TWI462899B - A polymerizable compound, a polymerizable composition containing the same, and a polymer - Google Patents

Description

Polymerizable compound, polymerizable composition containing the same, and polymer thereof

The present invention relates to a polymerizable compound which is simple in production method and excellent in photocurability, a polymerizable composition containing the polymerizable compound, and a polymer. The polymer is transparent and has little coloration and exhibits a high refractive index, and is useful for use in optical materials.

A transparent and high refractive index hardened material is indispensable for optical materials such as lenses and filters. Patent Document 1 discloses an episulfide compound having an anthracene skeleton which can be used as an optical material, and Patent Document 2 discloses a photocurable resin lens obtained by copolymerizing bromobisphenol. Further, Patent Documents 3 and 4 disclose a polymerizable composition containing an acrylate compound. However, these materials are not satisfactory in terms of hardness, adhesion, light resistance, etc., or there is a problem that the manufacturing method becomes complicated and is not suitable for mass production at a low cost.

Prior technical literature Patent literature

Patent Document 1: Japanese Patent Laid-Open Publication No. 2001-288177

Patent Document 2: Japanese Patent Laid-Open Publication No. 2001-124903

Patent Document 3: Japanese Patent Laid-Open Publication No. 2001-011109

Patent Document 4: European Patent Application Publication No. 2098544

An object of the present invention is to provide a polymer which is simple in production method, excellent in photocurability, less hardened and shrinkable at the time of film formation, and transparent and has a high refractive index.

The present inventors conducted intensive studies in turn, and as a result, obtained the following knowledge: A novel polymerizable compound having a benzo or naphthocycloalkane skeleton can achieve the above object.

That is, the present invention provides a compound represented by the following formula (I) based on the above knowledge.

(wherein A ¹ and A ² are each independently a hydrogen atom and a substituent represented by the following formula (II), formula (III) or formula (IV), and at least one of A ¹ and A ² In the substituent represented by the following formula (II), formula (III) or formula (IV), X, Y, Z ¹ and Z ² each independently represent a carbon atom which may be substituted by a halogen atom. An alkyl group of ~10, an aryl group having 6 to 20 carbon atoms which may be substituted by a halogen atom, an arylalkyl group having 7 to 20 carbon atoms which may be substituted by a halogen atom, and a carbon atom which may be substituted by a halogen atom a heterocyclic group of ~20 or a halogen atom, the methylene group in the alkyl group, the aryl group, the arylalkyl group may be interrupted by an unsaturated bond, -O- or -S-, and X may form a ring with each other by X, such rings It can be an aromatic ring, k represents the number of 0~4, p represents the number of 0~8, r and s respectively represent the number of 0~4, when k, p, r and / or s are 2 or more, the plural X, Y, Z ¹ and/or Z ² may be the same or different, x represents the number of 0~4, y represents the number of 0~4, and the total number of x and y is 2~4.)

(wherein, L ¹ , L ² and L ³ each independently represent an exoethyl or a propyl group, n and m each independently represent a number from 0 to 20, and f represents a number from 1 to 20, when n, m or When f is 2 or more, the unit represented by [RO] _n , [RO] _m or [RO] _f may be a random copolymer or a block copolymer of an extended ethyloxy group and a propyloxy group, M Represents a hydrogen atom or a methyl group.)

Furthermore, the present invention provides a polymerizable composition characterized in that at least one of A ¹ and A ² in the above formula (I) is one of the above formula (II) or formula (III). A compound represented by the group; further comprising a polymer obtained by polymerizing the above polymerizable composition.

The polymerizable compound of the present invention provides a polymer which has less hardening shrinkage and is transparent and has a high refractive index at the time of film formation.

Hereinafter, the compound, the polymerizable composition and the polymer of the present invention will be described in detail based on preferred embodiments.

The compound of the present invention is characterized in that it is a compound represented by the above formula (I) and has a benzo or naphthocycloalkane skeleton. Further, the compound of the present invention is a polymerizable compound contained in the polymerizable composition of the present invention, depending on the group represented by A ¹ and A ² in the formula (I) (hereinafter also referred to as the present invention). A polymerizable compound) or an intermediate (hereinafter also referred to as an intermediate compound of the present invention) which can be used for the production of the polymerizable compound. Here, the polymerizable compound of the present invention is in the above formula (I), and at least one of A ¹ and A ² is a group represented by any one of the above formula (II) or formula (III). The compound is used as a polymerizable compound in the polymerizable composition of the present invention. Further, the intermediate compound of the present invention is a compound of the above formula (I), and A ¹ and A ² are a hydrogen atom or a group represented by the above formula (IV).

In the intermediate compound and the polymerizable compound of the present invention, in the above formula (I), the methylene group in the alkyl group, the aryl group or the arylalkyl group represented by X, Y, Z ¹ and Z ² may be The unsaturated bond, -O- or -S-interruption, the substitution position of the halogen group, and the interrupt position of -O- or -S- are arbitrary, and also include -O- or -S- directly bonded to each ring.

The alkyl group having 1 to 10 carbon atoms which may be substituted by a halogen atom may, for example, be a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, a second butyl group, a third butyl group or an isobutyl group. , pentyl, isopentyl, third amyl, hexyl, heptyl, isoheptyl, third heptyl, n-octyl, isooctyl, trioctyl, 2-ethylhexyl, n-decyl, N-decyl, trifluoromethyl, difluoromethyl, monofluoromethyl, pentafluoroethyl, tetrafluoroethyl, trifluoroethyl, difluoroethyl, heptafluoropropyl, hexafluoropropyl, five Fluoropropyl, tetrafluoropropyl, trifluoropropyl, perfluorobutyl, methoxy, methoxyethoxy, methoxyethoxyethoxy, methylthio, ethoxy, ethylene oxide Base, propoxy, isopropoxy, butoxy, isobutoxy, tert-butoxy, tert-butoxycarbonylmethoxy, pentyloxy, isopentyloxy, third pentyloxy , neopentyloxy, hexyloxy, cyclohexyloxy, isohexyloxy, heptyloxy, octyloxy, 2-ethylhexyloxy, decyloxy, decyloxy, cyclopropyl, cyclobutyl , cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclodecyl, cyclodecyl, etc. Chain, branched and cyclic alkyl groups of.

Examples of the aryl group having 6 to 20 carbon atoms which may be substituted by a halogen atom include a phenyl group, a 1-naphthyl group, a 2-naphthyl group, a 1-fluorenyl group, a 1-phenanthryl group, an o-tolyl group, and an m-toluene. Base, p-tolyl, 3-indenyl, 9-fluorenyl, 1-tetrahydronaphthyl, 2-tetrahydronaphthyl, 1-dihydroindenyl, 1-indenyl, 2-indenyl, 4-ethene Phenylphenyl, 3-isopropylphenyl, 4-isopropylphenyl, 4-butylphenyl, 4-isobutylphenyl, 4-tert-butylphenyl, 4-hexylphenyl, 4-cyclohexylphenyl, 4-octylphenyl, 4-(2-ethylhexyl)phenyl, 2,3-dimethylphenyl, 2,4-dimethylphenyl, 2,5- Dimethylphenyl, 2,6-dimethylphenyl, 3,4-dimethylphenyl, 3,5-dimethylphenyl, 2,4-di-t-butylphenyl, 2 , 5-di-t-butylphenyl, 2,6-di-t-butylphenyl, 2,4-di-t-pentylphenyl, 2,5-di-t-pentylphenyl , cyclohexylphenyl, biphenyl, 2,4,5-trimethylphenyl, 4-chlorophenyl, 3,4-dichlorophenyl, 4-trichlorophenyl, 4-trifluorophenyl , perfluorophenyl, phenoxy, 2-methylphenoxy, 3-methylphenoxy, 4-methylphenoxy, 2,3-dimethylphenoxy, 2,4-di Methylbenzene , 2,5-dimethylphenoxy, 2,6-dimethylphenoxy, 3,4-dimethylphenoxy, 3,5-dimethylphenoxy, 2,3, 4-trimethylphenoxy, 2,3,5-trimethylphenoxy, 2,3,6-trimethylphenoxy, 2,4,5-trimethylphenoxy, 2, 4,6-trimethylphenoxy, 3,4,5-trimethylphenoxy, 2,3,4,5-tetramethylphenoxy, 2,3,4,6-tetramethyl Phenoxy, 2,3,5,6-tetramethylphenoxy, pentamethylphenoxy, ethylphenoxy, n-propylphenoxy, isopropylphenoxy, n-butylbenzene Oxyl, t-butylphenoxy, tert-butylphenoxy, n-hexylphenoxy, n-octylphenoxy, n-decylphenoxy, n-tetradecylphenoxy, 1- Naphthyloxy, 2-naphthyloxy, 1-decyloxy, 1-phenanthryloxy, o-tolyloxy, m-tolyloxy, p-tolyloxy, 9-decyloxy, 1-tetrahydronaphthyloxy , 2-tetrahydronaphthyloxy, 1-dihydrodecyloxy, 1-decyloxy, 2-decyloxy, and the like.

Examples of the arylalkyl group having 7 to 20 carbon atoms which may be substituted by a halogen atom include a benzyl group, a phenethyl group, a 2-phenylpropyl group, a diphenylmethyl group, a triphenylmethyl group, and a benzene group. Vinyl, cinnamyl, 4-chlorophenylmethyl, benzyloxy, 1-naphthylmethoxy, 2-naphthylmethoxy, 1-decylmethoxy, and the like.

Examples of the heterocyclic group having 2 to 20 carbon atoms which may be substituted by a halogen atom include pyrrolyl group, pyridyl group, pyrimidinyl group and fluorene group. Base Base, piperidinyl, pyranyl, pyrazolyl, tri , pyrrolidinyl, quinolyl, isoquinolyl, imidazolyl, benzimidazolyl, triazolyl, furyl, furanyl, benzofuranyl, thienyl, thiophenyl Benzothiophenyl, thiadiazolyl, thiazolyl, benzothiazolyl, Azolyl, benzo Azolyl, isothiazolyl, iso Azolyl, fluorenyl, Pyridyl, Olinyl, thio Lolinyl, 2-pyrrolidone-1-yl, 2-piperidin-1-yl, 2,4-dioxyimidazol-3-yl, 2,4-dioxy Zyridinyl-3-yl and the like.

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

Examples of the ring structure which can be formed by X each other include a cyclopentane ring, a cyclohexane ring, a cyclopentene ring, a benzene ring, and a piperidine ring. 5~7 member rings such as porphyrin ring, lactone ring and indole ring, and condensed rings such as naphthalene ring, anthracene ring, anthracene ring, acenaphthene ring, indane ring and tetralin ring.

In the intermediate compound and the polymerizable compound of the present invention, in the above formula (I), a compound wherein x is 2 and y is 0 is preferable because it is excellent in photocurability, and is represented by the following formula (V). The compounds are better because they are advantageous in terms of manufacturing.

(wherein A ¹ , A ² , X, Y, Z ¹ , Z ² , k, r and s are the same as those of the above formula (I).)

Further, in the above formula (I) or the above formula (V), a compound wherein Y is a phenyl group is preferably a polymer having a high refractive index, k is 0 or 1, and when k is 1, X is carbon. A compound having an alkyl group of 1 to 10 atoms or an aryl group having 6 to 20 carbon atoms is suitably used because it is more advantageous in terms of production.

Further, in the polymerizable compound of the present invention, in the above formula (I), a compound in which both A ¹ and A ² are represented by the above formula (II), and A ¹ and A ² are both The compound represented by the formula (III) is preferred because it provides a polymer having a high hardness.

Examples of the polymerizable compound of the present invention represented by the above formula (I) include the following compounds 1 to 56. Further, among the following compounds, n and m represent the number from 0 to 20.

And the intermediate compound is, in the present invention are intermediate compounds in the general formula (I), A ¹ and A ² by the above general formula (IV) represented in the above-described polymerizable compounds for the manufacture of n or m A particularly useful intermediate for 1 to 20 people. Examples of the intermediate compound include a compound in which the acryloyl group, the methacrylanyl group or the vinylbenzyl group of the above compound 1 to 56 is substituted with a hydrogen atom, and n or m is 1 to 20 Compound.

In the polymerizable compound of the present invention, m in the above formula (II) and m in the formula (III) represent a number of 0 to 20, and in terms of production, it is preferably 0 to 5, and further preferably. It is 0~3. Further, in the intermediate compound of the present invention, f in the above formula (IV) represents a number of from 1 to 20, preferably from 1 to 5, more preferably from 1 to 3.

The method for producing the intermediate compound and the polymerizable compound of the present invention is not particularly limited. For example, in the above formula (I), both of A ¹ and A ² are a polymerizable compound (IA) represented by the above formula (II). It can be obtained by reacting a bisphenol derivative (1) with a (meth) propylene hydride halide in the presence of a base or by reacting a bisphenol derivative (1) with (meth)acrylic acid in the presence of an acidic catalyst. The reaction formula is shown in the following formula. Further, X, Y, Z ¹ , Z ² , k, p, r, s, x, y in the following formula are the same as the above formula (I), and L ¹ , n and M are the same as the above formula (II). In the same manner, E ¹ represents a halogen atom or OH.

Further, in the above formula (I), both of A ¹ and A ² are the polymerizable compound (IB) represented by the above formula (III), and the bisphenol derivative (1) and the halogenated methylstyrene can be used. Obtained by reaction in the presence of a base. The reaction formula is shown in the following formula. Further, X, Y, Z ¹ , Z ² , k, p, r, s, x, y in the following formula are the same as the above formula (I), and L ² and m are the same as the above formula (III) And E ² represents a halogen atom.

Intermediate compound (IC) in the general formula (I), A ¹ and A ² by the above general formula (IV) may be used as the above-described bisphenol derivative represented by (1), bisphenol derivatives may be by (2) It is obtained by reacting a cyclic carbonate in the presence of a base or by subjecting a bisphenol derivative (2) to a polyaddition reaction with ethylene oxide or propylene oxide in the presence of a base catalyst. The reaction formula is shown in the following formula. Further, X, Y, Z ¹ , Z ² , k, p, r, s, x, y in the following formula are the same as the above formula (I), and L ³ and f are the same as the above formula (IV) , q is 0 or 1.

Examples of the acidic catalyst include methanesulfonic acid, benzenesulfonic acid, m-xylenesulfonic acid, p-toluenesulfonic acid, hydroxymethanesulfonic acid, 2-hydroxyethylsulfonic acid, hydroxypropylsulfonic acid, and the like. Sulfonic acid such as fluoromethanesulfonic acid, sulfosalicylic acid, sulfophthalic acid; sulfuric acid, anhydrous sulfuric acid, fuming sulfuric acid, chlorosulfuric acid, fluorosulfuric acid, hydrochloric acid, hydrogen chloride gas, oxalic acid, formic acid, phosphoric acid, trichloroacetic acid , trifluoroacetic acid, samarium tungstic acid, phosphotungstic acid and other heteropoly acid, strong acid ion exchange resin, activated clay, boron trifluoride, anhydrous aluminum carbide, zinc chloride and the like. The acid catalyst is preferably used in an amount of 0.1 to 50 parts by mass, more preferably 1 to 10 parts by mass, per 100 parts by mass of the bisphenol derivative (1).

Examples of the base used in the above reaction include alkali metal hydroxides such as lithium hydroxide, sodium hydroxide, and potassium hydroxide; alkaline earth metal hydroxides such as calcium hydroxide and magnesium hydroxide; and sodium methoxide; Metal alkoxides such as sodium ethoxide, magnesium dimethoxide, diethoxy magnesium, aluminum diisopropoxide, and aluminum tris-butoxide; organometallic compounds such as butyl lithium and third butyl lithium Alkali metal guanamine such as lithium decylamine or hexamethyldiazepine lithium salt; carbonate such as sodium carbonate or potassium carbonate; triethylamine, pyridine, benzylamine, benzylmethylamine, γ-dimethylaminopyridine , dimethylaniline, tributylamine, 4-(N-piperidyl)pyridine, 1,4-diazabicyclo[2.2.2]octane, 1,5-diazabicyclo[4.3.0] An amine compound such as 5-nonane or 1,8-diazabicyclo[5.4.0]-7-undecene. In the case of producing the above polymerizable compound, the above-mentioned base is used in an amount of from 0.1 to 2.0 mol, particularly from 0.3 to 1.5 mol, per one hydroxyl group of the bisphenol derivative (1). Further, in the case of producing the above intermediate compound, the base is used in an amount of from 0.01 to 2.0 mol, particularly from 0.05 to 0.5 mol, based on the hydroxyl group of the bisphenol derivative (2). use.

Further, a conventionally known solvent can be used for the above reaction, and examples of the solvent include aromatic hydrocarbon solvents such as toluene, xylene, and cumene; and terpene hydrocarbon oils such as turpentine, D-limonene, and decene; Paraffin solvent such as mineral oil, Swazol #310 (Cosmo Matsuyama Oil Co., Ltd.), Solvesso #100 (Exxon Chemical Co., Ltd.); alcohol solvent such as methanol or ethanol; ester solvent such as ethyl acetate; dichloroethane , halogenated solvents such as carbon tetrachloride, chloroform, trichloroethylene, dichloromethane, chlorobenzene; tetrahydrofuran, two a cyclic ether solvent such as an alkane; an ether, a cellosolve solvent, a ketone solvent, aniline, triethylamine, pyridine, Alkane, acetic acid, acetonitrile, carbon disulfide, and the like.

In the above reaction, when the compound (IC) is obtained from the bisphenol derivative (2), a mixture of a plurality of compounds having different numbers of f is obtained, but there is no problem, and it can also be used in a subsequent reaction to produce a polymerizable compound (IA). Or a mixture of a plurality of compounds having different numbers of n or m in (IB), and using them to prepare a polymerizable composition.

The intermediate compound and the polymerizable compound of the present invention described above are used in various applications as the polymerizable composition described below.

The polymerizable composition of the present invention contains a composition of the above polymerizable compound, and is mainly used in combination with a radical polymerization initiator and a solvent. In the polymerizable composition of the present invention, the polymerizable compound may be one type or a mixture of two or more types, and the content of the above polymerizable compound is the total mass of the total solid matter in which the solvent is removed from the self-polymerizable composition. The proportion of the medium is preferably 50 to 90% by mass, more preferably 60 to 80% by mass.

As the radical polymerization initiator, a previously known compound can be used, and examples thereof include benzamidine peroxide, 2,2'-azobisisobutyronitrile, benzophenone, and phenylbiphenyl ketone. 1-hydroxy-1-benzhydrylcyclohexane, benzil, benzil dimethyl ketal, 1-benzyl-1-dimethylamino-1- 4'-(N- Polinyl)benzhydryl)propane, 2- Lolinyl-2-(4'-methylindenyl) benzhydrylpropane, 9-oxosulfur (thioxanthone), 1-chloro-4-propoxy-(9-oxo-sulfur ), isopropyl (9-oxo-sulfur) ), diethyl (9-oxygen sulfur) ), ethyl hydrazine, 4-benzylidene-4'-methyldiphenyl sulfide, benzoin butyl ether, 2-hydroxy-2-benzhydrylpropane, 2-hydroxy-2-(4' -isopropyl)benzhydrylpropane, 4-butylbenzylidenetrichloromethane, 4-phenoxybenzhydryldichloromethane, methyl benzhydrazide, 1,7-bis ( 9'-Acridine)heptane, 9-n-butyl-3,6-bis(2'-(N- Phenyl)isobutyl) carbazole, 2-methyl-1-[4-(methylthio)phenyl]-2-(N- Polinyl)propan-1-one, p-methoxyphenyl-2,4-bis(trichloromethyl)-all three 2-methyl-4,6-bis(trichloromethyl)-all three , 2-phenyl-4,6-bis(trichloromethyl)-all three 2-naphthyl-4,6-bis(trichloromethyl)-all three , 2-(p-butoxystyryl)-all three , 2-(p-butoxystyryl)-5-trichloromethyl-1,3,4- Diazole, 9-phenyl acridine, 9,10-dimethylbenzophenone , benzophenone/micilone, hexaarylbiimidazole/mercaptobenzimidazole, 9-oxosulfur /amine, bis(2,4,6-trimethylbenzylidene)-phenylphosphine oxide, and the specification of US Pat. No. 6,596,445, the specification of US Pat. No. 6,949,678, and the Japanese Patent Laid-Open No. 2005-97141, The compounds described in the specification of U.S. Patent No. 7,648,738, U.S. Patent No. 7,189,489, Japanese Patent No. 3,798,008, and U.S. Patent Application Publication No. 2007/270522. Among these, a compound represented by the following formula (a) or (c) is preferred.

(wherein R ⁷¹ , R ⁷² and R ⁷³ each independently represent R ⁷⁶ , OR ⁷⁶ , COR ⁷⁶ , SR ⁷⁶ , CONR ⁷⁶ R ⁷⁷ or CN, and R ⁷⁶ and R ⁷⁷ each independently represent an alkyl group, an aryl group, An arylalkyl group or a heterocyclic group which may be substituted by a halogen atom and/or a heterocyclic group, wherein the alkyl group of the alkyl group and the arylalkyl group may be an unsaturated bond, an ether bond or a thioether bond. Or the ester bond is interrupted, and R ⁷⁶ and R ⁷⁷ may form a ring together, R ⁷⁴ represents a halogen atom or an alkyl group, and R ⁷⁵ represents a hydrogen atom, a halogen atom, an alkyl group or a substitution represented by the following formula (b) Base, g represents an integer from 0 to 4, and when g is 2 or more, a plurality of R ⁷⁴ may be different bases.)

(wherein ring M represents a cycloalkane ring, an aromatic ring or a heterocyclic ring, R ⁷⁶ represents a halogen atom or an alkyl group, Y ⁷¹ represents an oxygen atom, a sulfur atom or a selenium atom, and Z ⁷¹ represents an alkylene group having 1 to 5 carbon atoms. Base, h represents an integer from 0 to 4, and when h is 2 or more, a plurality of X ⁷³ may be different bases.)

(wherein R ¹ and R ² each independently represent R ¹¹ , OR ¹¹ , COR ¹¹ , SR ¹¹ , CONR ¹² R ¹³ or CN, and R ¹¹ , R ¹² and R ¹³ are each independently a hydrogen atom and have 1 carbon atom; An alkyl group of ~20, an aryl group having 6 to 30 carbon atoms, an arylalkyl group having 7 to 30 carbon atoms or a heterocyclic group having 2 to 20 carbon atoms, an alkyl group, an aryl group, an arylalkyl group and The hydrogen atom of the heterocyclic group may further be OR ²¹ , COR ²¹ , SR ²¹ , NR ²² R ²³ , CONR ²² R ²³ , -NR ²² -OR ²³ , -NCOR ²² -OCOR ²³ , -C(=N-OR ²¹ )-R ²² , -C(=N-OCOR ²¹ )-R ²² , CN, halogen atom, -CR ²¹ =CR ²² R ²³ , -CO-CR ²¹ =CR ²² R ²³ , carboxy, epoxy group R ²¹ , R ²² and R ²³ each independently represent a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms, an arylalkyl group having 7 to 30 carbon atoms or a carbon atom. a heterocyclic group of 2 to 20, wherein the methylene group of the alkyl group of the substituent represented by the above R ¹¹ , R ¹² , R ¹³ , R ²¹ , R ²² and R ²³ may be an unsaturated bond or an ether bond. The thioether bond, the ester bond, the thioester bond, the guanamine bond or the urethane bond is interrupted 1 to 5 times, and the alkyl moiety of the above substituent may be a branched side chain Further, it may be a cyclic alkyl group, and the alkyl terminal of the above substituent may be an unsaturated bond, and R ¹² and R ¹³ and R ²² and R ²³ may each form a ring together. R ³ and R ⁴ are each independently represented. R ¹¹ , OR ¹¹ , SR ¹¹ , COR ¹¹ , CONR ¹² R ¹³ , NR ¹² COR ¹¹ , OCOR ¹¹ , COOR ¹¹ , SCOR ¹¹ , OCSR ¹¹ , COSR ¹¹ , CSOR ¹¹ , CN, halogen atom or hydroxyl group, a and b Independently 0~ ⁴ . X ¹ represents direct bond or CO, X ² represents oxygen atom, sulfur atom, selenium atom, CR ³¹ R ³² , CO, NR ³³ or PR ³⁴ , R ³¹ , R ³² , R ³³ and R ³⁴ each independently represents R ¹¹ , OR ¹¹ , COR ¹¹ , SR ¹¹ , CONR ¹² R ¹³ or CN, and R ³ may be bonded to one of the carbon atoms of the adjacent benzene ring via -X ² - to form a ring structure. Or R ³ and R ⁴ may together form a ring, and R ³¹ , R ³³ and R ³⁴ may each independently form a ring together with a benzene ring adjacent thereto.)

In the polymerizable composition of the present invention, the content of the above-mentioned radical polymerization initiator is preferably from 0.1 to 40 by mass based on the total mass of the total solid matter from which the solvent is removed from the polymerizable composition. %, more preferably 1.0 to 10% by mass. In addition, one type of the above-mentioned radical polymerization initiators may be used, or two or more types may be used in combination.

The polymerizable composition of the present invention may contain a solvent, and is usually not particularly limited as long as it can dissolve or disperse the above components, and examples thereof include methyl ethyl ketone, methyl amyl ketone, and diethyl ether. Ketones such as ketone, acetone, methyl isopropyl ketone, methyl isobutyl ketone, cyclohexanone; ether, two An ether solvent such as an alkane, tetrahydrofuran, 1,2-dimethoxyethane, 1,2-diethoxyethane or dipropylene glycol dimethyl ether; methyl acetate, ethyl acetate, n-propyl acetate, acetic acid An ester solvent such as isopropyl ester or n-butyl acetate; a cellosolve solvent such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether or propylene glycol monomethyl ether acetate; methanol, ethanol, iso- or n-propanol, An alcohol solvent such as isobutyl or n-butanol or pentanol; a BTX solvent such as benzene, toluene or xylene; an aliphatic hydrocarbon solvent such as hexane, heptane, octane or cyclohexane; turpentine, D-limonene and hydrazine; Terpene hydrocarbon oil such as olefin; mineral oil, paraffin solvent such as Swazol #310 (Cosmo Matsuyama Oil Co., Ltd.), Solvesso #100 (Exxon Chemical Co., Ltd.); carbon tetrachloride, chloroform, trichloroethylene, Halogenated aliphatic hydrocarbon solvent such as dichloromethane; halogenated aromatic hydrocarbon solvent such as chlorobenzene; carbitol solvent, aniline, triethylamine, pyridine, acetic acid, acetonitrile, carbon disulfide, N,N-dimethylformamidine An amine, N-methylpyrrolidone or the like is preferable, and among them, a ketone or a cellosolve solvent is preferred. These solvents may be used alone or in combination of two or more.

In the polymerizable composition of the present invention, the content of the solvent is preferably from 5 to 60% by mass, more preferably from 20 to 50% by mass, based on the total solid content of the polymerizable composition. Adjustment. Moreover, the solvent used in the synthesis of the polymerizable compound of the present invention can be directly contained in the polymerizable composition of the present invention.

A monomer having a unsaturated bond, a chain transfer agent, a surfactant, or the like can be further used in combination in the polymerizable composition of the present invention.

Examples of the monomer having an unsaturated bond include 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, isobutyl acrylate, acrylic acid-n-octyl ester, isooctyl acrylate, isodecyl acrylate, and the like. Stearyl acrylate, methoxyethyl acrylate, dimethylaminoethyl acrylate, zinc acrylate, 1,6-hexanediol diacrylate, trimethylolpropane triacrylate, 2-hydroxy methacrylate Ethyl ester, 2-hydroxypropyl methacrylate, butyl methacrylate, methacrylic acid-tert-butyl ester, cyclohexyl methacrylate, trimethylolpropane trimethacrylate, dipentaerythritol pentaacrylate Ester, dipentaerythritol hexaacrylate, pentaerythritol tetraacrylate, pentaerythritol triacrylate, tricyclodecane dimethylol diacrylate, and the like.

In the polymerizable composition of the present invention, the content of the monomer having an unsaturated bond is preferably from 0.01 to 20 in terms of the total mass of the total solid matter in which the solvent is removed from the polymerizable composition. The mass% is more preferably 0.1 to 10% by mass. These may be used alone or in combination of two or more.

Examples of the chain transfer agent include thioglycolic acid, thiomalic acid, thiosalicylic acid, 2-mercaptopropionic acid, 3-mercaptopropionic acid, 3-mercaptobutyric acid, and N-(2-mercaptopropylpropane). Glycosyl)glycine, 2-mercaptonicotinic acid, 3-[N-(2-mercaptoethyl)aminemethylmercapto]propionic acid, 3-[N-(2-mercaptoethyl)amino]propyl Acid, N-(3-mercaptopropyl)alanine, 2-mercaptoethanesulfonic acid, 3-mercaptopropanesulfonic acid, 4-mercaptobutanesulfonic acid, dodecyl(4-methylthio)phenyl ether, 2-mercaptoethanol, 3-mercapto-1,2-propanediol, 1-mercapto-2-propanol, 3-mercapto-2-butanol, nonylphenol, 2-mercaptoethylamine, 2-mercaptoimidazole, 2-mercapto a mercapto compound such as -3-hydroxypyridine, 2-mercaptobenzothiazole, thioglycolic acid, trimethylolpropane tris(3-mercaptopropionate), pentaerythritol tetrakis(3-mercaptopropionate), or the like The alkylate compound obtained by the disulfide compound, iodoacetic acid, iodopropionic acid, 2-iodoethanol, 2-iodoethanesulfonic acid, 3-iodopropanesulfonic acid or the like is obtained. These may be used alone or in combination of two or more.

As the surfactant, an ionic surfactant such as a perfluoroalkyl phosphate or a perfluoroalkyl carboxylate, an anionic interfacial activity such as a higher fatty acid alkali salt, an alkyl sulfonate or an alkyl sulfate can be used. a cationic surfactant such as a higher amine halide or a quaternary ammonium salt, a nonionic such as a polyethylene glycol alkyl ether, a polyethylene glycol fatty acid ester, a sorbitan fatty acid ester, or a fatty acid monoglyceride. A surfactant such as a surfactant, an amphoteric surfactant, or a polysiloxane surfactant; these may be used alone or in combination of two or more.

Further, a thermoplastic organic polymer is further used in the polymerizable composition of the present invention, whereby the properties of the cured product can be improved. Examples of the thermoplastic organic polymer include polystyrene, polymethyl methacrylate, methyl methacrylate-ethyl acrylate copolymer, poly(meth)acrylic acid, and styrene-(meth)acrylic acid copolymer. , (meth)acrylic acid-methyl methacrylate copolymer, polyvinyl butyral, cellulose ester, polypropylene decylamine, saturated polyester, and the like. These may be used alone or in combination of two or more.

Further, in the polymerizable composition of the present invention, anisole, hydroquinone, pyrocatechol, t-butyl catechol, phenolthiophene may be added as needed. Isothermal polymerization inhibitor; plasticizer; followed by accelerator; filler; defoamer; dispersant; leveling agent; decane coupling agent; These may be used alone or in combination of two or more.

Further, the polymerizable composition of the present invention may contain a curing catalyst, a monoglycidyl ether, dioctyl phthalate, dibutyl phthalate, benzyl alcohol, coal tar, etc., as needed. Or non-reactive diluent (plasticizer); glass fiber, carbon fiber, cellulose, strontium sand, cement, kaolin, clay, aluminum hydroxide, bentonite, talc, cerium oxide, fine powder cerium oxide, titanium dioxide, Filler or pigment such as carbon black, graphite, iron oxide, asphalt material; γ-aminopropyltriethoxydecane, N-β-(aminoethyl)-γ-aminopropyltriethoxydecane , N-β-(Aminoethyl)-N'-β-(aminoethyl)-γ-aminopropyltriethoxydecane, γ-anilinopropyltriethoxydecane, γ- Glycidoxypropyltriethoxydecane, β-(3,4-epoxycyclohexyl)ethyltriethoxydecane, vinyltriethoxydecane, N-β-(N-vinyl Benzylaminoethyl)-γ-aminopropyltriethoxydecane, γ-methylpropenyloxypropyltrimethoxydecane, γ-chloropropyltrimethoxydecane, γ-mercaptopropyl Decane such as trimethoxy decane Coupling agent; candelilla wax, carnauba wax, wood wax, insect wax, beeswax, lanolin, cetyl wax, montan wax, petroleum wax, fatty acid wax, fatty acid ester, fatty acid ether, Aromatic ester, aromatic ether and other lubricants; thickener; thixotropic agent; antioxidant; light stabilizer; ultraviolet absorber; flame retardant; defoamer; rust inhibitor; colloidal cerium oxide, colloidal alumina A commonly used additive may be used in combination with an adhesive resin such as a xylene resin or a petroleum resin.

In the polymerizable composition of the present invention, the above-mentioned optional additives are preferably 100 parts by mass or less based on 100 parts by mass of the polymerizable composition of the present invention.

Next, the polymer of the present invention will be described.

The polymer of the present invention is obtained by polymerizing the above polymerizable composition, and can be applied to a support substrate such as metal, paper or plastic by a known method. Further, it may be temporarily applied to a support substrate such as a film, and then transferred to another support substrate, and the application method thereof is not limited.

The support substrate is not particularly limited, and preferred examples thereof include a glass plate, a polyethylene terephthalate plate, a polycarbonate plate, a polyimide plate, a polyamide plate, and a polymethyl methacrylate. Ester board, polystyrene board, polyvinyl chloride board, polytetrafluoroethylene board, cellulose board, enamel board, reflector board, cycloolefin polymer, calcite board, etc. It is particularly preferable to use a polyimide film or a polyvinyl alcohol alignment film to be applied to such a support substrate.

As a method of coating on the above-mentioned support substrate, a known method 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, or the like can be used. Immersion by a spray coating method, a slanting plate coating method, various screen printing, inkjet printing, a casting film forming method, and the like. In addition, the film thickness of the above-mentioned polymer is appropriately selected depending on the use, etc., and is selected from the range of 0.001 to 50 μm, more preferably 0.1 to 30 μm, particularly preferably 1 to 10 μm.

A known method of using light, heat or electromagnetic waves can be applied to the method of polymerizing the polymerizable composition of the present invention. Examples of the polymerization reaction using light or electromagnetic waves include radical polymerization, anionic polymerization, cationic polymerization, coordination polymerization, and living polymerization. The (co)polymer formed on the support substrate can be used as it is, or can be peeled off from the support substrate or transferred to another support substrate as needed.

Preferred types of the above light are ultraviolet rays, visible rays, infrared rays, and the like. Electromagnetic waves such as electron beams and X-rays can also be used. Generally preferred are ultraviolet or visible light. A preferred wavelength range is from 150 to 500 nm. A better range is 250 to 450 nm, and the best range is 300 to 400 nm. Examples of the light source include low-pressure mercury lamps (sterilization lamps, fluorescent chemical lamps, black lamps), high-pressure discharge lamps (high-pressure mercury lamps, metal halide lamps), or short-arc discharge lamps (ultra-high pressure mercury lamps, xenon lamps, mercury lamps), etc., preferably It is possible to use ultra high pressure mercury lamps. The light from the light source may be directly irradiated to the polymerizable composition, or the polymerizable composition may be irradiated to a specific wavelength (or a specific wavelength region) selected by the filter. Preferably, the irradiation energy density is 2 to 5000 mJ/cm ² , more preferably 10 to 3000 mJ/cm ² , and particularly preferably 100 to 2000 mJ/cm ² . The preferred illuminance is 0.1 to 5000 mW/cm ² , and the better illumination is 1 to 2000 mW/cm ² .

The polymerizable composition used in the polymer of the present invention can be cured by polymerization by light irradiation with ultraviolet rays or the like for several seconds to several minutes, thereby improving the production of optical parts such as various optical lenses represented by spectacle lenses. Productive. In addition, as described above, the radical polymerization reaction is preferably carried out by a polymerization reaction (photopolymerization) using light such as ultraviolet rays, and if necessary, a polymerization reaction by heat, a polymerization reaction by gamma rays, or the like. And use it.

The polymer of the present invention obtained by light-irradiating the polymerizable composition of the present invention has high hardness, excellent scratch resistance and adhesion, high transparency, less hardening shrinkage, and high refractive index, and is suitably used, for example. Lens such as eyeglass lenses, Fresnel lenses, Lenticular Lens, 稜鏡 lenses, and microlenses. In addition, it can also be used as a film forming material, a solder mask for printing (wiring circuit) substrates, a plating resist, an adhesive, a display, an optical fiber, an optical waveguide, a full image, and various coatings. Cloth, etc.

[Examples]

Hereinafter, the present invention will be described in more detail by way of examples and comparative examples, but the present invention is not limited by the examples and the like. Further, Example 1 shows a production example of an intermediate compound for producing the polymerizable compound of the present invention. Example 2 shows a production example of the polymerizable compound of the present invention. Example 3 and Comparative Example 1 show examples of production of the polymerizable composition of the present invention and the comparative polymerizable composition. Example 4, Example 5, Comparative Example 2, and Comparative Example 3 show production examples and evaluation examples of the polymer of the present invention and a comparative polymer.

[Example 1-1] Production of 1,1-bis[4-(2-hydroxyethoxy)phenyl]-3-phenylindan (hereinafter referred to as intermediate compound No. 1)

1,1 bis (4-hydroxyphenyl)-3-phenylindole 89.1 g, ethylene carbonate dilute 11.6 g, potassium carbonate 0.88 g and toluene 11.0 g were added to dimethyl acetamide 240.0 g. The reaction was carried out at 110 ° C for 10 hours. Thereafter, 1200 mL of ethyl acetate was added, and the mixture was washed three times with 500 mL of water to remove dimethylacetamide, potassium carbonate, and unreacted ethylene carbonate. The organic phase was dried over anhydrous magnesium sulfate and filtered. The solvent was distilled off to obtain a crude crystal. The crude crystals were washed with acetone and dried to give white crystals (yield: 82%). As a result of various analyses, the target intermediate compound No. 1 (a compound obtained by substituting a propylene group of the above compound 42 (n=1) with a hydrogen atom) was confirmed.

(analysis results) (1) Chemical shift of ¹ H-NMR (DMSO-d ₆ ) (ppm)

2.72 (t: 1H), 3.21 (dd: 1H), 3.68-3.77 (m: 4H), 3.; 93-4.07 (m: 4H), 4.15 (dd: 1H), 4.76-4.86 (m, 2H) 6.77 (d: 1H), 6.84-6.90 (m: 4H), 7.02-7.14 (m: 5H), 7.17-7.29 (m: 5H), 7.32-7.38 (m: 2H)

(2) IR spectrum (cm ^-1 )

3304, 2934, 1608, 1508, 1456, 1291, 1176, 1064, 919, 832, 762, 703

[Example 1-2] Production of 1,1-bis[4-(2-hydroxyethoxy)phenyl]-3,5-diphenylindan (hereinafter referred to as intermediate compound No. 2)

2,1 g of 1,1-bis(4-hydroxyphenyl)-3,5-diphenylindole, 9.30 g of ethylene carbonate, and 1.46 g of potassium carbonate were added to 120.0 g of dimethylacetamide. The reaction was carried out at 110 ° C for 6 hours. Thereafter, 500 mL of toluene was added, and the mixture was washed three times with 100 mL of water to remove dimethylacetamide, potassium carbonate, and unreacted ethylene carbonate. The organic phase was dried over anhydrous magnesium sulfate to filter and solvent. The solid of the reaction mixture was obtained by distillation. The mixture was crystallized as acetone, whereby 9.33 g (yield 40%) of pale yellow crystals was obtained. As a result of various analyses, the target intermediate compound No. 2 (a compound obtained by substituting a propylene group of the above compound 33 (n=1) with a hydrogen atom) was confirmed.

(analysis results) (1) Chemical shift of ¹ H-NMR (DMSO-d ₆ ) (ppm)

2.74 (t: 1H), 3.27 (dd: 1H), 3.68-3.75 (m: 4H), 3.95-4.01 (m: 4H), 4.22 (dd: 1H), 4.78-4.83 (m: 2H), 6.87- 6.93 (m: 4H), 6.98-7.01 (m: 1H), 7.06-7.11 (m: 2H), 7.14-7.21 (m: 3H), 7.25-7.42 (m: 8H), 7.49-7.55 (m: 3H) )

(2) IR spectrum (cm ^-1 )

3420, 2936, 1607, 1508, 1456, 1248, 1181, 1041, 915, 831, 765, 701

[Example 2-1]

Manufacture of 1,1-bis(4-propenyl phenyloxyphenyl)-3-phenylindole (hereinafter referred to as polymerizable compound No. 1)

Adding 50.0 mL of dry tetrahydrofuran and 3.38 g of triethylamine to 1,5 g of 1,1-bis(4-hydroxyphenyl)-3-phenylindole in argon to dissolve the system. For a temperature not exceeding 10 ° C, 2.99 g of acrylonitrile chloride was slowly added dropwise. While slowly returning to room temperature, the mixture was stirred for 1 hour, and then 75 g of 1% phosphoric acid and 100 mL of ethyl acetate were added and stirred, and the aqueous phase was discarded, and the mixture was washed three times with 100 mL of water until the aqueous phase became neutral. The organic phase was then dried over anhydrous magnesium sulfate, and the solvent was evaporated to give a mixture. This was separated and purified by silica gel column chromatography (developing solvent: hexane / ethyl acetate = 2 / 1) to afford white crystals 2.65 g (yield 41%). As a result of various analyses, the target polymerizable compound No. 1 (the above compound 42 (n = 0)) was confirmed.

(analysis results) (1) Chemical shift of ¹ H-NMR (DMSO-d ₆ ) (ppm)

2.49-2.53 (m: 1H), 2.70-2.78 (m: 1H), 4.24 (dd: 1H), 6.15-6.18 (m: 2H), 6.37-6.46 (m: 2H), 6.51-6.56 (m: 2H) ), 7.10-7.40 (m: 17H)

(2) IR spectrum (cm ^-1 )

3061,3031,2963,2936,2877,1924,1739,1634,1622,1603,1504,1471,1455,1404,1352,1295,1250,1209,1170,1112,1015,972,927,902,847,807,778,762,740,703

[Example 2-2]

Manufacture of 1,1-bis[4-(2-propenyloxyethoxy)phenyl]-3-phenylindan (hereinafter referred to as polymerizable compound No. 2)

Addition to 10.0 g of the intermediate compound No. 1 obtained in Example 1-1, 0.412 g of p-toluenesulfonic acid monohydrate, and 0.010 g of 2,6-di-tert-butyl-4-methylphenol. 92.7 g of acrylic acid was stirred at 60 ° C for 15 hours. Then, 200 mL of ethyl acetate was added, and the mixture was washed three times with 200 mL of water, and then washed twice with 100 mL of a 10% aqueous sodium hydrogencarbonate solution, and further washed with water (200 mL), and the organic phase was dried over anhydrous magnesium sulfate. The reaction mixture was obtained by distillation. This was separated and purified by silica gel column chromatography (developing solvent: hexane/ethyl acetate = 2/1) to obtain 7.70 g (yield: 64%) as a colorless transparent viscous liquid. As a result of various analyses, the target polymerizable compound No. 2 (the above compound 42 (n = 1)) was confirmed.

(analysis results) (1) Chemical shift of ¹ H-NMR (DMSO-d ₆ ) (ppm)

2.71 (dd: 1H), 3.20 (dd: 1H), 4.14 (dd, 1H), 4.18-4.25 (m: 4H), 4.40-4.48 (m, 4H), 5.94-6.00 (m, 2H), 6.17- 6.27 (m: 2H), 6.31-6.39 (m: 2H), 6.76-6.81 (m: 1H), 6.85-6.96 (m: 4H), 7.00-7.09 (m: 3H), 7.10-7.30 (m: 7H) ), 7.32-7.39 (m: 2H)

(2) IR spectrum (cm ^-1 )

3031, 2966, 2875, 1726, 1636, 1608, 1581, 1508, 1455, 1409, 1296, 1247, 1182, 1119, 1065, 1011, 984, 947, 829, 810, 777, 758, 735, 702

[Example 2-3]

Manufacture of 1,1-bis(4-propenylfluorenyloxyphenyl)-3,5-diphenylindan (hereinafter referred to as polymerizable compound No. 3)

Adding 50.0 mL of dry tetrahydrofuran and 2.50 g of triethylamine to 1,0 g of 1,1-bis(4-hydroxyphenyl)-3,5-diphenylindan under argon to dissolve The internal cooling of the system was not more than 10 ° C, and 1.99 g of acrylonitrile chloride was slowly added dropwise. After stirring for 1 hour while slowly returning to room temperature, 50 g of water and 100 mL of ethyl acetate were added and stirred, the aqueous phase was discarded, and the mixture was washed 3 times with 100 mL of water until the water phase became neutral, and then organic The phase was dried over anhydrous magnesium sulfate, and the solvent was evaporated to give a mixture. This was separated and purified by silica gel column chromatography (developing solvent: hexane / ethyl acetate = 2 / 1) to obtain 0.546 g (yield 11%) as a colorless solid. As a result of various analyses, it was confirmed that the target compound was polymerizable compound No. 3 (the above compound 33 (n = 0)).

(analysis results) (1) Chemical shift of ¹ H-NMR (DMSO-d ₆ ) (ppm)

2.88-2.95 (m: 1H), 3.00-3.05 (m: 1H), 4.22 (dd: 1H), 5.26-5.32 (m: 2H), 6.00-6.11 (m: 2H), 6.32-6.40 (m: 2H) ), 6.98-7.26 (m: 17H), 7.36 (s: 1H), 7.40-7.44 (m: 3H)

(2) IR spectrum (cm ^-1 )

3060,3029,2964,2870,1740,1634,1601,1504,1476,1455,1404,1295,1250,1206,1171,1151,1075,1015,982,901,843,801,764,701

[Example 2-4]

Manufacture of 1,1-bis[4-(2-propenylmethoxyethoxy)phenyl]-3,5-diphenylindan (hereinafter referred to as polymerizable compound No. 4)

Addition to 9.00 g of the intermediate compound No. 2 obtained in Example 1-2, p-toluenesulfonic acid monohydrate 0.650 g, and 2,6-di-t-butyl-4-methylphenol 0.010 g 71.7 g of acrylic acid was stirred at 70 ° C for 30 hours. Then, 200 mL of ethyl acetate was added, and the mixture was washed three times with 200 mL of water, and then washed twice with 100 mL of a 10% aqueous sodium hydrogencarbonate solution, and further washed with water (200 mL), and the organic phase was dried over anhydrous magnesium sulfate. The reaction mixture was obtained by distillation. This was separated and purified by silica gel column chromatography (developing solvent: toluene/ethyl acetate = 10/1) to afford 5.62 g (yield: 52%) of colorless crystals. As a result of various analyses, it was confirmed that the target polymerizable compound No. 4 (the above compound 33 (n = 1)).

(analysis results) (1) Chemical shift of ¹ H-NMR (DMSO-d ₆ ) (ppm)

2.70-2.83 (m: 1H), 3.21-3.30 (m: 1H), 4.18-4.26 (m, 5H), 4.42-4.48 (m: 4H), 5.93-6.02 (m, 2H), 6.17-6.28 (m , 2H), 6.32-6.40 (m: 2H), 6.87-7.00 (m: 5H), 7.05-7.12 (m: 2H), 7.14-7.23 (m: 3H), 7.25-7.44 (m: 8H), 7.48 -7.59 (m: 3H)

(2) IR spectrum (cm ^-1 )

3030, 2957, 2873, 1725, 1636, 1607, 1581, 1508, 1476, 1456, 1409, 1296, 1248, 1181, 1119, 1065, 1011, 984, 947, 863, 830, 810, 764, 701

[Example 2-5]

Manufacture of 1,1-bis[4-(4-vinylbenzyloxy)phenyl]-3-phenylindan (hereinafter referred to as polymerizable compound No. 5)

Mix 1,1-bis(4-hydroxyphenyl)-3-phenylindole 5.00 g with acetone 20.0 g, methanol 4.00 g, sodium hydroxide 1.16 g, heat to 55 ° C, slowly add 4-chloroform Base styrene 4.23 g. Further, after reacting at 55 ° C for 4 hours, 50 mL of methanol was added to the reaction mixture, and the mixture was thoroughly stirred to remove the supernatant liquid which was precipitated on the bottom of the viscous liquid by decantation. After 50 mL of acetone was added to the residual liquid and dissolved, the solvent was distilled off, and a yellow crystalline solid was obtained. This was subjected to acetone washing, whereby 3.31 g of a yellow crystal was obtained (yield: 41%). As a result of various analyses, it was confirmed that the target polymerizable compound No. 5 (the above compound 49 (m = 0)).

(analysis results) (1) Chemical shift of ¹ H-NMR (DMSO-d ₆ ) (ppm)

2.66-2.73 (m: 1H), 3.16-3.25 (m: 1H), 4.14 (dd: 1H), 5.03-5.10 (m: 4H), 5.23-5.31 (m: 2H), 5.81-5.86 (m: 2H) ), 6.68-6.81 (m: 3H), 6.91-7.10 (m: 7H), 7.11-7.30 (m: 7H), 7.31-7.39 (m: 2H), 7.39-7.46 (m: 4H), 7.46-7.54 (m: 4H)

(2) IR spectrum (cm ^-1 )

3025, 2964, 2940, 2868, 1629, 1606, 1579, 1507, 1457, 1407, 1381, 1291, 1245, 1179, 1117, 1045, 1012, 912, 877, 829, 758, 732, 700

[Example 3-1]

2.00 g of the polymerizable compound No. 1 obtained in Example 2-1, 0.100 g of 1-hydroxycyclohexyl phenyl ketone as a photoradical polymerization initiator, and F-470 manufactured by DIC Corporation as a leveling agent The mixture was dissolved in 0.0016 g and 2.10 g of ethyl acetate to obtain a polymerizable composition No. 1.

[Example 3-2]

1.50 g of the polymerizable compound No. 1 obtained in Example 2-1, and 1.50 g of 2,2-bis(4-propenylfluorenyloxyphenyl)propane (hereinafter referred to as compound a-1). 0.100 g of hydroxycyclohexyl phenyl ketone, 0.0016 g of F-470 manufactured by DIC Corporation, and 2.10 g of toluene were mixed and dissolved to obtain a polymerizable composition No. 2.

[Example 3-3]

2.00 g of the polymerizable compound No. 2 obtained in Example 2-2, 0.100 g of 1-hydroxycyclohexyl phenyl ketone, 0.0016 g of F-470 manufactured by DIC Corporation, and 2.10 g of ethyl acetate were thoroughly mixed to obtain a polymerization. Composition No. 3.

[Example 3-4]

0.500 g of the polymerizable compound No. 3 obtained in Example 2-3, 1.50 g of the compound a-1, 0.100 g of 1-hydroxycyclohexyl phenyl ketone, 0.0016 g of F-470 manufactured by DIC Corporation, and toluene 2.10. g mixed and dissolved to obtain a polymerizable composition No. 4.

[Example 3-5]

2.00 g of the polymerizable compound No. 4 obtained in Example 2-4, 0.100 g of 1-hydroxycyclohexyl phenyl ketone, 0.0016 g of F-470 manufactured by DIC Corporation, and 2.10 g of ethyl acetate were thoroughly mixed to obtain a polymerization. Composition No. 5.

[Examples 3-6]

0.500 g of the polymerizable compound No. 5 obtained in Example 2-5, 1.50 g of the compound a-1, 0.100 g of 1-hydroxycyclohexyl phenyl ketone, 0.0016 g of F-470 manufactured by DIC Corporation, and toluene 2.10. g mixed and dissolved to obtain a polymerizable composition No. 6.

[Comparative Example 1-1]

2.00 g of the compound a-1, 0.100 g of 1-hydroxycyclohexyl phenyl ketone, 0.0016 g of F-470 manufactured by DIC Corporation, and 2.10 g of ethyl acetate were sufficiently mixed to obtain a comparative polymerizable composition No. 1.

[Comparative Example 1-2]

2,2-bis[4-(2-propenylmethoxyethoxy)phenyl]propane (hereinafter referred to as compound a-2) 2.00 g, 1-hydroxycyclohexyl phenyl ketone 0.100 g, DIC Corporation 0.0016 g of F-470 and 2.10 g of ethyl acetate were thoroughly mixed to obtain Comparative Polymerizable Composition No. 2.

[Comparative Example 1-3]

9,9-bis[4-(2-propenylmethoxyethoxy)phenyl]indole (hereinafter referred to as compound a-3) 2.00 g, 1-hydroxycyclohexyl phenyl ketone 0.100 g, manufactured by DIC Corporation 0.0016 g of F-470 and 2.10 g of toluene were thoroughly mixed to obtain a comparative polymerizable composition No. 3.

Further, the compounds a-1 to a-3 are different from the polymerizable compounds of the present invention, and are polymerizable compounds having no benzo or naphthocycloalkane skeleton.

[Examples 4-1 to 4-6]

0.50 g of each of the polymerizable compositions No. 1 to No. 6 obtained in Examples 3-1 to 3-6 was applied onto a PET film, and prebaked in an oven at 80 ° C for 10 minutes. Thereafter, a light amount of 500 mJ/cm ^{2 was} exposed with a high pressure mercury lamp to obtain a cured film. The cured film was peeled off from the PET film to measure the refractive index.

The results are shown in [Table 1].

[Comparative Examples 2-1 and 2-2]

The comparative polymerizable compositions No. 1 and No. 2 obtained in Comparative Examples 1-1 and 1-2 were measured for refractive index in the same manner as in Examples 3-1 to 3-6. The results are shown together in [Table 1].

[Examples 5-1 and 5-2]

0.50 g of each of the polymerizable compositions No. 3 and No. 5 obtained in Examples 3-3 and 3-5 was applied to a TAC film of 50 mm × 80 mm × 80 μm using a bar coater #40 (Fuji On the FT-TDY80UL manufactured by Film, it was prebaked in an oven at 80 ° C for 10 minutes. Thereafter, a light amount of 500 mJ/cm ^{2 was} exposed with a high pressure mercury lamp to obtain a coating film. The film was placed on a flat surface, and the height of the four corners of the film from the plane was measured, and the total amount of film warpage deformation was evaluated as follows: ○ is less than 20 mm, Δ is 20 mm or more and less than 60 Mm, × is 60 mm or more. The results are shown in [Table 2].

[Comparative Examples 3-1 and 3-2]

The comparative polymerizable compositions No. 2 and No. 3 obtained in Comparative Examples 1-2 and 1-3 were each evaluated in the same manner as in Examples 5-1 and 5-2. The results are shown together in [Table 2].

According to the results of [Table 1] and [Table 2], it is understood that the polymer containing the polymerizable composition containing the polymerizable compound of the present invention exhibits a high refractive index as compared with the comparative polymer, and the film is warped at the time of film formation. Also, it can be used as an optical material.

Claims (12)

a compound represented by the following formula (I), (wherein A ¹ and A ² are each independently a hydrogen atom and a substituent represented by the following formula (II), formula (III) or formula (IV), and at least one of A ¹ and A ² In the substituent represented by the following formula (II), formula (III) or formula (IV), X, Y, Z ¹ and Z ² each independently represent a carbon atom which may be substituted by a halogen atom. An alkyl group of ~10, an aryl group having 6 to 20 carbon atoms which may be substituted by a halogen atom, an arylalkyl group having 7 to 20 carbon atoms which may be substituted by a halogen atom, and a carbon atom which may be substituted by a halogen atom a heterocyclic group of ~20 or a halogen atom, the methylene group in the alkyl group, the aryl group, the arylalkyl group may be interrupted by an unsaturated bond, -O- or -S-, and X may form a ring with each other by X, such rings It can be an aromatic ring, k represents the number from 0 to 4, p represents the number from 1 to 8, and r and s independently represent the number of 0 to 4, and when k, p, r and/or s are 2 or more, the plural X, Y, Z ¹ and/or Z ² may be the same or different, x represents the number of 0~4, y represents the number of 0~4, and the total number of x and y is 2~4) (wherein, L ¹ , L ² and L ³ each independently represent an exoethyl or a propyl group, n and m each independently represent a number from 0 to 20, and f represents a number from 1 to 20, when n, m or When f is 2 or more, the unit represented by [L ¹ O] _n , [L ² O] _m or [L ³ O] _f may be a random copolymer of a stretching ethyloxy group and a stretching propyloxy group or Block copolymer, M represents a hydrogen atom or a methyl group). The compound of claim 1, wherein in the above formula (I), x is 2 and y is 0. The compound of claim 1, which is represented by the following formula (V): (wherein A ¹ , A ² , X, Y, Z ¹ , Z ² , k, r and s are the same as in the above formula (I)). A compound according to claim 1 or 3, wherein in the above formula (I) or in the above formula (V), Y is a phenyl group. The compound of claim 1 or 3, wherein in the above formula (I) or the above formula (V), k is 0 or 1, and when k is 1, X is an alkyl group having 1 to 10 carbon atoms or carbon An aryl group with an atomic number of 6 to 20. The compound of claim 1 or 3, wherein in the above formula (I) or the above formula (V), both A ¹ and A ² represent a group represented by the above formula (IV). The compound of claim 1 or 3, wherein in the above formula (I) or the above formula (V), at least one of A ¹ and A ² is any one of the above formula (II) or formula (III) The basis of one. The compound of claim 1 or 3, wherein, in the above formula (I) or the above formula (V), both A ¹ and A ² are a group represented by the above formula (II). The compound of claim 1 or 3, wherein in the above formula (I) or in the above formula (V), both A ¹ and A ² are a group represented by the above formula (III). A polymerizable composition comprising the compound of claim 7. The polymerizable composition of claim 10 which contains a radical polymerization initiator. A polymer obtained by polymerizing the polymerizable composition of claim 10.