JP5054456B2 - Polymerizable composition containing polymerizable liquid crystal compound and radical photopolymerization initiator - Google Patents

Description

  The present invention relates to a polymerizable composition containing a polymerizable liquid crystal compound and a radical photopolymerization initiator, and more specifically, a polymerizable liquid crystal compound having a (meth) acryloyl group optionally substituted with a halogen atom as a polymerizable group; And a radical photopolymerization initiator having a carbazole skeleton and an acyloxime ester group. The polymerizable composition of the present invention has excellent effects on solvent solubility and orientation control, and a polymer film obtained by polymerizing the polymerizable composition has excellent orientation retention, a retardation film, a polarizing plate, and a light polarizing plate. It is useful as an optical material such as an optical film for prisms and displays.

  In recent years, liquid crystal materials are used for display media that utilize reversible motion of liquid crystal molecules such as display elements represented by TN type and STN type, as well as their orientation, refractive index, dielectric constant, and magnetic susceptibility. Application to optical anisotropic bodies such as retardation plates, polarizing plates, light deflecting prisms, and various optical filters has been studied using the anisotropy of physical properties such as the above.

  Thus, in an optical anisotropic body including a liquid crystal substance, in order to obtain stable and uniform optical characteristics, a uniform alignment state of liquid crystal molecules in a liquid crystal state is fixed semi-permanently and mechanically. It is essential to provide a polymer having a high glass transition temperature (hereinafter referred to as “Tg”) which is thermally stable and excellent in orientation.

  As a means for semi-permanently fixing the uniform alignment state of the liquid crystal molecules in the liquid crystal state, for example, a liquid crystal compound having a polymerizable functional group or a polymerizable liquid crystal composition containing such a compound is uniform in the liquid crystal state. There is already known a method of semi-permanently fixing a uniform alignment state by photopolymerization by irradiating energy rays such as ultraviolet rays after maintaining the liquid crystal state.

  In addition, the polymer is obtained by applying a polymerizable composition to a substrate and polymerizing it, but in order to obtain a polymer having a uniform film thickness, a method in which a polymerizable composition is dissolved in a solvent is applied. Is preferably used. If the polymerizable composition is insoluble in the solvent, the alignment control of the liquid crystal compound is greatly hindered, and therefore the solvent solubility of the polymerizable composition is required to be good.

  Usually, the polymerizable liquid crystal material is prepared by adding a polymerization initiator that is initiated by energy rays such as ultraviolet rays, and has a composition using an acylphosphine oxide compound as an initiator in Patent Document 1 below. Things are illustrated. Moreover, the following patent document 2 and patent document 3 are disclosing the composition characterized by using various oxime ester compounds as an initiator. However, when the radical photopolymerization initiators described in these documents are used, there is a problem that crystals may precipitate during the polymerization, or yellow may be colored, and uniform control of orientation may be difficult.

JP 2002-69450 A JP 2003-315761 A JP 2007-2065 A

  An object of the present invention is to provide a polymerizable composition having good solvent solubility and excellent alignment control ability, optical characteristics, and photocurability.

（式中、Ｒ ¹ 及びＲ ² は、それぞれ独立に、水素原子、メチル基又はハロゲン原子を表し、環Ａ ¹ 、環Ａ ² 及び環Ａ ³ は、それぞれ独立に、ベンゼン環、シクロヘキサン環、シクロヘキセン環、ナフタレン環、デカヒドロナフタレン環、テトラヒドロナフタレン環又はフェナントレン環を表し、これらの環中の−ＣＨ＝は、−Ｎ＝で、−ＣＨ ₂ −は、−Ｓ−又は−Ｏ−で置換されていてもよく、Ｚ ¹ 、Ｚ ² 及びＺ ³ は、それぞれ独立に、ハロゲン原子若しくはシアノ基で置換されてもよい炭素原子数１〜８のアルキル基、ハロゲン原子又はシアノ基を表し、該アルキル基のメチレン基は、−Ｏ−又は−ＣＯ−で置換されていてもよく、Ｌ ¹ 、Ｌ ² 、Ｌ ³ 及びＬ ⁴ は、それぞれ独立に、単結合、−ＣＯＯ−、−ＯＣＯ−、−（ＣＥ ₂ ） _p −、−ＣＥ＝ＣＥ−、−（ＣＥ ₂ ） _p Ｏ−、−Ｏ（ＣＥ ₂ ） _p −、−ＣＥ＝ＣＥＣＥ ₂ Ｏ−、−ＯＣＥ ₂ ＣＥ＝ＣＥ−、−Ｃ≡Ｃ−、−（ＣＥ ₂ ） _p ＣＯＯ−、−ＯＣＯ（ＣＥ ₂ ） _p −、−（ＣＥ ₂ ） _p ＯＣＯ−Ｏ−、−ＯＣＯ−Ｏ（ＣＥ ₂ ） _p −、−（ＣＥ ₂ ） _q Ｏ（ＣＥ ₂ ） _r Ｏ−又は−Ｏ（ＣＥ ₂ ） _q Ｏ（ＣＥ ₂ ） _r −を表し、Ｌ ¹ 及びＬ ⁴ におけるＥは、水素原子、メチル基又はエチル基を表し、Ｌ ² 及びＬ ³ におけるＥは、水素原子を表し、複数あるＥは同一でも異なっていてもよく、ａ、ｂ及びｃは、それぞれ環Ａ ¹ 、環Ａ ² 及び環Ａ ³ における置換基の数であって、それぞれの置換される単環又は縮合環に含まれる６員環の数をｔとすると、ａ、ｂ及びｃは、それぞれ独立に、２ｔ＋２以下の整数で、かつｂは１以上の整数を表し、ｐは、それぞれ独立に、１〜８の整数を表し、ｑ及びｒは、それぞれ独立に、１〜３の整数を表す。）

（式中、環Ｂ ¹ は芳香環又は複素環を表し、Ｘ ¹ は下記一般式（IV）で表される置換基を表し、Ｘ ² はハロゲン原子又はアルキル基を表し、Ｇは単結合又はカルボニル基を表し、Ｒ ¹¹ 、Ｒ ¹² 及びＲ ¹³ は、それぞれ独立に、Ｒ、ＯＲ、ＣＯＲ、ＳＲ、ＣＯＮＲＲ’又はＣＮを表し、Ｒ及びＲ’は、それぞれ独立に、アルキル基、アリール基、アリールアルキル基又は複素環基を表し、これらは、ハロゲン原子及び／又は複素環基で置換されていてもよく、これらのうちアルキル基及びアリールアルキル基のアルキレン部分は、不飽和結合、エーテル結合、チオエーテル結合又はエステル結合により中断されていてもよく、また、Ｒ及びＲ’は、一緒になって環を形成していてもよく、ｆは０又は１であり、ｇは０〜５の整数であり、ｇが２以上の時、複数のＸ ² は、同一の基でも、異なる基でもよく、該化合物はＸ ² を介して二量化していてもよい。）

（式中、環Ｂ ² はシクロアルカン環、芳香環又は複素環を表し、Ｘ ³ はハロゲン原子又はアルキル基を表し、Ｙ ¹ は酸素原子、硫黄原子又はセレン原子を表し、ｈは０〜４の整数であり、ｍは０〜５の整数であり、ｎは０又は１であり、ｈが２以上の時、複数のＸ ³ は、同一の基でも異なる基でもよい。） The present invention relates to a polymerization comprising a polymerizable liquid crystal compound having a (meth) acryloyl group optionally substituted with a halogen atom as a polymerizable group, and a compound having a carbazole skeleton and an acyloxime ester group as a radical photopolymerization initiator. A sex composition,
The polymerizable liquid crystal compound is a bifunctional (meth) acrylate compound represented by the following general formula (I), and the radical photopolymerization initiator is a compound represented by the following general formula (III). A polymerizable composition is provided.

(Wherein R ¹ and R ² each independently represent a hydrogen atom, a methyl group or a halogen atom, and ring A ¹ , ring A ² and ring A ³ are each independently a benzene ring, cyclohexane ring or cyclohexene. ring, a naphthalene ring, decahydronaphthalene ring represents a tetrahydronaphthalene ring or phenanthrene ring, -CH = may in these rings, is -N =, -CH ₂ - is substituted with -S- or -O- Z ¹ , Z ² and Z ³ each independently represents an alkyl group having 1 to 8 carbon atoms, a halogen atom or a cyano group which may be substituted with a halogen atom or a cyano group, The methylene group of the group may be substituted with —O— or —CO—, and L ¹ , L ² , L ³ and L ⁴ are each independently a single bond, —COO—, —OCO—, — (CE ₂ ) _p −, −CE = _{CE -, - (CE 2)} p O -, - O (CE 2) p -, - CE = CECE 2 O -, - OCE 2 CE = CE -, - C≡C -, - (CE 2) p COO _{-, - OCO (CE 2)} p -, - (CE 2) p OCO-O -, - OCO-O (CE 2) p -, - (CE 2) q O (CE 2) r O- or -O (CE ₂ ) _q O (CE ₂ ) _r- represents, E in L ¹ and L ⁴ represents a hydrogen atom, a methyl group or an ethyl group, E in L ² and L ³ represents a hydrogen atom, A certain E may be the same or different, and a, b and c are the numbers of substituents in the ring A ¹ , the ring A ² and the ring A ³ , respectively. When the number of 6-membered rings included is t, a, b and c are each independently an integer of 2t + 2 or less, b represents an integer of 1 or more, and p is To be independently represent an integer from 1 to 8, q and r each independently represents an integer of 1 to 3.)

(In the formula, ring B ¹ represents an aromatic ring or a heterocyclic ring, X ¹ represents a substituent represented by the following general formula (IV), X ² represents a halogen atom or an alkyl group, and G represents a single bond or R ¹¹ , R ¹² and R ¹³ each independently represent R, OR, COR, SR, CONRR ′ or CN, and R and R ′ each independently represent an alkyl group, an aryl group, Represents an arylalkyl group or a heterocyclic group, which may be substituted with a halogen atom and / or a heterocyclic group, and among these, the alkylene part of the alkyl group and the arylalkyl group is an unsaturated bond, an ether bond, R may be interrupted by a thioether bond or an ester bond, R and R ′ may be combined to form a ring, f is 0 or 1, and g is an integer of 0 to 5. Yes, when g is 2 or more, X ² numbers, even in the same group, may be a different group, the compound may be dimerized via a X ^2.)

(In the formula, ring B ² represents a cycloalkane ring, an aromatic ring or a heterocyclic ring, X ³ represents a halogen atom or an alkyl group, Y ¹ represents an oxygen atom, a sulfur atom or a selenium atom, and h represents 0-4. And m is an integer of 0 to 5, n is 0 or 1, and when h is 2 or more, the plurality of X ³ may be the same group or different groups.)

  Moreover, this invention is a polymerizable composition whose bifunctional (meth) acrylate compound represented by the said general formula (I) is a compound represented by the following general formula (II) among the said polymeric compositions. Is to provide.

（式中、Ｒ¹、Ｒ²、Ｌ¹、Ｌ⁴、Ａ¹、Ａ³、Ｚ¹、Ｚ³、ａ及びｃは、上記一般式（Ｉ）と同じであり、Ｒ³及びＲ⁴は、それぞれ独立に、水素原子、ハロゲン原子、シアノ基、ハロゲン原子又はシアノ基で置換されてもよい炭素原子数１〜８のアルキル基を表し、該アルキル基のメチレン基は、−Ｏ−又は−ＣＯ−で置換されていてもよく、Ｒ³及びＲ⁴の少なくともどちらか一方は、水素原子以外を表す。）

(In the formula, R ¹ , R ² , L ¹ , L ⁴ , A ¹ , A ³ , Z ¹ , Z ³ , a and c are the same as those in the general formula (I), and R ³ and R ⁴ are Each independently represents a hydrogen atom, a halogen atom, a cyano group, a halogen atom or an alkyl group having 1 to 8 carbon atoms which may be substituted with a cyano group, wherein the methylene group of the alkyl group is -O- or- CO— may be substituted, and at least one of R ³ and R ⁴ represents other than a hydrogen atom.)

  Moreover, this invention provides the polymeric composition whose all E is a hydrogen atom in the said general formula (I) or (II) among the said polymeric compositions.

The present invention, among the above polymerizable composition, the general formula (II), ring A ¹ and ring A ³ is intended to provide a polymerizable composition is a benzene ring or a naphthalene ring.

The present invention, among the above polymerizable composition, the above general formula (II), at least one of ring A ¹ and ring A ³ is intended to provide a polymerizable composition is naphthalene ring.

  Moreover, this invention provides the polymeric composition whose compound represented with the said general formula (III) is a compound represented with the following general formula (V) among the said polymeric compositions. .

（式中、Ｘ²、Ｒ¹¹、Ｒ¹²、Ｒ¹³及びｇは、上記一般式（III）と同じである。）

(In the formula, X ² , R ¹¹ , R ¹² , R ¹³ and g are the same as those in the general formula (III).)

  Moreover, this invention provides the polymeric composition whose compound represented by the said general formula (III) is a compound represented by the following general formula (VI) among the said polymeric compositions. .

（式中、Ｘ²、Ｒ¹¹、Ｒ¹²、Ｒ¹³及びｇは、上記一般式（III）と同じであり、Ｘ³、Ｙ¹、ｈ、ｍ及びｎは、上記一般式（IV）と同じであり、Ｙ²及びＹ³はそれぞれ独立に酸素原子、硫黄原子又はセレン原子を表す。）

(In the formula, X ² , R ¹¹ , R ¹² , R ¹³ and g are the same as those in the general formula (III), and X ³ , Y ¹ , h, m and n are the same as those in the general formula (IV). And Y ² and Y ³ each independently represent an oxygen atom, a sulfur atom or a selenium atom.)

  Moreover, this invention provides the polymeric composition which contains an optically active compound and expresses a cholesteric phase among the said polymeric compositions.

  Moreover, this invention provides the polymeric composition which shows a liquid crystal phase at 30 degrees C or less among the said polymeric compositions.

  The present invention also provides a polymer film prepared by photopolymerization in a state where the polymerizable composition exhibits a liquid crystal phase.

  Moreover, this invention provides the optical film for a display formed using the said polymeric film.

  The polymerizable composition of the present invention is excellent in solvent solubility and compatibility with other liquid crystal compounds. The polymer of the present invention produced by photopolymerization with orientation control in a state where the polymerizable composition exhibits a liquid crystal phase is excellent in orientation controllability, optical properties, photocurability, etc., and useful as an optical material. It is.

Hereinafter, the polymerizable composition of the present invention will be described in detail based on preferred embodiments thereof.
The polymerizable composition of the present invention has a polymerizable liquid crystal compound having a (meth) acryloyl group optionally substituted with a halogen atom as a polymerizable group, and a carbazole skeleton and an acyloxime ester group as a radical photopolymerization initiator. Compound.

  The polymerizable liquid crystal compound used in the polymerizable composition of the present invention is a compound having a (meth) acryloyl group as a polymerizable group and exhibiting a liquid crystal phase at a specific temperature, or a compound that can be in a liquid crystal state after polymerization. Among these compounds, the compound represented by the general formula (I) is particularly useful because it has good orientation.

In the general formula (I) and the general formula (II), L ¹ , L ² , L ³ and L ⁴ are each independently a single bond, —COO—, —OCO—, — (CE ₂ ) _p —. , -CE = CE -, - ( CE 2) p O -, - O (CE 2) p -, - CE = CECE 2 O -, - OCE 2 CE = CE -, - C≡C -, - (CE _{2) p COO -, - OCO} (CE 2) p -, - (CE 2) p OCO-O -, - OCO-O (CE 2) p -, - (CE 2) q O (CE 2) r O -Or -O (CE ₂ ) _q O (CE ₂ ) _r- , E in L ¹ and L ⁴ represents a hydrogen atom, a methyl group or an ethyl group, and E in L ² and L ³ represents a hydrogen atom. , a plurality of E may be the same or different, a, b and c, respectively ring a ^1, a number of substituents in the ring a ² and ring a ^3, monocyclic or condensed are each substituted Assuming that the number of 6-membered rings contained in the ring is t, a, b and c are each independently an integer of 2t + 2 or less, b is an integer of 1 or more, and p is independently 1 to 8 Represents an integer, q and r each independently represent an integer of 1 to 3; In particular, L ¹ is a single bond, — (CE ₂ ) _p —, —CE═CE—, — (CE ₂ ) _p O—, —CE═CECE ₂ O—, —C≡C—, — (CE ₂ ). _p COO-,-(CE ₂ ) _p OCO-O-,-(CE ₂ ) _q O (CE ₂ ) _r O- are preferred, L ⁴ is a single bond,-(CE ₂ ) _p -,- CE = CE -, - O ( CE 2) p -, - OCE 2 CE = CE -, - C≡C -, - OCO (CE 2) p -, - OCO-O (CE 2) p -, - O _{(CE 2) q O (CE} 2) r - a is preferably.

In the general formula (I) and the general formula (II), examples of the halogen atom represented by R ¹ and R ² include fluorine, chlorine, bromine, and iodine. Z ¹ , Z ² , Z ³ , R Examples of the alkyl group having 1 to 8 carbon atoms which may be substituted with a halogen atom or a cyano group represented by ³ and R ⁴ include methyl, ethyl, propyl, isopropyl, butyl, s-butyl, t-butyl, isobutyl , Amyl, isoamyl, t-amyl, hexyl, cyclohexyl, heptyl, isoheptyl, t-heptyl, n-octyl, isooctyl, t-octyl, 2-ethylhexyl, chloromethyl, dichloromethyl, trichloromethyl, trifluoromethyl, pentafluoro Ethyl, cyanomethyl and the like, and the methylene group in the alkyl group may be substituted with —O— or —CO—. Well, examples include acetyl, acetonyl, butan-2-one-1-yl, butan-3-one-1-yl, cyclohexane-4-one-1-yl, trichloroacetyl, trifluoroacetyl, methoxy, Ethoxy, propoxy, isopropoxy, butoxy, s-butoxy, t-butoxy, isobutoxy, amyloxy, isoamyloxy, t-amyloxy, hexyloxy, cyclohexyloxy, heptyloxy, isoheptyloxy, t-heptyloxy, n-octyloxy , Isooctyloxy, t-octyloxy, 2-ethylhexyloxy, chloromethoxy, dichloromethoxy, trichloromethoxy, trifluoromethoxy, pentafluoroethoxy, 2-hydroxyethoxy, 2-methyl-2-hydroxyethoxy 1-methyl-2-hydroxyethoxy, 3-hydroxypropoxy, 2- (2-hydroxyethoxy) ethoxy, 2-methoxyethoxy, 2-butoxyethoxy, 2-methyl-2-methoxyethoxy, 1-methyl-2-methoxy Ethoxy, 3-methoxypropoxy, 2- (2-methoxyethoxy) ethoxy and the like can be mentioned. Examples of the halogen atom with which the alkyl group having 1 to 8 carbon atoms may be substituted include fluorine, chlorine, bromine and iodine. It is done.

Among the polymerizable liquid crystal compounds represented by the above general formula (I), the compound represented by the above general formula (II) is preferable because of excellent liquid crystallinity, solvent solubility and compatibility with other liquid crystal compounds, Furthermore, a compound in which E is all hydrogen atoms is preferable because the temperature range in which a liquid crystal phase is expressed is wide. Further, a compound in which the rings A ¹ and A ³ are benzene rings or naphthalene rings is preferable, and a compound in which at least one of the rings A ¹ and A ³ is a naphthalene ring is excellent in orientation and heat resistance.

  Specific examples of the polymerizable liquid crystal compound that can be used in the polymerizable composition of the present invention include the following compound Nos. 1-No. 30. However, the present invention is not limited by the following compounds.

  Moreover, the said manufacturing liquid crystal compound is not specifically limited about the manufacturing method, It can manufacture by applying a well-known reaction, for example, esterifies (meth) acrylic acid halide with respect to phenol, ( It can be produced by mesylating a carboxylic acid group of a compound having a (meth) acryloyl group with methanesulfonyl chloride and then esterifying with a compound having a phenol group.

  The radical photopolymerization initiator used in the polymerizable composition of the present invention is a compound having a carbazole skeleton and an acyloxime ester group, and those represented by the general formula (III) are useful because they have particularly high sensitivity. It is.

In the general formulas (III) to (VI), examples of the alkyl group represented by R and R ′ in R ^{11 to} R ¹³ include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, s-butyl, t-butyl, amyl, isoamyl, t-amyl, hexyl, heptyl, octyl, isooctyl, 2-ethylhexyl, t-octyl, nonyl, isononyl, decyl, isodecyl, vinyl, allyl, butenyl, ethynyl, propynyl, methoxyethyl, ethoxy Ethyl, propyloxyethyl, methoxyethoxyethyl, ethoxyethoxyethyl, propyloxyethoxyethyl, methoxypropyl, monofluoromethyl, difluoromethyl, trifluoromethyl, trifluoroethyl, perfluoroethyl, 2- (benzoxazole-2′- Il) Ethenyl etc. It is, among others preferably an alkyl group having 1 to 8 carbon atoms. Examples of the aryl group represented by R and R ′ include phenyl, tolyl, xylyl, ethylphenyl, chlorophenyl, naphthyl, anthryl, phenanthrenyl, etc. Among them, an aryl group having 6 to 12 carbon atoms is preferable. Examples of the arylalkyl group represented by R and R ′ include arylalkyl having 7 to 13 carbon atoms such as benzyl, chlorobenzyl, α-methylbenzyl, α, α-dimethylbenzyl, phenylethyl, phenylethenyl and the like. Preferred is a group. Preferred examples of the heterocyclic group represented by R and R ′ include 5- to 7-membered heterocyclic rings such as pyridyl, pyrimidyl, pyrrolyl, furyl, and thiophenyl. Moreover, as a ring which R and R 'can form together, 5-7 membered rings, such as a piperidine ring and a morpholine ring, are mentioned preferably, for example.

  In the general formulas (III) to (VI), examples of the halogen atom that may substitute R and R ′ include fluorine as is apparent from the above examples of alkyl groups, as well as chlorine, bromine, iodine. Also mentioned. Examples of the heterocyclic group which may substitute R and R ′ include pyridyl, pyrimidyl, pyrrolyl, furyl, benzoxazol-2-yl, tetrahydropyranyl, pyrrolidyl, imidazolidyl, pyrazolidyl, thiazolidyl, isothiazolidyl, oxazolidyl , Isoxazolidyl, piperidyl, piperazyl, morpholinyl and the like 5- to 7-membered heterocyclic groups.

In the general formulas (III) to (VI), examples of the halogen atom represented by X ² and X ³ include fluorine, chlorine, bromine, and iodine. Further, the alkyl group represented by X ² and X ³ may be substituted with a halogen atom and / or a heterocyclic group as in R and R ′, and the alkylene part of the alkyl group is an unsaturated bond, It may be interrupted by an ether bond, a thioether bond or an ester bond. Examples of the alkyl group represented by X ² and X ³ include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, s-butyl, t-butyl, amyl, isoamyl, t-amyl, hexyl, heptyl, octyl, Isooctyl, 2-ethylhexyl, t-octyl, nonyl, isononyl, decyl, isodecyl, vinyl, allyl, butenyl, ethynyl, propynyl, methoxyethyl, ethoxyethyl, propyloxyethyl, methoxyethoxyethyl, ethoxyethoxyethyl, propyloxyethoxyethyl , Methoxypropyl, monofluoromethyl, difluoromethyl, trifluoromethyl, trifluoroethyl, perfluoroethyl, 2- (benzoxazol-2′-yl) ethenyl, etc., among which alkyl having 1 to 8 carbon atoms It is preferred.

In the general formula (IV), examples of the cycloalkane ring represented by the ring B ² include a cyclopropane ring, a cyclobutane ring, a cyclopentane ring, a cyclohexane ring, and the like, and an aromatic represented by the rings B ¹ and B ² Examples of the ring include a benzene ring, a naphthalene ring, an anthracene ring, and a phenanthrene ring. Examples of the heterocyclic ring represented by the rings B ¹ and B ² include a 1,3-dioxolane ring, a tetrahydrofuran ring, and a tetrahydrothiophene ring. , Oxirane ring, aziridine ring, furan ring, thiophene ring, pyridine ring, pyran ring, thiazole ring, imidazole ring, pyrazole ring, oxazole ring, pyrazine ring, pyrimidine ring, quinoline ring, carbazole ring, etc. The ring may be substituted with a halogen atom or an alkyl group, and a halogen atom or an alkyl group Substituted heterocycle, for example, 2,2-dimethyl-1,3-dioxolane ring, 2-chloro-2-methyl-1,3-dioxolane ring and the like.

Among these, the compounds represented by the general formulas (V) and (VI) are preferable because the raw materials are easily available and advantageous in terms of production. Further, among the compounds represented by the general formula (VI), the heterocyclic ring represented by B ² is a 1,3-dioxolane ring, tetrahydrofuran ring or furan ring optionally substituted with a halogen atom or an alkyl group. Among them, a 2,2-dimethyl-1,3-dioxolane ring or an unsubstituted tetrahydrofuran ring or furan ring is particularly preferable in terms of solubility and cost.

  Preferable specific examples of the above radical photopolymerization initiator include the following compound Nos. 31-No. 46. However, the present invention is not limited by the following compounds.

  The radical photopolymerization initiator is not particularly limited in its production method, and can be produced by applying a known reaction. For example, a carbazole compound is acylated with acid chloride and oximed with hydroxylamine hydrochloride. Then, it can manufacture by making an acid anhydride or an acid chloride react.

  In the polymerizable composition of the present invention, the blending ratio of the polymerizable liquid crystal compound and the radical photopolymerization initiator is not particularly limited as long as the effect of the present invention is not impaired. When the amount is 100 parts by mass, the radical photopolymerizable initiator is preferably 0.1 to 10 parts by mass, particularly 0.5 to 8 parts by mass. If the ratio of the radical photopolymerization initiator is less than 0.1 parts by mass, the polymerization reaction may not proceed. If the ratio is greater than 10 parts by mass, the radical photopolymerization initiator may precipitate from the polymerizable composition, The orientation of the product may decrease, and the optical properties of the cured film may deteriorate.

  In the polymerizable composition of the present invention, in addition to the polymerizable liquid crystal compound, another liquid crystal compound is added within a range where the effects of the present invention are not impaired (total amount of the polymerizable liquid crystal compound and the radical photopolymerization initiator is 100 mass). Preferably 1 to 100 parts by mass, more preferably 3 to 50 parts by mass). As the other liquid crystal compounds, generally used liquid crystal compounds can be used, and specific examples of the liquid crystal compounds are not particularly limited, but examples thereof include the liquid crystal compounds shown in the following [Chemical Formula 54]. It is done.

（〔化５４〕中、Ｗ₁は、水素原子、分岐を有してもよい炭素原子数１〜８のアルキル基、分岐を有してもよい炭素原子数１〜８のアルコキシ基、分岐を有してもよい炭素原子数２〜８のアルケニル基、分岐を有してもよい炭素原子数２〜８のアルケニルオキシ基、分岐を有してもよい炭素原子数２〜８のアルコキシアルキル基、分岐を有してもよい炭素原子数２〜８のアルカノイルオキシ基又は分岐を有してもよい炭素原子数２〜８のアルコキシカルボニル基を表し、Ｗ₃は、シアノ基、ハロゲン原子、分岐を有してもよい炭素原子数１〜８のアルキル基、分岐を有してもよい炭素原子数２〜８のアルカノイルオキシ基又は分岐を有してもよい炭素原子数２〜８のアルコキシカルボニル基を表し、Ｗ₂及びＷ₄は、各々独立に、水素原子、ハロゲン原子又はニトリル基を表す。）

(In [Chemical Formula 54], W ₁ represents a hydrogen atom, an alkyl group having 1 to 8 carbon atoms which may have a branch, an alkoxy group having 1 to 8 carbon atoms which may have a branch, or a branched group. An optionally substituted alkenyl group having 2 to 8 carbon atoms, an optionally branched alkenyloxy group having 2 to 8 carbon atoms, and an optionally branched alkoxyalkyl group having 2 to 8 carbon atoms Represents an alkanoyloxy group having 2 to 8 carbon atoms which may have a branch or an alkoxycarbonyl group having 2 to 8 carbon atoms which may have a branch, and W ₃ represents a cyano group, a halogen atom or a branched group. An alkyl group having 1 to 8 carbon atoms, which may have a branched chain, an alkanoyloxy group having 2 to 8 carbon atoms which may have a branched chain, or an alkoxycarbonyl having 2 to 8 carbon atoms which may have a branched chain It represents a group, W ₂ and W ₄ are each independently a hydrogen atom, c It represents a Gen atom or a nitrile group.)

  In addition to the radical photopolymerization initiator, a known radical polymerization initiator can be used in combination.

  Examples of the radical polymerization initiator include benzoyl peroxide, 2,2′-azobisisobutyronitrile, benzoin ethers, benzophenones, acetophenones, benzyl ketals, diaryl iodonium salts, triaryl sulfonium salts, diphenyl Iodonium tetrafluoroborate, diphenyliodonium hexafluorophosphonate, diphenyliodonium hexafluoroarsenate, diphenyliodonium tetra (pentafluorophenyl) borate, 4-methoxyphenylphenyliodonium tetrafluoroborate, 4-methoxyphenylphenyliodonium hexafluorophosphonate, 4- Methoxyphenylphenyliodonium hexafluoroarsenate, bis (4-tert-butylphenol) Nyl) iodonium diphenyliodonium tetrafluoroborate, bis (4-tert-butylphenyl) iodonium diphenyliodonium hexafluoroarsenate, bis (4-tert-butylphenyl) iodonium diphenyliodonium trifluoromethanesulfonate, triphenylsulfonium hexafluorophosphonate, tri Phenylsulfonium hexafluoroarsenate, triphenylsulfonium tetra (pentafluorophenyl) borate, 4-methoxyphenyldiphenylsulfonium tetrafluoroborate, 4-methoxyphenyldiphenylsulfonium hexafluorophosphonate, 4-methoxyphenyldiphenylsulfonium hexafluoroarsenate, 4 -Methoxyphenyl diphe Rusulfonium trifluoromethanesulfonate, 4-methoxyphenyldiphenylsulfonium triphenylsulfonium tetra (pentafluorophenyl) borate, 4-phenylthiophenyldiphenylsulfonium tetrafluoroborate, 4-phenylthiophenyldiphenylsulfonium hexafluorophosphonate, 4-phenylthio Phenyldiphenylsulfonium hexafluoroarsenate, p-methoxyphenyl-2,4-bis (trichloromethyl) -s-triazine, 2- (p-butoxystyryl) -s-triazine, 2- (p-butoxystyryl) -5 -Trichloromethyl-1,3,4-oxadiazole, 9-phenylacridine, 9,10-dimethylbenzphenazine, benzophenone / Michler's ketone Hexaarylbiimidazole / mercaptobenzimidazole, benzyl dimethyl ketal, thioxanthone / amine, triarylsulfonium hexafluorophosphate, bis (2,4,6-trimethylbenzoyl) - phenylphosphine oxide, and the like.

  In addition, the polymerizable composition of the present invention preferably exhibits a liquid crystal phase at least near room temperature, specifically 30 ° C. or less, and particularly preferably exhibits a liquid crystal phase at 25 ° C. or less, as an optical material. This is more preferable.

  In addition, in the polymerizable composition of the present invention, another monomer (a compound having an ethylenically unsaturated bond) used as necessary may be dissolved in a solvent together with the radical polymerization initiator to form a solution. it can.

Examples of the other monomer include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, s-butyl (meth) acrylate, and t-butyl (meth) acrylate. , Hexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, glycidyl (meth) acrylate, allyl (meth) acrylate, allyloxyl (meth) acrylate, cyclohexyl (meth) acrylate, benzyl ( (Meth) acrylate, 1-phenylethyl (meth) acrylate, 2-phenylethyl (meth) acrylate, furfuryl (meth) acrylate, diphenylmethyl (meth) acrylate, naphthyl (meth) acrylate, Ntachlorophenyl (meth) acrylate, 2-chloroethyl (meth) acrylate, methyl-α-chloro (meth) acrylate, phenyl-α-bromo (meth) acrylate, trifluoroethyl (meth) acrylate, tetrafluoropropyl (meth) Acrylate, polyethylene glycol di (meth) acrylate, 1,4-butanediol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate , (Meth) acrylic acid esters such as pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, diacetone Riruamido, styrene, vinyltoluene, divinylbenzene and the like.
In order to ensure the heat resistance and optical properties of the polymer film produced using the polymerizable composition of the present invention, the content of the other monomer is such that the polymerizable liquid crystal compound, the radical photopolymerization initiator, The total amount is preferably 50 parts by mass or less, more preferably 30 parts by mass or less.

  Moreover, the combination of the said radical polymerization initiator and a sensitizer can also be used preferably. Examples of the sensitizer include thioxanthone, phenothiazine, chlorothioxanthone, xanthone, anthracene, diphenylanthracene, and lupine. When the radical polymerization initiator and / or the sensitizer is added, the addition amount thereof is 10 parts by mass with respect to 100 parts by mass of the total amount of the polymerizable liquid crystal compound and the radical photopolymerization initiator, respectively. The content is preferably 5 parts by mass or less, more preferably 0.1 to 3 parts by mass.

  Examples of the solvent include benzene, toluene, xylene, mesitylene, n-butylbenzene, diethylbenzene, tetralin, methoxybenzene, 1,2-dimethoxybenzene, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexane. Pentanone, cyclohexanone, ethyl acetate, methyl lactate, ethyl lactate, ethylene glycol monomethyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, γ-butyrolactone, 2-pyrrolidone, N-methyl-2-pyrrolidone, dimethyl Formamide, chloroform, dichloromethane, carbon tetrachloride, dichloroethane, trichloro Styrene, tetrachlorethylene, chlorobenzene, and the like t- butyl alcohol, diacetone alcohol, glycerin, mono-acetylene, ethylene glycol, triethylene glycol, hexylene glycol, ethylene glycol monomethyl ether, ethyl cellosolve, butyl cellosolve. The solvent may be a single compound or a mixture. Among these solvents, those having a boiling point of 60 to 250 ° C are preferable, and those having a boiling point of 60 to 180 ° C are particularly preferable. If the temperature is lower than 60 ° C., the solvent is volatilized in the coating process and unevenness in the thickness of the film is likely to occur. In some cases, the orientation may be reduced.

  Further, by adding an optically active compound to the polymerizable composition of the present invention, a polymer having a helical structure of a liquid crystal skeleton can be obtained, and a cholesteric liquid crystal phase can be fixed. When the optically active compound is contained, the amount is preferably in the range of 0.1 to 100 parts by weight, and 1 to 50 parts by weight with respect to 100 parts by weight of the total amount of the polymerizable liquid crystal compound and the radical photopolymerization initiator. Part is more preferred. Examples of the optically active compound include the following Compound No. 47-No. 58.

  Further, the polymerizable composition of the present invention can further contain a surfactant having an excluded volume effect distributed on the air interface side. As the surfactant, those capable of easily applying the polymerizable composition to a support substrate or the like and controlling the alignment of the liquid crystal phase are preferable. Examples of such surfactants include quaternary ammonium salts, alkylamine oxides, polyamine derivatives, polyoxyethylene-polyoxypropylene condensates, polyethylene glycol and esters thereof, sodium lauryl sulfate, ammonium lauryl sulfate, amines of lauryl sulfate, alkyls. Examples thereof include substituted aromatic sulfonates, alkyl phosphates, perfluoroalkyl sulfonates, perfluoroalkyl carboxylates, perfluoroalkyl ethylene oxide adducts, and perfluoroalkyl trimethyl ammonium salts. The preferred amount of the surfactant used depends on the kind of the surfactant, the component ratio of the composition, etc., but is 0 with respect to 100 parts by mass of the total amount of the polymerizable liquid crystal compound and the radical photopolymerization initiator. The range is preferably 0.001 to 5 parts by mass, and more preferably 0.01 to 1 part by mass.

  In addition, the polymerizable composition of the present invention may further contain an additive as necessary in order to adjust the characteristics of the polymerizable composition. Examples of such additives include storage stabilizers, antioxidants, ultraviolet absorbers, infrared absorbers, fine particles such as inorganic substances and organic substances, and functional compounds such as polymers.

  The said storage stabilizer can provide the effect which improves the storage stability of polymeric composition. Examples of the stabilizer that can be used include hydroquinone, hydroquinone monoalkyl ethers, tert-butylcatechols, pyrogallols, thiophenols, nitro compounds, 2-naphthylamines, 2-hydroxynaphthalenes, and the like. When adding these, it is preferable that it is 1 mass part or less with respect to 100 mass parts of total amounts of the said polymeric liquid crystal compound and the said radical photoinitiator, and 0.5 mass part or less is especially preferable.

  The antioxidant is not particularly limited and a known compound can be used. Examples thereof include hydroquinone, 2,6-di-t-butyl-p-cresol, 2,6-di-t-butylphenol, Examples thereof include phenyl phosphite and trialkyl phosphite.

  The ultraviolet absorber is not particularly limited, and a known compound can be used. For example, a salicylic acid ester compound, a benzophenol compound, a benzotriazole compound, a cyanoacrylate compound, a nickel complex compound, or the like What gave absorption ability can be used.

  The fine particles can be used for adjusting the optical (refractive index) anisotropy (Δn) and increasing the strength of the polymer film. Examples of the material of the fine particles include inorganic substances, organic substances, metals, and the like. In order to prevent aggregation, the finely divided product preferably has a particle size of 0.001 to 0.1 μm, and more preferably 0.001 to 0.05 μm. Further, those having a sharp particle size distribution are preferred. The finely divided product can be preferably used within a range of 0.1 to 30 parts by mass with respect to 100 parts by mass of the total amount of the polymerizable liquid crystal compound and the radical photopolymerization initiator.

Examples of the inorganic material include ceramics, fluorine phlogopite, fluorine tetrasilicon mica, teniolite, fluorine vermiculite, fluorine hectorite, hectorite, saponite, stevensite, montmorillonite, beidellite, kaolinite, frypontite, ZnO, TiO ₂ , _{CeO 2, Al 2 O 3,} Fe 2 O 3, ZrO 2, MgF 2, SiO 2, SrCO 3, Ba (OH) 2, Ca (OH) 2, Ga (OH) 3, Al (OH) 3, Mg (OH) ₂ , Zr (OH) _{4 and the} like.
Further, fine particles such as calcium carbonate needle-like crystals have optical anisotropy, and the optical anisotropy of the polymer can be adjusted by such fine particles. Examples of the organic substance include carbon nanotubes, fullerenes, dendrimers, polyvinyl alcohol, polymethacrylates, and polyimides.

  The polymer can control the electrical properties and orientation of the polymerized film. As the polymer, a polymer compound soluble in the solvent can be preferably used. Examples of such a polymer compound include polyamide, polyurethane, polyurea, polyepoxide, polyester, polyester polyol, and the like.

Next, the polymer film of the present invention will be described.
The polymerized film of the present invention is, for example, after dissolving the polymerizable composition in a solvent, applying it to a support substrate, removing the solvent with the liquid crystal molecules in the polymerizable composition aligned, and then applying energy rays. It can be obtained by irradiation and polymerization.

  The support substrate is not particularly limited, but preferred examples include glass plates, polyethylene terephthalate plates, polycarbonate plates, polyimide plates, polyamide plates, polymethyl methacrylate plates, polystyrene plates, polyvinyl chloride plates, polytetrafluoroethylene. A board, a cellulose board, a silicon board, a reflecting plate, a calcite board, etc. are mentioned. A substrate obtained by applying a polyimide alignment film or a polyvinyl alcohol alignment film as described later on such a support substrate can be particularly preferably used.

  As a method for applying the solution of the polymerizable composition of the present invention to the support substrate, a known method can be used, such as a curtain coating method, an extrusion coating method, a roll coating method, a spin coating method, A dip coating method, a bar coating method, a spray coating method, a slide coating method, a printing coating method, a casting film forming method, and the like can be used. In addition, although the film thickness of the polymer film of the present invention is appropriately selected according to the use and the like, it is preferably 0.005 to 30 μm, more preferably 0.01 to 20 μm, and particularly preferably 0.05 to 15 μm. Selected.

  Examples of the method for aligning the liquid crystal molecules in the polymerizable composition of the present invention include a method in which an alignment treatment is performed on the support substrate in advance. As a preferable method for performing the alignment treatment, there is a method in which a liquid crystal alignment layer composed of various polyimide alignment films, polyamide alignment films, or polyvinyl alcohol alignment films is provided on a support substrate, and processing such as rubbing is performed. Moreover, the method of applying a magnetic field, an electric field, etc. to the composition on a support substrate is also mentioned.

  As a method for polymerizing the polymerizable composition of the present invention, a known method using light, electromagnetic waves or heat can be applied. Examples of the polymerization reaction by light or electromagnetic wave include radical polymerization, anionic polymerization, cationic polymerization, coordination polymerization, and living polymerization. According to these polymerization reactions, it is easy to perform polymerization under conditions where the polymerizable composition exhibits a liquid crystal phase. It is also preferable to crosslink while applying a magnetic field or electric field. The liquid crystal (co) polymer formed on the support substrate may be used as it is, but if necessary, it may be peeled off from the support substrate or transferred to another support substrate.

Preferred types of the light are ultraviolet rays, visible rays, infrared rays and the like. Electromagnetic waves such as electron beams and X-rays may be used. Usually, ultraviolet rays or visible rays are preferable. A preferable wavelength range is 150 to 500 nm. A more preferable range is 250 to 450 nm, and a most preferable range is 300 to 400 nm. Low light mercury lamps (sterilization lamps, fluorescent chemical lamps, black lights), high pressure discharge lamps (high pressure mercury lamps, metal halide lamps), or short arc discharge lamps (super high pressure mercury lamps, xenon lamps, mercury xenon lamps) However, it is preferable to use an ultrahigh pressure mercury lamp. The light from the light source may be irradiated to the polymerizable composition as it is, or the polymerizable composition may be irradiated with a specific wavelength (or a specific wavelength region) selected by a filter. Preferred irradiation energy density is 2~5000mJ / cm ^2, more preferably ranges are 10~3000mJ / cm ^2, particularly preferred range is 100 to 2000 mJ / cm ^2. A preferable illuminance is 0.1 to 5000 mW / cm ² , and a more preferable illuminance is 1 to 2000 mW / cm ² . The temperature when irradiating light can be set so that the polymerizable composition has a liquid crystal phase, but the preferable irradiation temperature is 100 ° C. or lower. Polymerization due to heat can occur at a temperature of 100 ° C. or higher, so that good alignment may not be obtained.

  The polymer film of the present invention can be used as a molded article having optical anisotropy. Examples of uses of the molded body include a retardation plate (1/2 wavelength plate, 1/4 wavelength plate, etc.), polarizing element, dichroic polarizing plate, liquid crystal alignment film, antireflection film, selective reflection film, field of view. It can be used for optical compensation of an angle compensation film or the like. In addition, it can also be used for information recording materials such as optical lenses such as liquid crystal lenses and microlenses, polymer dispersed liquid crystal (PDLC) electronic paper, and digital paper.

  EXAMPLES Hereinafter, although an Example and a comparative example are shown and this invention is demonstrated further in detail, this invention is not limited to these Examples etc.

[Examples 1-1 to 1-3 and Comparative Examples 1-1 to 1-3]
Compound No. which is a polymerizable liquid crystal compound. 1 or No. 6 in 2-butanone was dissolved in 4.0 g of compound No. 6 which is a radical photopolymerization initiator. 31, no. 37 or Comparative Compound No. 1-No. 0.03 g of No. 3 was added and completely dissolved, and then filtered through a 0.45 μm filter to obtain the polymerizable compositions of Examples 1-1 to 1-3 and Comparative Examples 1-1 to 1-3, respectively. It was. These solutions were coated on a rubbed glass substrate with polyimide using a spin coater and dried on a hot plate set at 100 ° C. for 3 minutes. After returning to room temperature and allowing to stand for 3 minutes, it was cured by irradiation with a high-pressure mercury lamp (120 W / cm) for 20 seconds to obtain polymer films of Examples 1-1 to 1-3 and Comparative Examples 1-1 to 1-3, respectively ( The spin coater rotation speed and time were adjusted so that the film thickness was about 1 μm). Each polymer film obtained was evaluated by the following method.

<Orientation>
The obtained polymer film was subjected to confirmation of the optical structure on the surface using an OPTIPHOT2-POL (Nikon) polarizing microscope. The case where the orientation is uniform and the orientation defect is not confirmed is marked with ◯, and the surface is transparent, the portion where the orientation unevenness is partially confirmed is marked with △, and the case where crystallization or orientation unevenness is confirmed is × It was.
<Curing property>
The surface curability of the obtained polymer film was confirmed visually. The case where it is uniformly cured and no tack remains is marked with ◯, and it is evenly cured, but when the tack remains a little, △, when the tack remains on the whole surface and the surface is sticky × It was.
<Heat resistance>
The obtained polymer film was measured for retardation at a wavelength of 546 nm at a room temperature of 25 ° C. according to a birefringence measurement method based on the Senarmon method using an OPTIPHOT2-POL (Nikon) polarizing microscope. Further, the polymer film was left in an oven at 150 ° C. for 30 minutes, cooled to room temperature, measured for retardation according to the above method, and the rate of change was calculated by the following formula. (It can be said that the smaller the rate of change, the smaller the change in optical properties due to heat and the higher the heat resistance.)
(Retardation change rate /%) = 100− (retardation (after heat test) / retardation (before heat test) × 100)

As can be seen from Table 1, the polymerizable compositions of Comparative Examples 1 and 2 remained tacky after curing, had a large retardation change after the heat resistance test, were poor in curability and heat resistance, and were polymerized in Comparative Example 3. It was confirmed that the polymer film obtained by curing the conductive composition was also inferior in heat resistance.
On the other hand, the polymerizable composition of the present invention can be confirmed to be uniformly cured, uniform in orientation, small in retardation change after the heat test, and excellent in curability, orientation and heat resistance. It was. In particular, compound no. It was confirmed that those using No. 1 were excellent in heat resistance.

[Example 2-1 and Comparative Examples 2-1 to 2-2]
Compound No. which is a polymerizable liquid crystal compound. 0.94 g of compound No. 1 and compound No. 1 which is an optically active compound. Compound No. 52, which is a radical photopolymerization initiator, was dissolved in 2.0 g of 2-butanone. 31 or Comparative Compound No. 1 or No. 0.03 g of No. 2 was added and completely dissolved, followed by filtration with a 0.45 μm filter to prepare polymerizable compositions of Example 2-1 and Comparative Examples 2-1 to 2-2. Using a spin coater, this solution was applied onto a glass substrate with a rubbed polyimide and dried on a hot plate set at 100 ° C. for 3 minutes. After returning to room temperature and allowing to stand for 3 minutes, it was cured by irradiation with a high-pressure mercury lamp (120 W / cm) for 20 seconds to obtain polymer films of Example 2-1 and Comparative Examples 2-1 to 2-2. (The rotational speed and time of the spin coater were adjusted so that the film thickness was about 4 μm.) The obtained polymer film was evaluated by the following method.

<Orientation>
The obtained polymer film was subjected to confirmation of the optical structure on the surface using an OPTIPHOT2-POL (Nikon) polarizing microscope. A sample in which selective reflection is uniformly confirmed and no alignment defect is confirmed is marked with ◯, and selective reflection can be confirmed, but a sample in which oily streak defect is confirmed is marked with △, and crystallization or alignment unevenness is confirmed. X.
<Curing property>
The surface curability of the obtained polymer film was confirmed visually. The case where it is uniformly cured and no tack remains is marked with ◯, and it is evenly cured, but when the tack remains a little, △, when the tack remains on the whole surface and the surface is sticky × It was.
<Selective reflection>
Using a spectrophotometer (U-3010 model: manufactured by Hitachi High-Technologies Corp.) equipped with a 5 ° specular reflection accessory, the reflectance measurement of the obtained polymerized film is carried out at 25 ° C. and in the wavelength range of 800 to 400 nm. Then, the selective reflection center wavelength (λ) was measured.

As can be seen from Table 2, it was confirmed that the polymerizable compositions of Comparative Examples 2-1 to 2-2 remained tacky after curing and had poor curability.
In contrast, it was confirmed that the polymerizable composition of the present invention was uniformly cured, uniform selective reflection was confirmed, and excellent curability and orientation.

Claims (11)

A polymerizable liquid crystal compound having a which may be (meth) acryloyl group substituted with a halogen atom as a polymerizable group, with a polymerizable composition containing a compound having a carbazole skeleton and acyl oxime ester group as a radical photopolymerization initiator There,
The polymerizable liquid crystal compound is a bifunctional (meth) acrylate compound represented by the following general formula (I), and the radical photopolymerization initiator is a compound represented by the following general formula (III). A polymerizable composition characterized.

(Wherein R ¹ and R ² each independently represent a hydrogen atom, a methyl group or a halogen atom, and ring A ¹ , ring A ² and ring A ³ are each independently a benzene ring, cyclohexane ring or cyclohexene. ring, a naphthalene ring, decahydronaphthalene ring represents a tetrahydronaphthalene ring or phenanthrene ring, -CH = may in these rings, is -N =, -CH ₂ - is substituted with -S- or -O- Z ¹ , Z ² and Z ³ each independently represents an alkyl group having 1 to 8 carbon atoms, a halogen atom or a cyano group which may be substituted with a halogen atom or a cyano group, The methylene group of the group may be substituted with —O— or —CO—, and L ¹ , L ² , L ³ and L ⁴ are each independently a single bond, —COO—, —OCO—, — (CE ₂ ) _p −, −CE = _{CE -, - (CE 2)} p O -, - O (CE 2) p -, - CE = CECE 2 O -, - OCE 2 CE = CE -, - C≡C -, - (CE 2) p COO _{-, - OCO (CE 2)} p -, - (CE 2) p OCO-O -, - OCO-O (CE 2) p -, - (CE 2) q O (CE 2) r O- or -O (CE ₂ ) _q O (CE ₂ ) _r- represents, E in L ¹ and L ⁴ represents a hydrogen atom, a methyl group or an ethyl group, E in L ² and L ³ represents a hydrogen atom, A certain E may be the same or different, and a, b and c are the numbers of substituents in the ring A ¹ , the ring A ² and the ring A ³ , respectively. When the number of 6-membered rings included is t, a, b and c are each independently an integer of 2t + 2 or less, b represents an integer of 1 or more, and p is To be independently represent an integer from 1 to 8, q and r each independently represents an integer of 1 to 3.)

(In the formula, ring B ¹ represents an aromatic ring or a heterocyclic ring, X ¹ represents a substituent represented by the following general formula (IV), X ² represents a halogen atom or an alkyl group, and G represents a single bond or R ¹¹ , R ¹² and R ¹³ each independently represent R, OR, COR, SR, CONRR ′ or CN, and R and R ′ each independently represent an alkyl group, an aryl group, Represents an arylalkyl group or a heterocyclic group, which may be substituted with a halogen atom and / or a heterocyclic group, and among these, the alkylene part of the alkyl group and the arylalkyl group is an unsaturated bond, an ether bond, R may be interrupted by a thioether bond or an ester bond, R and R ′ may be combined to form a ring, f is 0 or 1, and g is an integer of 0 to 5. Yes, when g is 2 or more, X ² numbers, even in the same group, may be a different group, the compound may be dimerized via a X ^2.)

(In the formula, ring B ² represents a cycloalkane ring, an aromatic ring or a heterocyclic ring, X ³ represents a halogen atom or an alkyl group, Y ¹ represents an oxygen atom, a sulfur atom or a selenium atom, and h represents 0-4. And m is an integer of 0 to 5, n is 0 or 1, and when h is 2 or more, the plurality of X ³ may be the same group or different groups.) The polymerizable composition according to claim 1 , wherein the bifunctional (meth) acrylate compound represented by the general formula (I) is a compound represented by the following general formula (II).

(In the formula, R ¹ , R ² , L ¹ , L ⁴ , A ¹ , A ³ , Z ¹ , Z ³ , a and c are the same as those in the general formula (I), and R ³ and R ⁴ are Each independently represents a hydrogen atom, a halogen atom, a cyano group, a halogen atom or an alkyl group having 1 to 8 carbon atoms which may be substituted with a cyano group, wherein the methylene group of the alkyl group is -O- or- CO— may be substituted, and at least one of R ³ and R ⁴ represents other than a hydrogen atom.) The polymerizable composition according to claim 1 or 2 , wherein in the general formula (I) or (II), all Es are hydrogen atoms. The polymerizable composition according to claim 2 or 3 , wherein, in the general formula (II), the ring A ¹ and the ring A ³ are a benzene ring or a naphthalene ring. The polymerizable composition according to claim 2 or 3 , wherein in general formula (II), at least one of ring A ¹ and ring A ³ is a naphthalene ring. The polymerizable composition according to any one of claims 1 to 5, wherein the compound represented by the general formula (III) is a compound represented by the following general formula (V).

(In the formula, X ² , R ¹¹ , R ¹² , R ¹³ and g are the same as those in the general formula (III).) The polymerizable composition according to any one of claims 1 to 5, wherein the compound represented by the general formula (III) is a compound represented by the following general formula (VI).

(In the formula, X ² , R ¹¹ , R ¹² , R ¹³ and g are the same as those in the general formula (III), and X ³ , Y ¹ , h, m and n are the same as those in the general formula (IV). And Y ² and Y ³ each independently represent an oxygen atom, a sulfur atom or a selenium atom.) It contains an optically active compound, the polymerizable composition according to any one of claims 1 to 7, a cholesteric phase. The polymerizable composition according to any one of claims 1 to 8 showing a liquid crystal phase at 30 ° C. or less. Claim polymerizable composition according to any one of 1 to 9 in a state exhibiting a liquid crystal phase, it fabricated polymerized film by photopolymerization. An optical film for a display comprising the polymer film according to claim 10 .