KR101698356B1 - Polymerizable compound, polymerizable composition containing same, and polymer thereof - Google Patents

Abstract

(식 중 A¹ 및 A²는 수소원자, 상기 일반식(Ⅱ), 일반식(Ⅲ) 또는 일반식(Ⅳ)로 표시되는 치환기를 나타내고, A¹ 및 A² 중 적어도 한쪽은 상기 일반식(Ⅱ), 일반식(Ⅲ) 또는 일반식(Ⅳ)로 표시되는 치환기이며, X, Y, Z¹ 및 Z²는 탄소원자수 1∼10의 알킬기 등을 나타내고, X는 X끼리 환을 형성하고 있어도 되며, 그들 환은 방향환이어도 되고, k는 0∼4의 수를 나타내며, p는 0∼8의 수를 나타내고, r 및 s는 0∼4의 수를 나타내며, x는 0∼4의 수를 나타내고, y는 0∼4의 수를 나타내며, x와 y의 수의 합계는 2∼4이고, L¹, L² 및 L³은 에틸렌기 등을 나타내며, n 및 m은 0∼20의 수를 나타내고, f는 1∼20의 수를 나타내며, n, m 또는 f가 2 이상일 경우, [L¹O]_n, [L²O]_m 또는 [L³O]_f로 표시되는 유닛은 에틸렌옥시기와 프로필렌옥시기의 랜덤 공중합체 또는 블록 공중합체여도 되고, M은 메틸기 등을 나타낸다.) An intermediate compound and a polymerizable compound represented by the following general formula (I), at least one of A ¹ and A ² in the following general formula (I) is a group represented by any one of the following general formula (II) or general formula (III) A polymerizable composition containing a polymerizable compound, and a polymer obtained by polymerizing the polymerizable composition.

(Wherein A ¹ and A ² represent a hydrogen atom, a substituent represented by the general formula (II), the general formula (III) or the general formula (IV), and at least one of A ¹ and A ² is a group represented by the general formula X, Y, Z ¹ and Z ² represent an alkyl group having 1 to 10 carbon atoms, etc., and X represents a ring of X each other, or a substituent represented by the general formula (III) or And p represents an integer of 0 to 8, r and s represent a number of 0 to 4, x represents a number of 0 to 4, , y represents a number of 0 to 4, the sum of the numbers of x and y is 2 to 4, L ¹ , L ² and L ³ represent an ethylene group and the like, n and m represent a number of 0 to 20 , f represents a number of 1 to 20, and when n, m or f is 2 or more, a unit represented by [L ¹ O] _n , [L ² O] _m or [L ³ O] _f is an ethyleneoxy group and propylene Even if it is a random copolymer or block copolymer of oxy group And M represents a methyl group, etc.).

Description

POLYMERIZABLE COMPOUND, POLYMERIZABLE COMPOSITION CONTAINING SAME, AND POLYMER THEREOF FIELD OF THE INVENTION The present invention relates to a polymerizable compound,

The present invention relates to a polymerizable compound which is easy to manufacture and has excellent photo-curability, a polymerizable composition containing the polymerizable compound and a polymer. The polymer is transparent, exhibits a low coloration, exhibits a high refractive index, and is useful for optical material applications.

A transparent and high refractive index cured product is 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 formed by copolymerizing bromobisphenol. Patent Documents 3 and 4 disclose a polymerizable composition containing an acrylate compound. However, these materials are not satisfactory in terms of hardness, adhesiveness, light fastness, and the like, and the manufacturing method is complicated, and therefore, it is not suitable for mass production at low cost.

Japanese Patent Application Laid-Open No. 2001-288177 Japanese Patent Application Laid-Open No. 2001-124903 Japanese Patent Application Laid-Open No. 2001-011109 European Patent Application Publication No. 2098544

An object of the present invention is to provide a polymer which is simple in the production process, excellent in photo-curability, less in curing shrinkage during film formation, and transparent and has a high refractive index.

As a result of intensive studies, the inventors of the present invention have 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 each independently a hydrogen atom, a substituent represented by the following general formula (II), (III) or (IV), and at least one of A ¹ and A ² is a Is a substituent represented by the formula (II), the formula (III) or the formula (IV)

X, Y, Z ¹ and Z ² each independently represents an alkyl group having 1 to 10 carbon atoms which may be substituted with a halogen atom, an aryl group having 6 to 20 carbon atoms which may be substituted with a halogen atom, An arylalkyl group of 7 to 20 carbon atoms, a heterocyclic group of 2 to 20 carbon atoms which may be substituted with a halogen atom or a halogen atom, and the methylene group in the alkyl group, aryl group or arylalkyl group may be substituted with an unsaturated bond, -O- or -S- X may form a ring with X, and the ring may be an aromatic ring,

k represents a number of 0 to 4, p represents a number of 0 to 8, r and s each independently represent a number of 0 to 4, and when k, p, r and / or s is 2 or more, X, Y, Z ¹ and / or Z ² may be the same or different,

x represents a number of 0 to 4, y represents a number of 0 to 4, and the sum of the numbers of x and y is 2 to 4.)

(Wherein L ¹ , L ² and L ³ each independently represent an ethylene group or a propylene group, n and m each independently represent a number of 0 to 20, f represents a number of 1 to 20, 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 or block copolymer of ethyleneoxy group and propyleneoxy group, Represents a hydrogen atom or a methyl group.

The present invention also relates to a polymerizable (meth) acrylic polymer comprising a compound represented by formula (I) wherein at least one of A ¹ and A ² is a group represented by any one of the general formula (II) or the general formula , And further to provide a polymer obtained by polymerizing the polymerizable composition.

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

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 a compound represented by the above general formula (I) and has a benzo or naphthocycloalkane skeleton. Further, the compound of the present invention can be obtained by polymerizing a polymerizable compound (hereinafter, also referred to as a polymerizable compound of the present invention) contained in the polymerizable composition of the present invention by the difference between the 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). Herein, the polymerizable compound of the present invention is a compound wherein at least one of A ¹ and A ² in the general formula (I) is a group represented by any one of the general formula (II) or the general formula (III) And is used in the polymerizable composition of the present invention. The intermediate compound of the present invention is a compound wherein 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 the polymerizable compound of the present invention, the methylene group in the alkyl group, aryl group or arylalkyl group represented by X, Y, Z ¹ and Z ² in the general formula (I) is an unsaturated bond, -O- or -S -, the substitution position of the halogen group, and the position where the -O- or -S- is interrupted are arbitrary, and -O- or -S- may be directly bonded to each ring.

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, , Heptyl, isoheptyl, t-heptyl, n-octyl, isooctyl, t-octyl, 2-ethylhexyl, n-nonyl, n-decyl, trifluoromethyl, difluoromethyl, monofluoromethyl, And examples thereof include fluoroethyl, tetrafluoroethyl, trifluoroethyl, difluoroethyl, heptafluoropropyl, hexafluoropropyl, pentafluoropropyl, tetrafluoropropyl, trifluoropropyl, perfluorobutyl, methyl Methoxyethoxy, methoxyethoxy, methylthio, ethoxy, vinyloxy, propoxy, isopropoxy, butoxy, isobutoxy, t-butoxy, t-butoxycarbonylmethoxy, Pentyloxy, isopentyloxy, t-pentyloxy, neopentyloxy, hexyloxy, cyclohexyloxy Cyclohexyl, cyclohexyl, cyclohexyl, cyclohexyl, cyclohexyl, cyclohexyl, cyclohexyl, cyclohexyl, cyclohexyl, cycloheptyl, cycloheptyl, cyclohexyl, Branched and cyclic alkyl groups of 1 to 20 carbon atoms.

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, 2-tetrahydronaphthyl, 1-acenaphthenyl, 1-indanyl, 2-indanyl, 4-fluorenyl, 4-hexylphenyl, 4-cyclohexylphenyl, 4-octylphenyl, 4-isopropylphenyl, 4-isopropylphenyl, 4-isopropylphenyl, Dimethylphenyl, 2,4-dimethylphenyl, 2,5-dimethylphenyl, 2,6-dimethylphenyl, 3,4-dimethylphenyl, 3,5-dimethylphenyl Di-t-butylphenyl, 2,5-di-t-butylphenyl, 2,6- cyclohexylphenyl, biphenyl, 2,4,5-trimethylphenyl, 4-chlorophenyl, 3,4-dichlorophenyl, 4-trichlorophenyl, 4-trifluorophenyl, perfluoro Phenyl, phenyl Methylphenoxy, 2-methylphenoxy, 4-methylphenoxy, 2,3-dimethylphenoxy, 2,4-dimethylphenoxy, 2,5-dimethylphenoxy, 2,6-dimethylphenoxy 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-tetra Methylphenoxy group, 2,3,5,6-tetramethylphenoxy, pentamethylphenoxy, ethylphenoxy, n-propylphenoxy, isopropylphenoxy, n-butylphenoxy, sec-butylphenoxy, tert -Butylphenoxy, n-hexylphenoxy, n-octylphenoxy, n-decylphenoxy, n-tetradecylphenoxy, 1-naphthoxy, 2- But are not limited to, oxy, o-tolyloxy, m-tolyloxy, p-tolyloxy, 9-fluorenyloxy, 1-tetrahydronaphthoxy, 2-tetrahydronaphthoxy, , 2- There may be mentioned oxy and the like.

Examples of the arylalkyl group having 7 to 20 carbon atoms which may be substituted with a halogen atom include benzyl, phenethyl, 2-phenylpropyl, diphenylmethyl, triphenylmethyl, styryl, cinnamyl, Oxime, 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, Thiazolyl, thiazolyl, furyl, furanyl, benzofuranyl, thienyl, thiophenyl, benzothiophenyl, thiadiazolyl, thiadiazolyl, thiadiazolyl, thiadiazolyl, thiadiazolyl, thiadiazolyl, Pyrrolidinon-1-yl, 2-pyrrolidinone, pyrimidinyl, pyrimidinyl, pyrimidinyl, pyrimidinyl, pyrimidinyl, pyrimidinyl, pyrimidinyl, pyrimidinyl, Pyridone-1-yl, 2,4-dioxiimidazolidin-3-yl, 2,4-dioxoxazolidin-3-yl, and the like.

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

Examples of the ring structure in which X may be formed include a 5- to 7-membered ring such as a cyclopentane ring, a cyclohexane ring, a cyclopentene ring, a benzene ring, a piperidine ring, a morpholine ring, a lactone ring and a lactam ring, and a naphthalene ring, A condensed ring such as a fluorene ring, an acenaphthene ring, an indane ring, and a tetralin ring.

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

(Wherein A ¹ , A ² , X, Y, Z ¹ , Z ² , k, r and s are as defined in the general formula (I)

Furthermore, a compound wherein Y in the general formula (I) or the general formula (V) is a phenyl group is preferable because k is 0 or 1, and when k is 1, X is a carbon atom number 1 To 10 carbon atoms or an aryl group having 6 to 20 carbon atoms is advantageously used because it is more advantageous in terms of production.

Among the polymerizable compounds of the present invention, all of A ¹ and A ² in the general formula (I) are the groups represented by the general formula (II), or all of A ¹ and A ² are represented by the general formula (III) Is preferred because it gives a polymer having a high hardness.

Examples of the polymerizable compound of the present invention represented by the above general formula (I) include the following compounds 1 to 56. On the other hand, in the following compounds, n and m represent a number of 0 to 20.

Among the intermediate compounds of the present invention, the intermediate compounds represented by the general formula (IV) in the general formula (I) in which all of A ¹ and A ² are represented by the general formula (IV) Is an especially useful intermediate. Examples of the above-mentioned intermediate compound include compounds wherein n or m is a number of 1 to 20, among compounds obtained by substituting the acryloyl group, methacryloyl group or vinylbenzyl group of the compounds 1 to 56 with hydrogen atoms.

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

The intermediate compound of the present invention and the method for producing the polymerizable compound are not particularly limited. For example, in the general formula (I), all of A ¹ and A ² are the polymerizable compound represented by the general formula (II) (IA) can be obtained by reacting a bisphenol derivative (1) with a (meth) acrylic acid halide in the presence of an alkali 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. X, Y, Z ¹ , Z ² , k, p, r, s, x and y in the following formulas are the same as in the general formula (I), L ¹ , n and M are as defined in the general formulas And E ¹ represents a halogen atom or OH.

The polymerizable compound (IB) represented by the general formula (III) in the general formula (I) wherein A ¹ and A ² are both represented by the general formula (III) is obtained by reacting the bisphenol derivative (1) with halogenated methylstyrene in the presence of an alkali have. The reaction formula is shown in the following formula. X, Y, Z ¹ , Z ² , k, p, r, s, x and y in the following formulas are the same as in the formula (I), L ² and m are the same as in the formula , And E ² represents a halogen atom.

In the general formula (Ⅰ), A ¹ and A intermediate compound (IC) ² are both represented by the general formula (Ⅳ) may be used as the bisphenol derivative (1), a bisphenol derivative (2) and the cyclic carbonate The ester can be obtained by reacting the bisphenol derivative (2) with ethylene oxide or propylene oxide in the presence of an alkali catalyst in the presence of an alkali in the presence of an alkali. The reaction formula is shown in the following formula. X, Y, Z ¹ , Z ² , k, p, r, s, x and y in the following formulas are the same as in the formula (I), L ³ and f are as defined in the formula , 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, sulfosalicylic acid, sulfo Sulfonic acids such as phthalic 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, tungstosilicic acid, tungstophosphoric acid ), Strongly acidic ion exchange resins, activated clay, boron trifluoride, anhydrous aluminum chloride, and zinc chloride. The acid catalyst is used in an amount of preferably 0.1 to 50 parts by mass, more preferably 1 to 10 parts by mass, based on 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; Metal alkoxides such as sodium methoxide, sodium ethoxide, magnesium dimethoxide, magnesium diethoxide, aluminum diisopropoxide and aluminum tri-t-butoxide; Organometallic compounds such as butyllithium and t-butyllithium; Alkali metal amides such as lithium amide and lithium hexamethyldisilazane; Carbonates such as sodium carbonate and potassium carbonate; Diazabicyclo [2.2.2] octane, 1,5-diazabicyclo [2.2.2] octane, 1,5-dimethylbenzylamine, -Diazabicyclo [4.3.0] -5-nonene, and 1,8-diazabicyclo [5.4.0] -7-undecene. When the polymerizable compound is prepared, the amount of the alkali to be used is in the range of 0.1 to 2.0 mol, particularly 0.3 to 1.5 mol, per one hydroxyl group of the bisphenol derivative (1). When the intermediate compound is prepared, the amount of the alkali to be used is in the range of 0.01 to 2.0 mol, especially 0.05 to 0.5 mol, per one hydroxyl group of the bisphenol derivative (2).

In addition, conventionally known solvents may be used for the reaction. Examples of the solvent include aromatic hydrocarbon solvents such as toluene, xylene and cumene; Terpene-based hydrocarbon oils such as terphenyl oil, D-limonene, and pinene; Paraffin type solvents such as mineral spirits, Swazor # 310 (Kosomo Matsuyama Sekiyu K.K.) and Solvesso # 100 (available from Exxon Chemical Co., Ltd.); Alcohol solvents such as methanol and ethanol; Ester solvents such as ethyl acetate; Halogenated solvents such as dichloroethane, carbon tetrachloride, chloroform, trichlorethylene, methylene chloride and 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.

When the compound (IC) is obtained from the bisphenol derivative (2) in the above reaction, the number of f may be obtained as a mixture of a plurality of compounds different from each other. ), A mixture of a plurality of compounds having different numbers of n or m may be prepared and used as a polymerizable composition.

The intermediate compound and the polymerizable compound of the present invention described above are used for various purposes as the 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 a mixture of two or more species, and the content of the polymerizable compound in the polymerizable composition preferably accounts for the total mass of all solids excluding the solvent 50 to 90 mass%, and more preferably 60 to 80 mass%.

As the radical polymerization initiator, conventionally known compounds can be used. Examples thereof include benzoyl peroxide, 2,2'-azobisisobutyronitrile, benzophenone, phenylbiphenyl ketone, 1-hydroxy- Benzoylcyclohexane, benzyl, benzyldimethylketal, 1-benzyl-1-dimethylamino-1- (4'-morpholinobenzoyl) propane, 2- Benzoyl-4'-methyldiphenylsulfide, benzoin butyl ether, benzoyl benzoyl ether, benzoyl benzoyl ether, benzoyl benzoyl ether, Benzoyl propane, 2-hydroxy-2-benzoyl propane, 2-hydroxy-2- (4'-isopropyl) benzoyl propane, 4-butylbenzoyl trichloromethane, 4-phenoxybenzoyl dichloromethane, Methyl-1- [4- (methylthio) heptane, 9-n-butyl-3,6-bis (2'-morpholinoisobutyryl) carbazole, ) Phenyl] - (Trichloromethyl) -s-triazine, 2-methyl-4,6-bis (trichloromethyl) -s- (Trichloromethyl) -s-triazine, 2- naphthyl-4,6-bis (trichloromethyl) -s-triazine, 2- Tridecyl) -s-triazine, 2- (p-butoxystyryl) -5-trichloromethyl-1,3,4-oxadiazole, 9-phenylacridine, 9,10- Phenazine, benzophenone / Michler's ketone, hexaarylbiimidazole / mercaptobenzimidazole, thioxanthone / amine, bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide, and US Patent No. 6596445, US Patent No. 6949678, Japanese Patent Application Publication No. 2005-97141, US Patent No. 7648738, US Patent No. 7189489, Japanese Patent Application No. 3798008, US Patent Application Publication Compounds described in the specification of Japanese Patent Application No. 2007/270522. Among them, the compound represented by the following general formula (a) or (c) is preferable.

(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 alkyl group, an arylalkyl group or a heterocyclic group, which may be substituted with a halogen atom and / or a heterocyclic group, and the alkylene moiety of the alkyl group and the arylalkyl group thereof is interrupted by an unsaturated bond, an ether bond, a thioether bond or an ester bond R ⁷⁶ and R ⁷⁷ may be taken together 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 may be different from each other.

(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 is 1 to 5 carbon atoms , H represents an integer of 0 to 4, and when h is 2 or more, plural X < ⁷³ >

(Wherein 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 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 heterocyclic group having 2 to 20 carbon atoms, and the hydrogen atoms of the alkyl group, ^{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, a carboxyl group, being optionally substituted with an epoxy group, R ^21, R ²² and R ²³ each independently represent a hydrogen atom, an alkyl group of carbon atoms 1 to 20, 6 to 30 carbon atoms, an aryl group, an arylalkyl group of carbon atoms or carbon atoms of the heterocyclic group of 2 to 20 atoms of 7 to 30, wherein R ^11, R ^{12, R 13, R 21,} R 22 and R ²³ coming from The methylene group of the alkylene portion of the substituent to be displayed may be interrupted one to five times by an unsaturated bond, an ether bond, a thioether bond, an ester bond, a thioester bond, an amide bond or a urethane bond, R ¹² and R ^13, and R ²² and R ²³ may be a single bond to form a ring. R ³ and R ⁴ , which may be the same or different, are each independently ^{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 a hydroxyl group And a and b each independently represent 0 to 4; X ¹ is a direct represents a 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, R 31, R 32} , R 33 and R ³⁴ are each And R ³ may be bonded to one of the carbon atoms of the adjacent benzene ring through -X ² - to form a ring structure, and R ¹¹ , OR ¹¹ , COR ¹¹ , SR ¹¹ , CONR ¹² R ¹³ , Or R ³ and R ⁴ may be taken together to form a ring, and R ³¹ , R ^33, and R ³⁴ may independently be bonded to any adjacent benzene ring to form a ring.

In the polymerizable composition of the present invention, the content of the radical polymerization initiator in the polymerizable composition is preferably 0.1 to 40% by mass, more preferably 1.0 to 10% by mass, relative to the total mass of all solids in the polymerizable composition excluding the solvent. to be. The radical polymerization initiator may be used singly or in combination of two or more.

The polymerizable composition of the present invention may contain a solvent and is not particularly limited as long as it is a solvent capable of dissolving or dispersing the above components. Examples of the solvent include methyl ethyl ketone, methyl amyl ketone, diethyl ketone, acetone, methyl Ketones such as isopropyl ketone, methyl isobutyl ketone, and cyclohexanone; Ether solvents such as ethyl ether, dioxane, tetrahydrofuran, 1,2-dimethoxyethane, 1,2-diethoxyethane and dipropylene glycol dimethyl ether; Esters such as methyl acetate, ethyl acetate, n-propyl acetate, isopropyl acetate, and n-butyl acetate; Cellosolve solvents such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether and propylene glycol monomethyl ether acetate; Alcohol-based solvents such as methanol, ethanol, iso-or n-propanol, iso- or n-butanol, and amyl alcohol; BTX type solvents such as benzene, toluene and xylene; Aliphatic hydrocarbon solvents such as hexane, heptane, octane and cyclohexane; Terpene-based hydrocarbon oils such as terphenyl oil, D-limonene, and pinene; Paraffin solvents such as Mineral Spirit, Swazor # 310 (Kosomo Matsuyama Sekiyu Co., Ltd.), Solvesso # 100 (Exxon Chemical Co., Ltd.); Halogenated aliphatic hydrocarbon solvents such as carbon tetrachloride, chloroform, trichlorethylene and methylene chloride; Halogenated aromatic hydrocarbon solvents such as chlorobenzene; N, N-dimethylformamide, N-methylpyrrolidone, etc. Among them, a ketone or a cellosolve solvent may be used as the solvent, and the solvent may be selected from the group consisting of acetone, acetonitrile, desirable. These solvents may be used singly or in combination of two or more.

In the polymerizable composition of the present invention, the content of the solvent may be adjusted so that the total solids concentration in the polymerizable composition is preferably from 5 to 60 mass%, more preferably from 20 to 50 mass%. The polymerizable compound of the present invention may be incorporated into the polymerizable composition of the present invention without removing the solvent used in the synthesis.

The polymerizable composition of the present invention may further contain monomers having an unsaturated bond, a chain transfer agent, a surfactant, and the like.

Examples of the monomer having an unsaturated bond include acrylic acid such as 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, isobutyl acrylate, n-octyl acrylate, isooctyl acrylate, isononyl acrylate, stearyl acrylate, methoxyacrylate Ethyl acrylate, dimethylaminoethyl acrylate, zinc acrylate, 1,6-hexanediol diacrylate, trimethylolpropane triacrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate, methacrylic acid Butyl acrylate, butyl acrylate, t-butyl methacrylate, cyclohexyl methacrylate, trimethylol propane trimethacrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, pentaerythritol tetraacrylate, pentaerythritol triacrylate, Tricyclodecane dimethyloldiacrylate, 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, more preferably 0.1 to 10% by mass in the total mass of all solids in the polymerizable composition excluding the solvent 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, , 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- Mercapto-2-butanol, mercaptophenol, 2-mercaptoethylamine, 2-mercaptoimidazole, 2-mercapto-3-pyridinol, 2-mercaptobenzothiazole A mercapto compound such as a sol, mercaptoacetic acid, trimethylolpropane tris (3-mercaptopropionate), pentaerythritol tetrakis (3-mercaptopropionate) There may be mentioned alkyl iodide compounds such as compound, the mercapto-disulfide compounds obtained by oxidizing the compound, ethyl iodide, iodine acid, 2-iodine-ethanol, 2-iodine-ethanesulfonic acid, 3-iodine-propanesulfonic acid. These may be used alone or in combination of two or more.

Examples of the surfactant include fluorine surfactants such as perfluoroalkylphosphoric acid esters and perfluoroalkylcarboxylic acid salts, anionic surfactants such as higher fatty acid alkali salts, alkylsulfonates and alkylsulfates, higher amine halides, A surfactant such as a cationic surfactant such as a polyoxyethylene alkyl ether, a polyoxyethylene alkyl ether, a polyoxyethylene alkyl ether, a polyoxyethylene alkyl ether, a polyoxyethylene alkyl ether, a polyoxyethylene alkyl ether, a polyoxyethylene alkyl ether, These may be used alone or in combination of two or more.

The polymerizable composition of the present invention may also improve the properties of the cured product by 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- Latex copolymer, polyvinyl butyral, cellulose ester, polyacrylamide, saturated polyester, and the like. These may be used alone or in combination of two or more.

The polymerizable composition of the present invention may optionally contain thermal polymerization inhibitors such as anisole, hydroquinone, pyrocatechol, t-butylcatechol, and phenothiazine; Plasticizers; Adhesion promoters; Fillers; Defoamer; Dispersing agent; Leveling agents; Silane coupling agents; Flame retardant and the like can be added. These may be used alone or in combination of two or more.

The polymerizable composition of the present invention may optionally contain a curing catalyst; Reactive or non-reactive diluents (plasticizers) such as monoglycidyl ethers, dioctyl phthalate, dibutyl phthalate, benzyl alcohol, coal tar; Silica, microcrystalline silica, titanium dioxide, carbon black, graphite, iron oxide, bitumen materials such as glass fiber, carbon fiber, cellulose, silica sand, cement, kaolin, clay, aluminum hydroxide, bentonite, talc, Fillers or pigments; aminopropyltriethoxysilane, N -? - (aminoethyl) -? - aminopropyltriethoxysilane, N-? - (aminoethyl) -N'- (3,4-epoxycyclohexyl) ethyltriethoxysilane, vinyltriethoxysilane, N (trimethylsilyl) ethane, N, N-dimethylaminopropyltriethoxysilane, ? - (N-vinylbenzylaminoethyl) -? - aminopropyltriethoxysilane,? -methacryloxypropyltrimethoxysilane,? -chloropropyltrimethoxysilane,? -mercaptopropyltrimethoxysilane Silane coupling agents such as; Such as candelilla wax, carnauba wax, Japanese wax, pewter, beeswax, lanolin, spermaceti, montan wax, petroleum wax, , Fatty acid waxes, fatty acid esters, fatty acid ethers, aromatic esters, aromatic ethers and the like; Thickener; Chisel tropic; Antioxidants; Light stabilizer; Ultraviolet absorber; Flame retardant; Defoamer; Corrosion inhibitors; Colloidal silica, colloidal alumina, and the like. Further, viscous resins such as xylene resin and petroleum resin may be used in combination.

In the polymerizable composition of the present invention, such optional additives are preferably 100 parts by mass or less in total, 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 is applied on a supporting substrate of metal, paper, plastic or the like by a known means. Alternatively, the film may be once transferred onto a support gas such as a film and then transferred onto another support gas.

The supporting substrate is not particularly limited, but preferable examples thereof include glass plates, polyethylene terephthalate plates, polycarbonate plates, polyimide plates, polyamide plates, polymethylmethacrylate plates, polystyrene plates, polyvinyl chloride plates, polytetrafluoroethylene A plate, a cellulose plate, a silicon plate, a reflector, a cycloolefin polymer, and an interference plate. A polyimide alignment film or a polyvinyl alcohol alignment film coated on such a support substrate can be particularly preferably used.

Examples of the method of applying the coating liquid to the support substrate include known methods such as a curtain coating method, an extrusion coating method, a roll coating method, a spin coating method, a dip coating method, a bar coating method, a spray coating method, , Various screen printing, ink jet printing, and the like can be used. On the other hand, the thickness of the polymer is appropriately selected depending on the use and the like, and is selected in the range of 0.001 to 50 탆, more preferably 0.1 to 30 탆, particularly preferably 1 to 10 탆.

As the method of polymerizing the polymerizable composition of the present invention, known methods using light, heat or electromagnetic waves can be applied. Examples of the polymerization reaction by light or electromagnetic waves include radical polymerization, anion polymerization, cation polymerization, coordination polymerization, and living polymerization. The (co) polymer formed on the support substrate may be used as it is, or may be separated from the support substrate or transferred to another support substrate if necessary.

Preferred types of the light include ultraviolet rays, visible rays, infrared rays, and the like. Electromagnetic waves such as electron beams and X-rays may be used. Usually, ultraviolet rays or visible rays are preferred. The preferred wavelength range is from 150 to 500 nm. A more preferred range is 250 to 450 nm, and a most preferred range is 300 to 400 nm. The light source may be a low pressure mercury lamp (sterilizing lamp, fluorescent chemical lamp, black light), a high pressure discharge lamp (high pressure mercury lamp, metal halide lamp), or a short arc discharge lamp (ultra high pressure mercury lamp, xenon lamp, mercury xenon lamp) But an ultra high pressure mercury lamp can be preferably used. The polymerizable composition may be irradiated with light from the light source as it is, or the polymerizable composition may be irradiated with a specific wavelength (or a specific wavelength range) selected according to the filter. The preferable irradiation energy density is 2 to 5000 mJ / cm 2, more preferably 10 to 3000 mJ / cm 2, particularly preferably 100 to 2000 mJ / cm 2. The preferable roughness is 0.1 to 5000 mW / cm2, and the more preferable roughness is 1 to 2000 mW / cm2.

The polymerizable composition used in the polymer of the present invention can be cured in a few seconds to several minutes by polymerization by irradiation of light such as ultraviolet rays, and can be cured in the production of optical parts such as various optical lenses represented by spectacle lenses Productivity can be increased. The radical polymerization reaction is preferably carried out by a polymerization reaction (photopolymerization) with light such as ultraviolet rays as described above. If necessary, the radical polymerization reaction may be used in combination with thermal polymerization reaction or polymerization reaction by gamma radiation.

The polymer of the present invention obtained by light irradiation of the polymerizable composition of the present invention has a high hardness, an excellent scratch resistance, an excellent adhesion, a high transparency, a low hardening shrinkage, a high refractive index, , A lenticular lens, a prism lens, a microlens, and the like. It is also used as a film-forming material, a solder mask for manufacturing a printed circuit (wiring circuit) substrate, a plating resist, an adhesive, a display, an optical fiber, an optical waveguide, a hologram and various coating agents.

<Examples>

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. On the other hand, 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 production examples 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 and comparative polymer of the present invention.

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

89.1 g of 1,1-bis (4-hydroxyphenyl) -3-phenylindane, 11.6 g of ethylene carbonate, 0.88 g of potassium carbonate and 11.0 g of toluene were added to 240.0 g of dimethylacetamide and reacted at 110 DEG C for 10 hours. Thereafter, 1200 mL of ethyl acetate was added, dimethylacetamide, potassium carbonate and unreacted ethylene carbonate were removed by washing three times with 500 mL of water, and then the organic phase was dried over anhydrous magnesium sulfate, filtered and solvent distilled off I got a coarse decision. This crude crystal was washed with acetone and dried to obtain 90.6 g (yield: 82%) of white crystals. As a result of various analyzes, it was confirmed that the aimed intermediate compound No. 1 (the compound in which the acryloyl group of the above compound 42 (n = 1) was substituted with a hydrogen atom).

(Analysis)

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

2H), 6.77 (d, 1H), 3.72-4.76 (m, 4H) : 1H), 6.84-6.90 (m, 4H), 7.02-7.14 (m, 5H), 7.17-7.29 (m, 5H), 7.32-7.38

(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)

20.0 g of 1,1-bis (4-hydroxyphenyl) -3,5-diphenyl indene, 9.30 g of ethylene carbonate, and 1.46 g of potassium carbonate were added to 120.0 g of dimethylacetamide and reacted at 110 DEG C for 6 hours. Thereafter, 500 mL of toluene was added, and 100 mL of water was washed three times to remove dimethylacetamide, potassium carbonate and unreacted ethylene carbonate. The organic phase was dried over anhydrous magnesium sulfate, filtered, and solvent distilled off to give a reaction A solid which is a mixture was obtained. This mixture was crystallized from acetone to obtain 9.63 g (yield: 40%) of pale yellow crystals. As a result of various analyzes, it was confirmed that the aimed intermediate compound No. 2 (a compound obtained by substituting the acryloyl group of the above compound 33 (n = 1) with a hydrogen atom).

(Analysis)

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

2H), 6.87 (m, 2H), 2.74 (d, 1H) 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]

Preparation of 1,1-bis (4-acryloyloxyphenyl) -3-phenylindan (hereinafter referred to as polymerizable compound No. 1)

50.0 mL of dry tetrahydrofuran and 3.38 g of triethylamine were added to 5.00 g of 1,1-bis (4-hydroxyphenyl) -3-phenylindane under an argon atmosphere to dissolve the system, , 2.99 g of acryloyl chloride was slowly added dropwise while cooling. 75 g of 1% phosphoric acid and 100 ml of ethyl acetate were added and stirred to discard the aqueous phase. The aqueous phase was further washed three times with 100 ml of water 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 analyzes, it was confirmed that the aimed polymerizable compound No. 1 (the above compound 42 (n = 0)).

(Analysis)

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

2H), 6.37-6.46 (m: 2H), 6.51-6.56 (m, 2H), 2.49-2.53 (m, ), 7.10-7.40 (m: 17H)

(2) IR spectrum (cm ^-1 )

1431, 1455, 1404, 1352, 1295, 1250, 1209, 1170, 1112, 1015, 972, 927, 902, 847, 807, 778, 762, 740, 703

[Example 2-2]

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

92.7 g of acrylic acid was added to 10.0 g of the intermediate compound No. 1 obtained in Example 1-1, 0.412 g of para-toluenesulfonic acid monohydrate and 0.010 g of 2,6-di-t-butyl-4-methylphenol, Lt; / RTI &gt; for 15 hours. Then, 200 mL of ethyl acetate was added, and the mixture was washed with 200 mL of water three times, then washed twice with 100 mL of a 10% aqueous solution of sodium hydrogencarbonate and further washed with 200 mL of water. The organic phase was dried over anhydrous magnesium sulfate, To obtain 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 (yield: 64%) of a colorless transparent viscous liquid. As a result of various analyzes, it was confirmed that the aimed polymerizable compound No. 2 (the above-mentioned compound 42 (n = 1)).

(Analysis)

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

2H), 6.17 (dd, 1H), 2.71 (dd, 1H), 3.20 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 ), 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)

50.0 mL of dry tetrahydrofuran and 2.50 g of triethylamine were added to and dissolved in 4.00 g of 1,1-bis (4-hydroxyphenyl) -3,5-diphenylindane in an argon atmosphere, And 1.99 g of acryloyl chloride was slowly added dropwise while cooling. The mixture was stirred for 1 hour while gradually returning to room temperature, and then 50 g of water and 100 ml of ethyl acetate were added and stirred to discard the aqueous phase. The aqueous phase was washed three times with 100 ml of water until the aqueous phase became neutral, and then the organic phase was washed with anhydrous magnesium sulfate Dried 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 colorless solid. As a result of various analyzes, it was confirmed that the objective polymerizable compound No. 3 (the above compound 33 (n = 0)).

(Analysis)

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

2H), 6.00-6.11 (m, 2H), 6.32-6.40 (m, 2H), 2.88-2.95 (m, ), 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]

Preparation of 1,1-bis [4- (2-acryloyloxyethoxy) phenyl] -3,5-diphenylindane (hereinafter referred to as polymerizable compound No. 4)

71.7 g of acrylic acid was added to 9.00 g of the intermediate compound No. 2 obtained in Example 1-2, 0.650 g of para-toluenesulfonic acid monohydrate and 0.010 g of 2,6-di-t-butyl-4-methylphenol, Lt; / RTI &gt; for 30 hours. Then, 200 mL of ethyl acetate was added, and the mixture was washed with 200 mL of water three times, then washed twice with 100 mL of a 10% aqueous solution of sodium hydrogencarbonate and further washed with 200 mL of water. The organic phase was dried over anhydrous magnesium sulfate, To obtain 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 (yield 52%) of colorless crystals. As a result of various analyzes, it was confirmed that the aimed polymerizable compound No. 4 (the above compound 33 (n = 1)).

(Analysis)

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

2H), 6.17-6.28 (m, 4H), 4.42-4.48 (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 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]

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

5.00 g of 1,1-bis (4-hydroxyphenyl) -3-phenylindane, 20.0 g of acetone, 4.00 g of methanol and 1.16 g of sodium hydroxide were mixed and heated up to 55 ° C. 4.23 g of 4-chloromethylstyrene was slowly added dropwise Respectively. After reacting at 55 DEG C for 4 hours, 50 mL of methanol was added to the reaction solution, stirred well, and the supernatant of the viscous liquid settling on the bottom was decanted. 50 mL of acetone was added to dissolve the remaining liquid, and 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 analyzes, it was confirmed that the aimed polymerizable compound No. 5 (the above compound 49 (m = 0)).

(Analysis)

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

2H), 5.81-5.86 (m, 2H), 2.36-2.73 (m, 1H), 3.16-3.25 ), 6.68-6.81 (m: 3H), 6.91-7.10 (m: 7H), 7.11-7.30 (m: 7H), 7.31-7.39 (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 photo radical polymerization initiator, 0.0016 g of F-470 manufactured by DIC as a leveling agent, and ethyl acetate 2.10 g were mixed and dissolved to obtain Polymerizable Composition No. 1.

[Example 3-2]

0.500 g of the polymerizable compound No. 1 obtained in Example 2-1, 1.50 g of 2,2-bis (4-acryloyloxyphenyl) propane (hereinafter referred to as a compound a-1) 0.100 g of cyclohexyl phenyl ketone, 0.0016 g of F-470 manufactured by DIC, and 2.10 g of toluene were mixed and dissolved to obtain 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 Co., and 2.10 g of ethyl acetate were mixed well to obtain Polymerizable Composition No . &Lt; / RTI &gt;

[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 Co., and 2.10 g Were 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 Co., and 2.10 g of ethyl acetate were mixed well to prepare a polymerizable composition No.5 was obtained.

[Example 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 Co., and 2.10 g Were mixed and dissolved to obtain 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, and 2.10 g of ethyl acetate were mixed well to obtain Comparative Polymerizable Composition No. 1.

[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, 0.0016 g of F-470 and 2.10 g of ethyl acetate were mixed well to obtain comparative polymerizable composition No. 2.

[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, 0.0016 g of the product F-470 and 2.10 g of toluene were mixed well to obtain Comparative Polymerizable Composition No. 3.

On the other hand, the compounds a-1 to a-3 are polymerizable compounds having no benzo or naphthocycloalkane skeleton unlike the polymerizable compounds of the present invention.

[Examples 4-1 to 4-6]

0.50 g each of the polymerizable compositions No.1 to No.6 obtained in Examples 3-1 to 3-6 was applied to a PET film and prebaked in an oven at 80 DEG C for 10 minutes. Thereafter, a light amount of 500 mJ / cm 2 was exposed to light 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 refractive index was measured for the comparative polymerizable compositions No. 1 and No. 2 obtained in Comparative Examples 1-1 and 1-2 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 Polymerizable Composition Nos. 3 and 5 obtained in Examples 3-3 and 3-5 was coated on a TAC film (FT-TDY80UL manufactured by Fuji Photo Film Co., Ltd.) of 50 mm x 80 mm x 80 micron with Bar Coater # 40 And prebaked in an oven at 80 DEG C for 10 minutes. Thereafter, a light amount of 500 mJ / cm 2 was exposed to light with a high-pressure mercury lamp to obtain a coated film. The film was placed on a flat surface, and the height from the plane of the four corners of the film was measured. The film was evaluated as having a film thickness of less than 20 mm, a thickness of not less than 20 mm and not more than 60 mm and a film thickness of not less than 60 mm, Respectively. The results are shown in Table 2.

[Comparative Examples 3-1 and 3-2]

The comparative polymerizable compositions Nos. 2 and 3 obtained in Comparative Examples 1-2 and 1-3 were evaluated for deformation in the same manner as in Examples 5-1 and 5-2. The results are shown together in Table 2.

The results of [Table 1] and [Table 2] show that the polymer composed of the polymerizable composition containing the polymerizable compound of the present invention exhibits a higher refractive index as compared with the comparative polymer, It is obvious that it is useful.

Claims (12)

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

(Wherein A ¹ and A ² are each independently a hydrogen atom, a substituent represented by the following general formula (II), (III) or (IV), A ¹ and A ² is a substituent represented by the following general formula (II), general formula (III) or general formula (IV)
X, Y, Z ¹ and Z ² each independently represents an alkyl group having 1 to 10 carbon atoms which may be substituted with a halogen atom, an aryl group having 6 to 20 carbon atoms which may be substituted with a halogen atom, An arylalkyl group of 7 to 20 carbon atoms, a heterocyclic group of 2 to 20 carbon atoms which may be substituted with a halogen atom or a halogen atom, and the methylene group in the alkyl group, aryl group or arylalkyl group may be substituted with an unsaturated bond, -O- or -S- X may form a ring with X, and the ring may be an aromatic ring,
k represents a number of 0 to 4, p represents a number of 0 to 8, r and s each independently represent a number of 0 to 4, and when k, p, r and / or s is 2 or more, X, Y, Z ¹ and / or Z ² may be the same or different,
x represents a number of 0 to 4, y represents a number of 0 to 4, and the sum of the numbers 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 represent an integer of 0 to 3, F is a number from 1 to 20, and when n, m or f is 2 or more, a unit represented by [L ¹ O] _n , [L ² O] _m or [L ³ O] _f May be a random copolymer or block copolymer of an ethyleneoxy group and a propyleneoxy group, and M represents a hydrogen atom or a methyl group. The method according to claim 1,
Wherein in the general formula (I), x is 2 and y is 0. The method according to claim 1,
Wherein said compound is represented by the following general formula (V).

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