WO2010101033A1

WO2010101033A1 - Polymerizable compound, polymerizable composition containing same, and polymer thereof

Info

Publication number: WO2010101033A1
Application number: PCT/JP2010/052550
Authority: WO
Inventors: 俊輔高日; 誠士増田
Original assignee: 株式会社Adeka
Priority date: 2009-03-04
Filing date: 2010-02-19
Publication date: 2010-09-10
Also published as: KR101698356B1; JP2010202778A; CN102239189A; TWI462899B; KR20110123238A; CN102239189B; TW201038529A; JP5466863B2

Abstract

An intermediate compound and a polymerizable compound which are represented by general formula (I); a polymerizable composition containing a polymerizable compound represented by general formula (I) in which A¹ and/or A² is a group represented by general formula (II) or (III); and a polymer obtained by polymerizing the polymerizable composition. (In the formulae, A¹ and A² each represents a hydrogen atom or a substituent represented by general formula (II), (III), or (IV), at least A¹ or A² being a substituent represented by general formula (II), (III), or (IV); X, Y, Z¹, and Z² each represents a C_1-10 alkyl, etc., and Xs may be bonded to one another to form one or more rings, which may be aromatic rings; k is 0-4; p is 0-8; r and s each is 0-4; x is 0-4 and y is 0-4, the sum of x and y being 2-4; L¹, L², and L³ each represents an ethylene group, etc.; n and m each is 0-20; f is 1-20; when n, m, or f is 2 or larger, then the unit represented by [RO]_n, [RO]_m, or [RO]_f may be a random polymer or block copolymer of ethyleneoxy and propyleneoxy; and M represents methyl, etc.)

Description

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

The present invention relates to a polymerizable compound having a simple manufacturing method and excellent photocurability, a polymerizable composition containing the polymerizable compound, and a polymer. The polymer is transparent and less colored, exhibits a high refractive index, and is useful for optical material applications.

Transparent and high refractive index cured products are indispensable for optical materials such as lenses and optical filters. Patent Document 1 discloses an episulfide compound having a fluorene skeleton useful as an optical material, and Patent Document 2 discloses a photocurable resin lens obtained by copolymerizing bromobisphenol. Patent Documents 3 and 4 disclose polymerizable compositions containing an acrylate compound. However, these materials are unsatisfactory in terms of hardness, adhesion, light resistance, etc., and there are problems that they are not suitable for mass production at low cost due to complicated manufacturing methods.

JP 2001-288177 A JP 2001-124903 A JP 2001-011109 A European Patent Application No. 2098544

An object of the present invention is to provide a polymer having a simple production method, excellent photocurability, little curing shrinkage during film formation, and a transparent and high refractive index.

As a result of extensive studies, the present inventor has found that a novel polymerizable compound having a benzo or naphthocycloalkane skeleton can achieve the above object.

That is, the present invention has been made based on the above findings and provides a compound represented by the following general formula (I).

(Wherein, A ¹ and A ² are independently a hydrogen atom, a substituent represented by the following formula (II), the general formula (III) or general formula (IV), A ¹ and A ² Is at least one substituent represented by the following general formula (II), general formula (III) or general formula (IV),
X, Y, Z ¹ and Z ² are each independently an alkyl group having 1 to 10 carbon atoms which may be substituted with a halogen atom, or 6 to 20 carbon atoms which may be substituted with a halogen atom. Represents an aryl group, an arylalkyl group having 7 to 20 carbon atoms which may be substituted with a halogen atom, a heterocyclic group having 2 to 20 carbon atoms which may be substituted with a halogen atom, or a halogen atom; Methylene group in the group, aryl group or arylalkyl group may be interrupted by an unsaturated bond, —O— or —S—, and X may form a ring with X, Can be an aromatic ring,
k represents a number from 0 to 4, p represents a number from 0 to 8, r and s each independently represent a number from 0 to 4, and k, p, r and / or s is 2 or more A plurality of X, Y, Z ¹ and / or Z ² may be the same or different,
x represents a number from 0 to 4, y represents a number from 0 to 4, and the total number of x and y is 2 to 4. )

(Wherein L ¹ , L ² and L ³ each independently represents an ethylene group or a propylene group, n and m each independently represents a number from 0 to 20, and f represents from 1 to 20) When n, m or f is 2 or more, the unit represented by [RO] _n , [RO] _m or [RO] _f is a random copolymer or block of an ethyleneoxy group and a propyleneoxy group A copolymer may be sufficient and M represents a hydrogen atom or a methyl group.)

Further, the invention is a compound of the formula (I), at least one of A ¹ and A ^2, which contains the above general formula (II) or compound is a group represented by any one of formulas (III) The present invention provides a polymerizable composition characterized by that, and further provides a polymer obtained by polymerizing the polymerizable composition.

The polymerizable compound of the present invention gives a transparent and high refractive index polymer with little cure shrinkage during film formation.

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

The compound of the present invention is a compound represented by the above general formula (I) and has a benzo or naphthocycloalkane skeleton. In addition, the compound of the present invention contains a polymerizable compound (hereinafter referred to as the polymerizable compound of the present invention) contained in the polymerizable composition of the present invention due to the difference in groups represented by A ¹ and A ² in the general formula (I). Or an intermediate useful for producing the polymerizable compound (hereinafter also referred to as an intermediate compound of the present invention). Here, in the polymerizable compound of the present invention, in the general formula (I), at least one of A ¹ and A ² is a group represented by either the general formula (II) or the general formula (III). It is a certain compound and is used as the polymerizable compound in the polymerizable composition of the present invention. The intermediate compound of the present invention is a compound in which A ¹ and A ^{2 in the} general formula (I) are a hydrogen atom or a group represented by the general formula (IV).

In the intermediate compound and polymerizable compound of the present invention, in the general formula (I), an alkyl group represented by X, Y, Z ¹ and Z ² , an aryl group, and a methylene group in the arylalkyl group are unsaturated bonds. , —O— or —S— may be interrupted, the substitution position of the halogen group and the interruption position of —O— or —S— are arbitrary, and —O— or —S— is directly bonded to each ring. Including those that combine.

Examples of the alkyl group having 1 to 10 carbon atoms which may be substituted with a halogen atom include methyl, ethyl, propyl, isopropyl, butyl, s-butyl, t-butyl, isobutyl, amyl, isoamyl, and t-amyl. , Hexyl, heptyl, isoheptyl, t-heptyl, n-octyl, isooctyl, t-octyl, 2-ethylhexyl, n-nonyl, n-decyl, trifluoromethyl, difluoromethyl, monofluoromethyl, pentafluoroethyl, tetrafluoro Ethyl, trifluoroethyl, difluoroethyl, heptafluoropropyl, hexafluoropropyl, pentafluoropropyl, tetrafluoropropyl, trifluoropropyl, perfluorobutyl, methoxy, methoxyethoxy, methoxyethoxyethoxy, Tylthio, ethoxy, vinyloxy, propoxy, isopropoxy, butoxy, isobutoxy, t-butoxy, t-butoxycarbonylmethoxy, pentyloxy, isopentyloxy, t-pentyloxy, neopentyloxy, hexyloxy, cyclohexyloxy, isohexyloxy Linear, branched and cyclic alkyl groups such as heptyloxy, octyloxy, 2-ethylhexyloxy, nonyloxy, decyloxy, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclononyl, cyclodecyl and the like.

Examples of the aryl group having 6 to 20 carbon atoms which may be substituted with a halogen atom include phenyl, 1-naphthyl, 2-naphthyl, 1-anthryl, 1-phenanthryl, o-tolyl, m-tolyl, p -Tolyl, 3-fluorenyl, 9-fluorenyl, 1-tetrahydronaphthyl, 2-tetrahydronaphthyl, 1-acenaphthenyl, 1-indanyl, 2-indanyl, 4-vinylphenyl, 3-isopropylphenyl, 4-isopropylphenyl, 4- Butylphenyl, 4-isobutylphenyl, 4-t-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-amylphenyl, 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-dimethylphenoxy, 2,5-dimethylphenoxy, 2 , 6-dimethylphenoxy, 3,4-dimethylphenoxy, 3,5-dimethylphenoxy, , 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-tetramethylphenoxy group, 2,3,5,6-tetramethylphenoxy, pentamethylphenoxy, ethylphenoxy, n-propyl Phenoxy, isopropylphenoxy, n-butylphenoxy, sec-butylphenoxy, tert-butylphenoxy, n-hexylphenoxy, n-octylphenoxy, n-decylphenoxy, n-tetradecylphenoxy, 1-naphthoxy, 2-naphthoxy, 1 -Anthryloxy, 1-phenanthryloxy , O-tolyloxy, m-tolyloxy, p-tolyloxy, 9-fluorenyloxy, 1-tetrahydronaphthoxy, 2-tetrahydronaphthoxy, 1-acenaphthenyloxy, 1-indanyloxy, 2-indanyloxy Etc.

Examples of the arylalkyl group having 7 to 20 carbon atoms which may be substituted with a halogen atom include, for example, benzyl, phenethyl, 2-phenylpropyl, diphenylmethyl, triphenylmethyl, styryl, cinnamyl, 4-chlorophenylmethyl, benzyl Examples thereof include an oxy group, 1-naphthylmethoxy group, 2-naphthylmethoxy group, 1-anthrylmethoxy and the like.

Examples of the heterocyclic group having 2 to 20 carbon atoms which may be substituted with a halogen atom include pyrrolyl, pyridyl, pyrimidyl, pyridazyl, piperazyl, piperidyl, pyranyl, pyrazolyl, triazyl, pyrrolidyl, quinolyl, isoquinolyl, imidazolyl, benzoimidazolyl , Triazolyl, furyl, furanyl, benzofuranyl, thienyl, thiophenyl, benzothiophenyl, thiadiazolyl, thiazolyl, benzothiazolyl, oxazolyl, benzoxazolyl, isothiazolyl, isoxazolyl, indolyl, yurolidyl, morpholinyl, thiomorpholinyl, 2-pyrrolidinone-1 -Yl, 2-piperidone-1-yl, 2,4-dioxyimidazolidin-3-yl, 2,4-dioxyoxazolidine-3-yl, etc. .

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

Examples of the ring structure that may be formed by X include cyclopentane ring, cyclohexane ring, cyclopentene ring, benzene ring, piperidine ring, morpholine ring, lactone ring, lactam ring, and the like, and naphthalene ring, anthracene Examples thereof include condensed rings such as a ring, a fluorene ring, an acenaphthene ring, an indane ring and a tetralin ring.

In the intermediate compound and polymerizable compound of the present invention, in the general formula (I), a compound in which x is 2 and y is 0 is preferable because of excellent photocurability, and among them, the following general formula (V) Is more preferable because it is advantageous in terms of production.

(In the formula, A ¹ , A ² , X, Y, Z ¹ , Z ² , k, r and s are the same as those in the general formula (I).)

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

Among the polymerizable compounds of the present invention, in the above general formula (I), A ¹ and A ² are both groups represented by the above general formula (II), and A ¹ and A ² are Both compounds which are groups represented by the above general formula (III) are preferable because they give a polymer having high hardness.

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

Among the intermediate compounds of the present invention, in the general formula (I), the intermediate compound in which A ¹ and A ² are both represented by the general formula (IV) is n or It is an intermediate particularly useful for the production of m from 1 to 20. Examples of the intermediate compound include compounds in which n or m is a number of 1 to 20 among compounds in which the acryloyl group, methacryloyl group or vinylbenzyl group of the above compounds 1 to 56 is substituted with a hydrogen atom.

In the polymerizable compound of the present invention, n in the general formula (II) and m in the general formula (III) represent a number of 0 to 20, preferably 0 to 5, and more preferably 0 to 3 in terms of production. Similarly, in the intermediate compound of the present invention, f in the general formula (IV) represents a number of 1 to 20, preferably 1 to 5, and more preferably 1 to 3.

The production method of the intermediate compound and the polymerizable compound of the present invention is not particularly limited. For example, in the general formula (I), A ¹ and A ² are both represented by the general formula (II). The polymerizable compound (IA) is prepared by reacting the bisphenol derivative (1) with a (meth) acrylic acid halide in the presence of an alkali, or reacting the bisphenol derivative (1) with (meth) acrylic acid in the presence of an acidic catalyst. It can obtain by making it react. The reaction formula is shown in the following formula. In the following formula, X, Y, Z ¹ , Z ² , k, p, r, s, x, and y are the same as those in the general formula (I), and L ¹ , n, and M are the same as those in the general formula. Same as in formula (II), E ¹ represents a halogen atom or OH.

In the above general formula (I), the polymerizable compound (IB) in which both A ¹ and A ² are represented by the above general formula (III) is an alkenyl derivative of bisphenol derivative (1) and halogenated methylstyrene. It can be obtained by reacting in the presence. The reaction formula is shown in the following formula. In the following formula, X, Y, Z ¹ , Z ² , k, p, r, s, x, y are the same as those in the general formula (I), and L ² and m are the same as those in the general formula ( III) and E ² represents a halogen atom.

In the above general formula (I), the intermediate compound (IC) in which both A ¹ and A ² are represented by the above general formula (IV) can be used as the bisphenol derivative (1). It can be obtained by reacting 2) with a cyclic carbonate in the presence of an alkali or by polyaddition reaction of a bisphenol derivative (2) with ethylene oxide or propylene oxide in the presence of an alkali catalyst. The reaction formula is shown in the following formula. In the following formula, X, Y, Z ¹ , Z ² , k, p, r, s, x, y are the same as those in the general formula (I), and L ³ and f are IV) and q is 0 or 1.

Examples of the acidic catalyst include methanesulfonic acid, benzenesulfonic acid, m-xylenesulfonic acid, p-toluenesulfonic acid, hydroxymethylsulfonic acid, 2-hydroxyethylsulfonic acid, hydroxypropylsulfonic acid, trifluoromethanesulfonic acid, Sulfonic acids such as sulfosalicylic acid and sulfophthalic acid; sulfuric acid, sulfuric anhydride, fuming sulfuric acid, chlorosulfuric acid, fluorosulfuric acid, hydrochloric acid, hydrogen chloride gas, oxalic acid, formic acid, phosphoric acid, trichloroacetic acid, trifluoroacetic acid, silicotungstic acid, phosphorus Examples include heteropolyacids such as tungstic acid, strongly acidic ion exchange resins, activated clay, boron trifluoride, anhydrous aluminum chloride, and zinc chloride. The acidic catalyst is preferably used in an amount of 0.1 to 50 parts by mass, more preferably 1 to 10 parts by mass with respect to 100 parts by mass of the bisphenol derivative (1).

Examples of the alkali 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; sodium methoxy Metal alkoxides such as sodium ethoxide, magnesium dimethoxide, magnesium diethoxide, aluminum diisopropoxide, aluminum tri-t-butoxide; organometallic compounds such as butyl lithium and t-butyl lithium; lithium amide, lithium hexa Alkali metal amides such as methyldisilazane; carbonates such as sodium carbonate and potassium carbonate; triethylamine, pyridine, benzylamine, benzylmethylamine, γ-dimethylaminopyridine, dimethylaniline, tributylamine, 4 Piperidinopyridine, 1,4-diazabicyclo [2.2.2] octane, 1,5-diazabicyclo [4.3.0] -5-nonene, 1,8-diazabicyclo [5.4.0] -7 -Amine compounds such as undecene. When the polymerizable compound is produced, the alkali is used in an amount of 0.1 to 2.0 mol, particularly 0.3 to 1.5 mol, based on one hydroxyl group of the bisphenol derivative (1). Is done. In the production of the intermediate compound, the amount of the alkali used is in the range of 0.01 to 2.0 mol, particularly 0.05 to 0.5 mol, based on one hydroxyl group of the bisphenol derivative (2). Used in.

In the above reaction, a conventionally known solvent can be used. Examples of the solvent include aromatic hydrocarbon solvents such as toluene, xylene and cumene; terpenes such as terpine oil, D-limonene and pinene. Hydrocarbon oils; mineral spirits, paraffinic solvents such as Swazol # 310 (Cosmo Matsuyama Oil Co., Ltd.), Solvesso # 100 (Exxon Chemical Co., Ltd.); alcoholic solvents such as methanol and ethanol; esters such as ethyl acetate Solvents: Halogen solvents such as dichloroethane, carbon tetrachloride, chloroform, trichloroethylene, methylene chloride, chlorobenzene; cyclic ether solvents such as tetrahydrofuran and dioxane; ethers, cellosolve solvents, ketone solvents, aniline, triethylamine, pyridine, dioxane , Acetic acid, acetonitrile , Carbon disulfide, and the like.

In the above reaction, when the compound (IC) is obtained from the bisphenol derivative (2), the compound (IC) may be obtained as a mixture of a plurality of compounds having different numbers of f. A mixture of a plurality of compounds having different numbers of n or m in (IA) or (IB) may be produced and used as a polymerizable composition.

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

The polymerizable composition of the present invention is a composition containing the above polymerizable compound, and is mainly used by mixing with a radical polymerization initiator and a solvent. In the polymerizable composition of the present invention, the polymerizable compound may be one kind or a mixture of two or more kinds, and the content of the polymerizable compound is a proportion of the total mass of the total solid excluding the solvent from the polymerizable composition. And preferably 50 to 90% by mass, more preferably 60 to 80% by mass.

As the radical polymerization initiator, conventionally known compounds can be used. For example, benzoyl peroxide, 2,2′-azobisisobutyronitrile, benzophenone, phenylbiphenyl ketone, 1-hydroxy-1- Benzoylcyclohexane, benzyl, benzyldimethyl ketal, 1-benzyl-1-dimethylamino-1- (4′-morpholinobenzoyl) propane, 2-morpholy-2- (4′-methylmercapto) benzoylpropane, thioxanthone, 1-chloro -4-propoxythioxanthone, isopropylthioxanthone, diethylthioxanthone, ethyl anthraquinone, 4-benzoyl-4'-methyldiphenyl sulfide, benzoin butyl ether, 2-hydroxy-2-benzoylpropane, 2-hydroxy 2- (4′-isopropyl) benzoylpropane, 4-butylbenzoyltrichloromethane, 4-phenoxybenzoyldichloromethane, methyl benzoylformate, 1,7-bis (9′-acridinyl) heptane, 9-n-butyl-3,6 -Bis (2'-morpholinoisobutyroyl) carbazole, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropan-1-one, p-methoxyphenyl-2,4-bis (trichloromethyl) ) -S-triazine, 2-methyl-4,6-bis (trichloromethyl) -s-triazine, 2-phenyl-4,6-bis (trichloromethyl) -s-triazine, 2-naphthyl-4,6- Bis (trichloromethyl) -s-triazine, 2- (p-butoxystyryl) -s-triazine, 2- (p-butoxy Cistyryl) -5-trichloromethyl-1,3,4-oxadiazole, 9-phenylacridine, 9,10-dimethylbenzphenazine, benzophenone / Michler's ketone, hexaarylbiimidazole / mercaptobenzimidazole, thioxanthone / amine, bis ( 2,4,6-trimethylbenzoyl) -phenylphosphine oxide, as well as US Pat. No. 6,596,445, US Pat. No. 6,949,678, JP-A-2005-97141, US Pat. No. 7,648,738, US Pat. Examples thereof include compounds described in JP 789489 A, Japanese Patent No. 3798008, and US Patent Application Publication No. 2007/270522. Among these, the compound represented by the following general formula (a) or (c) is preferable.

(Wherein R ⁷¹ , R ⁷² and R ⁷³ each independently represents R ⁷⁶ , OR ⁷⁶ , COR ⁷⁶ , SR ⁷⁶ , CONR ⁷⁶ R ⁷⁷ or CN; R ⁷⁶ and R ⁷⁷ are each independently Represents an alkyl group, an aryl group, 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 unsaturated. May be interrupted by a bond, an ether bond, a thioether bond or an ester bond, R ⁷⁶ and R ⁷⁷ may be combined to form a ring, R ⁷⁴ represents a halogen atom or an alkyl group, R ⁷⁵ represents a hydrogen atom, a halogen atom, an alkyl group or a substituent represented by the following general formula (b), g represents an integer of 0 to 4, and when g is 2 or more, a plurality of R ⁷⁴ are different. Base )

(In the formula, 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 the number of carbon atoms. 1 represents an alkylene group of 1 to 5, h represents an integer of 0 to 4, and when h is 2 or more, the plurality of X ⁷³ may be different groups.

(In the formula, R ¹ and R ² each independently represent R ¹¹ , OR ¹¹ , COR ¹¹ , SR ¹¹ , CONR ¹² R ¹³ or CN; R ¹¹ , R ¹² and R ¹³ are each independently Represents 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 heterocyclic group having 2 to 20 carbon atoms, an alkyl group, The hydrogen atoms of the aryl group, arylalkyl group and heterocyclic group are further 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 , carboxyl group, may be substituted with an epoxy group, R ^21, 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 or a C2-20 having 7 to 30 carbon atoms The methylene group of the alkylene part of the substituent represented by R ¹¹ , R ¹² , R ¹³ , R ²¹ , R ²² and R ²³ is an unsaturated bond, ether bond, thioether bond, ester It may be interrupted 1 to 5 times by a bond, a thioester bond, an amide bond or a urethane bond, and the alkyl part of the substituent may have a branched side chain, may be a cyclic alkyl, The alkyl terminal may be an unsaturated bond, and R ¹² and R ¹³ and R ²² and R ²³ may be combined to form a ring, and R ³ and R ⁴ are each independently , R ^{^11,} OR ^11, S ^{^{^{11, COR 11, CONR 12 R}}} 13, NR 12 COR 11, OCOR 11, COOR 11, SCOR 11, OCSR 11, COSR 11, CSOR 11, CN, a halogen atom or a hydroxyl group, a and b are each independently 0 to 4. X ¹ represents a direct bond or CO, X ² represents an oxygen atom, a sulfur atom, a selenium atom, CR ³¹ R ³² , CO, NR ³³ or PR ³⁴ , and 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 represents a carbon atom of the adjacent benzene ring via —X ² —. It may be bonded to one to form a ring structure, or R ³ and R ⁴ may be combined to form a ring, and R ³¹ , R ³³ and R ³⁴ are each independently adjacent to each other. Together with either benzene ring to form a ring It may be. )

In the polymerizable composition of the present invention, the content of the radical polymerization initiator is preferably 0.1 to 40% by mass, more preferably the ratio of the total solid content excluding the solvent from the polymerizable composition. 1.0 to 10% by mass. Moreover, the said radical polymerization initiator can be used by 1 type or in mixture of 2 or more types.

The polymerizable composition of the present invention may contain a solvent, and is not particularly limited as long as it is a solvent that can dissolve or disperse the above-mentioned components. For example, methyl ethyl ketone, methyl amyl ketone, diethyl ketone Ketones such as acetone, methyl isopropyl ketone, methyl isobutyl ketone, cyclohexanone; ether solvents such as ethyl ether, dioxane, tetrahydrofuran, 1,2-dimethoxyethane, 1,2-diethoxyethane, dipropylene glycol dimethyl ether; acetic acid Ester solvents such as methyl, ethyl acetate, acetic acid-n-propyl, isopropyl acetate, acetic acid-n-butyl; Cellsolve such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, propylene glycol monomethyl ether acetate Solvents: Alcohol solvents such as methanol, ethanol, iso- or n-propanol, iso- or n-butanol, amyl alcohol; BTX solvents such as benzene, toluene, xylene; Aliphatics such as hexane, heptane, octane, cyclohexane Hydrocarbon solvents: terpene hydrocarbon oils such as turpentine oil, D-limonene, pinene, etc .; paraffins such as mineral spirits, swazol # 310 (Cosmo Matsuyama Oil Co., Ltd.), Solvesso # 100 (Exxon Chemical Co., Ltd.) Solvent: Halogenated aliphatic hydrocarbon solvent such as carbon tetrachloride, chloroform, trichloroethylene, methylene chloride; Halogenated aromatic hydrocarbon solvent such as chlorobenzene; Carbitol solvent, aniline, triethylamine, pyridine, acetic acid, acetonitrile, Carbon disulfide, N, N Dimethylformamide, N- methylpyrrolidone, and among these, ketones or cellosolve solvent. These solvents can be used alone or in combination of two or more.
In the polymerizable composition of the present invention, the content of the solvent is adjusted so that the total solid content in the polymerizable composition is preferably 5 to 60% by mass, more preferably 20 to 50% by mass. . Moreover, you may make it contain in the polymeric composition of this invention as it is, without removing the solvent used when synthesize | combining the polymeric compound of this invention.

In the polymerizable composition of the present invention, a monomer having an unsaturated bond, a chain transfer agent, a surfactant and the like can be used in combination.

Examples of the monomer having an unsaturated bond include 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, isobutyl acrylate, n-octyl acrylate, isooctyl acrylate, isononyl acrylate, stearyl acrylate, acrylic Methoxyethyl acid, dimethylaminoethyl acrylate, zinc acrylate, 1,6-hexanediol diacrylate, trimethylolpropane triacrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate, butyl methacrylate, methacryl Acid-t-butyl, cyclohexyl methacrylate, trimethylolpropane trimethacrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, pentaerythris Tall 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 0.01 to 20% by mass based on the total mass of the total solid content excluding the solvent from the polymerizable composition. Preferably, the content is 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, N- (2-mercaptopropionyl) glycine, 2-mercaptonicotinic acid, 3- [N- (2-mercaptoethyl) carbamoyl] propionic acid, 3- [N- (2-mercaptoethyl) amino] propionic acid, N- (3-mercaptopropionyl) 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, mercap Phenol, 2-mercaptoethylamine, 2-mercaptoimidazole, 2-mercapto-3-pyridinol, 2-mercaptobenzothiazole, mercaptoacetic acid, trimethylolpropane tris (3-mercaptopropionate), pentaerythritol tetrakis (3-mercaptopro A disulfide compound obtained by oxidizing the mercapto compound, iodoacetic acid, iodopropionic acid, 2-iodoethanol, 2-iodoethanesulfonic acid, 3-iodopropanesulfonic acid, and the like. Compounds. These may be used alone or in combination of two or more.

Examples of the surfactant include fluorine surfactants such as perfluoroalkyl phosphates and perfluoroalkyl carboxylates, anionic surfactants such as higher fatty acid alkali salts, alkyl sulfonates, and alkyl sulfates, and higher amines. Cationic surfactants such as halogenates and quaternary ammonium salts, nonionic surfactants such as polyethylene glycol alkyl ethers, polyethylene glycol fatty acid esters, sorbitan fatty acid esters and fatty acid monoglycerides, amphoteric surfactants, silicone surfactants Surfactants such as agents can be used, and these can be used alone or in combination of two or more.

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

In addition, the polymerizable composition of the present invention includes, if necessary, thermal polymerization inhibitors such as anisole, hydroquinone, pyrocatechol, t-butylcatechol, phenothiazine; plasticizers; adhesion promoters; fillers; Conventional additives such as a dispersant, a leveling agent, a silane coupling agent, and a flame retardant can be added. These may be used alone or in combination of two or more.

In addition, the polymerizable composition of the present invention includes a curing catalyst; a reactive or non-reactive diluent (plasticizer) such as a curing catalyst; monoglycidyl ethers, dioctyl phthalate, dibutyl phthalate, benzyl alcohol, coal tar, and the like. ); Fillers such as glass fiber, carbon fiber, cellulose, silica sand, cement, kaolin, clay, aluminum hydroxide, bentonite, talc, silica, fine powder silica, titanium dioxide, carbon black, graphite, iron oxide, bitumen Or pigment; γ-aminopropyltriethoxysilane, N-β- (aminoethyl) -γ-aminopropyltriethoxysilane, N-β- (aminoethyl) -N′-β- (aminoethyl) -γ-amino Propyltriethoxysilane, γ-anilinopropyltriethoxysilane, γ-glycidoxypro Lutriethoxysilane, β- (3,4-epoxycyclohexyl) ethyltriethoxysilane, vinyltriethoxysilane, N-β- (N-vinylbenzylaminoethyl) -γ-aminopropyltriethoxysilane, γ-methacryloxypropyl Silane coupling agents such as trimethoxysilane, γ-chloropropyltrimethoxysilane, and γ-mercaptopropyltrimethoxysilane; candelilla wax, carnauba wax, wood wax, ibota wax, beeswax, lanolin, whale wax, montan wax, petroleum Lubricants such as waxes, fatty acid waxes, fatty acid esters, fatty acid ethers, aromatic esters, aromatic ethers; thickeners; thixotropic agents; antioxidants; light stabilizers; ultraviolet absorbers; Rust preventive agent; colloidal silica, colloidal Conventional additives such as rualumina may be contained, and adhesive resins such as xylene resin and petroleum resin may be used in combination.
In the polymerizable composition of the present invention, these optional additives are preferably 100 parts by mass or less in total with respect to 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 polymerizable composition, and is used by applying it on a supporting substrate such as metal, paper, and plastic by a known means. Moreover, after once applying on support bases, such as a film, it can also transfer on another support base | substrate, There is no restriction | limiting in the application method.

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 plates. , Cellulose plates, silicon plates, reflectors, cycloolefin polymers, calcite plates, and the like. What provided the polyimide alignment film or the polyvinyl alcohol alignment film on such a support substrate can be used especially preferably.

As a method of applying to the support substrate, known methods can be used, for example, curtain coating method, extrusion coating method, roll coating method, spin coating method, dip coating method, bar coating method, spray coating method, slide coating method. Methods, various screen printings, ink jet printings, immersion and casting film forming methods, and the like can be used. The film thickness of the polymer is appropriately selected depending on the application and the like, but is selected from the range of 0.001 to 50 μm, more preferably 0.1 to 30 μm, and particularly preferably 1 to 10 μm.

As a method for polymerizing the polymerizable composition of the present invention, a known method using light, heat or electromagnetic waves 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. The (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. You may use electromagnetic waves, such as an electron beam and an X-ray. 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. The light source is a low-pressure mercury lamp (sterilization lamp, fluorescent chemical lamp, black light), high-pressure discharge lamp (high-pressure mercury lamp, metal halide lamp), or short arc discharge lamp (super-high pressure mercury lamp, xenon lamp, mercury xenon lamp). Among them, an ultrahigh pressure mercury lamp can be preferably used. Light from the light source may be irradiated to the polymerizable composition as it is, or a specific wavelength (or a specific wavelength region) selected by a filter may be irradiated to the polymerizable composition. Preferred irradiation energy density is ² ~ 5000mJ / cm 2, more preferred range is 10 ~ 3000mJ / cm ^2, particularly preferred range is 100 ~ 2000mJ / cm ^2. Preferred illuminance is 0.1 ~ 5000mW / cm ^2, more preferred illuminance is 1 ~ 2000mW / cm ^2.

The polymerizable composition used in the polymer of the present invention can be cured in several seconds to several minutes by polymerization by irradiation with light such as ultraviolet rays, and can be used to manufacture optical components such as various optical lenses represented by spectacle lenses. It becomes possible to increase productivity at the time. In addition, as described above, the radical polymerization reaction is preferably carried out by a polymerization reaction (photopolymerization) by light such as ultraviolet rays, but if necessary, it can be used in combination with a polymerization reaction by heat, a polymerization reaction by gamma rays, or the like. There is no problem.

The polymer of the present invention obtained by irradiating the polymerizable composition of the present invention with light has high hardness, excellent scratch resistance and adhesion, high transparency, low curing shrinkage, and high refractive index. For example, it is suitably used in applications of lenses such as spectacle lenses, Fresnel lenses, lenticular lenses, prism lenses, and micro lenses. In addition, it is also used as a film forming material, a solder mask, a plating resist, an adhesive, a display, an optical fiber, an optical waveguide, a hologram, various coating agents, etc. in manufacturing a printed (wiring circuit) substrate.

Hereinafter, the present invention will be described in more detail with reference to Examples and Comparative Examples, but the present invention is not limited by these Examples and the like. In addition, Example 1 shows the manufacture example of the intermediate compound for manufacturing the polymeric compound of this invention. Example 2 shows a production example of the polymerizable compound of the present invention. Example 3 and Comparative Example 1 show production examples of the polymerizable composition of the present invention and a 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-phenylindane (hereinafter referred to as intermediate compound No. 1)

1,1-bis (4-hydroxyphenyl) -3-phenylindane (89.1 g), ethylene carbonate (11.6 g), potassium carbonate (0.88 g) and toluene (11.0 g) were added to dimethylacetamide (240.0 g) at 110 ° C. Reacted for 10 hours. Thereafter, 1200 mL of ethyl acetate was added, and after removing dimethylacetamide, potassium carbonate and unreacted ethylene carbonate by washing with 500 mL of water three times, the organic phase was dried over anhydrous magnesium sulfate, filtered and evaporated. Crude crystals were obtained. The crude crystals were washed with acetone and dried to obtain 90.6 g of white crystals (yield 82%). As a result of various analyses, the desired intermediate compound No. 1 (a compound obtained by substituting the acryloyl group of the compound 42 (n = 1) with a hydrogen atom).

(result of analysis)
(1) ¹ H-NMR (DMSO-d ₆ ) chemical shift (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-diphenylindane (hereinafter referred to as intermediate compound No. 2)

1,2-bis (4-hydroxyphenyl) -3,5-diphenylindane (20.0 g), ethylene carbonate (9.30 g), and potassium carbonate (1.46 g) were added to dimethylacetamide (120.0 g), and the mixture was heated at 110 ° C. for 6 hours. Reacted. Thereafter, 500 mL of toluene is added, and after removing dimethylacetamide, potassium carbonate and unreacted ethylene carbonate by washing with 100 mL of water three times, the organic phase is dried over anhydrous magnesium sulfate, filtered and evaporated to react. A solid mixture was obtained. The mixture was crystallized from acetone to obtain 9.63 g (yield 40%) of slightly yellow crystals. As a result of various analyses, the desired intermediate compound No. 2 (a compound obtained by substituting the acryloyl group of the compound 33 (n = 1) with a hydrogen atom).

(result of analysis)
(1) ¹ H-NMR (DMSO-d ₆ ) chemical shift (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]
Production of 1,1-bis (4-acryloyloxyphenyl) -3-phenylindane (hereinafter referred to as polymerizable compound No. 1)

In an argon atmosphere, 50.0 mL of dry tetrahydrofuran and 3.38 g of triethylamine are dissolved in 5.00 g of 1,1-bis (4-hydroxyphenyl) -3-phenylindane and dissolved, so that the temperature inside the system does not exceed 10 ° C. While cooling, 2.99 g of acryloyl chloride was slowly added dropwise. After stirring for 1 hour while gradually returning to room temperature, 75 g of 1% phosphoric acid and 100 mL of ethyl acetate were added and stirred, the aqueous phase was discarded, and further washed with 100 mL of water three times until the aqueous phase became neutral. The organic phase was dried over anhydrous magnesium sulfate, and the solvent was distilled off to obtain a mixture. This was separated and purified by silica gel column chromatography (developing solvent: hexane / ethyl acetate = 2/1) to obtain 2.65 g (yield 41%) of white crystals. As a result of various analyses, the target polymerizable compound No. 1 (the above-mentioned compound 42 (n = 0)).

(result of analysis)
(1) ¹ H-NMR (DMSO-d ₆ ) chemical shift (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]
Production of 1,1-bis [4- (2-acryloyloxyethoxy) phenyl] -3-phenylindane (hereinafter referred to as polymerizable compound No. 2)

Intermediate compound No. obtained in Example 1-1 12.7 g, paratoluenesulfonic acid monohydrate 0.412 g, and 2,6-di-tert-butyl-4-methylphenol 0.010 g were added 92.7 g of acrylic acid, and the mixture was heated at 60 ° C. for 15 hours. Stir. Then, 200 mL of ethyl acetate was added, washed with 200 mL of water three times, then washed twice with 100 mL of 10% aqueous sodium hydrogen carbonate solution and further with 200 mL of water, the organic phase was dried over anhydrous magnesium sulfate, and the solvent was retained. To give a reaction mixture. This was separated and purified by silica gel column chromatography (developing solvent: hexane / ethyl acetate = 2/1) to obtain 7.70 g of colorless transparent viscous liquid (yield 64%). As a result of various analyses, the target polymerizable compound No. 2 (the above-mentioned compound 42 (n = 1)).

(result of analysis)
(1) ¹ H-NMR (DMSO-d ₆ ) chemical shift (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]
Production of 1,1-bis (4-acryloyloxyphenyl) -3,5-diphenylindane (hereinafter referred to as polymerizable compound No. 3)

In an argon atmosphere, 50.0 mL of dry tetrahydrofuran and 2.50 g of triethylamine were dissolved in 4.00 g of 1,1-bis (4-hydroxyphenyl) -3,5-diphenylindane, and then the system temperature exceeded 10 ° C. While cooling, 1.99 g of acryloyl chloride was slowly added dropwise. After stirring for 1 hour while gradually 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 organic phase was washed with 100 mL of water three times until the aqueous phase became neutral. Was dried over anhydrous magnesium sulfate, and the solvent was distilled off to obtain 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%) of a colorless solid. As a result of various analyses, the target polymerizable compound No. 3 (the above-mentioned compound 33 (n = 0)).

(result of analysis)
(1) ¹ H-NMR (DMSO-d ₆ ) chemical shift (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]
Production of 1,1-bis [4- (2-acryloyloxyethoxy) phenyl] -3,5-diphenylindane (hereinafter referred to as polymerizable compound No. 4)

Intermediate compound No. obtained in Example 1-2 No. 2 of 9.00 g, paratoluenesulfonic acid monohydrate 0.650 g, and 2,6-di-tert-butyl-4-methylphenol 0.010 g were added 71.7 g of acrylic acid, and the mixture was stirred at 70 ° C. for 30 minutes. Stir for hours. Then, 200 mL of ethyl acetate was added, washed with 200 mL of water three times, then washed twice with 100 mL of 10% aqueous sodium hydrogen carbonate solution and further with 200 mL of water, the organic phase was dried over anhydrous magnesium sulfate, and the solvent was retained. To give a reaction mixture. This was separated and purified by silica gel column chromatography (developing solvent: toluene / ethyl acetate = 10/1) to obtain 5.62 g of colorless crystals (yield 52%). As a result of various analyses, the target polymerizable compound No. 4 (the above-mentioned compound 33 (n = 1)).

(result of analysis)
(1) ¹ H-NMR (DMSO-d ₆ ) chemical shift (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]
Production of 1,1-bis [4- (4-vinylbenzyloxy) phenyl] -3-phenylindane (hereinafter referred to as polymerizable compound No. 5)

1,1-bis (4-hydroxyphenyl) -3-phenylindane (5.00 g), acetone (20.0 g), methanol (4.00 g) and sodium hydroxide (1.16 g) were mixed and heated to 55 ° C. Styrene 4.23 g was slowly added dropwise. After further reacting at 55 ° C. for 4 hours, 50 mL of methanol was added to the reaction solution and stirred well, and the viscous liquid supernatant that had settled to the bottom was removed by decantation. The remaining liquid was dissolved by adding 50 mL of acetone, and then the solvent was distilled off to obtain a yellow crystalline solid. This was washed with acetone to obtain 3.31 g (yield 41%) of yellow crystals. As a result of various analyses, the target polymerizable compound No. 5 (the above-mentioned compound 49 (m = 0)).

(result of analysis)
(1) ¹ H-NMR (DMSO-d ₆ ) chemical shift (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]
The polymerizable compound No. obtained in Example 2-1. 2.00 g of 1; 0.100 g of 1-hydroxycyclohexyl phenyl ketone as a radical photopolymerization initiator; 0.0016 g of DIC F-470 as a leveling agent and 2.10 g of ethyl acetate were mixed and dissolved to obtain a polymerizable composition. Item No. 1 was obtained.

[Example 3-2]
The polymerizable compound No. obtained in Example 2-1. 1, 0.500 g, 2,2-bis (4-acryloyloxyphenyl) propane (hereinafter referred to as compound a-1) 1.50 g, 1-hydroxycyclohexyl phenyl ketone 0.100 g, F- Then, 0.0016 g of 470 and 2.10 g of toluene were mixed and dissolved. 2 was obtained.

[Example 3-3]
The polymerizable compound No. obtained in Example 2-2. No. 2 of 2.00 g, 1-hydroxycyclohexyl phenyl ketone 0.100 g, DIC F-470 0.0016 g and ethyl acetate 2.10 g were mixed well. 3 was obtained.

[Example 3-4]
The polymerizable compound No. obtained in Example 2-3 was used. 0.500 g of compound 3, 1.50 g of compound a-1, 0.100 g of 1-hydroxycyclohexyl phenyl ketone, 0.0016 g of DIC F-470 and 2.10 g of toluene were mixed and dissolved to obtain a polymerizable composition. No. 4 was obtained.

[Example 3-5]
The polymerizable compound No. obtained in Example 2-4. No. 4 of 2.00 g, 1-hydroxycyclohexyl phenyl ketone of 0.100 g, DIC F-470 of 0.0016 g and ethyl acetate of 2.10 g were mixed well. 5 was obtained.

[Example 3-6]
The polymerizable compound No. obtained in Example 2-5 was used. 0.500 g of compound 5, 1.50 g of compound a-1, 0.100 g of 1-hydroxycyclohexyl phenyl ketone, 0.0016 g of DIC F-470 and 2.10 g of toluene were mixed and dissolved, and a polymerizable composition was obtained. No. 6 was obtained.

[Comparative Example 1-1]
2.00 g of compound a-1, 0.100 g of 1-hydroxycyclohexyl phenyl ketone, 0.0016 g of F-470 manufactured by DIC, and 2.10 g of ethyl acetate were mixed well. 1 was obtained.

[Comparative Example 1-2]
2.00 g of 2,2-bis [4- (2-acryloyloxyethoxy) phenyl] propane (hereinafter referred to as compound a-2), 0.100 g of 1-hydroxycyclohexyl phenyl ketone, F-470 manufactured by DIC Of 0.0016 g of ethyl acetate and 2.10 g of ethyl acetate were mixed well. 2 was obtained.

[Comparative Example 1-3]
2.00 g of 9,9-bis [4- (2-acryloyloxyethoxy) phenyl] fluorene (hereinafter referred to as compound a-3), 0.100 g of 1-hydroxycyclohexyl phenyl ketone, F-470 manufactured by DIC Of 0.0016 g of toluene and 2.10 g of toluene were mixed well. 3 was obtained.

Note that, unlike the polymerizable compound of the present invention, the compounds a-1 to a-3 are polymerizable compounds having no benzo or naphthocycloalkane skeleton.

[Examples 4-1 to 4-6]
Polymerizable composition Nos. Obtained in Examples 3-1 to 3-6. 1-No. 0.50 g of each of 6 was applied to a PET film and prebaked at 80 ° C. for 10 minutes in an oven. 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 from the PET film, and the refractive index was measured. The results are shown in [Table 1].

[Comparative Examples 2-1 and 2-2]
Comparative polymerizable composition Nos. Obtained in Comparative Examples 1-1 and 1-2 1 and no. The refractive index of No. 2 was measured in the same manner as in Examples 3-1 to 3-6. The results are also shown in [Table 1].

[Examples 5-1 and 5-2]
The polymerizable composition No. obtained in Examples 3-3 and 3-5. 3, no. 0.50 g of each of No. 5 was applied to a 50 mm × 80 mm × 80 micron TAC film (FT-TDY80UL manufactured by FUJIFILM Corporation) using a bar coater # 40, and prebaked at 80 ° C. for 10 minutes in an oven. Thereafter, a light amount of 500 mJ / cm ² was exposed with a high-pressure mercury lamp to obtain a coated film. The film was allowed to stand on a flat surface, and the height from the flat surface at the four corners of the film was measured. For the total, ○ was less than 20 mm, Δ was 20 mm or more and less than 60 mm, and x was 60 mm or more. Evaluation was performed. The results are shown in [Table 2].

[Comparative Examples 3-1 and 3-2]
Comparative Polymerizable Composition Nos. Obtained in Comparative Examples 1-2 and 1-3 2, no. For each of the three, the amount of deformation was evaluated in the same manner as in Examples 5-1 and 5-2. The results are also shown in [Table 2].

From the results of [Table 1] and [Table 2], the polymer comprising the polymerizable composition containing the polymerizable compound of the present invention exhibits a higher refractive index than the comparative polymer, and film formation It is clear that sometimes it is less warped and is useful as an optical material.

Claims

The compound represented by the following general formula (I).

(Wherein, A 1 and A 2 are independently a hydrogen atom, a substituent represented by the following formula (II), the general formula (III) or general formula (IV), A 1 and A 2 Is at least one substituent represented by the following general formula (II), general formula (III) or general formula (IV),
X, Y, Z 1 and Z 2 are each independently an alkyl group having 1 to 10 carbon atoms which may be substituted with a halogen atom, or 6 to 20 carbon atoms which may be substituted with a halogen atom. Represents an aryl group, an arylalkyl group having 7 to 20 carbon atoms which may be substituted with a halogen atom, a heterocyclic group having 2 to 20 carbon atoms which may be substituted with a halogen atom, or a halogen atom; Methylene group in the group, aryl group or arylalkyl group may be interrupted by an unsaturated bond, —O— or —S—, and X may form a ring with X, Can be an aromatic ring,
k represents a number from 0 to 4, p represents a number from 0 to 8, r and s each independently represent a number from 0 to 4, and k, p, r and / or s is 2 or more A plurality of X, Y, Z 1 and / or Z 2 may be the same or different,
x represents a number from 0 to 4, y represents a number from 0 to 4, and the total number of x and y is 2 to 4. )

(Wherein L 1 , L 2 and L 3 each independently represents an ethylene group or a propylene group, n and m each independently represents a number from 0 to 20, and f represents from 1 to 20) When n, m or f is 2 or more, the unit represented by [RO] n , [RO] m or [RO] f is a random copolymer or block of an ethyleneoxy group and a propyleneoxy group It may be a copolymer, and M represents a hydrogen atom or a methyl group.)
The compound according to claim 1, wherein x is 2 and y is 0 in the general formula (I).
The compound of Claim 1 or 2 represented by the following general formula (V).

(In the formula, A 1 , A 2 , X, Y, Z 1 , Z 2 , k, r and s are the same as those in the general formula (I).)
The compound according to any one of claims 1 to 3, wherein Y in the general formula (I) or the general formula (V) is a phenyl group.
In the general formula (I) or the general formula (V), when k is 0 or 1 and k is 1, X is an alkyl group having 1 to 10 carbon atoms or an aryl group having 6 to 20 carbon atoms. The compound according to any one of claims 1 to 4, wherein
The compound according to any one of claims 1 to 5, wherein in the general formula (I) or the general formula (V), A 1 and A 2 are both groups represented by the general formula (IV).
In the general formula (I) or the general formula (V), at least one of A 1 and A 2 is a group represented by either the general formula (II) or the general formula (III). 6. The compound according to any one of 5 to 5.
The general formula (I) or the general formula (V), wherein A 1 and A 2 are both groups represented by the general formula (II). Compound.
The general formula (I) or the general formula (V), wherein A 1 and A 2 are both groups represented by the general formula (III). Compound.
A polymerizable composition comprising the compound according to any one of claims 7 to 9.
The polymerizable composition according to claim 10, comprising a radical polymerization initiator.
A polymer obtained by polymerizing the polymerizable composition according to claim 10 or 11.