a carbonyl group (—CO—), a carbonyloxy group (—COO—), an oxycarbonyl group (—O (CO) —), a sulfonyl group ( —SO ₂ —), sulfonyloxy group (—SO ₂ O—), oxysulfonyl group (—OSO ₂ —), ether bond (—O—), thioether bond (—S—), imino group (—NH—) Amide bond (—NHCO—, —CONH—), formula: —Si (R) ₂ —, formula: —Si (OR) ₂ O—, formula: —OSi (R) ₂ —, or formula: —OSi ( OR) ₂ - (in each of the formulas above, R is a hydrocarbon group having 1 to 10 carbon atoms Preferably methyl, bond or the like containing silicon atoms, represented by a is) alkyl group such as ethyl group and the like, or may be a linking group containing a plurality of these.

Examples of the structure in which the substituted or unsubstituted hydrocarbon group is bonded to the ring structure through the linking group include, for example, an alkoxy group, an acyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, an alkylcarbonyloxy Group, arylcarbonyloxy group, triorganosilyl group, triorganosiloxy group and the like.
More specifically, examples of the alkoxy group include a methoxy group and an ethoxy group; examples of the acyl group include an acetyl group and a benzoyl group; examples of the alkylcarbonyloxy group include: An acetoxy group, a propionyloxy group, and the like; examples of the arylcarbonyloxy group include a benzoyloxy group; examples of the alkoxycarbonyl group include a methoxycarbonyl group, an ethoxycarbonyl group, and the like; Examples of the carbonyl group include a phenoxycarbonyl group, a naphthyloxycarbonyl group, a fluorenyloxycarbonyl group, a biphenylyloxycarbonyl group, and the like; examples of the triorganosiloxy group include a trimethylsiloxy group and a triethylsiloxy group. And trialkoxysiloxy groups such as trimethoxysiloxy group and triethoxysiloxy group; examples of the triorganosilyl group include trialkylsilyl groups such as trimethylsilyl group and triethylsilyl group; Examples include trialkoxysilyl groups such as silyl groups and triethoxysilyl groups.

Next, examples of the polar group include a hydroxyl group; a cyano group; an amide group; an imino group (═NH); an amino group such as a primary amino group (—NH ₂ ); a sulfonic acid group (—SO ₃ H); And sulfino group (—SO ₂ H); carboxyl group (—COOH) and the like.
The vinyl polymer (B) is preferably a polymer having each repeating unit represented by the following general formula (5).

Wherein, R ₁ to R ₇ and n are the same as those defined and n R ₁ to R ₇ in the general formula (2) to (4).
x, y, and z represent the molar ratio of each repeating unit when x + y + z = 100 mol%, and preferably 1 <x <20 and 40 <y <99.
Further, 0 ≦ n <4, and R ^{1 to} R ⁴ are more preferably a hydrogen atom or a methyl group, particularly preferably R ₁ is a methyl group and R _{2 to} R ₄ are hydrogen atoms.

  Such vinyl polymer (B) can be a hydroxy (meth) acrylate monomer that can be a structural unit represented by the general formula (2) and a structural unit represented by the general formula (3). It can be obtained by copolymerizing an aromatic vinyl monomer and a vinyl monomer that can be a structural unit represented by the general formula (4).

<Hydroxy (meth) acrylate monomer>
Examples of the hydroxy (meth) acrylate monomer that can be the structural unit represented by the general formula (2) include 2-hydroxyethyl acrylate, 2-hydroxy-1-methylethyl acrylate, 2-hydroxy-n-propyl acrylate, 3 -Hydroxy-n-propyl acrylate, 4-hydroxybutyl acrylate, 2-hydroxybutyl acrylate, 3-chloro-2-hydroxypropyl acrylate, 2-hydroxy-3-phenoxypropyl acrylate, glycerin monoacrylate, 2-hydroxyethyl methacrylate, 2-hydroxy-1-methylethyl methacrylate, 2-hydroxy-n-propyl methacrylate, 3-hydroxy-n-propyl methacrylate, 4-hydroxybutyl methacrylate, 2-hydroxy Butyl methacrylate, 3-chloro-2-hydroxypropyl methacrylate, 2-hydroxy-3-phenoxypropyl methacrylate, and glycerin monomethacrylate. Among these, 2-hydroxyethyl acrylate and 2-hydroxyethyl methacrylate are preferable in that a vinyl polymer having good compatibility with the cyclic olefin resin can be obtained.

<Aromatic vinyl monomer>
Examples of the aromatic vinyl monomer that can be the structural unit represented by the general formula (3) include styrene; α-methylstyrene; alkyl-substituted styrene such as p-methylstyrene, m-methylstyrene, and o-methylstyrene. Halogen substituted styrenes such as 4-chlorostyrene and 4-bromostyrene; chloromethylstyrene; hydroxystyrenes such as p-hydroxystyrene, isopropenylphenol, 2-methyl-4-hydroxystyrene, and 3,4-dihydroxystyrene Vinyl benzyl alcohols; alkoxy-substituted styrenes such as p-methoxystyrene, pt-butoxystyrene, and mt-butoxystyrene; vinylbenzoic acids such as 3-vinylbenzoic acid and 4-vinylbenzoic acid; methyl 4-vinylbenzoate, ethyl 4-vinylbenzene Vinyl benzoates such as zoate; 4-vinylbenzyl acetate; 4-acetoxystyrene; amide styrenes such as p-sulfonamidostyrene; 3-aminostyrene, 4-aminostyrene, 2-isopropenylaniline, vinylbenzyldimethyl Aminostyrenes such as amines; nitrostyrenes such as 3-nitrostyrene and 4-nitrostyrene; cyanostyrenes such as 3-cyanostyrene and 4-cyanostyrene; vinylphenylacetonitrile; 4-vinylbiphenyl, 3-vinylbiphenyl , 1-vinylnaphthalene, 2-vinylnaphthalene, 9-vinylfluorene, 2-vinylfluorene, vinyl polycyclic aromatic compounds such as 9-vinylanthracene; 1,1-diphenylethylene and the like. Of these, styrene and α-methylstyrene are preferred because they are easily available industrially and are inexpensive.

<Vinyl monomer>
Examples of vinyl monomers that can be the structural unit represented by the general formula (4) include vinyl cyanides such as acrylonitrile and methacrylonitrile; methyl acrylate, ethyl acrylate, isobornyl acrylate, cyclohexyl acrylate, Aliphatic alkyl acrylates such as dicyclopentanyl acrylate, 2-methoxyethyl acrylate, 3-methoxybutyl acrylate; benzyl acrylate; aromatic acrylates such as phenyl acrylate; methyl methacrylate, ethyl methacrylate, isobornyl methacrylate, cyclohex Aliphatic alkyl methacrylates such as xyl methacrylate and dicyclopentanyl acrylate; benzyl methacrylate; aromatic methacrylates such as phenyl methacrylate Acrylamides such as acrylamide, N-isopropylacrylamide, N-isobutoxymethylacrylamide, N, N-dimethylacrylamide, N, N-diethylacrylamide; methacrylamides such as methacrylamide, diethylaminoethyl methacrylate, dimethylaminoethyl methacrylate Glycidyl methacrylate; tetrahydrofurfuryl methacrylate; acrolein; methacrolein; vinylpyridines such as 2-vinylpyridine and 4-vinylpyridine;
In particular, it is preferable that R ₇ in the general formula (4) is COOR ″ (R ″ is an alkyl group having 1 to 4 carbon atoms).

<Radical polymerization initiator>
When the vinyl polymer (B) used in the present invention is synthesized by radical polymerization, a known organic peroxide that generates free radicals or an azobis radical polymerization initiator can be used.
As organic peroxide,
Diacetyl peroxide, dibenzoyl peroxide, diisobutyroyl peroxide, di (2,4-dichlorobenzoyl) peroxide, di (3,5,5-trimethylhexanoyl) peroxide, dioctanoyl peroxide, dilauroyl Diacyl peroxides such as peroxide, distearoyl peroxide, bis [4- (m-toluoyl) benzoyl] peroxide;
Ketone peroxides such as methyl ethyl ketone peroxide, cyclohexanone peroxide, methylcyclohexanone peroxide, acetylacetone peroxide;
Hydrogen peroxide, t-butyl hydroperoxide, α-cumene hydroperoxide, p-menthane hydroperoxide, diisopropylbenzene hydroperoxide, 1,1,3,3-tetramethylbutyl hydroperoxide, t-hexyl Hydroperoxides such as hydroperoxide;
Di-t-butyl peroxide, dicumyl peroxide, dilauryl peroxide, α, α′-bis (t-butylperoxy) diisopropylbenzene, 2,5-dimethyl-2,5-bis (t-butylperoxide Dialkyl peroxides such as oxy) hexane, t-butylcumyl peroxide, 2,5-dimethyl-2,5-bis (t-butylperoxy) hexyne-3;
t-butyl peroxyacetate, t-butyl peroxypivalate, t-hexyl peroxypivalate, 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 -Ethyl hexanoate, t-butyl peroxyisobutyrate, t-butyl peroxy maleate, t-butyl peroxy 3,5,5-trimethyl hexanoate, t-butyl peroxy laurate, 2,5 -Dimethyl-2,5-bis (m-toluoylperoxy) hexane, α, α'-bis (neodecanoylpa Oxy) diisopropylpropylbenzene, cumylperoxyneodecanoate, 1,1,3,3-tetramethylbutylperoxyneodecanoate, 1-cyclohexyl-1-methylethylperoxyneodecanoate, t -Hexyl peroxyneodecanoate, t-butylperoxyneodecanoate, t-butylperoxybenzoate, t-hexylperoxybenzoate, bis (t-butylperoxy) isophthalate, 2,5-dimethyl- Peroxyesters such as 2,5-bis (benzoylperoxy) hexane, t-butylperoxy m-toluoyl benzoate, 3,3 ′, 4,4′-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-butylperoxy) butane, n -Peroxyketals such as butyl 4,4-bis (t-butylperoxy) pivalate, 2,2-bis (4,4-di-t-butylperoxycyclohexyl) propane;
Peroxymonocarbonates such as t-hexylperoxyisopropyl monocarbonate, t-butylperoxyisopropyl monocarbonate, t-butylperoxy 2-ethylhexyl monocarbonate, t-butylperoxyallyl monocarbonate;
Di-sec-butyl peroxydicarbonate, di-n-propyl peroxydicarbonate, diisopropyl peroxydicarbonate, bis (4-t-butylcyclohexyl) peroxydicarbonate, di-2-ethoxyethyl peroxydi Peroxydicarbonates such as carbonate, di-2-ethylhexyl peroxydicarbonate, di-2-methoxybutyl peroxydicarbonate, di (3-methyl-3-methoxybutyl) peroxydicarbonate;
In addition, although t-butyl trimethylsilyl peroxide etc. are mentioned, the organic peroxide used for this invention is not limited to these exemplary compounds.

Of these organic peroxides, polyfunctional peroxyketals are preferred in that a high molecular weight polymer can be easily obtained. In particular, tetrafunctional 2,2-bis (4,4-di-t-butylperoxycyclohexyl) propane is preferred.
As the azobis radical polymerization initiator, 2,2′-azobisisobutyronitrile, azobisisovaleronitrile, 2,2′-azobis (4-methoxy-2,4-dimethylvaleronitrile), 2,2 '-Azobis (2,4-dimethylvaleronitrile), 2,2'-azobis (2-methylbutyronitrile), 1,1-azobis (cyclohexane-1-carbonitrile), 2- (carbamoylazo) isobuty Ronitrile, 2,2′-azobis [2-methyl-N- [1,1-bis (hydroxymethyl) -2-hydroxyethyl] propionamide], 2,2′-azobis [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'-azobis [2- (2-imidazolin-2-yl) propane] 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-methylpropionamidoxime), dimethyl 2,2'-azobisbutyrate, 4,4'-azobis (4-cyanopentano) Ic acid), 2,2′-azobis (2,4,4-trimethylpentane) and the like, but the azobis radical polymerization initiator used in the present invention is not limited to these exemplified compounds. Among these azobis-based radical polymerization initiators, 2,2′-azobisisobutyronitrile, 2,2′-azobis (2,4-dimethylvaleronitrile), 1,1′-azobis (cyclohexane-1- (Carbonitrile) is particularly preferred in that a high molecular weight polymer can be obtained.

<Catalyst>
A catalyst may be used for the copolymerization reaction between the hydroxy (meth) acrylate monomer and, if necessary, the aromatic vinyl monomer and / or the vinyl monomer. This catalyst is not particularly limited, and examples thereof include known anion polymerization catalysts, coordination anion polymerization catalysts, and cation polymerization catalysts.

<Vinyl polymer (B)>
The vinyl polymer (B) used in the present invention comprises the hydroxy (meth) acrylate monomer, the aromatic vinyl monomer, and the vinyl monomer in the presence of the polymerization initiator and catalyst. It is obtained by polymerizing the polymer with a conventionally known method such as a bulk polymerization method, a solution polymerization method, a precipitation polymerization method, an emulsion polymerization method, a suspension polymerization method or a bulk-suspension polymerization method.

  In the vinyl polymer (B) thus obtained, the structural unit represented by the general formula (2), the structural unit represented by the general formula (3), and the general formula (4) In the structural unit represented, the proportion of the structural unit represented by the above general formula (2) (corresponding to x in the above general formula (5)) exceeds 1 mol% with respect to 100 mol% in total. 20 mol% or less, preferably 2 to 10 mol%, and the proportion of the structural unit represented by the general formula (3) (corresponding to y in the general formula (5)) exceeds 80 mol% and is 99 mol. %, Preferably 90 to 98 mol%. When the proportion of the structural unit represented by the general formula (5) is in the above range, the cyclic olefin polymer (A) and the vinyl polymer (B) are compatible with each other, and the resulting thermoplasticity is obtained. Resin compositions and optical films exhibit excellent low birefringence and improved weather resistance and heat resistance.

  The vinyl polymer (B) has a polystyrene-equivalent number average molecular weight (Mn) measured by gel permeation chromatography (GPC) of usually 500 to 500,000, preferably 500 to 25,000, more preferably. Is 9,000 to 15,000, and the weight average molecular weight (Mw) is usually 1,000 to 800,000, preferably 1,000 to 50,000, more preferably 19,000 to 30,000. It is desirable.

If the molecular weight is too small, the strength of the resulting molded product or film may be lowered. When the molecular weight is too large, the solution viscosity becomes too high, and the productivity and processability of the thermoplastic resin composition according to the present invention may be deteriorated.
The molecular weight distribution (Mw / Mn) of the vinyl polymer (B) is usually 1.0 to 10, preferably 1.2 to 5, and more preferably 1.2 to 3.

[Resin composition]
The resin composition of the present invention contains at least one kind of the norbornene polymer and at least one kind of the vinyl polymer.
The mass mixing ratio (A / B) of the vinyl polymer (B) having a hydroxyl group and the norbornene polymer (A) is preferably 99/1 to 50/50.
When the mixing ratio is in the above range, a thermoplastic resin composition or an optical film having low birefringence and excellent weather resistance and heat resistance can be obtained. When the blending amount of the vinyl polymer (B) is less than the lower limit, the birefringence value of the resulting thermoplastic resin composition or optical film may not be sufficiently small. Moreover, when the compounding quantity of a vinyl type polymer (B) exceeds the said upper limit, the heat resistance of the obtained thermoplastic resin composition and an optical film may fall, or the transparency of an optical film may fall. .

  In the resin composition of the present invention, the mass mixing ratio (B / A) of the vinyl polymer (B) and the norbornene polymer (A) is more preferably 50/50 to 5/95. More preferably, it is / 60-20 / 80. When such a thermoplastic resin composition is used, a retardation film having excellent retardation can be obtained.

[Resin composition film]
The resin composition film of the present invention refers to a film containing the resin composition of the present invention.

[Use of resin composition film]
The resin composition of the present invention is useful as a film material. In particular, films prepared using the polymer include substrates for liquid crystal display elements, light guide plates, polarizing films, retardation films, liquid crystal backlights, liquid crystal panels, OHP films, transparent conductive films, and the like. Suitable for optical use film. The norbornene-based polymer represented by the general formula (I) is suitably used for optical materials such as optical discs, optical fibers, lenses, and prisms, electronic components, medical devices, containers, and the like.

[Method for producing resin composition film]
The film of the present invention contains the resin composition of the present invention and can be produced by forming a film using the polymer as a raw material. There are two methods for film formation: hot melt film formation and solution film formation, and both are applicable, but in the present invention, a solution film formation method capable of obtaining an excellent surface film is used. preferable. The solution casting method is described below.

(Preparation of dope)
First, a solution (dope) of the polymer used for film formation is prepared. The organic solvent used for the preparation of the dope is not particularly limited as long as it can be dissolved, cast, and formed into a film, and the purpose can be achieved. For example, chlorinated solvents such as dichloromethane and chloroform, chain hydrocarbons having 3 to 12 carbon atoms (hexane, octane, isooctane, decane, etc.), cyclic hydrocarbons (cyclopentane, cyclohexane, decalin, etc.), aromatic carbonization Hydrogen (benzene, toluene, xylene, etc.), ester (ethyl formate, propyl formate, pentyl formate, methyl acetate, ethyl acetate, pentyl acetate, etc.), ketone (acetone, methyl ethyl ketone, diethyl ketone, diisobutyl ketone, cyclopentanone) , Cyclohexanone and methylcyclohexanone), ether (diisopropyl ether, dimethoxymethane, dimethoxyethane, 1,4-dioxane, 1,3-dioxolane, tetrahydrofuran, Preferably the solvent selected from over like Le and phenetole). Examples of the organic solvent having two or more kinds of functional groups include 2-ethoxyethyl acetate, 2-methoxyethanol and 2-butoxyethanol. The preferable boiling point of the organic solvent is 35 ° C to 200 ° C. The solvent used for the preparation of the solution can be used by mixing two or more kinds of solvents in order to adjust the solution properties such as drying property and viscosity. Further, as long as the solvent is dissolved in the mixed solvent, a poor solvent is added. It is also possible.

  A preferred poor solvent can be appropriately selected. When a chlorinated organic solvent is used as the good solvent, alcohols can be preferably used. The alcohols may preferably be linear, branched or cyclic, and among them, saturated aliphatic hydrocarbons are preferable. The hydroxyl group of the alcohol may be any of primary to tertiary. As the alcohol, fluorine-based alcohol is also used. Examples thereof include 2-fluoroethanol, 2,2,2-trifluoroethanol, 2,2,3,3-tetrafluoro-1-propanol and the like. Among the poor solvents, particularly monovalent alcohols have an effect of reducing the peeling resistance and can be preferably used. Particularly preferred alcohols vary depending on the good solvent to be selected, but considering the drying load, alcohols having a boiling point of 120 ° C. or lower are preferable, monohydric alcohols having 1 to 6 carbon atoms are more preferable, and alcohols having 1 to 4 carbon atoms Can be particularly preferably used.

  A particularly preferred mixed solvent for preparing the dope is a combination in which dichloromethane is the main solvent and at least one alcohol selected from methanol, ethanol, propanol, isopropanol, or butanol is a poor solvent.

  For the preparation of the dope, a method of stirring and dissolving at room temperature, and stirring the polymer at room temperature to swell the polymer, cooling to -20 ° C to -100 ° C, and cooling to 20 ° C to 100 ° C again to dissolve. There are a dissolution method, a high-temperature dissolution method that dissolves at a temperature equal to or higher than the boiling point of the main solvent in a closed container, and a method that dissolves at a high temperature and high pressure up to the critical point of the solvent. The viscosity of the dope is preferably in the range of 1 to 500 Pa · s at 25 ° C., more preferably in the range of 5 to 200 Pa · s.

  Prior to casting, it is preferable to filter off foreign matters such as undissolved matter, dust, and impurities using a suitable filter medium such as a wire mesh or flannel. The viscosity immediately before film formation may be in a range that allows casting during film formation, and is preferably adjusted to a range of 5 Pa · s to 1000 Pa · s, more preferably in a range of 15 Pa · s to 500 Pa · s. The range of 30 Pa · s to 200 Pa · s is more preferable. In addition, although the temperature at this time will not be specifically limited if it is the temperature at the time of the casting, Preferably it is -5-70 degreeC, More preferably, it is -5-35 degreeC.

(Additive)
The film of this invention may contain additives other than the said composition, and such an additive may be added in any step of the process of producing a film. Additives can be selected depending on the application, such as deterioration inhibitors, UV inhibitors, retardation (optical anisotropy) regulators, fine particles, peeling accelerators, infrared absorbers, etc. Can be mentioned. These additives may be solid or oily. In the case of film production by the solution casting method, the addition time may be added at any time during the dope preparation process, or an additive is added to the final preparation process of the dope preparation process. You may go. In the case of film production by the melting method, it may be added at the time of resin pellet production, or may be kneaded at the time of film production. The amount of each material added is not particularly limited as long as the function is manifested. Moreover, when a film is formed from a multilayer, the kind and addition amount of the additive of each layer may differ.

  From the viewpoint of preventing film deterioration, a deterioration (oxidation) inhibitor is preferably used. For example, 2,6-di-tert-butyl, 4-methylphenol, 4,4′-thiobis- (6-tert-butyl-3-methylphenol), pentaerythrityl-tetrakis [3- (3,5- Phenolic or hydroquinone antioxidants such as di-tert-butyl-4-hydroxyphenyl) propionate can be added. Furthermore, phosphorus antioxidants such as tris (4-methoxy-3,5-diphenyl) phosphite, tris (nonylphenyl) phosphite, bis (2,4-di-tert-butylphenyl) pentaerythritol diphosphite Is preferably added. The antioxidant is added in an amount of 0.05 to 5.0 parts by mass with respect to 100 parts by mass of the polymer.

  From the viewpoint of preventing deterioration of the polarizing plate or the liquid crystal, an ultraviolet absorber is preferably used. As the ultraviolet absorber, those excellent in the ability to absorb ultraviolet rays having a wavelength of 370 nm or less and having a small absorption of visible light having a wavelength of 400 nm or more are preferably used from the viewpoint of good liquid crystal display properties. Specific examples of ultraviolet absorbers preferably used in the present invention include, for example, hindered phenol compounds, oxybenzophenone compounds, benzotriazole compounds, salicylic acid ester compounds, benzophenone compounds, cyanoacrylate compounds, nickel complex salts Compound etc. are mentioned. The addition amount of these ultraviolet light inhibitors is preferably 1 ppm to 1.0%, more preferably 10 to 1000 ppm in terms of mass ratio with respect to the norbornene polymer.

  In order to improve the slipperiness of the film surface, fine particles (mat agent) are preferably used. By using this, unevenness is imparted to the film surface, that is, by increasing the roughness of the film surface (matization), the blocking between the films can be reduced. The presence of fine particles in the film or on at least one surface of the film significantly improves the adhesion between the polarizer and the film during polarizing plate processing. The matting agent used in the present invention is inorganic fine particles, for example, fine particles having an average particle size of 0.05 μm to 0.5 μm, preferably 0.08 μm to 0.3 μm, more preferably 0.1 μm to 0 μm. .25 μm. In the fine particles, silicon dioxide, silicone and titanium dioxide are preferable as the inorganic compound, fluororesin, nylon, polypropylene and chlorinated polyether are preferable as the polymer compound, silicon dioxide is more preferable, and surface treatment with organic matter is performed. Silicon is more preferred.

  In order to reduce the peeling resistance of the film, a peeling accelerator is preferably used. As preferred release agents, phosphate ester surfactants, carboxylic acid or carboxylate surfactants, sulfonic acid or sulfonate surfactants, and sulfate ester surfactants are effective. A fluorine-based surfactant in which part of the hydrogen atoms bonded to the hydrocarbon chain of the surfactant is substituted with fluorine atoms is also effective. The addition amount of the release agent is preferably 0.05 to 5% by mass, more preferably 0.1 to 2% by mass, and further preferably 0.1 to 0.5% by mass with respect to the norbornene-based polymer.

  Various additives are preferably used in order to control the optical performance of the film, such as Re, Rth, and wavelength dispersion. This includes a low molecular compound having a molecular weight of 1000 or less, an oligomer compound having a molecular weight of about 1000 to 10,000, and a polymer compound having a molecular weight of 10,000 or more.

(Film production)
For the method and equipment for producing the film of the present invention, the same solution casting film forming method and solution casting film forming apparatus as those used for producing a known cellulose triacetate film are preferably used. The dope prepared from the dissolving machine (kettle) is temporarily stored in a storage kettle, and the foam contained in the dope is defoamed for final preparation.

  JP 2000-301555, JP 2000-301558, JP 7-032391, JP 3-193316, JP 5-086212, JP 62-037113, JP 2-276607, The cellulose acylate film forming techniques described in JP-A-55-014201, JP-A-2-111511, and JP-A-2-208650 can be preferably employed in the present invention.

(Multilayer casting)
The dope may be cast as a single layer liquid on a smooth band or drum as a metal support, or a plurality of dopes of two or more layers may be cast. In the case of multilayer casting, the inner and outer thicknesses are not particularly limited, but preferably the outer thickness is 1 to 50% of the total film thickness, and more preferably 2 to 30%.

(Casting)
As a solution casting method, a method in which the prepared dope is uniformly extruded from a pressure die onto a metal support, and a method using a doctor blade in which the dope once cast on the metal support is adjusted with a blade is used. Alternatively, there is a method using a reverse roll coater that adjusts with a reverse rotating roll, and a method using a pressure die is preferable. The temperature of the dope used for casting is preferably −10 to 55 ° C., more preferably 25 to 50 ° C. In that case, all of the steps may be the same or different at various points in the step. When they are different, it is preferable that the temperature is a desired temperature immediately before casting.

(Dry)
Drying of the dope on the metal support in the production of the film is generally accomplished by applying hot air from the surface side of the metal support (eg, drum or band), that is, the surface of the web on the metal support, drum or A method of applying hot air from the back side of the band, contacting the temperature controlled liquid from the back side opposite the dope casting surface of the band or drum, and heating the drum or band by heat transfer to control the surface temperature Although there are methods, the back surface liquid heat transfer method is preferable. The surface temperature of the metal support before casting may be any number as long as it is not higher than the boiling point of the solvent used for the dope. However, in order to promote drying and to lose fluidity on the metal support, the temperature is set to 1 to 10 ° C. lower than the boiling point of the lowest boiling solvent among the solvents used. It is preferable. This is not the case when the casting dope is cooled and peeled off without drying.

(Peeling)
When peeling a raw dry film from a metal support, if the peeling resistance (peeling load) is large, the film is irregularly stretched in the film forming direction, resulting in uneven optical anisotropy. In particular, when the peeling load is large, a portion stretched stepwise in the film forming direction and a portion unstretched are alternately generated, resulting in a distribution in retardation. When loaded in a liquid crystal display device, the line or strip becomes uneven.

  The film peeling load can be easily predicted by the following test before the film is produced. That is, the produced dope is cast and formed using an applicator, a certain time elapses (peeling start time), the solvent is evaporated to form a film on the SUS plate, and then a web with a certain width is constant. The load when the film is peeled vertically from the SUS plate at a speed is measured with a load cell. The maximum stripping load obtained is determined, expressed as stripping load [gf / cm], and the values are compared.

  In the case of using the same polymer material, as a method for reducing the peeling load, there are a method of adding a release agent as described above and a method of selecting a solvent composition to be used. The preferable residual volatile content concentration at the time of peeling is 5 to 60% by mass. 10-50 mass% is further more preferable, and 20-40 mass% is especially preferable. Peeling with a high volatile content is preferable because the drying rate can be increased and productivity is improved. On the other hand, when the volatile content is high, the strength and elasticity of the film are small, and the film is cut or stretched against the peeling force. Further, the self-holding force after peeling is poor, and deformation, wrinkles and nicks are likely to occur. It also causes distribution in the retardation.

(Stretching)
When the film produced by the solution casting method is further stretched, it is preferably carried out in a state where the solvent still remains in the film immediately after peeling. The purpose of stretching is (1) to obtain a film having excellent flatness without wrinkles and deformation, and (2) to increase the in-plane retardation of the film. When stretching is performed for the purpose of (1), stretching is performed at a relatively high temperature, and stretching is performed at a low magnification from 1% to 10% at most. A stretch of 2-5% is particularly preferred. When stretching for the purposes of both (1) and (2) or only for the purpose of (2), the film is stretched at a relatively low temperature and a stretch ratio of 5 to 150%.

  The stretching of the film may be uniaxial stretching only in the longitudinal or lateral direction, or may be simultaneous or sequential biaxial stretching. The birefringence of the retardation film for a VA liquid crystal cell or OCB (Optically Compensatory Bend) liquid crystal cell is preferably such that the refractive index in the width direction is larger than the refractive index in the length direction. Therefore, it is preferable to stretch more in the width direction.

  The thickness of the finished film (after drying) of the present invention varies depending on the purpose of use, but is usually in the range of 20 to 500 μm, preferably in the range of 30 to 150 μm, particularly 40 to 110 μm for liquid crystal display devices. It is preferable.

[Characteristics of film]
In the film of the present invention, the difference ΔRe = Re ₆₃₀ −Re ₄₅₀ between the in-plane retardation Re ₄₅₀ at a wavelength of ₄₅₀ nm and the in-plane retardation Re _{630 at} a wavelength of 630 nm preferably satisfies 10 nm ≦ ΔRe ≦ 100 nm. ΔRe ≦ 80 nm is more preferable, and 10 nm ≦ ΔRe ≦ 60 nm is most preferable.
The preferred optical properties of the film of the present invention vary depending on the application of the film. Below, the preferable range in each use of in-plane retardation (Re) and thickness direction retardation (Rth) which converted the thickness of the film into 80 micrometers is shown.

  When used as a polarizing plate protective film: Re is preferably 0 nm ≦ Re ≦ 5 nm, and more preferably 0 nm ≦ Re ≦ 3 nm. Rth is preferably 0 nm ≦ Rth ≦ 50 nm, more preferably 0 nm ≦ Rth ≦ 35 nm, and particularly preferably 0 nm ≦ Rth ≦ 10 nm.

  When used as a retardation film: The range of Re and Rth varies depending on the type of retardation film and there are various needs, but 0 nm ≦ Re ≦ 100 nm and 0 nm ≦ Rth ≦ 400 nm are preferable. In the TN mode, 0 nm ≦ Re ≦ 20 nm, 40 nm ≦ Rth ≦ 80 nm, and in the VA mode, 20 nm ≦ Re ≦ 80 nm and 80 nm ≦ Rth ≦ 400 nm are more preferable. In particular, the preferable range in the VA mode is 30 nm ≦ Re ≦ 75 nm, 120 nm ≦ Rth. ≦ 250 nm, when compensating with one retardation film, 50 nm ≦ Re ≦ 75 nm, 180 nm ≦ Rth ≦ 250 nm, when compensating with two retardation films, 30 nm ≦ Re ≦ 50 nm, 80 nm ≦ Rth ≦ 140 nm. These are preferred embodiments as a VA mode compensation film in terms of color shift at the time of black display and the viewing angle dependency of contrast.

  The film of the present invention can achieve desired optical characteristics by appropriately adjusting process conditions such as copolymerization ratio, additive type and amount, stretch ratio, residual volatile content at the time of peeling.

  In this specification, Re (λ) and Rth (λ) represent in-plane retardation and retardation in the thickness direction at a wavelength λ, respectively. Re (λ) is measured by making light having a wavelength of λ nm incident in the normal direction of the film in KOBRA 21ADH or WR (manufactured by Oji Scientific Instruments). In selecting the measurement wavelength λnm, the wavelength selection filter can be exchanged manually, or the measurement value can be converted by a program or the like.

When the film to be measured is represented by a uniaxial or biaxial refractive index ellipsoid, Rth (λ) is calculated by the following method.
Rth (λ) is Re (λ), and the in-plane slow axis (determined by KOBRA 21ADH or WR) is the tilt axis (rotary axis) (if there is no slow axis, any in-plane film The light of wavelength λ nm is incident from each of the inclined directions in steps of 10 degrees from the normal direction to 50 degrees on one side with respect to the film normal direction (with the direction of the rotation axis as the rotation axis). KOBRA 21ADH or WR is calculated based on the measured retardation value, the assumed average refractive index, and the input film thickness value.

In the above case, in the case of a film having a direction in which the retardation value is zero at a certain tilt angle with the in-plane slow axis from the normal direction as the rotation axis, retardation at a tilt angle larger than the tilt angle. The value is calculated by KOBRA 21ADH or WR after changing its sign to negative.
In addition, the retardation value is measured from the two inclined directions, with the slow axis as the tilt axis (rotation axis) (in the absence of the slow axis, the arbitrary direction in the film plane is the rotation axis), Based on the value, the assumed value of the average refractive index, and the input film thickness value, Rth can also be calculated from the following equations (1) and (2).

Re (θ) in the formula (1) represents a retardation value in a direction inclined by an angle θ from the normal direction.
In formula (1), nx represents the refractive index in the slow axis direction in the plane, ny represents the refractive index in the direction perpendicular to nx in the plane, and nz represents the refractive index in the direction perpendicular to nx and ny. . d is the film thickness.

In the case where the film to be measured cannot be expressed by a uniaxial or biaxial refractive index ellipsoid, that is, a film having no so-called optic axis, Rth (λ) is calculated by the following method.
Rth (λ) is from −50 degrees to +50 degrees with respect to the normal direction of the film, with Re (λ) as the slow axis (indicated by KOBRA 21ADH or WR) as the tilt axis (rotation axis). The light of wavelength λ nm is incident from each inclined direction in 10 degree steps and measured at 11 points. Based on the measured retardation value, the assumed average refractive index, and the input film thickness value, KOBRA 21ADH or WR is calculated.
In the above measurement, as the assumed value of the average refractive index, the values in the polymer handbook (JOHN WILEY & SONS, INC) and catalogs of various optical films can be used. Those whose average refractive index is not known can be measured with an Abbe refractometer. The average refractive index values of the main optical films are exemplified below: cellulose acylate (1.48), cycloolefin polymer (1.52), polycarbonate (1.59), polymethyl methacrylate (1.49), Polystyrene (1.59). By inputting these assumed values of average refractive index and film thickness, KOBRA 21ADH or WR calculates nx, ny, and nz. Nz = (nx−nz) / (nx−ny) is further calculated from the calculated nx, ny, and nz.

In the case of using the film of the present invention as a protective film for polarizing plate, the value of the photoelastic is ^{0.5 × 10 -13 ~9.0 × 10 -13} [cm 2 / dyn], moisture permeability values However, it is preferable that the value (converted assuming the thickness of the film as 80 μm) is 180 to 435 [g / cm ² 24 h]. The value of photoelasticity is more preferably 0.5 × 10 ^{−13 to} 7.0 × 10 ⁻¹³ [cm ² / dyn], and 0.5 × 10 ^{−13 to} 5.0 × 10 ⁻¹³ [ More preferably, it is cm ² / dyn]. In addition, the value of moisture permeability (however, the value obtained by converting the film thickness to 80 μm) is more preferably 180 to 400 [g / cm ² 24h], and 180 to 350 [g / cm ² 24h]. Is more preferable. When the film of the present invention has the above-described properties, when it is used as a protective film for a polarizing plate, it is possible to reduce a decrease in performance due to the influence of humidity.

[Polarizer]
The film of the present invention can be applied to a polarizing plate. A polarizing plate can be produced using the film of the present invention and a polarizer. Usually, a polarizing plate has a polarizer and two protective films disposed on both sides thereof. The film of the present invention can be used as both or one protective film. A normal cellulose acetate film or the like may be used for the other protective film. Examples of the polarizer include an iodine polarizer, a dye polarizer using a dichroic dye, and a polyene polarizer. The iodine polarizer and the dye polarizer are generally produced using a polyvinyl alcohol film. When the film of the present invention is used as a polarizing plate protective film, the film is subjected to a surface treatment as described later, and then the film-treated surface and a polarizer are bonded together using an adhesive. Examples of the adhesive used include polyvinyl alcohol adhesives such as polyvinyl alcohol and polyvinyl butyral, vinyl latexes such as butyl acrylate, and gelatin. The polarizing plate is composed of a polarizer and a protective film that protects both surfaces of the polarizer, and is further constructed by laminating a protective film on one surface of the polarizing plate and a separate film on the opposite surface. The protective film and the separate film are used for the purpose of protecting the polarizing plate at the time of shipping the polarizing plate and at the time of product inspection. In this case, the protect film is bonded for the purpose of protecting the surface of the polarizing plate, and is used on the side opposite to the surface where the polarizing plate is bonded to the liquid crystal plate. Moreover, a separate film is used in order to cover the contact bonding layer bonded to a liquid crystal plate, and is used for the surface side which bonds a polarizing plate to a liquid crystal plate. The film is preferably bonded so that the transmission axis of the polarizer and the slow axis of the film coincide with each other.

(Film surface treatment)
In order to improve the adhesion between the polarizer and the protective film, the surface of the film is preferably surface-treated. As for the surface treatment, any method may be used as long as the adhesiveness can be improved. Preferred examples of the surface treatment include glow discharge treatment, ultraviolet irradiation treatment, corona treatment, and flame treatment. The glow discharge treatment here refers to so-called low temperature plasma that occurs under low pressure gas. In the present invention, plasma treatment under atmospheric pressure is also preferable. In addition, the details of the glow discharge treatment are described in US Pat. No. 3,462,335, US Pat. No. 3,761,299, US Pat. No. 4,072,769, and British Patent No. 891469. A method described in Japanese Patent Publication No. 59-556430 is also used in which the gas composition generated in the vessel is made only when the polyester support itself undergoes a discharge treatment after the discharge starts. In addition, the method described in Japanese Patent Publication No. 60-16614, in which the surface temperature of the film is set to 80 ° C. to 180 ° C. when performing the vacuum glow discharge treatment, can also be applied.

  As for the degree of surface treatment, the preferred range varies depending on the type of surface treatment, but as a result of the surface treatment, the contact angle with the pure water on the surface of the protective film subjected to the surface treatment is preferably less than 50 °. . The contact angle is more preferably 25 ° or more and less than 45 °. When the contact angle with the pure water on the surface of the protective film is in the above range, the adhesive strength between the protective film and the polarizing film becomes good.

(adhesive)
When laminating a polarizer made of polyvinyl alcohol and the surface-treated film of the present invention, it is preferable to use an adhesive containing a water-soluble polymer. Water-soluble polymers preferably used for the adhesive include N-vinyl pyrrolidone, acrylic acid, methacrylic acid, maleic acid, β-hydroxyethyl acrylate, β-hydroxyethyl methacrylate, vinyl alcohol, methyl vinyl ether, vinyl acetate. , Acrylamide, methacrylamide, diacetone acrylamide, vinyl imidazole, etc., homopolymers or polymers having ethylenically unsaturated monomers as constituents, polyoxyethylene, polyoxypropylene, poly-2-methyloxazoline, methylcellulose, hydroxyethylcellulose , Hydroxypropylcellulose, gelatin and the like. Of these, PVA and gelatin are preferred in the present invention. The thickness of the adhesive layer is preferably 0.01 to 5 μm after drying, and more preferably 0.05 to 3 μm.

(Antireflection layer)
It is preferable to provide a functional film such as an antireflection layer on the protective film disposed on the opposite side of the polarizing plate from the liquid crystal cell. In particular, in the present invention, at least a light scattering layer and a low refractive index layer are laminated in this order on the protective film, or an intermediate refractive index layer, a high refractive index layer, and a low refractive index layer are arranged in this order on the protective film. A laminated antireflection layer is preferably used.

(Light scattering layer)
The light scattering layer is formed for the purpose of contributing to the film light diffusibility due to surface scattering and / or internal scattering, and hard coat properties for improving the scratch resistance of the film. Therefore, it is formed to contain a binder for imparting hard coat properties, matte particles for imparting light diffusibility, and inorganic fillers for increasing the refractive index, preventing cross-linking shrinkage, and increasing the strength as necessary. The The thickness of the light scattering layer is preferably from 1 to 10 μm, more preferably from 1.2 to 6 μm, from the viewpoint of imparting hard coat properties and from the viewpoint of curling and suppressing deterioration of brittleness.

(Other layers of antireflection layer)
Further, a hard coat layer, a forward scattering layer, a primer layer, an antistatic layer, an undercoat layer, a protective layer, and the like may be provided.

(Hard coat layer)
The hard coat layer is provided on the surface of the support in order to impart physical strength to the protective film provided with the antireflection layer. In particular, it is preferably provided between the support and the high refractive index layer. The hard coat layer is preferably formed by a crosslinking reaction or a polymerization reaction of a light and / or heat curable compound. As the curable functional group, a photopolymerizable functional group is preferable, and the organometallic compound containing a hydrolyzable functional group is preferably an organic alkoxysilyl compound.

(Antistatic layer)
In the case of providing an antistatic layer, it is preferable to impart conductivity with a volume resistivity of 10 ⁻⁸ (Ωcm ⁻³ ) or less. The use of hygroscopic substances, water-soluble inorganic salts, certain surfactants, cationic polymers, anionic polymers, colloidal silica, etc. can give a volume resistivity of 10 ⁻⁸ (Ωcm ⁻³ ). There is a problem that dependency is large, and sufficient conductivity cannot be secured at low humidity. Therefore, a metal oxide is preferable as the conductive layer material.

[Liquid Crystal Display]
The film of the present invention, a retardation film comprising the film, and a polarizing plate using the film can be used for liquid crystal cells and liquid crystal display devices in various display modes. TN (Twisted Nematic), IPS (In-Plane Switching), FLC (Ferroelectric Liquid Crystals), AFLC (Anti-Ferroelectric Liquid Crystals), OCB (Optically Charged TNS). Various display modes such as HAN (Hybrid Aligned Nematic) have been proposed. Of these, the OCB mode or the VA mode can be preferably used.

  The present invention will be described more specifically with reference to the following examples. The materials, amounts used, ratios, processing details, processing procedures, and the like shown in the following examples can be changed as appropriate without departing from the spirit of the present invention. Therefore, the scope of the present invention is not limited to the specific examples shown below.

In the following Examples and Comparative Examples, various measurements, film formation and film evaluation were performed as follows.
(1) Molecular weight and molecular weight distribution: Gel permeation chromatography (GPC, manufactured by Tosoh Corporation, trade name: HLC-8020 / four columns: manufactured by Tosoh Corporation, trade name: TSKguardcolumn SuperHZ-H, TSKgel SuperHZM-H, The weight average molecular weight (Mw) and molecular weight distribution (Mw / Mn) in terms of polystyrene were determined using tetrahydrofuran (THF) solvent using TSKgel SuperHZ4000 and TSKgel SuperHZ2000). Mn represents the number average molecular weight.
(2) Polymer molecular structure: 1HNMR or 13CNMR was measured in deuterated methylene chloride using a superconducting nuclear magnetic resonance absorber (NMR, manufactured by Bruker, trade name: AVANCE400).
(3) Film formation: A norbornene polymer and a vinyl polymer composition were mixed in the following composition.
Norbornene polymer / vinyl polymer (see Table 1 for mass ratio) 100 parts by mass Methylene chloride / methanol (mass ratio 92/8) 320 parts by mass This was filtered under pressure. The obtained dope was cast on an A3 large hydrophobic glass plate using an applicator. This was dried in a 25 ° C. closed system for 1 minute, followed by drying in a blow dryer at 40 ° C. for 15 minutes. The film was peeled off from the glass plate and sandwiched between stainless steel frames, which were dried in a dryer at 100 ° C. for 30 minutes and in a dryer at 133 ° C. for 30 minutes to obtain a film.
(4) Film thickness measurement: An arbitrary portion was measured at three points with a digital micrometer, and an average value was taken.
(5) Haze measurement: The film was measured according to JIS K-6714 with a haze meter (HGM-2DP, Suga Test Instruments) at 25 ° C. and 60% RH.
(6) Re, Rth measurement: It measured by the above-mentioned method at wavelength 590nm using KOBRA 21ADH (made by Oji Scientific Instruments). The obtained values were converted as Re and Rth having a thickness of 80 μm.

[Synthesis of norbornene monomers]
(Synthesis Example 1: Synthesis of M-1)
572 g of dicyclopentadiene (manufactured by Wako Pure Chemical Industries, Ltd.), 1309 g of allyl acetate (manufactured by Wako Pure Chemical Industries, Ltd.) and 1 g of hydroquinone (manufactured by Wako Pure Chemical Industries, Ltd.) were charged into the autoclave, and the air gap was replaced with nitrogen. The mixture was stirred for 3 hours at an internal temperature of 270 ° C. in a closed system (rotational speed = 300 rpm). The reaction mixture was filtered and the volatile components were evaporated. The residue was subjected to simple distillation to obtain colorless and transparent M-1. When the peak purity was measured by gas chromatography, the purity was 98.7% and the endo / exo ratio was 59/41.

[Synthesis of norbornene polymer (A)]
(Synthesis of A-1)
332.1 g of M-1 was charged to the reaction vessel. Next, a solution obtained by reacting 85.5 mg of palladium bisacetylacetonate (manufactured by Tokyo Chemical Industry Co., Ltd.) and 88.5 mg of tricyclohexylphosphine (manufactured by Strem Co., Ltd.) with 10 mL of toluene was added. Subsequently, 454 mg of dimethylanilinium tetrakispentafluorophenyl borate (manufactured by Strem) dissolved in 5 mL of methylene chloride was added. Further, 1325 mL of toluene was added. The solution was stirred at 95 ° C. for 6 hours. 2.8 L of toluene was added, and 10 L of methanol was added dropwise over 3 hours while stirring. The resulting precipitate was filtered. This was washed in methanol and suction filtered again. Vacuum drying was performed at 120 ° C. for 6 hours. 314 g of A-1 as a white solid was obtained. As a result of measuring molecular weight, it was Mw = 308200 and Mn = 106000.

(Synthesis of A-2)
798.6 g of methyl norbornenecarboxylate (M-2: simply distilled from Tokyo Chemical Industry Co., Ltd .; purity 98.9% by gas chromatography, endo / exo ratio 50/50) was charged into a reaction vessel. Next, a solution obtained by reacting 318 mg of palladium bisacetylacetonate (manufactured by Tokyo Chemical Industry Co., Ltd.) and 296 mg of tricyclohexylphosphine (manufactured by Strem Co.) with 10 mL of toluene was added. Subsequently, 1700 mg of dimethylanilinium tetrakispentafluorophenyl borate (manufactured by Strem) dissolved in 5 mL of methylene chloride was added. Furthermore, 800 mL of toluene was added. The solution was stirred at 95 ° C. for 6 hours. 2 L of toluene was added, and 5 L of methanol was added dropwise over 3 hours while stirring. The resulting precipitate was filtered. This was washed in methanol and suction filtered again. Vacuum drying was performed at 120 ° C. for 6 hours. 630 g of white solid A-2 was obtained. As a result of measuring molecular weight, it was Mw = 123400 and Mn = 53200.

(Synthesis of A-3)
166.1 g M-1 and 152.2 g M-2 were charged to the reaction vessel. A catalyst was charged in the same manner as in Example 1 to obtain a white solid A-3. As a result of measuring molecular weight, it was Mw = 185600 and Mn = 76400.

The above A-3 was measured by ¹³ CNMR. From the comparison of the integrated value of the peak of acetyl group appearing at 172 ppm and the peak of methyl ester group appearing at 175 ppm, the ratio of acetyl group to methyl ester group was calculated as 60/40.

[Synthesis of vinyl polymer (B)]
(Synthesis of B-1)
Styrene (Wako Pure Chemical Industries) 106.8 g, n-butyl acrylate (Wako Pure Chemical Industries) 58.0 g, 2-hydroxyethyl methacrylate (Wako Pure Chemical Industries) 28.4 g, methyl ethyl ketone (Wako Pure Chemical Industries )) 32% of the 132.1 g monomer mixed solution was charged into a reaction vessel and stirred at 65 ° C. and 130 rpm. A mixed solution of the remaining monomer mixed solution and 2.1 g of 2,2′-azobis-2,4-dimethylvaleronitrile (V-65: manufactured by Wako Pure Chemical Industries, Ltd.) was added dropwise over 1 hour. The mixture was stirred for 2 hours, and a mixed solution of 2.1 g of V-65 and 21.0 g of methyl ethyl ketone was added dropwise over 3 hours, followed by stirring for 2 hours. After raising the temperature from 65 ° C. to 70 ° C., the mixture was stirred for 2 hours. The contents were reprecipitated in methanol and dried to obtain B-1. As a result of the GPC measurement, Mw = 25000 and Mn = 1300. When the integral ratio of the carbonyl carbon peak was compared by 13C NMR measurement, the molar ratio of the repeating unit derived from n-butyl acrylate / 2-hydroxyethyl methacrylate was 68/32. Furthermore, the integrated value of the peak in the vicinity of 7 ppm (phenyl group) and the integrated value of the peak at 0.5 to 4.5 ppm were compared by 1HNMR, and the result of 13CNMR was combined to determine the composition of 3 units. As a result, the molar ratio of the repeating unit derived from 2-hydroxyethyl methacrylate / styrene / n-butyl acrylate was 13/60/27.

(Synthesis of B-2)
The composition of the mixed solution of the three types of monomers was 96.8 g of styrene (manufactured by Wako Pure Chemical Industries), 63.0 g of n-butyl acrylate (manufactured by Wako Pure Chemical Industries), 2-hydroxyethyl methacrylate (manufactured by Wako Pure Chemical Industries) 33. As for 4g, the same operation as B-1 was performed to obtain B-2. Mw = 26400 and Mn = 13500. As described above, the molar ratio of the repeating unit derived from 2-hydroxyethyl methacrylate / styrene / n-butyl acrylate was 15/55/30 from 1HNMR and 13CNMR measurements.

(Synthesis of B-3)
The composition of the mixed solution of the three types of monomers was 116.8 g of styrene (manufactured by Wako Pure Chemical Industries), 53.0 g of n-butyl acrylate (manufactured by Wako Pure Chemical Industries), and 2-hydroxyethyl methacrylate (manufactured by Wako Pure Chemical Industries) 23. As 4g, the same operation as B-1 was performed to obtain B-3. Mw = 28900 and Mn = 14500. The molar ratio of the repeating unit derived from 2-hydroxyethyl methacrylate / styrene / n-butyl acrylate was 11/65/24 from 1HNMR and 13CNMR measurements as described above.

(Synthesis of B-4)
The mixed solution composition of the three types of monomers was 106.8 g of styrene (manufactured by Wako Pure Chemical Industries, Ltd.), 45.3 g of ethyl acrylate (manufactured by Wako Pure Chemical Industries, Ltd.), 23.4 g of 2-hydroxyethyl methacrylate (manufactured by Wako Pure Chemical Industries, Ltd.), As described above, the same operation as in B-1 was performed to obtain B-4. Mw = 24500 and Mn = 1100. As described above, the molar ratio of the repeating unit derived from 2-hydroxyethyl methacrylate / styrene / ethyl acrylate was 11/62/27 from 1HNMR and 13CNMR measurements.

(Synthesis of B-5)
The mixed solution composition of three types of monomers was 106.8 g of styrene (manufactured by Wako Pure Chemical Industries), 38.7 g of methyl acrylate (manufactured by Wako Pure Chemical Industries), 25.5 g of 2-hydroxyethyl methacrylate (manufactured by Wako Pure Chemical Industries, Ltd.), As described above, the same operation as in B-1 was performed to obtain B-5. Mw = 23200 and Mn = 10400. As described above, the molar ratio of the repeating unit derived from 2-hydroxyethyl methacrylate / styrene / methyl acrylate was 12/61/27 from 1HNMR and 13CNMR measurements.

(Synthesis of B-6)
The composition of the mixed solution of the three types of monomers was 106.8 g of styrene (manufactured by Wako Pure Chemical Industries), 58.0 g of n-butyl acrylate (manufactured by Wako Pure Chemical Industries), 2-hydroxyethyl acrylate (manufactured by Wako Pure Chemical Industries) 25. As in 5 g, the same operation as in B-1 was performed to obtain B-6. Mw = 21300 and Mn = 10000. The molar ratio of the repeating unit derived from 2-hydroxyethyl acrylate / styrene / n-butyl acrylate was 11/62/27 from 1HNMR and 13CNMR measurements as described above.

(Synthesis of B-7)
The composition of the mixed solution of the three types of monomers is 106.8 g of styrene (manufactured by Wako Pure Chemical Industries), 23.9 g of acrylonitrile (manufactured by Wako Pure Chemical Industries), and 25.5 g of 2-hydroxyethyl acrylate (manufactured by Wako Pure Chemical Industries, Ltd.). , B-1 was performed to obtain B-7. Mw = 19800 and Mn = 9500. As a result of quantitative measurement by an inverse gate decoupling method of 13C NMR (delay time 10 seconds, integration 3000 times), the molar ratio of repeating units derived from 2-hydroxyethyl methacrylate / styrene / acrylonitrile was 10/62/28. .

[Dope preparation and film production]
(Examples 1 to 15)
The norbornene polymer (A) and the vinyl polymer (B) obtained above were mixed by the above-described method at the combinations and mixing ratios shown in Table 1. This was formed into a film by the above-mentioned method. Haze and Rth were measured by the method described above. The results are shown in Table 1.

(Comparative Examples 1-3)
Dope preparation and film formation were performed in the same manner as in Example 1 using only A-1, A-2, and A-3 without adding the vinyl polymer (B). The results are shown in Table 1.

(Comparative Example 4)
Dope preparation and film formation were performed in the same manner as in Example 1 using polystyrene (C-1: Aldrich, Mw = 13000) instead of the vinyl polymer (B), but the film was whitened and evaluated. I couldn't.

(Comparative Example 5)
Instead of the vinyl polymer (B), poly (styrene-co-acrylonitrile) (C-2: manufactured by Aldrich: Mw = 165000, the molar ratio of repeating units derived from styrene / acrylonitrile is 75/25) Then, the dope was produced and formed in the same manner as in Example 1, but the film was whitened and could not be evaluated.

(Comparative Example 6)
A mixture (C-3) composed of styrene, n-butyl acrylate and 2-hydroxyethyl methacrylate and having the same molar ratio as B-1 was directly mixed with A-1 without polymerization. Dope preparation and film formation were performed in the same manner as in Example 1. The results are shown in Table 1.

  From Table 1, the film of the resin composition of the present invention has a small haze and can reduce Rth of the original norbornene-based polymer film (Comparative Examples 1 to 3). That is, it can be controlled to various values. On the other hand, the film outside the present invention was whitened or Rth was not reduced.

Claims (10)

A resin composition comprising a norbornene polymer (A) having a repeating unit represented by the following general formula (1) and a vinyl polymer (B) having a hydroxyl group.

(In the general formula (1), R ¹ , R ² , R ³ and R ⁴ are each independently a hydrogen atom or — (CH ₂ ) _m —OC (O) —R ″, — (CH ₂ ) _{m. -OH, - (CH 2) m} -C (O) -OH, - (CH 2) m -C (O) OR '', - (CH 2) m -OR '', - (CH 2) m - A functional substituent selected from the group consisting of OC (O) OR ″, — (CH ₂ ) _m —C (O) R ″, — (CH ₂ ) _m —O— (CH ₂ ) _m —OH; Wherein m is independently 0 to 10, R ″ represents a linear or branched alkyl group having 1 to 10 carbon atoms, and R ¹ and R ⁴ are bonded to each other. Together with the ring carbon atoms can form an anhydride or dicarboximide group, provided that at least one of R ^{1 to} R ⁴ is a functional substituent.) The resin composition according to claim 1, wherein the vinyl polymer (B) having a hydroxyl group is a polymer having a repeating unit represented by the following general formula (2).

(In General Formula (2), R _{1 to} R ₃ each independently represents a hydrogen atom; a halogen atom; an oxygen atom, a sulfur atom, a nitrogen atom or a silicon atom, which may have a linking group, An unsubstituted hydrocarbon group having 1 to 30 carbon atoms; or a polar group, and n is 0 or a positive integer.) The resin composition according to claim 2, wherein the vinyl polymer (B) having a hydroxyl group is a polymer further having at least one repeating unit selected from the following general formulas (3) and (4).

(In General Formulas (3) and (4), R _{4 to} R ₇ may each independently have a linking group containing 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, and all R _{5 s} may be the same atom or group or different from each other. The resin composition according to claim 3, wherein the vinyl polymer (B) having a hydroxyl group is a polymer having each repeating unit of the following general formula (5).

(In the general formula (5), R _{1 to} R ₇ are each independently a hydrogen atom; a halogen atom; an oxygen atom, a sulfur atom, a nitrogen atom or a silicon atom, which may have a linking group, An unsubstituted hydrocarbon group having 1 to 30 carbon atoms; or a polar group, and all R _{5 s} may be the same or different from each other, and n may be 0 or positive X, y and z represent the molar ratio of each repeating unit when x + y + z = 100 mol%, and 1 <x <20 and 40 <y <99 are satisfied.)   The resin composition according to any one of claims 1 to 4, wherein the vinyl polymer (B) having a hydroxyl group has a weight average molecular weight of 1,000 to 50,000 and a number average molecular weight of 500 to 25,000. 6. The resin composition according to claim 4, wherein R ₇ in the general formula (5) is COOR ″ (R ″ is an alkyl group having 1 to 4 carbon atoms).   The resin composition according to any one of claims 1 to 6, wherein the norbornene polymer (A) contains 50 to 100 mol% of a repeating unit represented by the general formula (1). One of R ¹ , R ² , R ³ and R ^{4 in} the general formula (1) is —CH ₂ —OC (O) —R ″ (R ″ is the same as described above) or —C (O) OR. The resin composition according to claim 1, wherein R is the same as above, and the remaining three are hydrogen atoms.   The mass mixing ratio (A / B) of the vinyl polymer (B) having the hydroxyl group and the norbornene polymer (A) is 99/1 to 50/50, according to any one of claims 1 to 8. Resin composition.   The film which consists of a resin composition in any one of Claims 1-9.