JP2010031163A - Compound, optical film containing the compound, and production method of the optical film - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a novel compound which gives an optical film capable of uniformly exchanging polarization in a wide range of wavelength. <P>SOLUTION: The compound has a structure unit originating from a compound comprising a cyclohexylene group and a group represented by -NH-CO-, which may be substituted, and a structural unit originated from a compound represented by the formula (II): wherein, X<SB>1</SB>and X<SB>2</SB>, being independent from each other, each represents an alkylene group having 2 to 6 carbon atoms, wherein the hydrocarbon atoms contained in the alkylene group may be substituted by an alkyl group having 1 to 6 carbon atoms or a hydroxyl group, and the methylene group contained in the alkylene group may be substituted by a carbonyl group; R, being independent from one another, represents a hydroxyl group, a halogen atom, an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, a glycidoxy group, a nitro group, or a cyano group; s and t, being independent from each other, each represents an integer of 0 to 6; and n, being independent from one another, each represents an integer of 0 to 4. <P>COPYRIGHT: (C)2010,JPO&INPIT

Description

  The present invention relates to a compound, an optical film containing the compound, a method for producing the optical film, and the like.

  There is a need for a technique for forming a retardation plate that gives uniform retardation characteristics with respect to incident light in the entire visible light region as a single layer rather than a laminate. For example, a norbornene-based resin as a polymer exhibiting positive birefringence It is known that a retardation plate obtained by stretching a single-layer film containing a polymer containing a negative birefringence is capable of uniform polarization conversion in a wide wavelength range (for example, patents) Reference 1).

JP 2001-337222 A

  An object of the present invention is to provide a new compound that provides an optical film capable of uniform polarization conversion in a wide wavelength range.

（式（ＩＩ）中、Ｘ_１及びＸ_２は、それぞれ独立に、炭素数２〜６のアルキレン基を表す。該アルキレン基に含まれる水素原子は、炭素数１〜６のアルキル基又は水酸基に置換されていてもよく、該アルキレン基に含まれるメチレン基は、カルボニル基に置換されていてもよい。Ｒは、それぞれ独立に、水酸基、ハロゲン原子、炭素数１〜６のアルキル基、炭素数１〜６のアルコキシ基、グリシドキシ基、ニトロ基又はシアノ基を表す。ｓ及びｔは、それぞれ独立に、０〜６の整数を表し、ｎは、それぞれ独立に、０〜４の整数を表す。） The present invention relates to a structural unit derived from a compound containing an optionally substituted cyclohexylene group and a group represented by -NH-CO-;
It is a compound which has a structural unit derived from the compound represented by Formula (II).

(In Formula (II), X ₁ and X ₂ each independently represent an alkylene group having 2 to 6 carbon atoms. The hydrogen atom contained in the alkylene group is an alkyl group or hydroxyl group having 1 to 6 carbon atoms. The methylene group contained in the alkylene group may be substituted with a carbonyl group, and each R is independently a hydroxyl group, a halogen atom, an alkyl group having 1 to 6 carbon atoms, or a carbon number. 1 to 6 represents an alkoxy group, a glycidoxy group, a nitro group, or a cyano group, s and t each independently represent an integer of 0 to 6, and n each independently represents an integer of 0 to 4. )

（式（Ａ−１）中、Ｒ_３２はヘテロ原子を含んでもよい炭素数１〜６のアルキレン基又は単結合を表し、該アルキレン基に含まれるメチレン基は、ヘテロ原子に置換されていてもよい。Ｒ_３３は、炭素数１〜１２の炭化水素基を表し、該炭化水素基に含まれるメチレン基は、ヘテロ原子又はカルボニル基に置換されていてもよい。ｎ_３１は、１〜１５の整数を表す。） Moreover, this invention is the said compound which has a structural unit derived from the compound further represented by Formula (A-1).

(In the formula (A-1), R ₃₂ represents an alkylene group or a single bond 1-6 carbon atoms which may contain a hetero atom, a methylene group contained in the alkylene group may have been replaced with a heteroatom good .R ₃₃ represents a hydrocarbon group having 1 to 12 carbon atoms, a methylene group contained in the hydrocarbon group may .n ₃₁ be replaced by a heteroatom or a carbonyl group, 1-15 Represents an integer.)

  In the present invention, the compound containing an optionally substituted cyclohexylene group and a group represented by -NH-CO- is an isophorone diisocyanate, 1,4-cyclohexylene diisocyanate, 1,3-bis (isocyanatomethyl). ) The above compound, which is one or more compounds selected from the group consisting of cyclohexane and dicyclohexylmethane 4,4′-diisocyanate.

  In the present invention, the compound represented by the formula (II) is 9,9-bis (4-hydroxyphenyl) fluorene, 9,9-bis (4-hydroxy-3-methylphenyl) fluorene, and 9,9- It is the above compound, which is one or more compounds selected from the group consisting of bis [4- (2-hydroxyethoxy) phenyl] fluorene.

  In the present invention, the compound represented by the formula (A-1) is ethylene glycol, propylene glycol, 1,4-butanediol, tripropylene glycol, 1,6-hexanediol, polyethylene glycol, polypropylene glycol, 1, The compound is one or more compounds selected from the group consisting of 4-cyclohexanedimethanol, 1,4-cyclohexanediol, 1,3-cyclohexanediol, hexamethylene carbonate diol and polyhexamethylene carbonate diol.

  Moreover, this invention is a composition containing a compound and a photoinitiator (2).

（式（ＸＩ）中、Ｒ_１１は、水素原子又はメチル基を表し、Ｒ_１２は、５〜２０員環の芳香族炭化水素基又は芳香族複素環基を表す。該芳香族炭化水素基及び該芳香族複素環基に含まれる水素原子は、水酸基、炭素数１〜１２のアルキル基、炭素数１〜１２のアルコキシ基、炭素数６〜１２のアリール基、炭素数７〜１２のアラルキル基、グリシドキシ基、炭素数２〜４のアシル基又はハロゲン原子に置換されていてもよく、該芳香族炭化水素基及び該芳香族複素環基に含まれるメチレン基は、カルボニル基に置換されていてもよい。）

（式（ＸＩＩ）中、Ｒ_１３は水素原子又はメチル基を表し、Ｒ_１４及びＲ_１５は、それぞれ独立に、水素原子又は炭素数１〜６のアルキル基を表す。又はＲ_１４及びＲ_１５は、Ｒ_１４及びＲ_１５が連結して形成される炭素数４〜６のアルキレン基を表す。該アルキル基及び該アルキレン基に含まれる水素原子は、水酸基に置換されていてもよく、該アルキル基及び該アルキレン基に含まれるメチレン基は、酸素原子、硫黄原子又は窒素原子に置換されていてもよい。Ｒ_１６は単結合又は炭素数２〜６のオキシアルキレン基を表す。）

（式（ＸＩＩＩ）中、Ｒ_１７は水素原子又はメチル基を表し、Ｒ_１８は、水素原子、メチル基又は５〜２０員環の環状炭化水素基を表す。該環状炭化水素基に含まれる水素原子は、水酸基、炭素数１〜１２のアルキル基、炭素数１〜１２のアルコキシ基、炭素数６〜１２のアリール基、炭素数７〜１２のアラルキル基、グリシドキシ基、炭素数２〜４のアシル基又はハロゲン原子に置換されていてもよく、該環状炭化水素基に含まれるメチレン基は、カルボニル基、酸素原子、硫黄原子又は窒素原子に置換されていてもよい。該アルキル基、該アルコキシ基、該アリール基及び該アラルキル基に含まれる水素原子は、水酸基又はハロゲン原子に置換されていてもよい。） The present invention further includes a polymer (3) obtained by polymerizing at least one monomer (3) selected from the group consisting of monomers represented by formulas (XI) to (XIII), and monomer (3). )
It is the said composition containing at least 1 sort (s) chosen from the group which consists of.

(In the formula (XI), R ₁₁ represents a hydrogen atom or a methyl group, and R ₁₂ represents a 5- to 20-membered aromatic hydrocarbon group or aromatic heterocyclic group. The aromatic hydrocarbon group and The hydrogen atom contained in the aromatic heterocyclic group includes a hydroxyl group, an alkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, an aryl group having 6 to 12 carbon atoms, and an aralkyl group having 7 to 12 carbon atoms. , A glycidoxy group, an acyl group having 2 to 4 carbon atoms or a halogen atom, and the methylene group contained in the aromatic hydrocarbon group and the aromatic heterocyclic group is substituted with a carbonyl group. May be.)

(In the formula _{(XII), R 13} represents a hydrogen atom or a methyl _{group, R 14} and _{R 15} each independently represent a hydrogen atom or an alkyl group having 1 to 6 carbon atoms. Or _{R 14} and _{R 15} , R ₁₄ and R ₁₅ represent an alkylene group having 4 to 6 carbon atoms formed by linking, and the alkyl group and the hydrogen atom contained in the alkylene group may be substituted with a hydroxyl group. And the methylene group contained in the alkylene group may be substituted with an oxygen atom, a sulfur atom or a nitrogen atom, and R ₁₆ represents a single bond or an oxyalkylene group having 2 to 6 carbon atoms.)

(In formula (XIII), R ₁₇ represents a hydrogen atom or a methyl group, and R ₁₈ represents a hydrogen atom, a methyl group or a 5- to 20-membered cyclic hydrocarbon group. Hydrogen contained in the cyclic hydrocarbon group The atoms include a hydroxyl group, an alkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, an aryl group having 6 to 12 carbon atoms, an aralkyl group having 7 to 12 carbon atoms, a glycidoxy group, and 2 to 4 carbon atoms. The methylene group contained in the cyclic hydrocarbon group may be substituted with a carbonyl group, an oxygen atom, a sulfur atom, or a nitrogen atom, and may be substituted with an acyl group or a halogen atom. The hydrogen atom contained in the group, the aryl group and the aralkyl group may be substituted with a hydroxyl group or a halogen atom.)

  Moreover, this invention is an optical film formed by extending | stretching the film | membrane containing the said compound.

  Moreover, this invention is an optical film formed by photopolymerizing the said composition and extending | stretching.

Moreover, this invention is the said optical film with which phase difference value Re ((nu)) in wavelength (nu) nm of the transmitted light which permeate | transmits a film satisfies the following formula.
Re (450) <Re (550) <Re (650)

  Moreover, this invention is a phase difference plate which consists of said optical film.

  Moreover, this invention is a manufacturing method of the optical film which extends | stretches the film | membrane containing the said compound.

  Moreover, this invention is a manufacturing method of the optical film which photopolymerizes and stretches the said composition.

  Moreover, this invention is a manufacturing method of the optical film which extends | stretches the film | membrane obtained by forming into a film by casting the solution containing the said compound on a smooth surface, and distilling a solvent off.

  Moreover, this invention is a manufacturing method of the optical film which photopolymerizes and stretch | stretches the film | membrane obtained by forming into a film by casting the solution containing the said composition on a smooth surface, and distilling a solvent off.

According to the compound of the present invention, an optical film capable of uniform polarization conversion in a wide wavelength range can be provided.

  Hereinafter, the present invention will be described in detail. The “optical film” refers to a film that can transmit light and has an optical function. The optical function means refraction, birefringence and the like.

The compound of the present invention (hereinafter sometimes referred to as “compound (1)”) is a compound containing an optionally substituted cyclohexylene group and a group represented by —NH—CO— (hereinafter “compound (B)”). In some cases).
Examples of the compound (B) include isophorone diisocyanate, 1,4-cyclohexylene diisocyanate, 1,3-bis (isocyanatomethyl) cyclohexane, dicyclohexylmethane 4,4′-diisocyanate and the like.

  The content of the structural unit derived from the compound (B) is, for example, 30 to 50 mol%, preferably 40 to 50 mol%, particularly preferably 45 to 50 mol with respect to 100 mol% of the structural unit constituting the compound (1). Mol%. Within the above range, it is preferable because the optical film can perform more uniform polarization conversion in a wide wavelength range.

Compound (1) contains a structural unit derived from the compound represented by formula (II).
As a compound represented by the formula (II), 9,9-bis (4-hydroxyphenyl) fluorene, 9,9-bis (4-hydroxy-3-methylphenyl) fluorene, 9,9-bis [4- ( 2-hydroxyethoxy) phenyl] fluorene and the like.

  The content of the structural unit derived from the compound represented by the formula (II) is, for example, 20 to 50 mol%, preferably 25 to 45 mol%, particularly 100 mol% of the structural unit constituting the compound (1). Preferably it is 30-40 mol%. Within the above range, it is preferable because the optical film can perform more uniform polarization conversion in a wide wavelength range.

  Compound (1) may further contain a structural unit derived from the compound represented by formula (A-1).

  Examples of the compound represented by Formula (A-1) include compounds represented by Formula (A-2) to Formula (A-4).

式（Ａ−２）中、Ｒ_２８は、それぞれ独立に、単結合又は炭素数１〜６のアルキレン基を表す。該アルキレン基に含まれるメチレン基は、ヘテロ原子に置換されていてもよい。

In formula (A-2), R < ₂₈ > represents a single bond or a C1-C6 alkylene group each independently. The methylene group contained in the alkylene group may be substituted with a hetero atom.

式（Ａ−３）中、Ｒ_２９は、それぞれ独立に、単結合又は炭素数１〜８のアルキレン基を表す。該アルキレン基に含まれるメチレン基は、ヘテロ原子に置換されていてもよい。Ｒ_３０は、それぞれ独立に、単結合、−Ｏ−又は炭素数１〜８のアルキレン基を表す。該アルキレン基に含まれるメチレン基は、ヘテロ原子に置換されていてもよい。ｖ_２９は、０〜１８の整数を表す。

In formula (A-3), R ₂₉ each independently represents a single bond or an alkylene group having 1 to 8 carbon atoms. The methylene group contained in the alkylene group may be substituted with a hetero atom. R < ₃₀ > represents a single bond, -O-, or a C1-C8 alkylene group each independently. The methylene group contained in the alkylene group may be substituted with a hetero atom. v ₂₉ represents an integer of 0 to 18.

式（Ａ−４）中、Ｒ_３１は、それぞれ独立に、単結合又は炭素数１〜８のアルキレン基を表す。該アルキレン基に含まれる水素原子は、炭素数１〜４のアルキル基に置換されていてもよい。ｖ_３１は、０〜１８の整数を表す。

In formula (A-4), R ₃₁ each independently represents a single bond or an alkylene group having 1 to 8 carbon atoms. The hydrogen atom contained in the alkylene group may be substituted with an alkyl group having 1 to 4 carbon atoms. v ₃₁ represents an integer of 0 to 18.

  Examples of the compound represented by the formula (A-1) include ethylene glycol, propylene glycol, 1,4-butanediol, tripropylene glycol, 1,6-hexanediol, polyethylene glycol, polypropylene glycol, and the like. Examples of the compound represented by A-2) include 1,4-cyclohexanedimethanol, 1,4-cyclohexanediol, and 1,3-cyclohexanediol. As the compound represented by the formula (A-3), Examples include hexamethylene carbonate diol and polyhexamethylene carbonate diol.

  The content of the structural unit derived from the compound represented by the formula (A-1) is, for example, 0 to 30 mol%, preferably 0 to 20 mol% with respect to 100 mol% of the structural unit constituting the compound (1). Especially preferably, it is 0-10 mol%. Within the above range, it is preferable because the optical film can perform more uniform polarization conversion in a wide wavelength range.

Compound (1) is
A compound (hereinafter sometimes referred to as “polyurethane”) obtained by reacting the compound (B), a compound represented by the formula (II), and a polyol compound (hereinafter sometimes referred to as “polyol”);
A compound (hereinafter sometimes referred to as “polyurethane urea”) obtained by further reacting a polyurethane with a polyamine compound (hereinafter sometimes referred to as “polyamine”);
A compound obtained by reacting polyurethane with at least one compound selected from the group consisting of an acrylate compound and a methacrylate compound having a hydroxyl group (hereinafter sometimes referred to as “polyurethane acrylate”);
A compound obtained by reacting polyurethane urea with at least one compound selected from the group consisting of an acrylate compound and a methacrylate compound further having a hydroxyl group (hereinafter sometimes referred to as “polyurethane urea acrylate”);
It is preferable that A polyol refers to a compound having two or more hydroxyl groups.

The compound (B) is preferably a compound represented by the formula (B).

In formula (B), R ₁ and n represent the same meaning as described above.

  Examples of the compound (B) include isophorone diisocyanate, 1,4-cyclohexylene diisocyanate, 1,3-bis (isocyanatomethyl) cyclohexane, dicyclohexylmethane 4,4′-diisocyanate, and isophorone diisocyanate is particularly preferable. .

  Examples of the polyol include a low molecular weight polyol and a polyol having a molecular weight of 50 or more and less than 400. For example, aliphatic, alicyclic, aromatic, and heterocyclic dihydroxy compounds, trihydroxy compounds, tetrahydroxy compounds, and the like can be given. Specifically, ethylene glycol, propylene glycol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,7-heptanediol, 1,8-octanediol, decamethylenediol, 2-ethyl-1,6-hexanediol, 2-methyl-1,3-propanediol, 2,5-dimethyl-2,5-hexanediol, 1,3-cyclohexanediol, 1,4-cyclohexanediol, cyclohexane Dimethanol, bis (β-hydroxyethoxy) benzene, p-xylenediol, dihydroxyethyltetrahydrophthalate, 2-methylpropane-1,2,3-triol, 1,2,6-hexanetriol, pentaerythritol, neopentyl Glycol, diethylene glycol, Triethylene glycol, dipropylene glycol, tripropylene glycol, glycerine, selected from trimethylol propane.

  The low molecular weight polyol is preferably a diol compound, particularly propylene glycol, 1,4-butanediol, tripropylene glycol, 1,4-cyclohexanedimethanol, 1,4-cyclohexanediol and 1,6-hexane. It is preferably selected from diols and the like. The molecular weight of the low molecular weight polyol is preferably 50 or more and 200 or less, more preferably 62 or more and 200 or less. It is preferable for the molecular weight of the low molecular weight polyol to be 62 or more and 200 or less because the stretchability of the optical film of the present invention can be suppressed.

  Examples of the high molecular weight polyol include polyols having an average molecular weight of 400 or more. For example, polyester polyols, polyether polyols, polycarbonate polyols, silicone polyols, polyolefin polyols, and copolymers thereof are used.

  The high molecular weight polyol is preferably a diol compound, preferably a compound selected from polyalkylene diols having 1 to 6 carbon atoms in the alkylene group and polycarbonate diols, particularly polypropylene glycol and polyhexamethylene carbonate diol. Is preferred. The average molecular weight of the high molecular weight polyol is preferably 400 or more and 7000 or less, and more preferably 400 or more and 5000 or less. Further, it is particularly preferably 400 or more and 2000 or less. It is preferable that the average molecular weight of the high molecular weight polyol is 400 or more and 2000 or less because the optical film of the present invention is given flexibility.

Examples of the polyester polyol include dicarboxylic acids selected from succinic acid, glutaric acid, adipic acid, azelaic acid, dodecanoic acid, phthalic anhydride, isophthalic acid, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, maleic anhydride, fumaric acid and the like. And a low molecular weight polyol. As another method, lactone compounds such as β-propiocraton, pivalolactone, δ-valerolactone, methyl-δ-valerolactone, ε-caprolactone, methyl-ε-caprolactone, dimethyl-ε-caprolactone, trimethyl-ε-caprolactone, etc. Some have reacted with a low molecular weight polyol.
Examples of the polyether polyol include polytetramethylene glycol, polyethylene glycol, polypropylene glycol, and polyoxypropylene glycol.

  Polycarbonate polyols are those obtained by transesterification from low molecular weight polyols and compounds selected from diallyl carbonate, dialkyl carbonate and ethylene carbonate, such as poly-1,6-hexamethylene carbonate, poly-2,2 ′. -Bis (4-hydroxyhexyl) propane carbonate and the like.

  The polyol is not particularly limited, and a plurality of polyols may be used in combination. From the viewpoint of flexibility and durability of the resulting film, it is preferable to combine at least one low molecular weight polyol and at least one high molecular weight polyol. In particular, a high molecular weight polyol having an average molecular weight of 400 or more and 10,000 or less and a compound containing a low molecular weight diol compound having a molecular weight of 50 or more and less than 400 unlike a high molecular weight polyol is preferable.

As the polyamine, both aromatic polyamines and aliphatic polyamines can be used. Examples of aromatic polyamines include tolylenediamine, phenylenediamine, diaminodiphenylmethane, 1-methyl-3,5-diethyl-2,4-diaminobenzene, 1-methyl-3,5-diethyl-2,6-diamino. Examples include benzene, 1,3,5-triethyl-2,6-diaminobenzene, 3,5,3 ′, 5′-tetraethyl-4,4′-diaminodiphenylmethane, and the like. Examples of the aliphatic polyamine include ethylenediamine, propylenediamine, hexamethylenediamine, diaminocyclohexylmethane, and 3-aminomethyl-3,5,5-trimethylcyclohexylamine (isophoronediamine).
Aliphatic polyamines are preferred because of less discoloration. In particular, polyamines having an alicyclic structure are preferred because optical properties tend to be good. Examples of the polyamine having an alicyclic structure include diaminocyclohexylmethane and isophoronediamine.

  As the (meth) acrylate having a hydroxyl group (“(meth) acrylate” is a generic term for “acrylate” and “methacrylate”), monohydroxy mono (meth) acrylate, monohydroxy oligo (meth) acrylate, Although there exists oligohydroxy oligo (meth) acrylate, monohydroxyalkyl mono (meth) acrylate is preferable from a reactive viewpoint. Examples of the monohydroxyalkyl mono (meth) acrylate include 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl acrylate, 2-hydroxypropyl methacrylate, 4-hydroxybutyl acrylate, 4-hydroxybutyl methacrylate, and the like. Can be mentioned.

  The polyaddition reaction or the like, which is a method for producing the compound (1), may be performed using an organic solvent or without a solvent. The organic solvent is not particularly limited as long as it does not react with an isocyanate group. For example, hydrocarbons such as toluene, xylene, chlorobenzene and mineral terpenes; ester solvents such as ethyl acetate, butyl acetate, isobutyl acetate, methyl glycol acetate, cellosolve acetate; acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclopentanone, cyclohexanone, etc. And ketone solvents. Further, an aprotic polar solvent such as N, N-dimethylformamide, N, N-dimethylacetamide, dimethyl sulfoxide, N-methyl-2-pyrrolidone, and γ-butyrolactone may be used.

  In the production of the compound (1), in order to accelerate the urethanization reaction, a catalyst used in a normal urethane reaction may be used as necessary. Specifically, tertiary amines such as triethylamine, N-ethylmorpholine, triethylenediamine; organotin catalysts such as dibutyltin dilaurate, dioctyltin dilaurate and tin octylate; and organic titanium catalysts such as tetrabutyltitanate , Etc.

  When compound (1) is polyurethaneurea or polyurethaneurea acrylate, a chain extender such as diamine and a solution obtained by dissolving a reaction terminator described later in a solvent are added to the polyurethane solution to cause a chain extension reaction. Alternatively, a chain extender and, if necessary, a reaction terminator may be added to the polyurethane solution to cause a chain extension reaction. Examples of the reaction terminator used in the production of polyurethaneurea include dialkylamines such as di-n-butylamine; aromatic amines such as benzylamine and dibenzylamine; alkanolamines such as diethanolamine; ethanol and isopropyl alcohol Alcohols.

  Further, in the production of the compound (1), it is also preferable to use a polymerization inhibitor in order to suppress polymerization of the acrylate being synthesized. Specifically, hydroquinone polymerization inhibitors such as methoquinone, hydroquinone and t-butylhydroquinone, hindered phenol polymerization inhibitors such as 2,6-di-tert-butyl-4-methylphenol and t-butylcatechol, Common things, such as a phenothiazine and a nitroso compound, can be used. One or two or more polymerization inhibitors may be used, and the amount used is generally 10 to 50000 ppm, preferably about 50 to 1000 ppm.

  The molecular weight of the compound (1) is not particularly limited, but is preferably in the range of 1,000 to 100,000 in terms of number average molecular weight from the viewpoint of viscosity and solubility. The compound may be a low molecular weight resin such as a urethane oligomer or a urethane urea oligomer.

  The optical film of the present invention can be obtained by stretching a film containing the compound (1). Moreover, the optical film of this invention can also be obtained by extending | stretching the film | membrane formed by photopolymerizing the composition of this invention containing a compound (1).

  The composition of the present invention may contain a photopolymerization initiator (2). Examples of the photopolymerization initiator (2) include benzoins, benzophenones, benzyl ketals, α-hydroxyketones, α-aminoketones, iodonium salts, sulfonium salts, and the like. More specifically, Irgacure ( Irgacure) 907, Irgacure 184, Irgacure 651, Irgacure 250, Irgacure 369 (all manufactured by Ciba Specialty Chemicals Co., Ltd.), Seiko All BZ, Seiko All Z, Seiko All BEE (all manufactured by Seiko Chemical Co., Ltd.), Kaya Cure ( kayacure) BP100 (manufactured by Nippon Kayaku Co., Ltd.), Kayacure UVI-6992 (manufactured by Dow), Adekaoptomer SP-152 and Adekaoptomer SP-170 (all above, ADEKA Corporation) and the like. it can.

  Moreover, the usage-amount of a photoinitiator (2) is 0.1 weight part-30 weight part with respect to 100 weight part of total amounts of a compound (1) and the monomer (3) mentioned later, for example, Preferably 0.5 parts by weight to 10 parts by weight. If it is in the said range, a monomer can be polymerized, without reducing the transmittance | permeability.

  The composition of the present invention may contain a polymerization inhibitor in order to control the photopolymerization of the monomer and improve the stability of the resulting optical film. Examples of the polymerization inhibitor include hydroquinones having a substituent such as hydroquinone and alkyl ether, catechols having a substituent such as alkyl ether such as butylcatechol, pyrogallols, 2,2,6,6-tetramethyl-1 -Radical scavengers such as piperidinyloxy radicals, thiophenols, β-naphthylamines or β-naphthols.

  The amount of the polymerization inhibitor used is, for example, 0.1 to 30 parts by weight, preferably 0.5 parts by weight based on 100 parts by weight of the total amount of the compound (1) and the monomer (3) described later. -10 parts by weight. If it is in the said range, a monomer can be polymerized, without reducing the transmittance | permeability.

  The composition of the present invention may contain a photosensitizer in order to increase the sensitivity of the reaction of the photopolymerization initiator. Examples of the photosensitizer include xanthones such as xanthone and thioxanthone, anthracene having a substituent such as anthracene and alkyl ether, phenothiazine, and rubrene.

The usage-amount of a photosensitizer is 0.1 weight part-30 weight part with respect to 100 weight part of total amounts of a compound (1) and the monomer (3) mentioned later, Preferably it is 0.5 weight. Parts to 10 parts by weight. Within the above range, the monomer can be polymerized with high sensitivity without lowering the transmittance.
The composition of the present invention may contain a monomer (3) and / or a polymer obtained by polymerizing the monomer (3). As monomer (3), the monomer represented by monomer (XI)-monomer (XIV) is mentioned.

In the monomer (XI), R ₁₁ is preferably a hydrogen atom.
In the monomer (XI), specific examples of the aromatic hydrocarbon group and the aromatic heterocyclic group include aromatic hydrocarbon groups such as phenyl group, benzyl group, naphthyl group, and anthracenyl group, pyrrole group, furanyl group, and pyrazinyl group. , Aromatic heterocyclic groups such as pyrazole group, pyridinyl group and thiazole group.

  The hydrogen atom contained in the aromatic hydrocarbon group and the aromatic heterocyclic group is, for example, an alkyl group having 1 to 12 carbon atoms such as a methyl group, an ethyl group, an isopropyl group, a t-butyl group and an octyl group, such as a methoxy group and Alkoxy groups having 1 to 12 carbon atoms such as ethoxy groups, halogen atoms such as fluorine atoms, chlorine atoms and bromine atoms, acyl groups having 2 to 4 carbon atoms such as acetyl groups, hydroxyl groups, glycidoxy groups or carboxyl groups May be substituted.

The aromatic hydrocarbon group and the aromatic heterocyclic group are monovalent groups formed by bonding one or more groups selected from the group consisting of a plurality of aromatic hydrocarbon groups and aromatic heterocyclic groups via a linking group. It may be. As the linking group, for example, a methylene group, an ethylidene group, a propylidene group, an isopropylidene group, a cyclohexylidene group, an ethylene group and a propylene group, etc., a hydrocarbon group having about 1 to 6 carbon atoms, an oxygen atom, a sulfur atom, a carbonyl group or -CO ₂ - and the like. A group selected from a plurality of aromatic hydrocarbon groups and aromatic heterocyclic groups may be bonded by a single bond.

  Specific examples include a biphenyl group in which a plurality of aromatic hydrocarbon groups are bonded by a single bond, and a group represented by the following formula in which a plurality of aromatic hydrocarbon groups are bonded by an isopropylidene group.

Examples of the monomer (XI) include styrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, 2,4-dimethylstyrene, o-ethylstyrene, p-ethylstyrene, trimethylstyrene, propylstyrene, tert- Alkyl styrene such as butyl styrene, cyclohexyl styrene, dodecyl styrene, such as hydroxy styrene, t-butoxy styrene, vinyl benzoic acid, vinyl benzyl acetate, o-chloro styrene, p-chloro styrene, amino styrene, etc. Substituted styrene to which a group selected from an alkoxy group, a carboxyl group, an acyloxy group, a halogen, and an amino group is bonded, such as 4-vinylbiphenyl, 2-ethyl-4benzylstyrene, 4- (phenylbutyl) styrene, and the like A vinyl biphenyl compound such as -hydroxy-4'-vinylbiphenyl, a compound having a condensed ring and a vinyl group such as vinylnaphthalene and vinylanthracene, an aromatic hydrocarbon group such as N-vinylphthalimide, a heterocyclic group and a vinyl group. And the like.
Examples of the monomer (XI) having an aromatic heterocyclic group include N-vinylcarbazole, N-phenylmaleimide, N-vinylpyridine, N-vinylphthalimide and N-vinylindole.

In the monomer (XII), R ₁₃ is preferably a hydrogen atom.
A plurality of different monomers may be used in combination as the monomer (XII).

Specific examples of the monomer (XII) include, for example, N-methyl (meth) acrylamide, N-ethyl (meth) acrylamide, N-isopropyl (meth) acrylamide, N-butyl (meth) acrylamide in addition to (meth) acrylamide. Or N-substituted (meth) acrylamides such as N- (2-hydroxyethyl) acrylamide, such as N, N-dimethyl (meth) acrylamide, N, N-diethyl (meth) acrylamide, N, N-dipropyl (meth) acrylamide N, N-substituted (meth) acrylamide such as (meth) acryloylmorpholine, 2-dimethylaminoethyl (meth) acrylate or 2-diethylaminoethyl (meth) acrylate.
As the monomer (XII), N, N-dimethylacrylamide, N, N-diethylacrylamide, N- (2-hydroxyethyl) acrylamide, N-isopropylacrylamide, acryloylmorpholine, 2-dimethylaminoethyl (meth) acrylate or 2-diethylaminoethyl (meth) acrylate is preferred.
Monomer (XII) is commercially available from, for example, Wako Pure Chemical Industries, Ltd., Tokyo Chemical Industry Co., Ltd., Sigma Aldrich Japan Co., Ltd. and the like. Monomer (XII), which is commercially available, may be used as it is.

In the monomer (XIII), R ₁₆ is preferably a hydrogen atom.
In the monomer (XIII), examples of the 5- to 20-membered cyclic hydrocarbon group include aromatic hydrocarbon groups such as a phenyl group, a naphthyl group, and an anthranyl group, such as a cyclopentyl group, a cyclohexyl group, an isobornyl group, and a tricyclodecanyl group. And cycloalkyl groups such as an adamantyl group and the like.

The cyclic hydrocarbon group includes an alkyl group having 1 to 12 carbon atoms such as a methyl group, an ethyl group, an isopropyl group, a t-butyl group and an octyl group, for example, an alkoxy group having 1 to 12 carbon atoms such as a methoxy group and an ethoxy group. A group, for example, a halogen atom such as a fluorine atom, a chlorine atom and a bromine atom, for example, an acyl group having 2 to 4 carbon atoms such as an acetyl group, an aryl group having 6 to 12 carbon atoms, an aralkyl group having 7 to 12 carbon atoms, A group selected from the group consisting of a hydroxyl group, a glycidoxy group and a carboxyl group may be bonded.
The methylene group contained in the cyclic hydrocarbon group may be substituted with a hetero atom such as an oxygen atom, a sulfur atom and a nitrogen atom.
A plurality of different monomers may be used in combination as the monomer (XIII).

  Specific examples of the monomer (XIII) include (meth) acrylic acid, methyl (meth) acrylate, phenyl (meth) acrylate, naphthyl (meth) acrylate, anthracenyl (meth) acrylate, cyclohexyl (meth) acrylate, 2-tetrahydropyrani Examples include ru (meth) acrylate, isobornyl (meth) acrylate, tricyclodecanyl (meth) acrylate, adamantyl (meth) acrylate, 1-acryloyl-4-methoxynaphthalene, etc., and particularly methyl (meth) acrylate, 1- Acryloyl-4-methoxynaphthalene, cyclohexyl (meth) acrylate, 2-tetrahydropyranyl (meth) acrylate, isobornyl (meth) acrylate, tricyclodecanyl (meth) acrylate, adama Chill (meth) acrylate, phenyl (meth) acrylate or naphthyl (meth) acrylate.

式（ＸＩＶ−ａ）中、Ｒ_１８は前記Ｒ_１６と同じ意味を表し、ｓは１〜２０の整数を表し、Ｒ_１９は前記Ｒ_１７と同じ意味を表す。 In addition to the monomers (XI) to (XIII), a repeating unit derived from the monomer (XIV) copolymerizable with the monomers (XI) to (XIII) may be contained. Examples of the copolymerizable monomer (XIV) include a monomer represented by the formula (XIV-a) (hereinafter sometimes referred to as a monomer (XIV-a)), vinyl acetate, (anhydrous) maleic acid, maleimide, Glycidyl (meth) acrylate, benzyl (meth) acrylate, (meth) acrylate having an alkyl ester having 2 to 12 carbon atoms, ethylene, an α-olefin compound having 3 to 20 carbon atoms, a cyclic olefin having 5 to 20 carbon atoms, carbon Examples thereof include vinyl compounds having an alicyclic structure of several 5 to 20.

In formula (XIV-a), R ₁₈ represents the same meaning as R ₁₆ , s represents an integer of 1 to 20, and R ₁₉ represents the same meaning as R ₁₇ .

（式（ＸＩＶ−１）中、Ｒ_１８及びｓは前記と同じ意味を表し、Ｒは、それぞれ独立に、水酸基、炭素数１〜６のアルキル基、炭素数１〜６のアルコキシ基、グリシドキシ基を表す。ｔは０〜４の数を表し、ｕは０〜５の数を表す。）

（式（ＸＩＶ−２）中、Ｒ_１８、Ｒ、ｓ及びｔは前記と同じ意味を表す。） As the monomer (XIV-a), a monomer represented by the formula (XIV-1) or the formula (XIV-2) is preferable.

(In formula (XIV-1), R ₁₈ and s represent the same meaning as described above, and each R independently represents a hydroxyl group, an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, or a glycidoxy group. T represents a number of 0 to 4, and u represents a number of 0 to 5.)

(In formula (XIV-2), R ₁₈ , R, s and t have the same meaning as described above.)

Specific examples of the monomer (XIV-a) include the following monomers.

As a method for producing the monomer (XIV), for example, a phenol compound is used as a compound that gives the structure of R ₁₉ , and the compound is reacted with an alkylene oxide such as ethylene oxide to produce R ₁₉ — (CH ₂ —CH ₂ —O). ) The method etc. which obtain _s- H and esterify acrylic acid or methacrylic acid etc. are mentioned.

  The compounds represented by formula (XIV-1-1) and formula (XIV-2-1) are NK ester L-4 [monomer represented by formula (XIV-1-1) from Shin-Nakamura Chemical Co., Ltd. ] And NK ester A-CMP-1E [monomer represented by the formula (XIV-2-1)].

Examples of the α-olefin compound having 3 to 20 carbon atoms used as the copolymerizable monomer (XIV) include propylene, 1-butene, 1-pentene, 1-hexene, 1-octene, 1-decene, 1-decene, C3-C20 linear α-olefins such as dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene, 1-eicocene, 4-methyl-1-pentene, 3-methyl-1-pentene And branched α-olefins having 4 to 20 carbon atoms such as 3-methyl-1-butene.
Among ethylene and α-olefin compounds having 3 to 20 carbon atoms, ethylene, propylene and 1-butene, which are linear α-olefins having 3 or 4 carbon atoms, are formed into a film. It is preferable because it is excellent in flexibility, and ethylene is particularly preferable.

  The cyclic olefin used as the copolymerizable monomer (XIV) is a compound having a polymerizable carbon-carbon double bond in the carbocycle. Accordingly, in the main chain of the polymer (1) obtained by copolymerizing the cyclic olefin with the monomer (XI) to the monomer (XIII), for example, a cyclobutane ring, a cyclopentane ring, a cyclohexane ring, two or more of them are bonded. It is a monomer capable of introducing an alicyclic ring such as Specifically, bicyclo [2,2,1] hept-2-ene, 6-alkylbicyclo [2,2,1] hept-2-ene, 5,6-dialkylbicyclo [2,2,1] Methyl group, ethyl group, butyl, such as hept-2-ene, 1-alkylbicyclo [2,2,1] hept-2-ene, 7-alkylbicyclo [2,2,1] hept-2-ene A norbornene derivative having an alkyl group having 1 to 4 carbon atoms such as a group introduced therein, tetracyclo [4,4,0,12,5,17,10] -3-dodecene, also called dimethanooctahydronaphthalene, 8 -Alkyltetracyclo [4,4,0,12,5,17,10] -3-dodecene, 8,9-dialkyltetracyclo [4,4,0,12,5,17,10] -3-dodecene Of dimethanooctahydronaphthalene Dimethanooctahydronaphthalene derivative in which an alkyl group having 3 or more carbon atoms is introduced at the position and / or 9 position, norbornene derivative in which one or more halogens are introduced in the molecule, position 8 and / or 9 position And derivatives of dimethanooctahydronaphthalene into which halogen is introduced.

  Examples of the vinyl compound having an alicyclic structure used as a copolymerizable monomer (XIV) include, for example, a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a cyclooctyl group, a cyclodecanyl group, and a norbornenyl group. And a compound comprising an alicyclic hydrocarbon group having about 3 to 12 carbon atoms such as an adamantyl group, and a vinyl group.

  As the copolymerizable monomer (XIV), two or more types of copolymerizable monomers may be used in combination.

  The composition of the present invention may contain a polyfunctional monomer. As the polyfunctional monomer, polyvalent (meth) acrylate is preferable. The polyvalent (meth) acrylate preferably has an alicyclic hydrocarbon group or a group having aromaticity in the molecule, for example, preferably bisphenol fluorene.

  The composition of the present invention may contain a trifunctional or higher polyfunctional photopolymerizable compound. Examples of the trifunctional or higher polyfunctional photopolymerizable compound include pentaerythritol tetraacrylate, pentaerythritol tetramethacrylate, dipentaerythritol pentaacrylate, dipentaerythritol pentamethacrylate, dipentaerythritol hexaacrylate, and dipentaerythritol hexamethacrylate. It is done. The copolymerizable monomers may be used alone or in combination of two or more. The trifunctional or higher polyfunctional photopolymerizable compound may be one type or two or more types of trifunctional or higher polyfunctional photopolymerizable compounds.

  The composition of the present invention may contain a solvent (4). Examples of the organic solvent include ethers, aromatic hydrocarbons, ketones, alcohols, esters, amides and the like.

  Examples of ethers include tetrahydrofuran, tetrahydropyran, 1,4-dioxane, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol mono Butyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol dipropyl ether, diethylene glycol dibutyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, Chill cellosolve acetate, ethyl cellosolve acetate, ethyl carbitol acetate, butyl carbitol acetate, propylene glycol methyl ether acetate, methoxybutyl acetate, methoxy pentyl acetate, anisole, include phenetol or methyl anisole and the like.

  Examples of aromatic hydrocarbons include benzene, toluene, xylene, mesitylene and the like.

  Examples of ketones include acetone, 2-butanone, 2-heptanone, 3-heptanone, 4-heptanone, 4-methyl-2-pentanone, cyclopentanone, and cyclohexanone.

  Examples of alcohols include methanol, ethanol, propanol, butanol, hexanol, cyclohexanol, ethylene glycol, and glycerin.

  Examples of the esters include ethyl acetate, n-butyl acetate, isobutyl acetate, amyl formate, isoamyl acetate, isobutyl acetate, butyl propionate, isopropyl butyrate, ethyl butyrate, butyl butyrate, alkyl esters, methyl lactate, ethyl lactate, Methyl oxyacetate, ethyl oxyacetate, butyl oxyacetate, methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, methyl 3-oxypropionate, ethyl 3-oxypropionate, 3-methoxypropionate Acid methyl, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, methyl 2-oxypropionate, ethyl 2-oxypropionate, propyl 2-oxypropionate, 2-methoxy Methyl propionate, ethyl 2-methoxypropionate, propyl 2-methoxypropionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate, methyl 2-oxy-2-methylpropionate, 2-oxy-2-methyl Ethyl propionate, methyl 2-methoxy-2-methylpropionate, ethyl 2-ethoxy-2-methylpropionate, methyl pyruvate, ethyl pyruvate, propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, 2-oxobutanoic acid Examples thereof include methyl, ethyl 2-oxobutanoate, 3-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, and γ-butyrolactone.

Examples of amides include N, N-dimethylformamide and N, N-dimethylacetamide.
Examples of other solvents include N-methylpyrrolidone and dimethyl sulfoxide.
A solvent can be used individually or in combination of 2 types or more, respectively.

  The composition of the present invention may contain a leveling agent. Examples of leveling agents include Torre Silicone DC3PA, SH7PA, DC11PA, SH21PA, SH28PA, 29SHPA, SH30PA, polyether-modified silicone oil SH8400 (manufactured by Torresilicone), KP321, KP322, KP323, KP324. , KP326, KP340, KP341 (manufactured by Shin-Etsu Silicone), TSF400, TSF401, TSF410, TSF4300, TSF4440, TSF4445, TSF-4446, TSF4452, TSF4460 (manufactured by GE Toshiba Silicone), Florinato (trade name) FC430, FC431 (Manufactured by Sumitomo 3M Co., Ltd.), MegaFuck (trade name) F142D, F171, F172, F173, F177, F183 R30 (manufactured by Dainippon Ink & Chemicals, Inc.), Ftop (trade name) EF301, EF303, EF351, EF352 (manufactured by Shin-Akita Kasei Co., Ltd.), Surflon (tradename) S381, S382, SC101, SC105 (Asahi Glass Co., Ltd.), E5844 (Daikin Fine Chemical Laboratory Co., Ltd.), BM-1000, BM-1100 (all trade names: manufactured by BM Chemie), Megafuck (trade name) R08, the same BL20, the same F475, the same F477 or the same F443 (manufactured by Dainippon Ink & Chemicals, Inc.).

By using a leveling agent, the obtained film (membrane) can be smoothed. Furthermore, in the production process of film formation, the fluidity of the composition can be controlled, and the crosslinking density of the film obtained by polymerizing the composition can be adjusted.
The content of the leveling agent is 0.001 weight with respect to a total of 100 parts by weight of the monomer (1), the compound (2), the photopolymerization initiator (3) and the copolymerizable monomer contained as necessary. Parts to 2.0 parts by weight, preferably 0.005 parts to 1.5 parts by weight. If it is in the said range, a monomer can be polymerized, without reducing the transmittance | permeability.

  The composition of the present invention may contain a plasticizer. As the plasticizer, phosphoric acid ester, carboxylic acid ester or glycolic acid ester is used. Examples of phosphate esters include triphenyl phosphate (TPP), tricresyl phosphate (TCP), cresyl diphenyl phosphate, octyl diphenyl phosphate, diphenyl biphenyl phosphate, trioctyl phosphate or tributyl phosphate.

The carboxylic acid ester is typically a phthalic acid ester or a citric acid ester. Examples of phthalic acid esters include dimethyl phthalate (DMP), diethyl phthalate (DEP), dibutyl phthalate (DBP), dioctyl phthalate (DOP), diphenyl phthalate (DPP) or diethyl hexyl phthalate (DEHP). Examples of citrate esters include O-acetyl triethyl citrate (OACTE), O-acetyl tributyl citrate (OACTB), acetyl triethyl citrate or acetyl tributyl citrate.
Examples of other carboxylic acid esters include butyl oleate, methylacetyl ricinoleate, dibutyl sebacate, and various trimellitic acid esters.

  Examples of glycolic acid esters include triacetin, tributyrin, butyl phthalyl butyl glycolate, ethyl phthalyl ethyl glycolate, methyl phthalyl ethyl glycolate or butyl phthalyl butyl glycolate. Also trimethylolpropane tribenzoate, pentaerythritol tetrabenzoate, ditrimethylolpropane tetraacetate, ditrimethylolpropane tetrapropionate, pentaerythritol tetraacetate, sorbitol hexaacetate, sorbitol hexapropionate, sorbitol triacetate tripropionate, inositol pentaacetate Or sorbitan tetrabutyrate is also a good example.

  Among the plasticizers, triphenyl phosphate, tricresyl phosphate, cresyl diphenyl phosphate, tributyl phosphate, dimethyl phthalate, diethyl phthalate, dibutyl phthalate, dioctyl phthalate, diethyl hexyl phthalate, triacetin, ethyl phthalyl ethyl glycolate, trimethylol Propane tribenzoate, pentaerythritol tetrabenzoate, ditrimethylolpropane tetraacetate, pentaerythritol tetraacetate, sorbitol hexaacetate, sorbitol hexapropionate, sorbitol triacetate tripropionate, etc. are preferred, especially triphenyl phosphate, diethyl phthalate, ethyl phthalyl Ethyl glycolate, trimethylo Le propane tribenzoate, pentaerythritol tetrabenzoate, ditrimethylolpropane tetra acetate, sorbitol hexaacetate, sorbitol hexapropionate or sorbitol triacetate tripropionate are preferred.

  One or more plasticizers may be used in combination. The addition amount of the plasticizer may be appropriately selected within a range that does not significantly impair the film properties of the present invention, and is, for example, about 0.1 to 30% by weight relative to the total solid content of the composition of the present invention.

  Specific examples of the plasticizer include (di) pentaerythritol esters described in JP-A No. 11-124445, glycerol esters described in JP-A No. 11-246704, and diglycerol esters described in JP-A No. 2000-63560. Citrate esters described in JP-A No. 11-92574, substituted phenyl phosphate esters described in JP-A No. 11-90946, and the like.

The optical film of the present invention can be obtained by stretching a film containing the compound of the present invention or by stretching a film obtained by photopolymerizing the composition of the present invention.
The composition of the present invention is cured by photopolymerization with ultraviolet light (UV). Examples of ultraviolet light generation sources include fluorescent chemical lamps, black lights, low pressure, high pressure, ultrahigh pressure mercury lamps, metal halide lamps, and sunlight. The irradiation intensity of the ultraviolet light may be constant throughout, or the physical properties after curing can be finely adjusted by changing the intensity during the curing.
In the composition of the present invention, a compound, a photopolymerization initiator (2) and a monomer (3) are mixed, and a solvent (4), a polymerization inhibitor, a photosensitizer, a leveling agent or a plasticizer is mixed as necessary. To be prepared.
The amount of the organic solvent in producing the composition is such that the total concentration of the compound and the monomer (3) is adjusted to 10% by weight or more, preferably 20 to 50% by weight.

  The optical film of the present invention is usually produced by forming the composition into a film (filming), photopolymerizing, and further stretching the obtained film. Examples of a method for forming a film of the composition include, for example, a solvent casting method in which a solution containing the composition is cast on a smooth surface to distill off the solvent, and the composition is extruded into a film with a melt extruder or the like. And melt extrusion method. In particular, the solvent casting method is preferable because a solution containing the composition can be directly formed into a film.

Examples of the stretching method include a stretching method by a tenter method and a stretching method by roll-to-roll stretching.
Stretching may be either uniaxial stretching or biaxial stretching, and may be either longitudinal stretching or lateral stretching. In particular, from the viewpoint of productivity, uniaxial stretching is preferable, and uniaxial longitudinal stretching is particularly preferable.

The ratio ([Re (450)] / [Re (550)]) of the retardation [Re (450)] having a wavelength of 450 nm and the retardation [Re (550)] having a wavelength of 550 nm of the light transmitted through the optical film is a wavelength. It is defined as a dispersion coefficient α, and in order for the optical film to perform uniform polarization conversion in a wide wavelength range, it is preferable that the optical film has a wavelength dispersion characteristic that the wavelength dispersion coefficient α is less than 1.00. The optical film of the present invention thus obtained usually has a wavelength dispersion coefficient α of less than 1.00.
The retardation value Re (ν) at a wavelength νnm of light transmitted through the optical film is generally increased to the right in the visible range of 300 to 700 nm, such as satisfying the relationship of Re (450) <Re (550) <Re (650). Therefore, uniform polarization conversion can be performed in a wide wavelength range.

Since the optical film of the present invention can perform uniform polarization conversion in a wide wavelength range, it is used as a retardation plate such as a λ / 2 plate or a λ / 4 plate, a viewing angle improving film, or the like. If the optical film is a λ / 4 plate, it can be combined with a linear polarizing plate to make a circular polarizing plate in a wide wavelength range, and if it is a λ / 2 plate, it can be combined with a linear polarizing plate. A polarization rotation element having a wide wavelength range can be obtained. Therefore, it can be used for various liquid crystal display devices, cathode ray tubes (CRT), touch panels, antireflection filters in electroluminescence (EL) lamps, and liquid crystal projectors.
The retardation plate of the present invention is thus composed of the above optical film, and can perform uniform polarization conversion in a wide wavelength range.

  Hereinafter, the present invention will be described in more detail with reference to examples. In the examples, “%” and “parts” are by weight and parts by weight unless otherwise specified. The optical anisotropy was determined by the following method.

(Optical anisotropy)
When the polymer main chain is uniaxially oriented by stretching, it has negative birefringence when the orientation direction and the direction in which the refractive index is maximum are different (for example, orthogonal). is doing. On the other hand, when the alignment direction and the direction in which the refractive index is maximum coincide with each other or almost coincide with each other (for example, when the difference between the alignment direction and the direction in which the refractive index is maximum is within 10 degrees, etc.), Refractive. The direction in which the refractive index is maximized can be obtained from an automatic birefringence meter.

(Synthesis Example 1)
In a reaction vessel equipped with a stirrer, a thermometer and a reflux condenser, 5.16 parts of polyhexamethylene carbonate diol (average molecular weight 860), 18.92 parts of 9,9-bis (4-hydroxyphenyl) fluorene, 2,6 -0.10 parts of di-tert-butyl-4-methylphenol, 0.10 parts of dibutyltin dilaurate, and 62.00 parts of propylene glycol monomethyl ether acetate are added dropwise under stirring in a nitrogen stream and 14.67 parts of isophorone diisocyanate. Then, after completion of the dropping, the reaction was carried out at 120 ° C. for 4 hours under a nitrogen stream to obtain polyurethane 1 having a number average molecular weight of 3.2 × 10 ³ .

(Synthesis Example 2)
In a reaction vessel equipped with a stirrer, a thermometer and a reflux condenser, 10.32 parts of polyhexamethylene carbonate diol (average molecular weight 860), 16.82 parts of 9,9-bis (4-hydroxyphenyl) fluorene, 2,6 -0.10 parts of di-tert-butyl-4-methylphenol, 0.10 parts of dibutyltin dilaurate, and 66.90 parts of propylene glycol monomethyl ether acetate were added dropwise with 14.67 parts of isophorone diisocyanate under stirring in a nitrogen stream. Then, after completion of the dropping, the reaction was carried out at 120 ° C. for 4 hours under a nitrogen stream to obtain polyurethane 2 having a number average molecular weight of 3.7 × 10 ³ .

(Synthesis Example 3)
In a reaction vessel equipped with a stirrer, a thermometer and a reflux condenser, 15.48 parts of polyhexamethylene carbonate diol (average molecular weight 860), 14.72 parts of 9,9-bis (4-hydroxyphenyl) fluorene, 2,6 -0.10 parts of di-tert-butyl-4-methylphenol, 0.10 parts of dibutyltin dilaurate, 71.79 parts of propylene glycol monomethyl ether acetate were added dropwise, and 14.67 parts of isophorone diisocyanate was added dropwise under stirring in a nitrogen stream. After completion of the dropwise addition, the reaction was carried out at 120 ° C. for 4 hours under a nitrogen stream to obtain polyurethane 3 having a number average molecular weight of 4.3 × 10 ³ .

(Synthesis Example 4)
In a reaction vessel equipped with a stirrer, a thermometer and a reflux condenser, 10.32 parts of polyhexamethylene carbonate diol (average molecular weight 860), 16.82 parts of 9,9-bis (4-hydroxyphenyl) fluorene, 2,6 -0.10 parts of di-tert-butyl-4-methylphenol, 0.10 parts of dibutyltin dilaurate, and 66.90 parts of propylene glycol monomethyl ether acetate were added dropwise with 14.67 parts of isophorone diisocyanate under stirring in a nitrogen stream. After completion of the dropping, the mixture was reacted at 120 ° C. for 4 hours under a nitrogen stream, cooled to 50 ° C., charged with 2.68 parts of 2-hydroxyethyl acrylate, reacted at 50 ° C. for 1 hour, and the number average molecular weight: 3. 9 × 10 ³ urethane acrylate 4 was obtained.

(Synthesis Example 5)
In a reaction vessel equipped with a stirrer, a thermometer and a reflux condenser, 5.16 parts of polyhexamethylene carbonate diol (average molecular weight 860), 14.72 parts of 9,9-bis (4-hydroxyphenyl) fluorene, 1,4 -1.73 parts of cyclohexanedimethanol, 0.10 parts of 2,6-di-tert-butyl-4-methylphenol, 0.10 parts of dibutyltin dilaurate, 55.28 parts of propylene glycol monomethyl ether acetate, and nitrogen 14.67 parts of isophorone diisocyanate was added dropwise with stirring under a stream of air, and after completion of the dropping, the mixture was reacted at 120 ° C. for 4 hours under a stream of nitrogen to obtain polyurethane 5 having a number average molecular weight of 4.9 × 10 ³ .

(Synthesis Example 6)
In a reaction vessel equipped with a stirrer, a thermometer and a reflux condenser, 5.16 parts of polyhexamethylene carbonate diol (average molecular weight 860), 14.72 parts of 9,9-bis (4-hydroxyphenyl) fluorene, 1,4 -Cyclohexanediol 1.39 parts, 2,6-di-tert-butyl-4-methylphenol 0.10 parts, dibutyltin dilaurate 0.10 parts, propylene glycol monomethyl ether acetate 55.28 parts, nitrogen stream under stirring, it was added dropwise 14.67 parts of isophorone diisocyanate, after the completion of the dropwise addition, under a nitrogen stream, and reacted for 4 hours at 120 ° C., a number average molecular weight: 3.1 to obtain a polyurethane 6 × 10 ^3.

(Synthesis Example 7)
In a reaction vessel equipped with a stirrer, a thermometer and a reflux condenser, 8.40 parts of polypropylene glycol (average molecular weight 700), 16.82 parts of 9,9-bis (4-hydroxyphenyl) fluorene, 2,6-di- 0.10 parts of tert-butyl-4-methylphenol, 0.10 parts of dibutyltin dilaurate and 63.82 parts of propylene glycol monomethyl ether acetate were added, and 14.67 parts of isophorone diisocyanate was added dropwise with stirring in a nitrogen stream. After completion, the reaction was carried out at 120 ° C. for 4 hours under a nitrogen stream to obtain polyurethane 7 having a number average molecular weight of 4.4 × 10 ³ .

(Synthesis Example 8)
In a reaction vessel equipped with a stirrer, a thermometer and a reflux condenser, 10.32 parts of polyhexamethylene carbonate diol (average molecular weight 860), 16.82 parts of 9,9-bis (4-hydroxyphenyl) fluorene, 2,6 -0.10 parts of di-tert-butyl-4-methylphenol, 0.10 parts of dibutyltin dilaurate, and 66.90 parts of propylene glycol monomethyl ether acetate were added dropwise with 14.67 parts of isophorone diisocyanate under stirring in a nitrogen stream. After completion of the dropping, the mixture was reacted at 120 ° C. for 4 hours under a nitrogen stream, cooled to 50 ° C., and a solution prepared by mixing 2.02 parts of isophoronediamine with 31.98 parts of isopropyl alcohol was dropped, and the mixture was stirred at 50 ° C. for 1 hour. Reaction was performed to obtain polyurethaneurea 8 having a number average molecular weight of 1.6 × 10 ⁴ .

(Synthesis Example 9)
In a reaction vessel equipped with a stirrer, a thermometer and a reflux condenser, 10.32 parts of polyhexamethylene carbonate diol (average molecular weight 860), 16.82 parts of 9,9-bis (4-hydroxyphenyl) fluorene, 2,6 -0.10 parts of di-tert-butyl-4-methylphenol, 0.10 parts of dibutyltin dilaurate, and 66.90 parts of propylene glycol monomethyl ether acetate were added dropwise with 14.67 parts of isophorone diisocyanate under stirring in a nitrogen stream. After completion of dropping, the mixture was reacted at 120 ° C. for 4 hours under a nitrogen stream, cooled to 50 ° C., and a solution prepared by mixing 1.91 parts of isophoronediamine with 30.64 parts of isopropyl alcohol was added dropwise, and the mixture was stirred at 50 ° C. for 1 hour. Further, 2.68 parts of 2-hydroxyethyl acrylate was added and reacted at 50 ° C. for 1 hour. So, the number-average molecular weight: to obtain a 1.6 × 10 ⁴ urethane urea acrylates 9.

(Synthesis Example 10)
In a reaction vessel equipped with a stirrer, a thermometer and a reflux condenser, 10.32 parts of polyhexamethylene carbonate diol (average molecular weight 860), 18.17 parts of 9,9-bis (4-hydroxy-3-methylphenyl) fluorene , 2,6-di-tert-butyl-4-methylphenol 0.10 parts, dibutyltin dilaurate 0.10 parts, propylene glycol monomethyl ether acetate 66.90 parts, and under a nitrogen stream stirring, isophorone diisocyanate 14.2. 67 parts were added dropwise, and after completion of the addition, the mixture was reacted at 120 ° C. for 4 hours under a nitrogen stream to obtain polyurethane 10 having a number average molecular weight: 3.5 × 10 ³ .

(Synthesis Example 11)
In a reaction vessel equipped with a stirrer, a thermometer and a reflux condenser, 10.32 parts of polyhexamethylene carbonate diol (average molecular weight 860), 9,9-bis [4- (2-hydroxyethoxy) phenyl] fluorene 21.05 Parts, 2,6-di-tert-butyl-4-methylphenol 0.10 parts, dibutyltin dilaurate 0.10 parts, propylene glycol monomethyl ether acetate 100.49 parts, and under a nitrogen stream stirring, isophorone diisocyanate 14 .67 parts was added dropwise, and after completion of the dropwise addition, the mixture was reacted at 120 ° C. for 4 hours under a nitrogen stream to obtain polyurethane 11 having a number average molecular weight of 9.3 × 10 ³ .

(Synthesis Example 12)
In a reaction vessel equipped with a stirrer, a thermometer and a reflux condenser, 10.32 parts of polyhexamethylene carbonate diol (average molecular weight 860), 16.82 parts of 9,9-bis (4-hydroxyphenyl) fluorene, 2,6 -0.10 parts of di-tert-butyl-4-methylphenol, 0.10 parts of dibutyltin dilaurate, 66.90 parts of propylene glycol monomethyl ether acetate, and 1,3-bis (isocyanato) under stirring in a nitrogen stream 12.82 parts of methyl) cyclohexane was added dropwise, and after completion of the addition, the mixture was reacted at 120 ° C. for 4 hours under a nitrogen stream to obtain polyurethane 12 having a number average molecular weight of 1.4 × 10 ⁴ .

(Synthesis Example 13)
In a reaction vessel equipped with a stirrer, a thermometer and a reflux condenser, 10.32 parts of polyhexamethylene carbonate diol (average molecular weight 860), 16.82 parts of 9,9-bis (4-hydroxyphenyl) fluorene, 2,6 -0.10 parts of di-tert-butyl-4-methylphenol, 0.10 parts of dibutyltin dilaurate, 96.73 parts of propylene glycol monomethyl ether acetate, and dicyclohexylmethane 4,4'-di under stirring in a nitrogen stream 17.32 parts of isocyanate was added dropwise, and after completion of the addition, the reaction was carried out at 120 ° C. for 4 hours under a nitrogen stream to obtain polyurethane 13 having a number average molecular weight of 1.2 × 10 ⁴ .

Example 1
The polyurethane 1 obtained in Synthesis Example 1 was coated on a polyethylene terephthalate release film with a 300 μm gap applicator, dried at 100 ° C. for 30 minutes, and a temperature-controlled autograph stretching machine (Toyo Seiki Seisakusho Co., Ltd.) Manufactured by Strograph T) and stretched 3.0 times to obtain an optical film. The obtained optical film was measured for wavelength dispersion characteristics using an automatic birefringence meter (KOBRA-WR, manufactured by Oji Scientific Instruments) in the wavelength range of 450 nm to 750 nm. The optical film had the optical properties shown in Table 2.

(Examples 2 to 11)
An optical film was obtained in the same manner as in Example 1 except that the polyurethane 1 in Example 1 was changed to that shown in Table 1. The obtained optical films had optical properties shown in Table 2, respectively.

Example 12
20.0 g of urethane acrylate 4 prepared in Synthesis Example 4, 0.1 g of photopolymerization initiator (2) (Irgacure 184, manufactured by Ciba Specialty Chemicals Co., Ltd.), polyether-modified silicone oil SH8400 (produced by Torre Silicone Co., Ltd.) After 0.05 g was mixed and dissolved, it was coated on a polyethylene terephthalate release film with a 300 μm gap applicator, dried at 100 ° C. for 30 minutes, and irradiated with UV (high pressure mercury lamp: 200 mJ / cm ² per pass: 365 nm. Further, the film was stretched 3.0 times using a temperature-controlled autograph stretching machine (Strograph T, manufactured by Toyo Seiki Seisakusho Co., Ltd.) to obtain an optical film. When the wavelength dispersion characteristics were measured in the same manner as in Example 1, the optical characteristics shown in Table 2 were obtained.

(Example 13)
15.0 g of urethane acrylate 4 prepared in Synthesis Example 4, 0.1 g of photopolymerization initiator (2) (Irgacure 184, manufactured by Ciba Specialty Chemicals), 5 parts of methyl methacrylate [monomer (3)], polyether-modified After mixing and dissolving 0.05 g of silicon oil SH8400 (manufactured by Torre Silicone Co., Ltd.) and 2 parts of propylene glycol monomethyl ether acetate, an optical film was obtained in the same manner as in Example 12, and the wavelength dispersion characteristics were measured. The optical characteristics shown in FIG.

(Example 14)
15.0 g of urethane acrylate 4 prepared in Synthesis Example 4, 0.1 g of photopolymerization initiator (2) (Irgacure 184, manufactured by Ciba Specialty Chemicals), 4 parts of methyl methacrylate [monomer (3)], N-vinyl After mixing and dissolving 1 part of carbazole [monomer (3)], 0.05 g of polyether-modified silicone oil SH8400 (manufactured by Tore Silicone Co., Ltd.) and 2 parts of propylene glycol monomethyl ether acetate, an optical film was obtained in the same manner as in Example 12. When the chromatic dispersion characteristics were measured, the optical characteristics shown in Table 2 were obtained.

(Example 15)
An optical film was obtained in the same manner as in Example 12 except that the urethane acrylate 4 in Example 12 was changed to that shown in Table 1. The obtained optical film had the optical properties shown in Table 2.

  The optical films of Examples 1 to 15 all showed positive birefringence.

  According to the compound of the present invention, an optical film capable of uniform polarization conversion in a wide wavelength range can be provided.

Claims (15)

A structural unit derived from a compound containing an optionally substituted cyclohexylene group and a group represented by -NH-CO-;
A compound having a structural unit derived from the compound represented by formula (II).

(In Formula (II), X ₁ and X ₂ each independently represent an alkylene group having 2 to 6 carbon atoms. The hydrogen atom contained in the alkylene group is an alkyl group or hydroxyl group having 1 to 6 carbon atoms. The methylene group contained in the alkylene group may be substituted with a carbonyl group, and each R is independently a hydroxyl group, a halogen atom, an alkyl group having 1 to 6 carbon atoms, or a carbon number. 1 to 6 represents an alkoxy group, a glycidoxy group, a nitro group, or a cyano group, s and t each independently represent an integer of 0 to 6, and n each independently represents an integer of 0 to 4. ) Furthermore, the compound of Claim 1 which has a structural unit derived from the compound represented by Formula (A-1).

(In Formula (A-1), R ₃₂ represents a C 1-6 alkylene group which may contain a hetero atom or a single bond, and the methylene group contained in the alkylene group may be substituted with a hetero atom. good .R ₃₃ represents a hydrocarbon group having 1 to 12 carbon atoms, a methylene group contained in the hydrocarbon group may .n ₃₁ be replaced by a heteroatom or a carbonyl group, 1-15 Represents an integer.)   Compounds containing an optionally substituted cyclohexylene group and a group represented by -NH-CO- are isophorone diisocyanate, 1,4-cyclohexylene diisocyanate, 1,3-bis (isocyanatomethyl) cyclohexane and dicyclohexylmethane. The compound according to claim 1 or 2, which is one or more compounds selected from the group consisting of 4,4'-diisocyanate.   The compound represented by the formula (II) is 9,9-bis (4-hydroxyphenyl) fluorene, 9,9-bis (4-hydroxy-3-methylphenyl) fluorene and 9,9-bis [4- ( The compound according to any one of claims 1 to 3, which is one or more compounds selected from the group consisting of (2-hydroxyethoxy) phenyl] fluorene.   The compound represented by the formula (A-1) is ethylene glycol, propylene glycol, 1,4-butanediol, tripropylene glycol, 1,6-hexanediol, polyethylene glycol, polypropylene glycol, 1,4-cyclohexanedimethanol. The compound according to any one of claims 2 to 4, which is one or more compounds selected from the group consisting of 1,4-cyclohexanediol, 1,3-cyclohexanediol, hexamethylene carbonate diol and polyhexamethylene carbonate diol.   The composition containing the compound and photoinitiator (2) in any one of Claims 1-5. Furthermore, at least one monomer (3) selected from the group consisting of monomers represented by formula (XI) to formula (XIII), and a polymer (3) obtained by polymerizing monomer (3)
The composition according to claim 6, comprising at least one selected from the group consisting of:

(In the formula (XI), R ₁₁ represents a hydrogen atom or a methyl group, and R ₁₂ represents a 5- to 20-membered aromatic hydrocarbon group or aromatic heterocyclic group. The aromatic hydrocarbon group and The hydrogen atom contained in the aromatic heterocyclic group includes a hydroxyl group, an alkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, an aryl group having 6 to 12 carbon atoms, and an aralkyl group having 7 to 12 carbon atoms. , A glycidoxy group, an acyl group having 2 to 4 carbon atoms or a halogen atom, and the methylene group contained in the aromatic hydrocarbon group and the aromatic heterocyclic group is substituted with a carbonyl group. May be.)

(In Formula (XII), R ₁₃ represents a hydrogen atom or a methyl group, R ₁₄ and R ₁₅ each independently represent a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, or R ₁₄ and R ₁₅ represent , R ₁₄ and R ₁₅ represent an alkylene group having 4 to 6 carbon atoms formed by linking, and the alkyl group and the hydrogen atom contained in the alkylene group may be substituted with a hydroxyl group. And the methylene group contained in the alkylene group may be substituted with an oxygen atom, a sulfur atom or a nitrogen atom, and R ₁₆ represents a single bond or an oxyalkylene group having 2 to 6 carbon atoms.)

(In formula (XIII), R ₁₇ represents a hydrogen atom or a methyl group, and R ₁₈ represents a hydrogen atom, a methyl group or a 5- to 20-membered cyclic hydrocarbon group. Hydrogen contained in the cyclic hydrocarbon group The atoms include a hydroxyl group, an alkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, an aryl group having 6 to 12 carbon atoms, an aralkyl group having 7 to 12 carbon atoms, a glycidoxy group, and 2 to 4 carbon atoms. The methylene group contained in the cyclic hydrocarbon group may be substituted with a carbonyl group, an oxygen atom, a sulfur atom, or a nitrogen atom, and may be substituted with an acyl group or a halogen atom. The hydrogen atom contained in the group, the aryl group and the aralkyl group may be substituted with a hydroxyl group or a halogen atom.)   The optical film formed by extending | stretching the film | membrane containing the compound in any one of Claims 1-5.   An optical film obtained by photopolymerizing and stretching the composition according to claim 6. The optical film according to claim 8 or 9, wherein a retardation value Re (ν) at a wavelength νnm of transmitted light passing through the film satisfies the following formula.
Re (450) <Re (550) <Re (650)   The phase difference plate which consists of an optical film in any one of Claims 8-10.   The manufacturing method of the optical film which extends | stretches the film | membrane containing the compound in any one of Claims 1-5.   The manufacturing method of the optical film which photopolymerizes and stretches the composition of Claim 6 or 7.   The manufacturing method of the optical film which extends | stretches the film | membrane obtained by forming into a film by casting the solution containing the compound in any one of Claims 1-5 on a smooth surface, and distilling a solvent off.   A method for producing an optical film, wherein a film obtained by forming a film by casting a solution containing the composition according to claim 6 or 7 on a smooth surface and distilling off the solvent is photopolymerized and stretched.