JP5407677B2 - Optical compensation film and manufacturing method thereof - Google Patents

Description

  The present invention relates to an optical compensation film excellent in optical properties such as wavelength dependency and adhesion to a substrate, in particular, an optical compensation film for a liquid crystal display device having an optical compensation function even in an unstretched state after coating, and its production It is about the method. Specifically, it is an optical compensation film with an increased Rth (out-of-plane retardation), and a thinner optical compensation film is expected.

  Liquid crystal displays are widely used as the most important display devices in the multimedia society, from mobile phones to computer monitors, notebook computers, and televisions. Many optical films are used in liquid crystal displays to improve display characteristics.

  In particular, the optical compensation film plays a major role in improving the contrast when viewed from the front or obliquely, compensating for the color tone, and the like. As a conventional optical compensation film, a stretched film of polycarbonate, cyclic polyolefin, or cellulose resin is used. However, these films have problems such as a need for a stretching process and difficulty in obtaining uniformity of retardation in the stretching process. In particular, in a large-area film, it becomes even more difficult to control the retardation produced by stretching.

  As a method for solving the problem due to stretching, studies have been made on an optical compensation film that exhibits an uncompensated optical compensation function by coating.

  Harris and Chen of Akron University have proposed an optical compensation film made of rigid rod-shaped polyimide, polyester, polyamide, poly (amide-imide), and poly (ester-imide) (see, for example, Patent Documents 1 and 2). ), These materials have the characteristic of expressing a phase difference without undergoing a stretching process by coating because of their spontaneous molecular orientation.

  Furthermore, an optical compensation film made of polyimide with improved polyimide coating properties (solubility in a solvent) (see, for example, Patent Document 3), and a polarizing plate in which a protective film of a polarizing plate is coated with a discotic liquid crystal compound ( For example, see Patent Document 4).

  Moreover, the stretched film (for example, refer patent document 5) which consists of a phenylmaleimide-isobutene copolymer is proposed.

  Moreover, an optical compensation film made of maleimide resin is disclosed (for example, see Patent Document 6).

US Pat. No. 5,344,916 Japanese National Patent Publication No. 10-508048 Japanese Patent Laid-Open No. 2005-070745 Japanese Patent No. 2565644 JP 2004-269842 A JP 2008-287226 A

  However, since the polymer used in the methods proposed in Patent Documents 1 to 3 is an aromatic polymer, the wavelength dependence of the retardation is large, and when used as an optical compensation film of a liquid crystal display element, image quality such as color shift is obtained. It had the subject of a fall.

  In addition, the method using the discotic liquid crystal compound proposed in Patent Document 4 not only has problems such as requiring uniform alignment of the liquid crystal compound, complicating the coating process, and large alignment unevenness. Since the liquid crystal compound is mainly composed of an aromatic compound, it also has a quality problem that the wavelength dependency of retardation is large.

  The stretched film obtained in Patent Document 5 does not develop a phase difference only by coating (nx = ny = nz).

  Patent Document 6 describes that, for example, an ultraviolet absorber such as benzotriazole, benzophenone, triazine, benzoate, or the like may be blended as necessary, but Rth (surface The effect of increasing the external phase difference amount) is not described.

  Therefore, the present invention aims to provide an optical compensation film having excellent optical characteristics. More specifically, the present invention exhibits an optical compensation function when applied, and the wavelength dependence of the phase difference. It is an object of the present invention to provide an optical compensation film that is small in size, excellent in adhesion to a substrate, and expected to be thinned by increasing Rth (out-of-plane retardation).

  As a result of intensive studies in view of the above problems, the present inventors have found that a coating film made of a specific resin and a cyclic hydrocarbon-based compound has an optical compensation function, particularly a coating suitable for optical compensation for a liquid crystal display element. As a result, the present invention has been completed.

  That is, the present invention is a coating film comprising a maleimide-based resin and a cyclic hydrocarbon-based compound, and any two axes orthogonal in the plane of the coating film are defined as an x-axis and a y-axis, and an out-of-plane direction is z. The three-dimensional refractive index relationship when the refractive index in the x-axis direction is nx, the refractive index in the y-axis direction is ny, and the refractive index in the z-axis direction is nz is nx≈ny> nz. The present invention relates to an optical compensation film.

  Hereinafter, the optical compensation film of the present invention will be described in detail.

  The optical compensation film of the present invention is a coating film comprising a maleimide resin and a cyclic hydrocarbon compound, and any two axes orthogonal in the plane of the coating film are x-axis and y-axis, and are out of plane. The direction is the z-axis, the refractive index in the x-axis direction is nx, the refractive index in the y-axis direction is ny (if nx and ny are different, the smallest refractive index is ny), and the refractive index in the z-axis direction is nz. In this optical compensation film, the three-dimensional refractive index relationship is nx≈ny> nz.

  By adding the above cyclic hydrocarbon compound, nx and ny increase and nz decreases, so the relationship of nx≈ny> nz is strengthened, and the cyclic hydrocarbon is added without adding a complicated stretching step. Larger Rth can be expressed only by changing the addition amount of the system compound.

  Examples of the maleimide resin used in the optical compensation film of the present invention include N-substituted maleimide polymer resin, N-substituted maleimide-maleic anhydride copolymer resin, and the like, and N-substituted resin constituting the maleimide resin. Examples of maleimide residue units include N-substituted maleimide residue units represented by the following general formula (1).

（ここで、Ｒ_１は、炭素数１〜１８の直鎖状アルキル基，炭素数１〜１８の分岐状アルキル基，炭素数１〜１８の環状アルキル基、ハロゲン基、エーテル基、エステル基、アミド基を示す。）
一般式（１）で示されるＮ−置換マレイミド残基単位におけるＲ_１は、炭素数１〜１８の直鎖状アルキル基，炭素数１〜１８の分岐状アルキル基，炭素数１〜１８の環状アルキル基、ハロゲン基、エーテル基、エステル基、アミド基であり、炭素数１〜１８の直鎖状アルキル基としては、例えばメチル基、エチル基、クロロエチル基、メトキシエチル基、ｎ−プロピル基、ｎ−ブチル基、ｎ−ヘキシル基、ｎ−オクチル基、ｎ−ラウリル基等が挙げられ、炭素数１〜１８の分岐状アルキル基としては、例えばイソプロピル基、イソブチル基、ｓ−ブチル基、ｔ−ブチル基等が挙げられ、炭素数１〜１８の環状アルキル基としては、例えばシクロヘキシル基等が挙げられ、ハロゲン基としては、例えば塩素、臭素、フッ素、ヨウ素等の１種又は２種以上が挙げられ、特にＲｔｈが大きく、溶剤への溶解性、機械的強度に優れる光学補償膜となることから、ｎ−ブチル基、イソブチル基、ｓ−ブチル基、ｔ−ブチル基、ｎ−ヘキシル基、ｎ−オクチル基等が好ましい。

(Here, R ₁ is a linear alkyl group having 1 to 18 carbon atoms, a branched alkyl group having 1 to 18 carbon atoms, a cyclic alkyl group having 1 to 18 carbon atoms, a halogen group, an ether group, an ester group, Indicates an amide group.)
R ₁ in the N-substituted maleimide residue unit represented by the general formula (1) is a linear alkyl group having 1 to 18 carbon atoms, a branched alkyl group having 1 to 18 carbon atoms, or cyclic having 1 to 18 carbon atoms. An alkyl group, a halogen group, an ether group, an ester group, an amide group, and examples of the linear alkyl group having 1 to 18 carbon atoms include a methyl group, an ethyl group, a chloroethyl group, a methoxyethyl group, an n-propyl group, An n-butyl group, an n-hexyl group, an n-octyl group, an n-lauryl group, and the like can be mentioned. Examples of the branched alkyl group having 1 to 18 carbon atoms include isopropyl group, isobutyl group, s-butyl group, t -Butyl group etc. are mentioned, As a C1-C18 cyclic alkyl group, a cyclohexyl group etc. are mentioned, for example, As a halogen group, one sort of chlorine, bromine, fluorine, iodine, etc., or Two or more types can be mentioned, and since it becomes an optical compensation film having particularly large Rth and excellent solubility in a solvent and mechanical strength, n-butyl group, isobutyl group, s-butyl group, t-butyl group, n -A hexyl group, n-octyl group, etc. are preferable.

  Specific examples of the N-substituted maleimide residue unit include, for example, an N-methylmaleimide residue unit, an N-ethylmaleimide residue unit, an N-chloroethylmaleimide residue unit, an N-methoxyethylmaleimide residue unit, Nn-propylmaleimide residue unit, N-isopropylmaleimide residue unit, Nn-butylmaleimide residue unit, N-isobutylmaleimide residue unit, Ns-butylmaleimide residue unit, Nt- 1 type or 2 types, such as a butyl maleimide residue unit, a Nn-hexyl maleimide residue unit, a N-cyclohexyl maleimide residue unit, a Nn-octyl maleimide residue unit, a Nn-lauryl maleimide residue unit In particular, since the Rth is large, it becomes an optical compensation film excellent in solubility in a solvent and mechanical strength. Maleimide residue unit, N-isobutylmaleimide residue unit, Ns-butylmaleimide residue unit, Nt-butylmaleimide residue unit, Nn-hexylmaleimide residue unit, Nn-octylmaleimide residue Base units and the like are preferred.

  Examples of the N-substituted maleimide polymer resin include N-methylmaleimide polymer resin, N-ethylmaleimide polymer resin, N-chloroethylmaleimide polymer resin, N-methoxyethylmaleimide polymer resin, Nn- Propylmaleimide polymer resin, N-isopropylmaleimide polymer resin, Nn-butylmaleimide polymer resin, N-isobutylmaleimide polymer resin, Ns-butylmaleimide polymer resin, Nt-butylmaleimide polymer Examples thereof include resin, Nn-hexylmaleimide polymer resin, N-cyclohexylmaleimide polymer resin, Nn-octylmaleimide polymer resin, and Nn-laurylmaleimide polymer resin.

  Examples of the N-substituted maleimide-maleic anhydride copolymer resin include N-methylmaleimide-maleic anhydride copolymer resin, N-ethylmaleimide-maleic anhydride copolymer resin, and N-chloroethylmaleimide-anhydride. Maleic acid copolymer resin, N-methoxyethylmaleimide-maleic anhydride copolymer resin, Nn-propylmaleimide-maleic anhydride copolymer resin, N-isopropylmaleimide-maleic anhydride copolymer resin, N -N-butylmaleimide-maleic anhydride copolymer resin, N-isobutylmaleimide-maleic anhydride copolymer resin, Ns-butylmaleimide-maleic anhydride copolymer resin, Nt-butylmaleimide-anhydrous Maleic acid copolymer resin, Nn-hexylmaleimide-maleic anhydride copolymer resin, N- Black hexyl maleimide - maleic anhydride copolymer resin, N-n-octyl maleimide - maleic anhydride copolymer resin, N-n-lauryl maleimide - can be mentioned maleic anhydride copolymer resin.

  Among them, the Nn-butylmaleimide polymer resin, the Nn-butylmaleimide polymer resin, and the Nn-butylmaleimide polymer resin, which are particularly excellent in film forming properties during film formation and become an optical compensation film excellent in optical compensation function and heat resistance, Nn-octylmaleimide polymer resin, Nn-octylmaleimide-maleic anhydride copolymer resin and the like are preferable, and Nn-butylmaleimide polymer resin and Nn-hexylmaleimide polymer are particularly preferable. Resins are preferred.

  Further, the maleimide resin constituting the optical compensation film of the present invention contains a residue unit other than the N-substituted maleimide residue unit and the maleic anhydride residue unit without departing from the object of the present invention. The residue unit may be, for example, a styrene residue unit such as a styrene residue unit or an α-methylstyrene residue unit; an acrylic acid residue unit; a methyl acrylate residue unit, or an ethyl acrylate residue. Units, acrylate residue units such as butyl acrylate residue units; methacrylic acid residue units; methacrylic acid ester residues such as methyl methacrylate residue units, ethyl methacrylate residue units, butyl methacrylate residue units Unit: vinyl ester residue such as vinyl acetate residue and vinyl propionate residue; acrylonitrile residue; one or two of methacrylonitrile residue It can be mentioned more.

Moreover, as this maleimide-type resin, the number average molecular weight (Mn) of standard polystyrene conversion obtained from the elution curve measured by gel permeation chromatography (henceforth GPC) is 1 * 10 < ³ > or more. In particular, it is preferably 2 × 10 ⁴ or more and 2 × 10 ⁵ or less because it becomes an optical compensation film having excellent mechanical properties and excellent moldability during film formation.

  The maleimide resin constituting the optical compensation film of the present invention may be produced by any method as long as the maleimide resin is obtained. For example, N-substituted maleimides, maleic anhydride, and in some cases It can be produced by performing radical polymerization or radical copolymerization using a monomer copolymerizable with N-substituted maleimides. Examples of N-substituted maleimides include N-methylmaleimide, N-ethylmaleimide, N-chloroethylmaleimide, N-methoxyethylmaleimide, Nn-propylmaleimide, N-isopropylmaleimide, Nn- 1 such as butylmaleimide, N-isobutylmaleimide, Ns-butylmaleimide, Nt-butylmaleimide, Nn-hexylmaleimide, N-cyclohexylmaleimide, Nn-octylmaleimide, Nn-laurylmaleimide Examples of the copolymerizable monomer include styrenes such as styrene and α-methylstyrene; acrylic acid; acrylic esters such as methyl acrylate, ethyl acrylate, and butyl acrylate. Methacrylic acid; methyl methacrylate, methacrylate Methacrylic acid esters such as butyl methacrylate, vinyl acetate, vinyl propionate, vinyl pivalate, vinyl laurate, vinyl stearate, etc .; acrylonitrile; one or more of methacrylonitrile, etc. Can be mentioned.

  Further, as the radical polymerization method, it can be carried out by a known polymerization method, and for example, any of a bulk polymerization method, a solution polymerization method, a suspension polymerization method, a precipitation polymerization method, an emulsion polymerization method and the like can be adopted. .

  Examples of the polymerization initiator used in the radical polymerization method include benzoyl peroxide, lauryl peroxide, octanoyl peroxide, acetyl peroxide, di-t-butyl peroxide, t-butyl cumyl peroxide, and dicumyl peroxide. , Organic peroxides such as t-butylperoxyacetate and t-butylperoxybenzoate; 2,2′-azobis (2,4-dimethylvaleronitrile), 2,2′-azobis (2-butyronitrile), 2 , 2′-azobisisobutyronitrile, dimethyl-2,2′-azobisisobutyrate, 1,1′-azobis (cyclohexane-1-carbonitrile) and the like.

  And there is no restriction | limiting in particular as a solvent which can be used in a solution polymerization method, a suspension polymerization method, a precipitation polymerization method, and an emulsion polymerization method, For example, aromatic solvents, such as benzene, toluene, xylene; Methanol, ethanol, propyl alcohol, butyl alcohol Alcohol solvents such as cyclohexane, dioxane, tetrahydrofuran (THF), acetone, methyl ethyl ketone, dimethylformamide, isopropyl acetate, water, N-methylpyrrolidone, and the like, and mixed solvents thereof.

  Moreover, the polymerization temperature at the time of performing radical polymerization can be suitably set according to the decomposition temperature of a polymerization initiator, and generally it is preferable to carry out in the range of 40-150 degreeC.

  In the optical compensation film of the present invention, the cyclic hydrocarbon compound is added for the purpose of strengthening the three-dimensional refractive index relationship (nx≈ny> nz) of the film, that is, expressing a larger Rth.

  The inventors' research has revealed that the Rth of a film made of a maleimide resin is increased by blending a cyclic hydrocarbon compound with the maleimide resin. The cyclic hydrocarbon compound is preferably a compound satisfying any one of the following general formulas (2), (3), and (4), particularly preferably a compound satisfying the general formulas (2) and (3). Or two or more types can be used in combination.

（式中、Ｘ_１、Ｘ_２、Ｘ_３はそれぞれ水素原子、ハロゲン原子、置換もしくは無置換のアミノ基、メルカプト基、スルホン酸基、アルコキシ基、アルデヒド基、カルボキシル基、アルキル基、アルケニル基、アルキニル基、芳香族環を表し、それぞれが同一のものであっても、異なるものであってもよい。）
一般式（２）のＸ_１、Ｘ_２、Ｘ_３におけるハロゲン原子としては、例えばＦ、Ｃｌ、Ｂｒ、Ｉ等が挙げられ、置換もしくは無置換のアミノ基としては、例えば−ＮＨ_２、−ＮＨＣＨ_３、−Ｎ（ＣＨ_３）_２、−ＮＨＣ_２Ｈ_５、−Ｎ（Ｃ_２Ｈ_５）_２、−ＮＨＣ_３Ｈ_７、−Ｎ（Ｃ_３Ｈ_７）_２、−ＮＨ（Ｃ_４Ｈ_９）、−Ｎ（Ｃ_４Ｈ_９）_２、−ＮＨＰｈ等が挙げられ、アルコキシ基としては、例えばメトキシ基、エトキシ基、ｎ−プロポキシ基、ｉ−プロポキシ基、ｎ−ブトキシ基、イソブトキシ基、ｔ−ブトキシ基、ｓ−ブトキシ基等が挙げられ、アルキル基としては炭素原子数１〜８であることが好ましく、例えばメチル、エチル、ｎ−ブチル、ｎ−ヘキシル等が挙げられ、アルケニル基としては炭素原子数２〜８であることが好ましく、例えばビニル、アリル、１−ヘキセニル等が挙げられ、アルキニル基としては炭素原子数２〜８であることが好ましく、例えばエチニル、１−ブチニル、１−ヘキシニル等が挙げられる。

(Wherein X ₁ , X ₂ and X ₃ are each a hydrogen atom, a halogen atom, a substituted or unsubstituted amino group, a mercapto group, a sulfonic acid group, an alkoxy group, an aldehyde group, a carboxyl group, an alkyl group, an alkenyl group, An alkynyl group and an aromatic ring, each of which may be the same or different.
Examples of the halogen atom in X ₁ , X ₂ , and X ₃ in the general formula (2) include F, Cl, Br, and I. Examples of the substituted or unsubstituted amino group include —NH ₂ and —NHCH. _{3, -N (CH 3) 2} , -NHC 2 H 5, -N (C 2 H 5) 2, -NHC 3 H 7, -N (C 3 H 7) 2, -NH (C 4 H 9) , —N (C ₄ H ₉ ) ₂ , —NHPh and the like. Examples of the alkoxy group include a methoxy group, an ethoxy group, an n-propoxy group, an i-propoxy group, an n-butoxy group, an isobutoxy group, t- A butoxy group, a s-butoxy group, etc. are mentioned, As an alkyl group, it is preferable that it is C1-C8, for example, methyl, ethyl, n-butyl, n-hexyl etc. are mentioned, and an alkenyl group is carbon. 2 to 8 atoms There are preferably, for example, vinyl, allyl, 1-hexenyl and the like, and the alkynyl group preferably has 2 to 8 carbon atoms, for example, ethynyl, 1-butynyl, 1-hexynyl and the like.

  In addition to the aromatic hydrocarbon ring, the aromatic ring includes an aromatic heterocyclic ring and an aromatic condensed ring. Examples of the aromatic hydrocarbon ring include a benzene ring, a furan ring, a thiophene ring, a pyrrole ring, an oxazole ring, Examples include a thiazole ring, an imidazole ring, a triazole ring, a pyridine ring, a pyrimidine ring, a pyrazine ring, and a 1,3,5-triazine ring. The number of aromatic rings is preferably 1-20, more preferably 1-12, and particularly preferably 1-8.

  The aromatic heterocycle is preferably a 5-membered ring, 6-membered ring or 7-membered ring, more preferably a 5-membered ring or 6-membered ring. As the hetero atom, a nitrogen atom, an oxygen atom and a sulfur atom are preferable, and a nitrogen atom is particularly preferable. Examples of the aromatic heterocycle include, for example, furan ring, thiophene ring, pyrrole ring, oxazole ring, isoxazole ring, thiazole ring, isothiazole ring, imidazole ring, pyrazole ring, furazane ring, triazole ring, pyran ring, pyridine ring. , Pyridazine ring, pyrimidine ring, pyrazine ring, 1,3,5-triazine ring and the like.

  Examples of the aromatic condensed ring include, for example, indene ring, naphthalene ring, azulene ring, fluorene ring, phenanthrene ring, anthracene ring, acenaphthylene ring, biphenylene ring, naphthacene ring, pyrene ring, indole ring, isoindole ring, benzofuran ring, Benzothiophene ring, indolizine ring, benzoxazole ring, benzothiazole ring, benzimidazole ring, benzotriazole ring, purine ring, indazole ring, chromene ring, quinoline ring, isoquinoline ring, quinolidine ring, quinazoline ring, cinnoline ring, quinoxaline ring , Phthalazine ring, pteridine ring, carbazole ring, acridine ring, phenanthridine ring, xanthene ring, phenazine ring, phenothiazine ring, phenoxathiin ring, phenoxazine ring, thianthrene ring, naphthalene ring, azulene , Indole ring, benzoxazole ring, benzothiazole ring, benzimidazole ring, benzotriazole ring, quinoline ring and the like.

  The aromatic ring may have a substituent. However, the substituent is required not to sterically hinder the conformation of the two aromatic rings. In steric hindrance, the type and position of substituents are problematic. As the type of the substituent, a sterically bulky substituent (for example, a tertiary alkyl group) tends to cause steric hindrance. As the position of the substituent, steric hindrance is likely to occur when a position adjacent to the bond of the aromatic ring (ortho position in the case of a benzene ring) is substituted.

  Examples of the substituent include, for example, a halogen atom (F, Cl, Br, I), hydroxyl, carboxyl, cyano, amino, nitro, sulfo, carbamoyl, sulfamoyl, ureido, alkyl group, alkenyl group, alkynyl group, aliphatic acyl Group, aliphatic acyloxy group, alkoxy group, alkoxycarbonyl group, alkoxycarbonylamino group, alkylthio group, alkylsulfonyl group, aliphatic amide group, aliphatic sulfonamido group, aliphatic substituted amino group, aliphatic substituted carbamoyl group, fatty acid Group-substituted sulfamoyl group, aliphatic substituted ureido group, non-aromatic heterocyclic group and the like.

  It is preferable that the alkyl group has 1 to 8 carbon atoms. A chain alkyl group is preferable to a cyclic alkyl group, and a linear alkyl group is particularly preferable. The alkyl group may further have a substituent (eg, hydroxy, carboxy, alkoxy group, alkyl-substituted amino group). Examples of alkyl groups (including substituted alkyl groups) include methyl, ethyl, n-butyl, n-hexyl, 2-hydroxyethyl, 4-carboxybutyl, 2-methoxyethyl, 2-diethylaminoethyl and the like. .

  The alkenyl group preferably has 2 to 8 carbon atoms. A chain alkenyl group is preferable to a cyclic alkenyl group, and a linear alkenyl group is particularly preferable. The alkenyl group may further have a substituent. Examples of alkenyl groups include vinyl, allyl, 1-hexenyl and the like.

  The alkynyl group preferably has 2 to 8 carbon atoms. A chain alkynyl group is preferable to a cyclic alkynyl group, and a linear alkynyl group is particularly preferable. The alkynyl group may further have a substituent. Examples of alkynyl groups include ethynyl, 1-butynyl, 1-hexynyl and the like.

  The number of carbon atoms in the aliphatic acyl group is preferably 1-10. Examples of the aliphatic acyl group include acetyl, propanoyl, butanoyl and the like.

  The number of carbon atoms in the aliphatic acyloxy group is preferably 1-10. Examples of aliphatic acyloxy groups include acetoxy, for example.

  The number of carbon atoms of the alkoxy group is preferably 1-8. The alkoxy group may further have a substituent (eg, a substituted alkoxy group). Examples of alkoxy groups (including substituted alkoxy groups) include methoxy, ethoxy, butoxy, methoxyethoxy and the like.

  The number of carbon atoms of the alkoxycarbonyl group is preferably 2-10. Examples of the alkoxycarbonyl group include methoxycarbonyl, ethoxycarbonyl and the like.

  The number of carbon atoms of the alkoxycarbonylamino group is preferably 2-10. Examples of the alkoxycarbonylamino group include methoxycarbonylamino, ethoxycarbonylamino and the like.

  The alkylthio group preferably has 1 to 12 carbon atoms. Examples of the alkylthio group include, for example, methylthio, ethylthio, octylthio and the like.

  The alkylsulfonyl group preferably has 1 to 8 carbon atoms. Examples of the alkylsulfonyl group include methanesulfonyl, ethanesulfonyl and the like.

  The number of carbon atoms in the aliphatic amide group is preferably 1-10. Examples of aliphatic amide groups include, for example, acetamide.

  The number of carbon atoms of the aliphatic sulfonamide group is preferably 1-8. Examples of the aliphatic sulfonamide group include methanesulfonamide, butanesulfonamide, n-octanesulfonamide and the like.

  The number of carbon atoms of the aliphatic substituted amino group is preferably 1-10. Examples of the aliphatic substituted amino group include dimethylamino, diethylamino, 2-carboxyethylamino and the like.

  The number of carbon atoms in the aliphatic substituted carbamoyl group is preferably 2-10. Examples of the aliphatic substituted carbamoyl group include, for example, methylcarbamoyl, diethylcarbamoyl and the like.

  The number of carbon atoms in the aliphatic substituted sulfamoyl group is preferably 1-8. Examples of the aliphatic substituted sulfamoyl group include, for example, methylsulfamoyl, diethylsulfamoyl and the like.

  The number of carbon atoms in the aliphatic substituted ureido group is preferably 2-10. Examples of aliphatic substituted ureido groups include, for example, methylureido.

  Examples of non-aromatic heterocyclic groups include piperidino and morpholino.

Among these, as X ₁ , X ₂ and X ₃ in the general formula (2), a mercapto group and an aromatic ring are preferable.

  Specific examples of the compound represented by the general formula (2) include 2,4-diamino-6-butylamino-1,3,5-triazine, 2,4,6-trimercapto-1,3,5- Triazine, 2,4,6-triphenyl-1,3,5-triazine, 2-methoxy-4-methyl-6- (methylamino) -1,3,5-triazine, 2-amino-4-methoxy- 6-methyl-1,3,5-triazine and the like, particularly 2,4,6-trimercapto-1,3,5-triazine, 2,4,6-triphenyl-1,3,5-triazine Is preferred.

（式中Ｘ_４、Ｘ_５、Ｘ_６はそれぞれ、単結合またはアルキレン基、アルケニレン基、アルキニレン基、芳香族環、−ＮＨ−、−ＮＲ−、−Ｓ−、−ＣＯ−、−Ｏ−、を表し、Ｒ_２、Ｒ_３、Ｒ_４は水素原子、置換もしくは無置換のアルキル基、アルケニル基、芳香族環を表す。）
一般式（３）のＸ_４、Ｘ_５、Ｘ_６におけるアルキレン基としては炭素原子数１〜８であることが好ましく、例えばメチレン、エチレン、ｎ−ブチレン、ｎ−ヘキシレン等が挙げられ、アルケニレン基としては炭素原子数２〜８であることが好ましく、例えばビニレン、アリレン、１−ヘキセニレン等が挙げられ、アルキニレン基としては炭素原子数２〜８であることが好ましく、例えばエチニレン、１−ブチニレン、１−ヘキシニレン等が挙げられる。

(Wherein X ₄ , X ₅ and X ₆ are each a single bond or an alkylene group, an alkenylene group, an alkynylene group, an aromatic ring, —NH—, —NR—, —S—, —CO—, —O—, R ₂ , R ₃ and R ₄ represent a hydrogen atom, a substituted or unsubstituted alkyl group, an alkenyl group and an aromatic ring.
The alkylene group in X ₄ , X ₅ and X ₆ in the general formula (3) preferably has 1 to 8 carbon atoms, and examples thereof include methylene, ethylene, n-butylene, n-hexylene, and the like, alkenylene group Is preferably 2 to 8 carbon atoms, for example, vinylene, arylene, 1-hexenylene, etc., and the alkynylene group preferably has 2 to 8 carbon atoms, such as ethynylene, 1-butynylene, Examples include 1-hexynylene.

The aromatic ring includes an aromatic heterocyclic ring and an aromatic condensed ring in addition to the aromatic hydrocarbon ring, and examples thereof include an aromatic ring of X ₁ , X ₂ , and X _{3 in} the general formula (2).

The substituted or unsubstituted alkyl group in R ₂ , R ₃ and R ₄ in the general formula (3) preferably has 1 to 8 carbon atoms, such as methyl, ethyl, n-butyl, n-hexyl and the like. The alkenyl group preferably has 2 to 8 carbon atoms, such as vinyl, allyl, 1-hexenyl and the like, and the alkynyl group preferably has 2 to 8 carbon atoms, such as ethynyl. , 1-butynyl, 1-hexynyl and the like.

The aromatic ring includes an aromatic heterocyclic ring and an aromatic condensed ring in addition to the aromatic hydrocarbon ring, and examples thereof include an aromatic ring of X ₁ , X ₂ , and X _{3 in} the general formula (2).

  Specific examples of the compound represented by the general formula (3) include 2,4-diamino-6- [2- (2-methyl-1-imidazolyl) ethyl] -1,3,5-triazine, 6- ( Dibutylamino) -2,4-dimercapto-1,3,5-triazine, 2- (3,4-dimethoxystyryl) -4,6-bis (trichloromethyl) -1,3,5-triazine, 2- ( 3-carboxyanilino) -4,6-dichloro-1,3,5-triazine, 2- (4-methoxyphenyl) -4,6-bis (trichloromethyl) -1,3,5-triazine, 2, 4,6-trianilinyl-1,3,5-triazine, 2,4-diamino-6-diallylamino-1,3,5-triazine, 2- [2- (5-methylfuran-2-yl) vinyl] -4,6-bis (trichloromethyl -1,3,5-triazine and the like, in particular 2,4,6-trianilinyl-1,3,5-triazine, 6- (dibutylamino) -2,4-dimercapto-1,3,5-triazine 2,4-diamino-6-diallylamino-1,3,5-triazine is preferred.

（式中Ｘ_７、Ｘ_８、Ｘ_９はそれぞれ、単結合またはアルキレン基、アルケニレン基、アルキニレン基、芳香族環、−ＮＨ−、−ＮＲ−、−Ｓ−、−ＣＯ−、−Ｏ−を表し、Ｒ_５、Ｒ_６、Ｒ_７は水素原子、置換もしくは無置換のアルキル基、アルケニル基、芳香族環を表す。）
一般式（４）のＸ_７、Ｘ_８、Ｘ_９におけるアルキレン基としては炭素原子数１〜８であることが好ましく、例えばメチレン、エチレン、ｎ−ブチレン、ｎ−ヘキシレン等が挙げられ、アルケニレン基としては炭素原子数２〜８であることが好ましく、例えばビニレン、アリレン、１−ヘキセニレン等が挙げられ、アルキニレン基としては炭素原子数２〜８であることが好ましく、例えばエチニレン、１−ブチニレン、１−ヘキシニレン等が挙げられる。

(Wherein X ₇ , X ₈ and X ₉ are each a single bond or an alkylene group, an alkenylene group, an alkynylene group, an aromatic ring, —NH—, —NR—, —S—, —CO—, —O—). R ₅ , R ₆ and R ₇ represent a hydrogen atom, a substituted or unsubstituted alkyl group, an alkenyl group and an aromatic ring.
The alkylene group in X ₇ , X ₈ and X ₉ in the general formula (4) preferably has 1 to 8 carbon atoms, and examples thereof include methylene, ethylene, n-butylene, n-hexylene, and the like, alkenylene group Is preferably 2 to 8 carbon atoms, for example, vinylene, arylene, 1-hexenylene, etc., and the alkynylene group preferably has 2 to 8 carbon atoms, such as ethynylene, 1-butynylene, Examples include 1-hexynylene.

The aromatic ring includes an aromatic heterocyclic ring and an aromatic condensed ring in addition to the aromatic hydrocarbon ring, and examples thereof include an aromatic ring of X ₁ , X ₂ , and X _{3 in} the general formula (2).

The substituted or unsubstituted alkyl group in R ₅ , R ₆ and R ₇ in the general formula (4) preferably has 1 to 8 carbon atoms, such as methyl, ethyl, n-butyl, n-hexyl, etc. The alkenyl group preferably has 2 to 8 carbon atoms, such as vinyl, allyl, 1-hexenyl, etc., and the alkynyl group preferably has 2 to 8 carbon atoms. For example, ethynyl, 1-butynyl, 1-hexynyl and the like.

The aromatic ring includes an aromatic heterocyclic ring and an aromatic condensed ring in addition to the aromatic hydrocarbon ring, and examples thereof include an aromatic ring of X ₁ , X ₂ , and X _{3 in} the general formula (2).

  Specific examples of the compound represented by the general formula (4) include 1,3,5-benzenetrithiol, 1,3,5-benzenetricarbonyltrichloride, 1,3,5-triphenylbenzene, N, N ″, N ″ ″-triphenyl-1,3,5-benzenetriamine, 1,3,5-tri (9H-carbazol-9-yl) benzene, 1,3,5-tri-t-butyl Examples include benzene, 1,3,5-triacetylbenzene, 1,3,5-trimethoxybenzene, 1,3,5-tris (4-bromophenyl) benzene, and more particularly 1,3,5-triphenyl. Benzene, N, N ″, N ″ ″-triphenyl-1,3,5-benzenetriamine are preferred.

  The molecular weight of these cyclic hydrocarbon compounds is preferably 100 to 800.

  The blending ratio of the maleimide resin and the cyclic hydrocarbon compound in the optical compensation film of the present invention is such that an optical compensation film having excellent adhesion to the substrate can be obtained, so that the cyclic carbonization is performed with respect to 100 parts by weight of the maleimide resin. The hydrogen compound is preferably 0.01 to 20 parts by weight, more preferably 0.1 to 10 parts by weight, and particularly preferably 1 to 5 parts by weight.

  Moreover, there is no restriction | limiting in particular as a compounding method of a maleimide type resin and a cyclic hydrocarbon type compound, For example, it can carry out by adding a cyclic hydrocarbon type compound to the solution which melt | dissolved the maleimide type resin in the solvent. The solvent used in that case is not particularly limited as long as the maleimide resin can be dissolved, for example, aromatic solvents such as toluene, xylene, chlorobenzene, nitrobenzene; acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, etc. Ketone solvents; ether solvents such as dimethyl ether, diethyl ether, methyl-t-butyl ether, tetrahydrofuran and dioxane; acetate solvents such as methyl acetate, ethyl acetate, acetic acid-n-propyl, isopropyl acetate and butyl acetate; hexane, Hydrocarbon solvents such as cyclohexane, octane, decane; alcohol solvents such as methanol, ethanol, propanol, butanol; salts such as carbon tetrachloride, chloroform, methylene chloride, dichloroethane, trichloroethane System solvent; dimethylformamide, amide solvents such as dimethylacetamide; N- methylpyrrolidone and the like, which may be used in combination of two or more.

  The optical compensation film of the present invention is characterized by comprising a maleimide resin and a coating film made of a cyclic hydrocarbon compound, and as a preferred production method, a glass substrate, a film made of a cellulose resin such as triacetyl cellulose, etc. Examples of the maleimide resin include a maleimide resin and a cyclic hydrocarbon compound, and a method of manufacturing the resin by drying. A maleimide resin represented by the above general formula (1) is particularly preferable. A maleimide resin composed of a base unit is preferred.

  The coating method involves coating a solution obtained by dissolving a maleimide resin and a cyclic hydrocarbon compound in a solvent on a substrate such as a glass substrate or a cellulose resin film such as triacetyl cellulose, and then heating the solvent. It is a method of removing. As a coating method at that time, for example, a doctor blade method, a bar coater method, a gravure coater method, a slot die coater method, a lip coater method, a comma coater method or the like is used. In industry, the gravure coater method is generally used for thin film coating, and the comma coater method is generally used for thick film coating.

  The solvent to be used is not particularly limited as long as the maleimide resin can be dissolved. For example, aromatic solvents such as toluene, xylene, chlorobenzene and nitrobenzene; ketone solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone and cyclohexanone. Ether solvents such as dimethyl ether, diethyl ether, methyl-t-butyl ether, tetrahydrofuran and dioxane; acetate solvents such as methyl acetate, ethyl acetate, acetic acid-n-propyl, isopropyl acetate and butyl acetate; hexane, cyclohexane and octane Hydrocarbon solvents such as decane; alcohol solvents such as methanol, ethanol, propanol and butanol; chlorine solvents such as carbon tetrachloride, chloroform, methylene chloride, dichloroethane and trichloroethane ; Dimethylformamide, amide solvents such as dimethylacetamide; N- methylpyrrolidone and the like, which may be used in combination of two or more.

  In solution coating, since an optical compensation film having higher transparency and excellent thickness accuracy and surface smoothness can be obtained, the solution viscosity is preferably 10 to 10000 cps, particularly 10 to 5000 cps. It is preferable that

  In this case, the coating thickness of the film composed of the maleimide resin and the cyclic hydrocarbon compound is determined by the Rth (out-of-plane retardation) of the coating film, and among them, excellent surface smoothness and improved viewing angle. Is preferably 0.1 to 100 μm after drying, more preferably 0.5 to 50 μm, and particularly preferably 1 to 20 μm.

  The optical compensation film of the present invention is a coating film composed of the maleimide resin and a cyclic hydrocarbon compound, and is particularly excellent in the optical compensation function when used as an optical compensation film. When a film made of a polymer is used as an optical compensation film, the three-dimensional refractive index of the film is generally controlled by stretching the film. However, the stretching process may complicate the manufacturing process and quality control. There is a problem such as. On the other hand, the optical compensation film of the present invention is a coating film composed of a maleimide resin and a cyclic hydrocarbon compound, and any two axes orthogonal in the plane of the coating film are defined as an x axis and a y axis. , The out-of-plane direction is the z axis, the refractive index in the x axis direction is nx, the refractive index in the y axis direction is ny (if nx and ny are different, the smallest refractive index is nx), and the refractive index in the z axis direction Is an optical compensation film characterized in that the three-dimensional refractive index relationship is nx≈ny> nz, where the refractive index in the thickness direction of the film is small in an unstretched state (unstretched film). It has been found that it exhibits a unique behavior.

  The optical compensation film of the present invention preferably has an Rth (out-of-plane retardation amount) represented by the following general formula (5) by adding a cyclic hydrocarbon compound as compared with the case where no addition is performed. It can be increased to 2 times or more, more preferably 1.5 times or more.

Rth = ((nx + ny) / 2−nz) × d (5)
(Here, d represents the film thickness (nm) of the optical compensation film.)
As described above, these cyclic hydrocarbon compounds can increase the Rth of the optical compensation film with a relatively small amount of use, and can adjust the increase amount of Rth according to the addition amount. Moreover, since it is relatively compatible with the maleimide resin, it is difficult to precipitate (bleed out) on the surface of the film. Therefore, by using such a cyclic hydrocarbon compound, a film in which Rth of the optical compensation film remains unstretched (by coating only) without causing a bleed-out problem is obtained. be able to.

  The Rth of the optical compensation film of the present invention can be easily controlled by changing the thickness of the coating film composed of the maleimide resin and the cyclic hydrocarbon compound and the blending ratio of the maleimide resin and the cyclic hydrocarbon compound. Rth is preferably in the range of 50 to 2000 nm, and further excellent in the viewing angle improvement effect of the liquid crystal display device. Therefore, it is preferably in the range of 60 to 1000 nm, particularly preferably in the range of 70 to 300 nm.

  The optical compensation film of the present invention is preferably a liquid crystal display element having a small color shift when used in a liquid crystal display element, so that the wavelength dependency of the retardation amount is preferably small, and the coating film is inclined by 40 degrees. The wavelength dependency (R450 / R589) of the phase difference indicated by the ratio of the phase difference amount (R450) measured with light having a measurement wavelength of 450 nm and the phase difference amount (R589) measured with light having a measurement wavelength of 589 nm is 1. It is preferably 1 or less, and particularly preferably 1.08 or less.

  Since the optical compensation film of the present invention has good image quality characteristics when used in a liquid crystal display element, the light transmittance measured according to JIS K 7361-1 (1997 edition) is 85% or more. It is preferable that it is 90% or more. Further, the haze (cloudiness) measured in accordance with JIS K 7136 (2000 version) is preferably 2% or less, and particularly preferably 1% or less.

  The optical compensation film of the present invention preferably has high heat resistance from the stability of quality when used in a liquid crystal display element, and preferably has a glass transition temperature of 100 ° C. or higher for the maleimide resin used, Furthermore, what is 120 degreeC or more is preferable, and what is especially 135 degreeC or more is preferable.

  Further, the optical compensation film of the present invention may contain an antioxidant in order to improve the thermal stability. Examples of the antioxidant include hindered phenol antioxidants, phosphorus antioxidants, and other antioxidants. These antioxidants may be used alone or in combination. And since an antioxidant effect | action improves synergistically, it is preferable to use together and use a hindered phenolic antioxidant and phosphorus antioxidant, for example, 100 weight part of hindered phenolic antioxidants in that case It is particularly preferable to use 100 to 500 parts by weight of a phosphorus-based antioxidant. Further, the addition amount of the antioxidant is preferably 0.01 to 10 parts by weight, particularly preferably 0.5 to 1 part by weight, with respect to 100 parts by weight of the maleimide resin constituting the optical compensation film of the present invention.

  The optical compensation film of the present invention is blended with other polymers, polymer electrolytes, conductive complexes, inorganic fillers, pigments, dyes, antistatic agents, antiblocking agents, lubricants and the like within the scope of the invention. It may be.

  The optical compensation film of the present invention can be used by being laminated with a polarizing plate. The optical compensation film may be a laminate of the optical compensation film of the present invention and a film such as a cellulose resin film.

  The optical compensation film of the present invention can be used as an optical compensation film for liquid crystal display elements such as a viewing angle improving film and a color compensation film for liquid crystal display elements.

  The optical compensation film of the present invention is composed of a maleimide resin and a cyclic hydrocarbon compound that exhibit an optical compensation function only by coating. By increasing Rth (out-of-plane retardation), the optical compensation film can be used. Since a compensation film is expected and the control of its optical compensation function is easy, it is useful as an optical compensation film effective for improving the contrast and viewing angle characteristics of a liquid crystal display element, particularly a VA-mode liquid crystal television.

  EXAMPLES The present invention will be described in detail below with reference to examples, but the present invention is not limited to these examples.

~ Measurement of number average molecular weight (Mn) ~
Using gel permeation chromatography (GPC) (manufactured by Tosoh Corporation, trade name HLC-802A), dimethylformamide was used as a solvent to obtain a standard polystyrene equivalent value.

~ Measurement of glass transition temperature ~
A differential scanning calorimeter (manufactured by Seiko Denshi Kogyo Co., Ltd., trade name DSC2000) was used and the temperature was 10 ° C / min. It measured at the temperature increase rate of.

~ Measurement of light transmittance ~
As an evaluation of transparency, light transmittance was measured in accordance with JIS K 7361-1 (1997 edition).

~ Measurement of haze ~
As an evaluation of transparency, haze was measured according to JIS K 7136 (2000 version).

~ Measurement of refractive index ~
It measured using the Abbe refractometer (product made from Atago) based on JISK7142 (1981 edition).

~ Calculation of 3D refractive index ~
Using a sample tilt type automatic birefringence meter (trade name KOBRA-WR, manufactured by Oji Scientific Instruments Co., Ltd.), the elevation angle was changed and the three-dimensional refractive index was measured with light having a measurement wavelength of 589 nm. Further, Rth (out-of-plane retardation) and Re (in-plane retardation) represented by the following formula (6) were calculated from the three-dimensional refractive index.

Re = (nx−ny) × d (6)
(Here, d represents the film thickness (nm) of the optical compensation film.)
~ Measurement of wavelength dependence of phase difference ~
The wavelength dependence (R450 / R589) of the retardation amount is determined by tilting the coating film by 40 degrees and measuring the retardation amount (R450) measured with light having a measurement wavelength of 450 nm and the retardation amount measured with light having a measurement wavelength of 589 nm (R589). ) Ratio.

-Cross cut method 100 mass test evaluation-
In accordance with JIS K 5400 (1999 edition), 100 lattice patterns were cut into the coated film at a specified cut interval, and the specific peeling was determined. At this time, the determination was made based on a good number of 100 lattice patterns. Moreover, the peeling condition was observed by sticking and peeling the adhesive tape on the lattice pattern. The determination at this time was also made based on the good number of 100 lattice patterns.

Synthesis Example 1 (Example of production of Nn-butylmaleimide polymer resin)
A glass sealed tube was charged with 32.4 g of Nn-butylmaleimide and 0.054 g of dimethyl-2,2′-azobisisobutyrate as a polymerization initiator, and after substitution with nitrogen, a polymerization temperature of 60 ° C. and a polymerization time of 5 The radical polymerization reaction was performed under time conditions. After the reaction, chloroform was added to form a polymer solution, and the polymer was precipitated by mixing with excess methanol. The obtained polymer was filtered, washed sufficiently with methanol and dried at 80 ° C. to obtain 20 g of Nn-butylmaleimide polymer resin. The number average molecular weight of the obtained Nn-butylmaleimide polymer resin was 120,000. The glass transition temperature (hereinafter referred to as Tg) was 185 ° C.

Synthesis Example 2 (Production Example of Nn-Hexylmaleimide Polymer Resin)
In a glass sealed tube, 40 g of Nn-hexylmaleimide and 0.05 g of dimethyl-2,2′-azobisisobutyrate as a polymerization initiator are charged, and after nitrogen substitution, a polymerization temperature of 60 ° C. and a polymerization time of 5 hours. The radical polymerization reaction was performed under the following conditions. After the reaction, chloroform was added to form a polymer solution, and the polymer was precipitated by mixing with excess methanol. The obtained polymer was filtered, sufficiently washed with methanol, and dried at 80 ° C. to obtain 32 g of Nn-hexylmaleimide polymer resin. The number average molecular weight of the obtained Nn-hexylmaleimide polymer resin was 160000. Moreover, Tg was 148 degreeC.

Comparative Example 1
The Nn-butylmaleimide polymer resin obtained in Synthesis Example 1 was dissolved in a mixed solvent composed of 50 parts by weight of toluene and 50 parts by weight of methyl ethyl ketone, made into a 13% solution, and applied to a glass substrate with a coater. It dried at room temperature for 48 hours, and obtained the coating film film (coating film + glass substrate) of width 50mm and thickness 15micrometer (thickness only of a coating film). The obtained coating film has a light transmittance of 91.1%, a haze of 0.6%, a three-dimensional refractive index of nx = 1.51742, ny = 1.51742, nz = 1.51422, Rth = 48.0 m, Re = 0.0 nm. Furthermore, R450 / R589 which shows the wavelength dependence of phase difference amount was 1.05.

  In the cut evaluation in the cross cut method 100 mass test, 100 pieces out of 100 lattice patterns showed good adhesion, and 100 pieces out of 100 lattice patterns showed good adhesion even when the tape was peeled off.

Example 1
The solution prepared in the same manner as in Comparative Example 1 was further added with 2,4,6-trimercapto-1,3,5-cyclic hydrocarbon compound to 100 parts by weight of Nn-butylmaleimide polymer resin. After adding 1 part by weight of triazine (compound of general formula (2)), a coating film film (coating film + glass) having a width of 50 mm and a thickness of 15 μm (thickness of the coating film only) was applied in the same manner as in Comparative Example 1. Substrate).

  The obtained coating film has a light transmittance of 91.0% and a haze of 0.7%, and the three-dimensional refractive index is nx = 1.51843, ny = 1.1.5842, nz = 1.51226 (nx≈ny > Nz), and Rth = 92.5 m and Re = 0.1 nm. Furthermore, R450 / R589 which shows the wavelength dependence of phase difference amount was 1.05.

  As a result, the obtained coating film had a tendency of nx≈ny> nz stronger than the coating film of only the Nn-butylmaleimide polymer resin shown in Comparative Example 1, and the cyclic hydrocarbon type It is a film in which Rth is increased by the compound. In addition, since the wavelength dependency is small, it can be said that a thin film is expected and it is more excellent as an optical compensation film.

  In the cut evaluation in the cross cut method 100 mass test, 100 pieces out of 100 lattice patterns showed good adhesion, and 100 pieces out of 100 lattice patterns showed good adhesion even when the tape was peeled off.

Example 2
Except for changing the amount of 2,4,6-trimercapto-1,3,5-triazine added to 3 parts by weight, the width was 50 mm and the thickness was 15 μm (thickness of the coating film only) in the same manner as in Example 1. Coating film (coating film + glass substrate) was obtained.

  The obtained coating film has a light transmittance of 91.0% and a haze of 0.6%, and the three-dimensional refractive index is nx = 1.51848, ny = 1.51848, nz = 1.51028 (nx = ny). > Nz), and Rth = 13.0 m and Re = 0 nm. Furthermore, R450 / R589 which shows the wavelength dependence of phase difference amount was 1.06.

  As a result, the obtained coating film had a tendency of nx≈ny> nz stronger than the coating film of only the Nn-butylmaleimide polymer resin shown in Comparative Example 1, and the cyclic hydrocarbon type It is a film in which Rth is increased by the compound. In addition, since the wavelength dependency is small, it can be said that a thin film is expected and it is more excellent as an optical compensation film.

  In the cut evaluation in the cross cut method 100 mass test, 100 pieces out of 100 lattice patterns showed good adhesion, and 100 pieces out of 100 lattice patterns showed good adhesion even when the tape was peeled off.

Example 3
Except for changing the cyclic hydrocarbon compound to 6- (dibutylamino) -2,4-dimercapto-1,3,5-triazine (compound of general formula (3)), the width is the same as in Example 1. A coating film film (coating film + glass substrate) having a thickness of 50 mm and a thickness of 15 μm (thickness only of the coating film) was obtained.

  The obtained coating film has a light transmittance of 91.2% and a haze of 0.6%, and the three-dimensional refractive indexes are nx = 1.51828, ny = 1.51827, nz = 1.51187 (nx≈ny). > Nz), and Rth = 96.1 m and Re = 0.2 nm. Furthermore, R450 / R589 which shows the wavelength dependence of phase difference amount was 1.05.

  As a result, the obtained coating film had a tendency of nx≈ny> nz stronger than the coating film of only the Nn-butylmaleimide polymer resin shown in Comparative Example 1, and the cyclic hydrocarbon type It is a film in which Rth is increased by the compound. In addition, since the wavelength dependency is small, it can be said that a thin film is expected and it is more excellent as an optical compensation film.

  In the cut evaluation in the cross cut method 100 mass test, 100 pieces out of 100 lattice patterns showed good adhesion, and 100 pieces out of 100 lattice patterns showed good adhesion even when the tape was peeled off.

Example 4
The width was 50 mm and the thickness was 15 μm (coating film) in the same manner as in Example 3 except that the amount of 6- (dibutylamino) -2,4-dimercapto-1,3,5-triazine was changed to 3 parts by weight. (Thickness only) of coating film (coating film + glass substrate) was obtained.

  The obtained coating film has a light transmittance of 91.1% and a haze of 0.6%, and the three-dimensional refractive index is nx = 1.51816, ny = 1.51816, nz = 1.51090 (nx = ny). > Nz), and Rth = 108.9 m and Re = 0 nm. Furthermore, R450 / R589 which shows the wavelength dependence of phase difference amount was 1.05.

  As a result, the obtained coating film had a tendency of nx≈ny> nz stronger than the coating film of only the Nn-butylmaleimide polymer resin shown in Comparative Example 1, and the cyclic hydrocarbon type It is a film in which Rth is increased by the compound. In addition, since the wavelength dependency is small, it can be said that a thin film is expected and it is more excellent as an optical compensation film.

  In the cut evaluation in the cross cut method 100 mass test, 100 pieces out of 100 lattice patterns showed good adhesion, and 100 pieces out of 100 lattice patterns showed good adhesion even when the tape was peeled off.

Comparative Example 2
The Nn-hexylmaleimide polymer resin obtained in Synthesis Example 2 was dissolved in a mixed solvent consisting of 30 parts by weight of toluene and 70 parts by weight of methyl ethyl ketone, made into a 15% solution, and applied to a glass substrate with a coater. It dried under room temperature nitrogen stream for 24 hours, and obtained the coating film film (coating film + glass substrate) of width 20mm and thickness 15micrometer (thickness only of a coating film).

  The obtained coating film has a light transmittance of 91.8%, a haze of 0.6%, a three-dimensional refractive index of nx = 1.51566, ny = 1.515565, nz = 1.51342, and Rth. = 33.5 m, Re = 0.2 nm. Furthermore, R450 / R589 which shows the wavelength dependence of phase difference amount was 1.06.

  In the cut evaluation in the cross cut method 100 mass test, 100 pieces out of 100 lattice patterns showed good adhesion, and 100 pieces out of 100 lattice patterns showed good adhesion even when the tape was peeled off.

Example 5
To the solution prepared in the same manner as in Comparative Example 2, 100 parts by weight of Nn-hexylmaleimide polymer resin was further added as a cyclic hydrocarbon compound, 2,4-diamino-6-diallylamino-1,3, After adding 1 part by weight of 5-triazine (compound of general formula (3)), a coating film film (coating film) having a width of 20 mm and a thickness of 15 μm (thickness only of the coating film) is obtained in the same manner as in Comparative Example 2. + Glass substrate).

  The obtained coating film has a light transmittance of 91.8% and a haze of 0.5%, and the three-dimensional refractive index is nx = 1.51721, ny = 1.51721, nz = 1.51342 (nx = ny). > Nz), and Rth = 56.8 m and Re = 0 nm. Furthermore, R450 / R589 which shows the wavelength dependence of phase difference amount was 1.07.

  As a result, the obtained coating film had a tendency of nx≈ny> nz stronger than the coating film of only the Nn-hexylmaleimide polymer resin shown in Comparative Example 2, and the cyclic hydrocarbon type It is a film in which Rth is increased by the compound. In addition, since the wavelength dependency is small, it can be said that a thin film is expected and it is more excellent as an optical compensation film.

  In the cut evaluation in the cross cut method 100 mass test, 100 pieces out of 100 lattice patterns showed good adhesion, and 100 pieces out of 100 lattice patterns showed good adhesion even when the tape was peeled off.

Example 6
Except for changing the addition amount of 2,4-diamino-6-diallylamino-1,3,5-triazine to 3 parts by weight, the width was 20 mm and the thickness was 15 μm (only the coating film only) in the same manner as in Example 5. (Thickness) coating film film (coating film + glass substrate) was obtained.

  The obtained coating film had a light transmittance of 91.7% and a haze of 0.6%, and the three-dimensional refractive index was nx = 1.51735, ny = 1.51734, nz = 1.51329 (nx≈ny > Nz), and Rth = 60.8 m and Re = 0.2 nm. Furthermore, R450 / R589 which shows the wavelength dependence of phase difference amount was 1.06.

  As a result, the obtained coating film had a tendency of nx≈ny> nz stronger than the coating film of only the Nn-hexylmaleimide polymer resin shown in Comparative Example 2, and the cyclic hydrocarbon type It is a film in which Rth is increased by the compound. In addition, since the wavelength dependency is small, it can be said that a thin film is expected and it is more excellent as an optical compensation film.

  In the cut evaluation in the cross cut method 100 mass test, 100 pieces out of 100 lattice patterns showed good adhesion, and 100 pieces out of 100 lattice patterns showed good adhesion even when the tape was peeled off.

Example 7
Except for changing the cyclic hydrocarbon compound to N, N ′, N ″ -triphenyl-1,3,5-benzenetriamine (compound of the general formula (4)), the width is the same as in Example 5. A coating film film (coating film + glass substrate) having a thickness of 20 mm and a thickness of 15 μm (thickness only of the coating film) was obtained.

  The obtained coating film has a light transmittance of 91.8% and a haze of 0.7%, and the three-dimensional refractive indexes are nx = 1.51729, ny = 1.51729, nz = 1.51152 (nx = ny). > Nz), and Rth = 86.6 m and Re = 0 nm. Furthermore, R450 / R589 which shows the wavelength dependence of phase difference amount was 1.07.

  As a result, the obtained coating film had a tendency of nx≈ny> nz stronger than the coating film of only the Nn-hexylmaleimide polymer resin shown in Comparative Example 2, and the cyclic hydrocarbon type It is a film in which Rth is increased by the compound. In addition, since the wavelength dependency is small, it can be said that a thin film is expected and it is more excellent as an optical compensation film.

  In the cut evaluation in the cross cut method 100 mass test, 100 pieces out of 100 lattice patterns showed good adhesion, and 100 pieces out of 100 lattice patterns showed good adhesion even when the tape was peeled off.

Example 8
The width was 20 mm and the thickness was 15 μm (coating film) in the same manner as in Example 7, except that the amount of N, N ′, N ″ -triphenyl-1,3,5-benzenetriamine was changed to 3 parts by weight. (Thickness only) of coating film (coating film + glass substrate) was obtained.

  The obtained coating film had a light transmittance of 91.7% and a haze of 0.8%, and the three-dimensional refractive index was nx = 1.51780, ny = 1.51780, nz = 1.51198 (nx = ny). > Nz), and Rth = 87.3 m and Re = 0 nm. Furthermore, R450 / R589 which shows the wavelength dependence of phase difference amount was 1.07.

  As a result, the obtained coating film had a tendency of nx≈ny> nz stronger than the coating film of only the Nn-hexylmaleimide polymer resin shown in Comparative Example 2, and the cyclic hydrocarbon type It is a film in which Rth is increased by the compound. In addition, since the wavelength dependency is small, it can be said that a thin film is expected and it is more excellent as an optical compensation film.

  In the cut evaluation in the cross cut method 100 mass test, 100 pieces out of 100 lattice patterns showed good adhesion, and 100 pieces out of 100 lattice patterns showed good adhesion even when the tape was peeled off.

Comparative Example 3
The solution prepared in the same manner as in Comparative Example 1 was further added to 100 parts by weight of Nn-butylmaleimide polymer resin, not a cyclic hydrocarbon compound, and general formulas (2), (3), (4) After adding 3 parts by weight of tri (2-ethylhexyl) phosphate not belonging to any of the above, a coating film film (coating film) having a width of 50 mm and a thickness of 15 μm (thickness of the coating film only) was applied in the same manner as in Comparative Example 1. Membrane + glass substrate).

  The obtained coating film had a light transmittance of 91.9% and a haze of 0.5%, and a three-dimensional refractive index of nx = 1.5742, ny = 1.57441, nz = 1.49191, Rth = 37.6 m, Re = 0 nm. Furthermore, R450 / R589 which shows the wavelength dependence of phase difference amount was 1.05.

  As a result, the obtained coating film had a tendency of nx≈ny> nz smaller than the coating film of only the Nn-butylmaleimide polymer resin shown in Comparative Example 1, and the cyclic hydrocarbon type It can be seen that Rth is reduced by using a compound that is not a compound. Therefore, it can be said that a compound that is not such a cyclic hydrocarbon compound and does not belong to any of the general formulas (2), (3), and (4) has no effect of increasing the Rth of the maleimide resin film.

  Table 1 shows the evaluation results of the above optical characteristics.

Claims (9)

Maleimide resin, 2,4,6-trimercapto-1,3,5-triazine, 2,4,6-triphenyl-1,3,5-triazine, 2,4,6-trianilinyl-1,3 , 5-triazine, 6- (dibutylamino) -2,4-dimercapto-1,3,5-triazine, 2,4-diamino-6-diallylamino-1,3,5-triazine A coating film made of a system compound, wherein any two axes orthogonal in the plane of the coating film are x-axis and y-axis, the out-of-plane direction is z-axis, and the refractive index in the x-axis direction is nx and y-axis An optical compensation film, wherein a three-dimensional refractive index relationship is nx≈ny> nz when a refractive index in the direction is ny and a refractive index in the z-axis direction is nz. 2. The optical compensation film according to claim 1, comprising a maleimide resin composed of an N-substituted maleimide residue unit represented by the following general formula (1).

(Here, R ₁ is a linear alkyl group having 1 to 18 carbon atoms, a branched alkyl group having 1 to 18 carbon atoms, a cyclic alkyl group having 1 to 18 carbon atoms, a halogen group, an ether group, an ester group, Represents an amide group.) The optical compensation according to claim 1 or 2 Rth represented by the following formula when measured at a measurement wavelength 589nm of light (5) (out-of-plane retardation amount) is characterized in that in the range of 50~2000nm film.
Rth = ((nx + ny) / 2−nz) × d (5)
(Here, d represents the film thickness (nm) of the optical compensation film.) The wavelength dependence of the phase difference amount indicated by the ratio of the phase difference amount (R450) measured with light having a measurement wavelength of 450 nm with the coating film inclined by 40 degrees and the phase difference amount (R589) measured with light having a measurement wavelength of 589 nm ( R450 / R589) is an optical compensation film according to any one of claims 1 to 3, wherein the more than 1.1. The optical compensation film according to any one of claims 1 to 4, wherein the coating film is unstretched film. The optical compensation film according to any one of claims 1 to 5, characterized in that an optical compensation film for a liquid crystal display device. An optical compensation film comprising a laminate of the optical compensation film according to any one of claims 1 to 6 and a cellulose resin film. Maleimide resin on substrate, 2,4,6-trimercapto-1,3,5-triazine, 2,4,6-triphenyl-1,3,5-triazine, 2,4,6-trianilinyl -1,3,5-triazine, 6- (dibutylamino) -2,4-dimercapto-1,3,5-triazine, 2,4-diamino-6-diallylamino-1,3,5-triazine A method for producing an optical compensation film, which comprises applying a solution comprising a cyclic hydrocarbon compound and drying the solution. The method for producing an optical compensation film according to claim 8 , wherein the maleimide resin solution is a solution of a maleimide resin comprising a maleimide residue unit represented by the general formula (1).