TW201038529A - Polymeric compound, polymeric composition containing the same and polymer thereof - Google Patents

Abstract

The invention provides an intermediate compound and a polymeric compound represented by the following formula (I), a polymeric composition containing the polymeric compound, wherein in the formula (I), at least one of A.sup.1 and A.sup.2 is a group represented by any one of the following formula (II) or formula (III), and a polymer formed by polymerization of the polymeric composition. (In the formula, A.sup.1 and A.sup.2 represent hydrogen atoms and substituents represented by the foregoing formula (II), the formula (III) or a formula (IV), At least one of A.sup.1 and A.sup.2 is the substituent represented by the foregoing formula (II), the formula (III) or the formula (IV). X, Y, Z.sup.1 and Z.sup.2 represent alkyl of 1 to 10 carbon atoms. X can form a ring with other X. The rings can be an aromatic ring. k represents a number of 0 to 4. p represents a number 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 numbers x and y is 2 to 4. L.sup.1, L.sup.2, L.sup.3 represent ethylene groups and so on. n and m represent numbers of 0 to 20. f represents a number of 1 to 20. When n, m or f is above 2, the unit represented by [RO].sub.n, [RO].sub.m or [RO].sub.f can be a random copolymer or block copolymer of ethylene oxygroup and propylene oxygroup. M represents methyl and so on.)

Description

[Technical Field] The present invention relates to a polymerizable compound which is simple in the production method and excellent in photocurability, a polymerizable composition containing the polymerizable compound, and a polymer. The polymer is transparent and has little coloration and exhibits a high refractive index, and is useful for optical materials. [Prior Art] A cured product having a refractive index and a refractive index for an optical material such as a lens or a filter. Indispensable. In the patent document, an episulfide compound having an anthracene skeleton which can be used as an optical material is disclosed, and Patent Document 2 discloses a photocurable resin lens obtained by copolymerizing bromobisphenol. Further, Patent Documents 3 and 4 disclose a polymerizable composition containing an acryl vinegar compound. However, such materials are not satisfactory in terms of hardness, adhesion, light resistance, etc., or there is a problem that the manufacturing method becomes complicated and is not suitable for mass production at a low cost. PRIOR ART DOCUMENT PATENT DOCUMENT PATENT DOCUMENT PATENT DOCUMENT PATENT DOCUMENT PATENT DOCUMENT PATENT DOCUMENT PATENT DOCUMENT PATENT DOCUMENT PATENT DOCUMENT 2 Patent Document 2 SUMMARY OF THE INVENTION PROBLEMS TO BE SOLVED BY THE INVENTION An object of the present invention is to provide a polymer which is simple in production method and excellent in photocurability, and is formed into a film. At the same time, the hardening shrinkage is less 'transparent and high refractive index. 146652.doc 201038529 Technical Solution to Problem The present inventors conducted intensive research, and as a result, obtained the following knowledge: A novel polymerizable compound having a stupid or naphthocyclic hydrocarbon skeleton can achieve the above object. Namely, the present invention provides a compound represented by the following general formula (I) based on the above knowledge. [Chemical 1]

(wherein A1 and A2 are each independently a hydrogen atom and a substituent represented by the following formula (9), formula (III) or formula (IV), and at least one of VIII! and VIII is as follows The substituent represented by the formula (π), the formula (m) or the formula (IV), ❹ X, y, z1 and z2 each independently represent a hospital having 1 to 10 carbon atoms which can be substituted by a Gu atom. An aryl group having 6 to 2 carbon atoms which may be substituted by a halogen atom, an aryl group having 7 to 2 carbon atoms which may be substituted by an atom, and a carbon atom which may be substituted by a halogen atom a heterocyclic group of -20 or a halogen atom, the methylene group in the alkyl group, the aryl group or the aryl group may be interrupted by an unsaturated bond or -S-, and X may form a ring with each other, and the rings may be aromatic. Ring, k represents the number of 0~4, p represents the number of 〇~8, r&s independently represents the number of 0~4, when k, p, !* and/or 3 are 2 or more, plural χ , γ, y and / or Z2 may be the same or different I46652.doc 9 201038529 X is not 0~4, y is the number of 〇~4, and the total number of 乂 and 丫 is 2~4 〇) 2]

(In the formula, B, L and L· respectively represent an extended ethyl group or a stretching propyl group, η and m respectively represent the number of 〇~20, and f represents the number of 〇2〇 when η, melon or £ is 2 or more The unit represented by [R〇]n, [11〇]〇1 or 〇^ can be a random copolymer or a block copolymer of an ethyloxy group and a propyloxy group, and M represents hydrogen. Further, the present invention provides a polymerizable composition characterized by containing at least one of ruthenium and osmium 2 in the above formula (I), or any one of the above formula (π) or formula (III) A compound represented by the group; further comprising a polymer obtained by polymerizing the above polymerizable composition. EFFECT OF THE INVENTION The polymerizable compound of this month provides a polymer which has less hardening shrinkage and is transparent and has a high refractive index at the time of film formation. [Embodiment] The composition and the polymer are preferably described in detail. The compound of the present invention is characterized in that it is a stupid or naphthene-hydrocarbon skeleton having a shoulder I# of the above formula (1). X, the invention 146652.doc 201038529

The hydrazine compound is a polymerizable compound (hereinafter also referred to as a polymerizable compound of the present invention) contained in the polymerizable composition of the present invention, or can be used for production, depending on the group represented by the oxime > Α2 in the formula (1). An intermediate of the polymerizable compound (hereinafter also referred to as an intermediate compound of the present invention), wherein the polymerizable compound of the present invention is in the above formula (1), at least one of α^α2 is represented by the above formula (8) or A compound represented by the formula of the formula (N) is used as a polymerizable compound in the polymerizable composition of the present invention. Further, the intermediate compound of the present invention is in the above formula (1), gossip and oxime 2 a compound which is a hydrogen atom or a group represented by the above formula (IV). In the intermediate compound and the polymerizable compound of the present invention, the alkyl group represented by ', Υ, Ζι and Ζ2 in the above formula (1), # The fluorenyl group in the aryl group can be an unsaturated bond, _0- or each interrupt, the substitution position of the halogen group, and the interrupt position of _〇_ or -s_ are arbitrary, and also include m and each ring directly Bonded as a (tetra) atom A group having a carbon number of 1 to H), for example, a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, a second butyl group, a second butyl group, an isobutyl group, a pentyl group, Isoamyl, third amyl, hexyl, heptyl 'isoheptyl, third heptyl, n-octyl, isooctyl, trioctyl, 2-ethylhexyl, n-decyl, n-decyl, tri Oxymethyl, difluoromethyl, monochamethyl, pentafluoroethyl, tetraethyl, triethyl, trifluoroethyl, seven propyl, hexafluoropropyl, pentafluoropropyl, tetra Fluoropropyl, trifluoropropyl, perfluorobutyl, methoxy, methoxyethoxy, methoxyethoxyethoxy, methylthio: ethoxy, vinyloxy, propoxy , isopropoxy, butoxy, isobutyl lactyl, tert-butoxy, tert-butoxymethyloxy, pentyloxy 146652.doc 201038529 base, isopentyloxy, third pentyloxy , neopentyloxy, hexyloxy, cyclohexyloxy, isohexyloxy, heptyloxy, octyloxy, 2-ethylhexyloxy, decyloxy, decyloxy, cyclopropyl, cyclobutyl , cyclopentyl, cyclohexyl, cycloheptyl, anthranyl, cyclodecyl, cyclodecyl, etc. The linear group, the branched group, and the cyclic alkyl group. Examples of the aryl group having 6 to 2 ring carbon atoms which may be substituted by a halogen atom include a phenyl group, a 1-naphthyl group, a 2-naphthyl group, and a fluorene group. , phenanthrenyl, o-phenylene, m-tolyl, p-nonylphenyl, 3-fluorenyl, 9-fluorenyl, hydrazine-tetrahydronaphthyl, 2-tetrahydronaphthyl, anthracenyl-indanyl, ^], benzyl group, 'vinyl phenyl, 3-isopropylphenyl, 4-isopropylphenyl, 4-butylphenyl, 4-isobutylphenyl, 4-tert-butyl Phenyl, 4-hexylphenyl, 4-cyclohexylphenyl, 4-octylphenyl, 4-(2-ethylhexyl)phenyl, 2,3-dimethylphenyl, 2,4-a Phenylphenyl, 2,5-dimethylphenyl, 2,6-dimethylphenyl, 3,4-monomethylphenyl, 3,5-dimethylphenyl, 2,4_di- Tributylphenyl, 2,5-mono-t-butylphenyl, 2,6-di-t-butylphenyl, 2,4-di-t-pentylphenyl, 2,5-di - a third amylphenyl group, a cyclohexylphenyl group, a biphenyl group, a 2.4.5-trimethylphenyl group, a 4-chlorophenyl group, a 3,4-diphenyl group, a 'trichlorophenyl group, 4 Difluorophenyl, perfluorophenyl, phenoxy, 2-methylphenoxy, % methylphenoxy , 4-methylphenoxy, 2,3-dimethylphenoxy, 2,4-dimethylphenoxy, 2,5-dimercaptophenoxy, 2,6-dimethylbenzene Oxyl, -didecylphenoxy, 3,5. dimethylphenoxy, 2,3,4-trimethylphenoxy, =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, 2,3,5,tetramethylphenoxy, pentamethylphenoxy, ethylphenoxy, positive Propylphenoxy 146652.doc 201038529 base, isopropylphenoxy, n-butylphenoxy, t-butylphenoxy, tert-butylphenoxy, n-hexylphenoxy, n-octylbenzene Oxyl, n-decylphenoxy, n-tetradecylphenoxy, 1-naphthyloxy, 2-naphthyloxy, 1-decyloxy, 1-phenanthryloxy, o-tolyloxy, m-toluene Oxyl, p-tolyloxy, 9-decyloxy, 1-tetrahydronaphthyloxy, 2-tetradecyloxy, 1-dihydromethoxy, 1-decyloxy, 2-decyloxy, etc. . Examples of the arylalkyl group having 7 to 20 carbon atoms which may be substituted by a halogen atom include a benzyl group, a phenethyl group, a 2-phenylpropyl group, a diphenylmethyl group, a triphenylmethyl group, and a benzene group. Ethylene, cinnamyl, 4-chlorophenylmethyl, benzyloxy, 1-naphthylmethoxy, 2-naphthylmethoxy, 1-decylmethoxy, and the like. The heterocyclic group having 2 to 20 carbon atoms which may be substituted by a halogen atom may, for example, be a pyrrolyl group, a pyridyl group, a pyrimidinyl group, a hydrazine group, a piperylene group or a piperidinyl group. Compared with the south base, the ratio of α to the base, the three p well base, the σ ratio, the π-base, the salinyl group, the iso-golden-based group, the stilbene group, the benzo-flavor β-based group, and the three-β-based group. Fury 1 , furanyl, benzofuranyl, thienyl, phenylene, benzothiophenyl, anthracenyl. Caesarean, benzo-plug. Sit-base, η-salt base, benzo-indenyl-salt, iso-s-beta-sitting group, hetero-β-sitting group, °-inducing η-based, blowing 17 sigma-based, taste-leaching, thio-indenyl, 2 -. Comparing each of the ketone-1 -yl, 2 - brittle ketone-1 -yl, 2,4-dioxyimidazolidine-3-yl, 2,4-dioxaoxazolidin-3-yl, etc. . Examples of the halogen atom include fluorine, chlorine, moisture, and a block. Examples of the ring structure which can be formed by X each other include a cyclopentane ring, a cyclohexane ring, a cyclopentene ring, a cyclopentane, a piperidine ring, a porphyrin ring, a lactone ring, and a decylamine ring. Ring and naphthalene ring, anthracene ring, anthracene ring, ethane naphthalene 146652.doc 201038529 (acenaphthene) ring, indane ring, tetralin ring and other condensation ring. In the intermediate compound and the polymerizable compound of the present invention, the compound of the above formula (1) wherein X is 2 and y is oxime is excellent in photocurability, and the compound represented by the following formula (V) is preferable. It is advantageous and better in terms of manufacturing. [Chemical 3]

(In the formula, A1, A2, X, Y, Z1, Z2, k, and iodine are the same as in the above formula (1).) Further, in the above formula (1) or the above formula (V), a compound in which fluorene is a phenyl group is provided. A polymer having a high refractive index is preferred, and ^ is 1 or a compound wherein X is an alkyl group having 1 to 10 carbon atoms or an aryl group having 6 to 20 carbon atoms is advantageous in terms of production. Suitable for use. Further, in the polymerizable compound of the present invention, in the above formula (1), eight! Further, it is preferred that the compound represented by the above formula (11) and the compound represented by the above formula (III) are both a compound having a high hardness. The polymerizable compound of the present invention represented by the above formula (I) may, for example, be the following compound 丨 to compound 56. Further, among the following compounds, η and m represent the number of 〇~20. 146652.doc 201038529

Compound 1 Compound 2 Compound 3 Compound 4 Compound 5 Compound 6 146652.doc 11 - 201038529 [Chemical 5]

Compound 7 Compound 8 Compound 9 Compound 10 Compound 11 Compound 12 146652.doc -12- 201038529 [Chemical 6]

Compound 13 compound 14 compound 15 compound 16

Compound 17 146652.doc -13 - 201038529 [Chem. 7]

Compound 18 Compound 19 Compound 20 Compound 21 Compound 22 146652.doc -14- 201038529 [Chemical 8]

Compound 23 Compound 24 Compound 25 Compound 26 Compound 27 146652.doc -15- 201038529 [Chemical 9]

>卜4^ Compound 28

~. t compound 29

. Bu. Compound 30

Compound 31

) Bu. Compound 32 146652.doc -16- 201038529 [Chemical]

Compound 33 Compound 34 Compound 35 Compound 36 Compound 37 146652.doc -17· 201038529 [化η]

Compound 38 Compound 3 9 Compound 40 Compound 41 146652.doc • 18- 201038529 [Chem. 12]

Compound 42 Compound 43 Compound 44 Compound 45 Compound 46 146652.doc • 19- 201038529 [Chem. 13]

Compound 47 Compound 48

Compound 49 Compound 50 Compound 51 146652.doc -20- 201038529 [Chemical 14] Ο ❹

Compound 52 Compound 53 Compound 54 Compound 55 Compound 56 Further, in the intermediate compound of the present invention, in the above formula (I), Α1 and 146652.doc • 21 · 201038529 A2 are represented by the above formula (IV). The intermediate compound is particularly useful as an intermediate in the production of the above-mentioned polymerizable compound. Examples of the intermediate compound include a compound in which a propylene group, a methacryl fluorenyl group or a vinyl benzyl group of the above compound is substituted with a hydrogen atom, and η or a compound having a number of 丨~2〇. . In the polymerizable compound of the present invention, η in the above formula (11) and m in the formula (ΠΙ) represent the number of 〇~2〇, and it is preferably 〇~, and further preferably in terms of production. It is G~3. Further, in the intermediate compound of the present invention, the number represented by f in the above formula (IV) is preferably 丨5 to 5, and more preferably 1 to 3. The method for producing the intermediate compound and the polymerizable compound of the present invention is not particularly limited. For example, in the above formula (1), the polymerizable compound (I_A) represented by the above formula (II) can be The bisphenol derivative 〇) is reacted with (meth) propylene hydrazine in the presence of a base or by reacting a bisphenol derivative (1) with (meth)acrylic acid in the presence of an acidic catalyst. The reaction formula is shown in the following formula. Further, in the following formula, X'Y'y'fk, P sx, y are the same as the above formula (I), and L1, η and ] VI are the same as the above formula (π) 'E1 represents a halogen atom or a hydrazine. Hey. 146652.doc •22- 201038529 [Chem. 15]

The polymerizable compound (I_B) can be obtained by reacting a bisphenol derivative (1) with a halogenated methyl stupylene in the presence of a base. The reaction formula is shown in the following formula. Further, in the following formula, it is the same as the above formula (1), L2 and m are the same as the above formula (ΙΠ), and E2 is a halogen atom. [Chemistry 16]

(Bu B) 146652.doc -23- 201038529 In the formula (1), the intermediate compound (4) represented by the above formula (IV) in both A1 and A2 can be used as the above-mentioned money derivative (1), which can be made by Ht(2) reacts with a cyclic carbon (4) in the presence of a base, or bis(tetra)bio)di, ethylene or propylene oxide in a polyaddition reaction in the presence of a base catalyst, and the reaction formula is shown in the following formula in. Further, X, Y, Zl, Z2, k, P, r, S, xmW_, L3 and £ are the same as the above formula GV), and q is 〇 or j. [Chem. 17]

Examples of the above-mentioned acidic catalyst include, for example, methyl benzoic acid, benzoic acid, m-xylene acid, benzalkonium, ketone methyl, (tetra)ethyl ethyl acid, propyl propyl, trifluoromethyl Sister, 4 base water acid, base phthalic acid and other acid; (4), anhydrous sulfuric acid, fuming sulfuric acid, gas sulfuric acid, fluorosulfuric acid, hydrochloric acid, hydrogen chloride gas, oxalic acid, formic acid, squaric acid, trichloroacetic acid, three Heteropoly acid such as fluoroacetic acid, acid acid, and phosphoharic acid, strong acid ion exchange resin, activated clay, Sanrui (four), anhydrous chlorinated, and chlorinated. The acidic catalyst is preferably used in an amount of from 0 to 50 parts by mass, more preferably from 1 to 10 parts by mass, based on 1 part by mass of the bisphenol derivative. Examples of the base to be used in the above reaction include alkali metal ruthenium oxides such as lithium hydroxide, sodium hydroxide, and potassium hydroxide; calcium hydroxide and hydrogen oxy 146652.doc -24·201038529: soil test metals such as towns Hydroxide; sodium ethoxide, sodium ethoxide, dimethoxy = glycerin, diethoxymagnesium, diisopropoxy, tri-tert-butoxysole, etc.; An organometallic compound such as a third butyl group; a metal amine such as a clockamine, a hexamethyl diazepine salt, a carbonate such as sodium carbonate or potassium citrate; and a triethylamine. Ding, amide 1 Ο ❹ 》 比 ... ... 甲基 甲基 甲基 甲基 甲基 甲基 甲基 甲基 比 比 比 比 比 比 比 比 比 比 比 比 比 比 比 比 比 比 比 比 比 比 比 比 比 比 比 比 比 比 比 比 比 比 比 比An amine compound such as diazabicyclo[5.4.0]_7-undecene. In the case of producing the above polymerizable compound, the amount used in the above test is relative to the base of the desired derivative (1)! And used in the range of O.bU Mo, especially q 3~i # ear. Further, in the case of producing the above intermediate compound, the above-mentioned base is used in an amount of one hydroxy group relative to the bisphenol derivative, and in the range of 〇.〇1 to 2.0 mol, especially 〇.〇5~〇5 Within the scope of the ear (four). Further, in the above reaction, a solvent which is known in the prior art may be used, and examples thereof include a solvent of a sulphuric hydrocarbon such as toluene, xylene, and a sulphuric acid; turpentine, D-moneylen, Alkenyl hydrocarbon oil, mineral oil, mineral oil, 8 bridle 1 #310 (Cosmo Songshan Petroleum (share)), s〇lvess〇#ι〇〇 (Εχχ (10) chemical (share)) and other paraffinic solvents; methanol An alcohol solvent such as ethanol; a hydrazine solvent such as ethyl acetate; a halogen solvent such as dichloroethane, carbon tetrachloride, gas, trichloroethylene, dioxane or chlorobenzene; tetrahydrofuran, dioxane, etc. A cyclic ether solvent 'ether, a cellosolve solvent, a ketone solvent, benzene, r-Caamine, σ ratio bite, bis-p-burn, acetic acid, acetonitrile, carbon disulfide, or the like. In the above reaction, when the compound (I_C) is obtained from the bisphenol derivative (2), a mixture of a plurality of compounds having different numbers of f is obtained, but there is no problem, and 146652.doc -25-201038529 can also be used in the subsequent reaction. A mixture of a plurality of compounds having different numbers of η or m in the polymerizable compound (I_A) or (I_B) is produced, and a polymerizable composition is prepared using the mixture. The intermediate compound and the polymerizable compound of the present invention described above are used in various applications as the polymerizable composition described below. The polymerizable composition of the present invention contains a composition containing the above polymerizable compound and is mainly used in combination with a radical polymerization initiator and a solvent. In the polymerizable composition of the present invention, the polymerizable compound may be one type or a mixture of two or more types, and the content of the above polymerizable compound is the total mass of the total solid matter in which the solvent is removed from the self-polymerizable composition. The ratio of the proportion of 60 is better than 50 to 90. /. 'Better is 6〇~8〇% by mass. As the above-mentioned radical polymerization initiator, a previously known compound can be used, and examples thereof include: benzamidine peroxide, 2,2,-azobisisobutyronitrile, dicuminone, phenylbiphenyl ketone, Hydroxy_丨_benzylidenecyclohexane, benzil, stupid dimethyl _ (匕6112; 11 dimethyl ketal), 1-benzyl-1-nonylamino-1- (4'-(Ν-tyrosolinyl;)benzimidyl)propane, 2-tyrosolinyl-2-(4'-methylindenyl)benzhydrylpropane, 9-oxopurine (thi〇xanth) 〇ne), ^ chloro-4-propoxy-(9-oxothiopurine), isopropyl (9-oxopurine), diethyl (9-oxothione), ethyl hydrazine, 4_Benzyl _4,_mercaptodiphenyl sulfide, benzoin butyl ether, 2-hydroxy-2-benzoylpropane, 2-hydroxy-2_(4,-isopropyl)benzamide Propane, 4-butylbenzylidene trichloromethane, 4-phenoxyphenylindenyldioxane, decylmercaptocarboxylate, anthracene, 7-bis(9,-acridinyl)g Alkane, 9-n-butyl_3,6-bis(2,_(N_morpholinyl)isobutyl) carbazole, methyl-1-[4-(methylthio)phenyl]_2·(Ν _ tyrosinyl) acetone, oxime 146652.doc •26· 201038529 Phenylphenyl-2,4-bis(trichloroindenyl)-all three tillage, 2-methyl-4,6-bis(trichloromethyl)-all three tillage, 2_ Phenyl-4,6-bis(trichloroindenyl)_all three sprays, 2_caiyl-4,6-bis(trichloromethyl)-all three tillage, 2-(p-butoxystyryl) Three tillage, 2-(p-butoxystyryl)-5-trichloroindenyl-ι, 3,4_ρ No. 2. Sit, 9-phenyl acridine, 9,10-dimethylbenzino , benzophenone/micilenone, hexaarylbiimidazole/mercaptobenzimidazole, 9-oxosulfonium sulphate/amine, bis(2,4 6 _ 曱 甲 basic base) 'U.S. Patent No. 6,596, 444, the specification of the U.S. Patent No. 6,949,678, the disclosure of the U.S. Patent No. 2,5,97,141, the specification of U.S. Patent No. 7,648,738, the specification of U.S. Patent No. 7,189,489, and the Japanese Patent No. 3798008, The compound or the like described in the specification of Patent Application Publication No. 2007/270522. Among these, it is preferably a compound represented by the following formula 0) or (〇) η.

(8) R72 (wherein R71, R72 and R each independently represent r76, 〇76, COR, SR76, c〇NR76R77 or CN 'R76Ar77 independently represent a aryl Haryl group or a heterocyclic group, respectively. The excipient group which can be substituted by the _ atom and/or the heterocyclic group '(4) and the aryl group can be 146652.doc -27· 201038529 from the unsaturated bond, (4) 'sulfur (four) or (four) Forming a ring, R, showing a halogen atom or a burnt group, and r: a: a halogen atom, an alkyl group, or a substituent represented by the following formula (b): 2: 4 敕 敕 k 巧 (), g means [two integers, when "more than 2", a plurality of R74 can be different bases.)

(wherein, ring Μ represents a cyclodane hydrocarbon ring, an aromatic ring or a heterocyclic ring, R76 represents a (iv) atom or a burnt group, f represents an oxygen atom, a sulfur atom is an atom, and z71 represents a carbon atom number i~5 of a stretching group, h An integer representing 0 to 4, and when 11 is 2 or more, 'plural X73 may be a different base.) [Chemical 2 (η

(wherein R1 and R2 independently represent R", ORii, CORii, SR", CONRUr»3 or CN, R", R12&R" are independently a hydrogen atom, a carbon atom having a carbon number of 1 to 20, An aryl group having 6 to 30 carbon atoms, an arylalkyl group having 7 to 3 carbon atoms or a heterocyclic group having 2 to 20 carbon atoms, an alkyl group, an aryl group, an aryl group and a heterocyclic group The atom may further pass through R21, COR21, SR21, NR22R23, conr22r23, _NR22_or23, _nc〇r22 〇c〇r23 -c(=n-or21)-r22, -c(=n-ocor21)-r22, CN, _ Atom, 146652.doc -28- 201038529 -crWy, _c〇_cr2I=cr22r23, carboxyl group, epoxy group substituted, R, R22 and R23 each independently represent a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, a carbon atom An aryl group having 6 to 30 aryl groups, an arylalkyl group having 7 to 30 carbon atoms or a heterocyclic group having 2 to 20 carbon atoms, and a substituent represented by the above R", Rl3, r21, R and 11 The methylene group of the alkylene moiety may be interrupted 1 to 5 times by an unsaturated bond, an ether bond, a thioether bond, an ester bond, a thioester bond, a guanamine bond or a urethane bond, and the alkyl group of the above substituent Part of the branch side chain 0 may also be a cyclic alkyl group, the alkyl terminal of the above substituent may be an unsaturated bond, and R12 and RU and the ruler 22 and 1^3 may form a ring, respectively. ... and the ruler 4 respectively represent R11, OR", SRU, C〇Rii, C〇nr12r13, NR12CORu, OCORn, c〇〇Rll, SC0R", 〇CSR丨丨, COSR CSOR, CN, halogen atom or radical, & and b are independent 〇~ 4. X1 represents a direct bond or c〇, χ2 represents an oxygen atom, a sulfur atom, a helium atom, CR31R32, CO, a service 33 or a sigh 34, r31, r32, r33 and r34 respectively represent R1丨, ORii, COR丨1 , SR1丨, CONR12R13 or O CN, R3 may form a ring structure with the carbon bond of the adjacent benzene ring via -χ2_, or R3 and R4 may form a ring together, R3!, R3W4 may be independently Forming a ring together with a benzene ring adjacent thereto.) • In the polymerizable composition of the present invention, the content of the above-mentioned radical polymerization initiator: the total mass of the total solid matter obtained by removing the solvent from the self-polymerizable composition The proportion of the medium is preferably 0.^40% by mass, more preferably 1〇~1〇% by mass. The base polymerization initiator may be used in combination or in combination of two or more. The polymerizable composition of the present invention may contain a solvent, and usually, the components described in 146652.doc -29-201038529 may be dissolved or dispersed. The solvent 'is not particularly limited, and examples thereof include methyl ethyl hydrazine, methyl mercapto ketone, diethyl ketone, acetone, methyl isopropyl ketone, methyl isobutyl ketone, and ketones such as cyclohexanone. ; an ether solvent such as ether, dioxane, tetrahydroanion, 1,2-dimethylhydrogen; 7. rolled ethane, hydrazine, 2-diethoxyethane, dipropylene glycol dioxime ether; W, ethyl sulfonate, ethyl acetate, n-propyl acetate, isopropyl acetate, acetic acid, n- 酉曰4酉曰>gluten; ethylene glycol monoterpene scale, ethylene glycol single y, And - the seedlings in -% monoterpene ether acetate and other cellosolve solvent; sterol, ethanol, two or two, sub-n-propyl, iso- or n-butanol, pentanol and other alcohol-based solvents; Benzene, toluene, dimethyl stupid, etc. ''m-guided β-pilose agent; hexane, heptane, Xinxuan·, cyclohexin and other aliphatic cigarettes and plums _ 士, μ 糸 ♦ agent, turpentine, D- lemon , terpene-specific olefinic hydrocarbon oil; mineral spirits, s ZOI #310 (Cosmo Songshan Petroleum (share)), Solvesso #l〇〇^ (Exxon Chemical (share)) and other paraffinic solvents; Chloroform, triethylene ethene, sulphur methane, etc. _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ Amine, pyridine, acetic acid, January, a stone, carbon, N,N-dimethylformamide, N-methyl n, 洛 嗣, etc., Li, -, such as -#, Τ, preferably A ketone or cellosolve agent. These solvents can be used in combination with two or more types: 3⁄4. In the polymerizable composition of the present invention, the content of the above-mentioned agent is preferably from 5 to 60% by mass, more preferably from 20 to 60% by mass, based on the polymerizability. 50% by mass of the way ^ ag . ^ Flying into the 仃 week. Further, the polymerizable compound of the present invention may be used in the polymerizable composition of the present invention without being removed by the use of the above-mentioned polymerizable compound. L, splicing. The polymerizable composition H of the present invention is further used in combination with a monomer chain transfer agent having an unsaturated bond, a surfactant, and the like. 146652.doc -30· 201038529 As the above monomer having an unsaturated bond, there may be mentioned 2-hydroxyethyl acrylate, 2-propyl propyl acrylate, isobutyl acrylate, and acrylic acid. N-octyl ester, isooctyl acrylate, isodecyl acrylate, stearyl acrylate, methoxyethyl acrylate, dimethylaminoethyl acrylate, acrylic acid, 1, 6_ hexanediol diacrylate, trimethylolpropane triacrylate, 2-propyl ethyl methacrylate, 2-propyl propyl methacrylate, butyl methacrylate, methacrylic acid - tert-butyl ester, cyclohexyl methacrylate, trioxindole q-propane trimethacrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, pentaerythritol tetrapropionate, pentaerythritol triacrylate, three Cyclodecane dihydroxydecyl diacrylate and the like. In the polymerizable composition of the present invention, the content of the monomer having an unsaturated bond is preferably from 0.01 to 20 in terms of the total mass of the total solid matter in which the solvent is removed from the polymerizable composition. The mass% is more preferably 0.1 to 10% by mass. These can be used! Kinds, or a mixture of two or more types may be used. Examples of the chain transfer agent include thioglycolic acid, thioplycolic acid, thiosalicylic acid, 2-sodium propionic acid, 3-sodium propionic acid, 3-s-butyric acid, and N-( 2-sodium propyl hydrazide) glycine acid, 2-mercapto nicotinic acid, 3_[N_(2_ethylethyl)amine hydrazino]propionic acid, 3-[N-(2-mercaptoethyl)amine Propionate, N-(3-mercaptopropyl)alanine, 2-mercaptoethanesulfonic acid, 3-mercaptopropanesulfonic acid, 4-mercaptobutanesulfonic acid, dodecyl (4-sulfonylthio) Phenyl ether, 2_mercaptoethanol, 3_mercapto-1,2-propanediol, i_mercapto-2-propanol, 3-hydrazino-2-butanol, nonylphenol, 2-mercaptoethylamine, 2-mercapto Mercapto group such as imidazole, 2_fluorenyl-3-hydroxypyridine, 2-mercaptobenzothiazole, thioglycolic acid, trimethylolpropane tris(3-mercaptopropionate), pentaerythritol tetrakis(3-mercaptopropionate) a compound obtained by oxidizing the thiol 146652.doc -31· 201038529 compound - one of a compound, iodoacetic acid, iodopropionic acid, 2 iodine HW ethyl hydrazine, 3 hydrazine propionic acid, etc. One type may be used or two or more types may be used in combination. As the above surfactant, an anionic interfacial activity such as a perfluoroester, a fluorosurfactant such as an all-gas alkyl carboxylate, or a higher fatty acid alkali salt, an alkyl sulfonate or a phenanthyl sulfate can be used. Agent, high-grade amine (tetra) salt, quaternary salt salt and other cationic surfactants, non-ionic interfacial activity such as polyethylene glycol base-seam, poly(ethylene glycol) fatty acid ester, sorbitan fatty acid ester, fatty acid monoglyceride Surfactant, an amphoteric surfactant, a surfactant such as a polyoxo-based surfactant; these may be used in combination or in combination of two or more. Further, a thermoplastic organic polymer is further used in the polymerizable composition of the present invention, whereby the properties of the cured product can be improved. As the thermoplastic organic polymer, there are exemplified by polyethylene, polyacrylic acid acryl, decyl acrylate-ethyl acrylate copolymer, poly(indenyl)acrylic acid, styrene_(methyl Acrylic copolymer, (meth)acrylic acid-methyl methacrylate copolymer, polyvinyl butyral, cellulose ester, polypropylene decylamine, saturated polyester, and the like. These may be used alone or in combination of two or more. Further, the polymerizable composition of the present invention may be added with heat such as beryllone, hydroquinone, pyrocatechol, tert-butylcatechol (t-butyl catech〇l), phenol thiophene, etc. as needed. Polymerization inhibitor; plasticizer; subsequent accelerator; filler; antifoaming agent; dispersing agent; leveling agent; decane coupling agent, 'fualing agent and the like. These may be used alone or in combination of two or more. 146652.doc •32- 201038529 The polymerizable composition of the present invention may optionally contain: a hardening catalyst; a monoglycidyl ether, dioctyl phthalate, dibutyl phthalate benzyl alcohol Reactive or non-reactive diluent (plasticizer) such as coal tar 'glass fiber, carbon fiber, cellulose, strontium sand, cement 'kaolin, clay, aluminum hydroxide' bentonite, talc, cerium oxide, fine powder Filler or pigment such as cerium oxide, titanium dioxide, carbon black, graphite, iron oxide, asphalt, etc.; γ-aminopropyltriethoxydecane, aminomethyl)-γ-aminopropyltriethoxy Basear, Ν-β-(aminoethyl)-oxime, _β_(aminoethyl)-γ-aminopropyltriethoxydecane, γ-anilinopropyltriethoxydecane, γ- Glycidoxypropyltriethoxydecane, ρ_(3,4-epoxycyclohexyl)ethyltriethoxydecane, vinyltriethoxydecane, Ν_ρ_(Ν-vinylbenzylamino Ethylaminopropyltriethoxydecane, mercaptopropenyloxypropyltrimethoxydecane, γ-glycoltrimethoxysilane, _ 疏 基 二甲 二甲 二甲 夕 夕 夕 夕 夕 ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; Lignite wax, petroleum wax, fatty acid wax, fatty acid ester, fatty acid shout, aromatic ester, aromatic shouting lubricant; thickener; thixotropic agent; antioxidant; light stabilizer; ultraviolet absorber; Defoaming agent; rust inhibitor; colloidal cerium oxide, colloidal alumina, etc., and other additives, and may also be used together with an adhesive resin such as a xylene resin or a petroleum resin. The amount of the additive is preferably 100 parts by mass or less based on 100 parts by mass of the polymerizable composition of the present invention. 146652.doc -33- 201038529

Next, the polymer of the present invention will be described. D The polymer of the present invention is obtained by polymerizing the above polymerizable composition, and can be applied to a support substrate such as metal, paper or plastic by a known method. Further, it may be temporarily applied to a support substrate such as a film, and then transferred to another support substrate, and the application method is not limited. The support substrate is not particularly limited, and preferred examples thereof include a glass plate, a polyethylene terephthalate plate, a polycarbonate plate, a polyimide plate, a polyamide plate, and a polymethacrylic acid. A methyl ester plate, a polystyrene plate, a polyvinyl chloride plate, a polytetrafluoroethylene plate, a cellulose plate, a seesaw, a reflector, a cycloolefin polymer, a calcite plate, and the like. It is particularly preferable to use a polyimide film or a polyvinyl alcohol alignment film to be applied to such a support substrate. As a method of applying to the above-mentioned support substrate, a known method such as a curtain coating method, an extrusion coating method, a roll coating method, a spin coating method, a /X-crush coating method, or a bar coating method can be used. Method, spray coating method, slant plate coating method, various screen printing, ink jet printing, etc., and casting film forming method. In addition, the film thickness of the polymer is appropriately selected depending on the use, etc., and is selected from the range of 0.001 to 50 μΓη, more preferably 0丨 to 川μηη, particularly preferably 1 to. A method of polymerizing the polymerizable composition of the present invention can be applied to a known method using light, heat or electromagnetic waves. Examples of the polymerization reaction by light or electromagnetic waves 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, or may be peeled off from the support substrate or transferred to another support substrate as needed. 146652.doc -34· 201038529 The preferred types of light are ultraviolet light, visible light, infrared light, and the like. Electromagnetic waves such as electron beam X-rays can also be used. Generally preferred are ultraviolet or visible light. A preferred wavelength range is from 150 to 500 nm. The better range is

The optimum range of 250 to 450 nm' is _~-th nm. Examples of the light source include low-pressure mercury lamps (sterilization lamps, fluorescent chemical lamps, black lamps), high-pressure discharge lamps (high-pressure mercury lamps, metal-tin lamps), or short-arc discharge lamps (ultra-high pressure mercury lamps, xenon lamps, mercury lamps), and the like. It is preferred to use ultra high pressure water (4). The light from the light source may be directly irradiated to the polymerizable composition, or the polymerizable composition may be irradiated with a specific wavelength (or a specific wavelength region) selected by the filter. Preferably, the irradiation energy density is 2 to 5 〇〇〇 mJ/cm 2 , and more preferably 10 to 3000 mW Å. The preferred range is 1 〇〇 2 〇〇〇 mW. Preferably, the illuminance is from 0.1 to 5000 mW/cm2, and more preferably the illuminance is from 1 to 2 〇〇〇 mW/cm2. The polymerizable composition used in the polymer of the present invention can be cured by polymerization by light irradiation with ultraviolet rays or the like for several seconds to several minutes, thereby improving the production of optical parts such as various optical lenses represented by spectacle lenses. Productive. In addition, as described above, the radical polymerization reaction is preferably carried out by a polymerization reaction (photopolymerization) using light such as ultraviolet rays, and if necessary, a polymerization reaction by heat, a polymerization reaction by gamma rays, or the like. And use it. The polymer of the present invention obtained by light-irradiating the polymerizable composition of the present invention has high hardness, excellent scratch resistance and adhesion, high transparency, less hardening shrinkage, and high refractive index, and is suitably used, for example. Lens such as eyeglass lenses, Fresnel lenses, Lenticular Lens, 稜鏡 lenses, and microlenses. In addition, it can also be used as a film-forming material, a printing (wiring circuit) substrate for the manufacture of anti-mite paint (s〇ider 146652.doc • 35-201038529 mask), a plating resist, an adhesive, a display, Optical fiber, optical waveguide, full-image film, various coating agents, and the like. [Examples] Hereinafter, the present invention will be described in more detail by way of examples and comparative examples, but the present invention is not limited by the examples and the like. Further, Example 1 shows an example of the production 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. In the third embodiment and the comparative example 1, the production examples of the polymerizable composition of the present invention and the comparative polymerizable composition are shown. 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-phenyl (indicated as intermediate compound No. 1) [Chem. 21]

1,1 bis(4-light phenyl)-3 - stupid ruthenium 89.1 g, ethylenediacetate blind 11.6 g, carbonic acid slanting 0.88 g, and sputum 11.0 g were added to dimethyl acetamide 240.0 In g, it was reacted at 110 ° C for 1 hour. Thereafter, 1200 mL of ethyl acetate was added, and the mixture was washed three times with 500 mL of water to remove dimethyl acetamide, potassium carbonate, and unreacted ethylene carbonate. The organic phase was dried over anhydrous magnesium sulfate and filtered. The solvent was distilled off to obtain a crude crystal. The crude crystals 146652.doc -36· 201038529 were washed with acetone and dried, whereby white crystals 9 〇 6 g (yield 82%) were obtained. As a result of various analyses, it was confirmed that the target intermediate compound n〇. 1 (a compound obtained by substituting a propylene aryl group of the above compound 42 (n = 1) with a hydrogen atom). (Analysis results) (1) Chemical shift (ppm) of W-NMI^DMSO-cU) 2.72 (t: 1H), 3.21 (dd: 1H), 3.68-3.77 (m: 4H), 3. ; 93-4.07 (m: 4H), 4.15 (dd: 1H), 4.76-4.86 (m, 2H) 6.77 (d: 1H), 6.84-6.90 (m: 4H), 7.02-7.14 (m: 5H), 7.17-7.29 ( m: 5H), 7.32-7.38 (m: 2H) (2) IR spectrum (cm·1) 3304, 2934, 1608, 1508, 1456, 1291, 1176, 1064, 919, 832, 762, 703 [Example 1 -2] Production of 1,1-bis[4-(2-hydroxyethoxy)phenyl]_3,5-diphenylindan (hereinafter referred to as intermediate compound No. 2) [Chem. 22]

2,1 g of 1,1-bis(4-cyanophenyl)-3,5-diphenylindole, 9.30 g of ethylene carbonate, and 1.46 g of potassium carbonate were added to 120.0 g of dimercaptoacetamide. The reaction was carried out at 110 ° C for 6 hours. Thereafter, 500 mL of toluene was added, and the washing was performed three times with water 146652.doc -37-201038529 1 〇〇mL to remove the dimethyl acetamide, potassium carbonate and unreacted ethylene carbonate, and the organic phase was Drying over anhydrous magnesium sulfate, filtration and solvent distillation to obtain a solid of the reaction mixture. The mixture was subjected to crystallization in propylene hydrazine to thereby obtain a yellowish crystal of 9,63 g (yield: 4%). As a result of various analyses, it was confirmed that the target intermediate compound N〇. 2 (a compound obtained by substituting a propylene group of the above compound 33 (n = 1) with a hydrogen atom). (Analytical results) (1) Chemical shift of iH-NMI^DMSO-dd (pprn) 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] 1,1 -Bis(4-propenylfluorenyloxyphenyl)-3 -indolyl (hereinafter referred to as polymerizable compound No. 1) ] 146652.doc

201038529 In the mood of the wind, add 4 mL of dry tetrahydrogen WmL and 3.38 g of triethylamine to the bis(4-pyridylphenyl)·3-phenyl moiety 5.00 g, and then cool the system to no More than 1 〇t, while slowly adding propylene argon 8 * slowly return to room temperature 'after stirring for 1 hour, add

1%% 175 g was stirred with ethyl acetate 1 citrus, the aqueous phase was discarded, and the water phase was washed 3 times with 100 mL of water until the aqueous phase became neutral. Then the organic phase was dried over anhydrous magnesium sulfate, and the solvent was distilled. The mixture was removed to obtain. This was separated and purified by a so-called column chromatography (developing solvent: & calcination / acetic acid = 2 / 1) to obtain white crystals (2 65 g, yield 41%). As a result of various analyses, it was confirmed that the target polymerizable compound N〇丨 (the above compound 42 (11 = 0)). (Analysis results) (1) Chemical shift of W-NMR^DMSO-D (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-propenyloxyethoxy)phenyl]-3-phenylindan (hereinafter referred to as polymerizable compound No. 2) 146652 .doc -39- 201038529

To the intermediate compound N〇.1, 1〇.〇g, p-toluenesulfonic acid monohydrate 〇·412 g, and 1,6_di-t-butyl-4-__ 92 7 g of acrylic acid was added to 0.010 g of phenol, and stirred at 6 ° C for 15 hours. Thereafter, 200 mL of ethyl acetate was added, and the mixture was washed three times with 200 mL of water, and then washed twice with 1 mL of 10% aqueous sodium hydrogencarbonate solution, and further washed with water, and the organic phase was anhydrous sulfuric acid. The magnesium is dried, and the solvent is distilled off to obtain a reaction mixture. The product was separated and purified by silica gel column chromatography (developing solvent: ethyl acetate ethyl ester = 2/1) to obtain a colorless transparent alkane/B, a thick liquid, 7.70 g (yield: 64%). As a result of the analysis, it was confirmed that the target compound = No. 2 (the above compound 42 (n = 1 : :, s I' (analysis result) (1) W-NMR PMSO-I chemical shift (ppm) 2.71 (dd: 1H), 3.20 (dd: 1H), 4.14 (dd,lH), ,4.1 g_4 25 ( 4H), 4.40-4.48 (m,4H), 5.94-6.00 (m,2H) Yang: ,}, ^-17-6 27 r 2H), 6.31-6.39 (m: 2H), 6.76-6.81 (m: im . ^ 6.85-6 ( 4H), 7.00-7.09 (m: 3H), 7.10-7.30 (m· 7H^ 7 ·(10): /-32-7 3〇/ 2H) 146652.doc -40- 1 IR spectrum (cm-1) 201038529 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] 1,1-bis(4-propenyloxyphenyl) Manufacture of -3,5-diphenylindan (hereinafter referred to as polymerizable compound No. 3) [Chem. 25]

Adding dry tetrahydrofuran 50 0 mL and triethylamine 2·50 g to 1,1 bis(4-hydroxyphenyl)-3,5-diphenylindane 4.4g under argon atmosphere After dissolving, the system was cooled to not more than 1 (rc, while 1.94 g of propylene helium was slowly added dropwise. While stirring slowly to room temperature, stirring for 丨 hours, adding 50 g of water and ethyl acetate 1 〇 〇mL was stirred, the aqueous phase was discarded, and washed with water 100 mL three times until the aqueous phase became neutral, and then the organic phase was dried over anhydrous magnesium sulfate. The solvent was distilled off to obtain a mixture. Chromatography (developing solvent: hexane/ethyl acetate = 2/1) was used to carry out separation and purification to obtain 546 g (yield: 11%) as a colorless solid. As a result of various analysis, it was confirmed that it was a polymerizable compound of the target. · 3 (the above compound 33 (η = 0)). (analytical results) 146652.doc •41 - 201038529 (1) h-NMR^chemical shift of DMSO-dd (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] 1,1-bis[4-(2-propenylmethoxyethoxy)phenyl]_3,5-diphenylindole ( The following is referred to as the production of the polymerizable compound No. 4) [Chem. 26]

To the intermediate compound ν〇·2 of 9·00 g obtained in Example 1-2, p-toluenesulfonic acid monohydrate 0.650 g, and 2,6-di-t-butyl-4-indolylphenol Add 71_7 g of acrylic acid to 0.010 g and mix for 3 hours at 7 °C. Thereafter, 200 mL of ethyl acetate was added, and after washing 3 times with 2 mL of water, the ratio was 10 . /. The solution was washed twice with 100 mL of an aqueous solution of hydrogen sulphate, and then washed with water for 2 liters [washing, the organic phase was dried over anhydrous magnesium sulfate, and the solvent was distilled away to obtain a reaction mixture. This was separated and purified by silica gel column chromatography (developing solvent: hexane/ethyl 146652.doc • 42-201038529 acid ethyl acetate = 10/1) to obtain 5 62 g (yield 523⁄4) as colorless crystals. As a result of various analyses, it was confirmed that the target polymerizable compound N〇. 4 (the above compound 33 (n=l)). (Analysis results) (1) Chemical shift (ppm) of [H-NMIUDMSO-cU) 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), 〇6.32-6.40 (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] Μ-double [4-(4 Production of -vinylbenzyloxy)phenyl]-3-phenylindan (hereinafter referred to as Q polymerizable compound No. 5) [Chem. 27]

1,1-bis(4-hydroxyphenyl)-3-phenylindan 5.00 g was mixed with acetone 20.0 g, sterol 4·00 g, and sodium hydroxide 1.16 g, and heated to 55. (:, slowly add 146652.doc -43- 201038529 4-gas methyl styrene 4.23 g. Further, after reacting at 55 ° C for 4 hours, 50 mL of methanol was added to the reaction mixture, and the mixture was thoroughly stirred for decantation. To remove the supernatant from the viscous liquid deposited on the bottom. After adding 50 mL of acetone to the residual liquid to dissolve it, the solvent was distilled off to obtain a yellow crystalline solid, which was obtained by acetone washing. The yellow crystals were 3.3 g (yield: 41 °/). As a result of various analyses, it was confirmed that the target polymerizable compound No. 5 (the above compound 49 (m = 0)). (analysis results) (1) W-NMR ^DMSO-dfi) 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, 11 17, 1045, 1012, 912, 877, 829, 758, 732, 700 [Example 3-1] In Example 2-1 2.00 g of the polymerizable compound N〇.1, 丨-hydroxycyclohexyl phenyl ketone oxime 1 〇〇g as a photoradical polymerization initiator, and 0.0016 g of F-470 manufactured by DIC Corporation as a leveling agent And ethyl acetate 2.10 g mixed to dissolve 'to obtain a polymerizable composition N〇. [Example 3-2] 0.500 g of the polymerizable compound N〇. 1 obtained in Example 2-1, 146652.doc • 44 · 201038529 2,2-bis(4-propenyloxyphenyl) I.50 g of propane (hereinafter referred to as compound palpitary), 0.100 g of dicyclohexyl phenyl ketone, F_〇〇16 g of F-470 manufactured by DIC Corporation, and bismuth Benzene 2·1〇g are mixed and dissolved to obtain a polymerization. Composition N〇[化28]

实施 [Example 3-3] 2.00 g of the polymerizable compound n〇. 2 obtained in Example 2-2, 1-cyclohexyl phenyl ketone oxime. 1 〇〇 §, £) 1 (: : The company's 17-47 〇〇〇 16 § and the acetic acid vinegar 2.10 g were thoroughly mixed to obtain a polymerizable composition N 〇. 3. [Example 3-4] The polymerizable compound obtained in Example 2-3 was obtained. 0.500 g of 〇·3, 1.50 g of compound a-Ι, 1〇〇g of 1-hydroxycyclohexyl phenyl ketone oxime, 〇16 g of F·470 manufactured by DIC Corporation, and 2.10 g of toluene were mixed and dissolved to obtain a polymerization. The compound U composition No. 4. [Example 3-5] The polymerizable compound No. 4 obtained in Example 2_4, 2·00 g, 1-hydroxycyclohexyl phenyl ketone 0.100 g, manufactured by mc. F-47 〇〇〇 16 g and 2.10 g of ethyl acetate were thoroughly mixed to obtain a polymerizable composition n 〇. 5. [Example 3-6] The polymerizable compound N 所得 obtained in Example 2-5 0.50 g of 5, 1.50 g of compound a-oxime, hydroxycyclohexyl phenyl ketone oxime 1 〇〇 g, mc company 146652.doc -45- 201038529 FF-470 〇·0016 g and benzene benzene 2· 10 g of the mixture was dissolved to obtain a polymerizable composition N 〇. 6. [Comparative Example 1 -1 ] 2.00 g of the compound a-oxime, 0.100 g of 1-hydroxycyclohexyl phenyl ketone, 0.0016 g of f-470 manufactured by DIC Corporation, and 2.10 g of ethyl acetate were sufficiently mixed to obtain a comparative polymerizable composition No. 1. [Comparative Example 1 - 2] 2,2-bis[4-(2-propenylmethoxyethoxy)phenyl]propane (hereinafter referred to as compound a-2) 2.00 g, 1-hydroxycyclohexyl phenyl ketone O.ioo g, 0.001 6 g of F-470 manufactured by mc company and 2-10 g of ethyl acetate were thoroughly mixed to obtain a comparative polymerizable composition No. 2. [Chem. 29]

[Comparative Example 1-3] 9,9-bis[4-(2-propenylmethoxyethoxyethoxy)phenyl] (hereinafter referred to as compound a-3) 2.00 g, 1-hydroxycyclohexylphenyl 0.100 g of ketone, 0.0016 g of F-470 manufactured by Dlc Co., Ltd. and 2.10 g of toluene were thoroughly mixed to obtain a comparative polymerizable composition N 〇. [化30]

Further, the compounds a-1 to a-3 are different from the polymerizable compound of the present invention as a polymerizable compound having no benzo or naphthocycloalkane skeleton. [Examples 4-1 to 4-6] The 0.50 g of each of the polymerizable compositions No. 1 to No. 6 obtained in Examples 3-1 to 3-6 was applied onto a PET film in an oven. Prebaking was carried out at 80 ° C for 10 minutes. Thereafter, the amount of light of 500 mJ/cm2 was exposed with a high pressure mercury lamp to obtain a hardened film. The cured film was peeled off from the PET film to measure the refractive index. The results are shown in [Table 1]. 〇 [Comparative Examples 2-1 and 2-2] The comparative polymerizable compositions No. 1 and No. 2 obtained in Comparative Examples 1-1 and 1-2 were the same as in Examples 3-1 to 3-6. The operation is performed to measure the refractive index. The results are shown together in [Table 1]. [Table 1] Example composition refractive index nc Example 4-1 Polymerizable composition No. 1 1.646 Example 4-2 Polymerizable composition No. 2 1.592 Example 4-3 Polymerizable composition No. 3 1.622 Example 4-4 Polymerizable Composition No. 4 1.596 Example 4-5 Polymerizable Composition No. 5 1.625 Example 4-6 Polymerizable Composition No. 6 1.600 Comparative Example 2-1 Comparative Polymerizable Composition No. 1 1.586 Comparative Example 2-2 Comparative Polymerizable Composition No. 2 1.573 [Examples 5-1 and 5-2] Polymerizable Composition No. 3 and No. obtained in Examples 3-3 and 3-5 5 Each 0.50 g was applied to a 50 mm x 80 mm x 80 μm TAC film (FT-TDY80UL manufactured by Fuji Film Co., Ltd.) using a bar coater #40, and was carried out in an oven at 146652.doc •47-201038529 80°C. Pre-bake in minutes. Thereafter, a coating film was obtained by exposing a light amount of 500 mJ/cm 2 with a high pressure mercury lamp. The film was placed on a flat surface, and the heights of the four corners of the film from the plane were measured, and the total amount of film warpage deformation was evaluated as follows: 〇 was less than 20 mm, Δ was 20 mm or more and less than 60 Mm, X is 60 mm or more. The results are shown in [Table 2]. [Comparative Examples 3-1 and 3-2] The comparative polymerizable compositions No. 2, No. 3 obtained in Comparative Examples 1 - 2, and 1 - 3 were the same as in Examples 5-1 and 5-2. The method is used to evaluate the amount of deformation. The results are shown together in [Table 2]. [Table 2]

Example Composition Deformation Example 5-1 Polymerizable Composition No. 3 〇 Example 5-2 Polymerizable Composition No. 5 〇 Comparative Example 2-1 Comparative Polymerizable Composition No. 2 Δ Comparative Example 2 2 Comparative Polymerizable Composition No. 3 X According to the results of [Table 1] and [Table 2], it is understood that the polymer containing the polymerizable composition containing the polymerizable compound of the present invention is compared with the comparative polymer. The high refractive index and the warpage of the film are small, and it can be used as an optical material. 146652.doc -48-

Claims (1)

201038529 VII. Scope of application for patent ·· Show compound Ο 1· One is expressed by the following general formula (1) [Chemical 1] (Indole and A are independently a hydrogen atom and a substituent represented by the following formula (π), formula (10) or formula (IV), and at least one of α^α2 is represented by the following formula ( II), 诵-+ ij ) a substituent represented by the formula (ΠΙ) or the formula (IV), X, Ζ Ζ and Ζ respectively represent a carbon atom which can be substituted by a perion atom, a group of 1G, an aryl group which can be substituted with a halogen atom, and an aryl group having 6 to 2 carbon atoms, which can be substituted by a halogen atom. An arylalkyl group having an atomic number of 7 to 2 Å, a heterocyclic group or a dentate atom having 2 to 2 carbon atoms which may be substituted by an il atom, and a methylene group in the alkyl group, the aryl group and the aryl group The base may be interrupted by an unsaturated bond, -Ο- or -S-, X may form a ring with each other, the rings may be aromatic rings, k represents the number of 〇~4, and p represents the number of 0~8 'r and s respectively The number of 〇~4 is independently expressed. When k, p, r, and/or s is 2 or more, plural χ, 1 and/or Z2 may be the same or different, X represents the number of 〇~4, and y represents 0. ~4 number 'X and y number of people ^ mouth δ ten is 146652.doc 201038529 2~4) [Chemical 2] (Π) (III) (IV) (wherein, L, L2 and L3 each independently represent an extended ethyl group or a stretched propyl group, and η and m each independently represent the number of 〇~2〇, and f represents the number of 丨~2〇. Or when f is 2 or more, the unit represented by [R0]n, [R〇]m4[R〇]]^ may be a random copolymer or block copolymer of an extended ethyloxy group and a propyloxy group. 'Μ denotes a hydrogen atom or a methyl group). 2. The compound of claim 1, wherein in the above formula (1), hydrazine is 2 and hydrazine is hydrazine. 3. The compound of claim 1, which is represented by the following formula (v): [Chemical 3] the same). 4. The compound of claim 1 or 3, wherein the above formula (1) or the above formula, Y is a phenyl group. 146652.doc 201038529 5. The compound of claim 1 or 3 wherein 'k' is 0 or 1 in the above formula (1) or the above formula (V), and when k is 1, X is a number of carbon atoms An alkyl group or an aryl group having 6 to 20 carbon atoms. 6. The compound of the above-mentioned formula (1) or the above formula (v), wherein both A1 and A2 represent a group represented by the above formula (IV). 7. The compound of claim 1 or 3, wherein the above formula (1) or the above formula In (V), at least one of A and A is a group represented by any one of the above formulas or formulas. 8. The compound of claim 1 or 3, wherein in the above formula (1) or in the above formula (V), both of Α1 and Α2 are groups represented by the above formula (π). 9 =1 The compound of Item 1 or 3, wherein the above formula (1) or the above formula, Α1 and Α2 are each a group represented by the above formula (III). 10·=polymerizable composition' is characterized by containing a drug as required. 11. As requested. The polymerizable composition of item 10 contains a radical polymerization initiation 12. a polymerized polymer which polymerizes the polymerizable composition as claimed in claim 10 146652.doc 201038529 IV. Designated representative figure: (1) The designated representative figure is: (none) (2) The symbolic symbol of the representative figure is simple: Ο 5. If there is a chemical formula in this case, please disclose the chemical formula that best shows the characteristics of the invention: 146652.doc