KR101183742B1 - Multifunctional methacrylate and method for producing same - Google Patents

Abstract

A polymerizable composition is comprised from the polyfunctional (meth) acrylate which has a fluorene skeleton represented by following formula (1). The polymerizable composition may contain a polymerization initiator (such as a photopolymerization initiator) or polysilane.

≪ Formula 1 >

(Wherein R ^1a , R ^1b , R ^2a and R ^2b represent a substituent, R ^3a and R ^3b represent an alkylene group, and R ^4a and R ^4b represent a hydrogen atom or a methyl group. K1 and k2 represent 0 to 4) M1 and m2 represent integers of 0 to 3, n1 and n2 represent integers of 0 or 1 or more, and p1 and p2 represent integers of 2 to 4. However, m1 + p1 and m2 + p2 Is an integer from 2 to 5)

Multifunctional (meth) acrylate, polymerization initiator, fluorene backbone

Description

Multifunctional (meth) acrylate and its manufacturing method {MULTIFUNCTIONAL (METH) ACRYLATE AND METHOD FOR PRODUCING SAME}

INDUSTRIAL APPLICABILITY The present invention can form materials such as optical material applications (optical overcoat agent, hard coat agent, antireflection film, spectacle lens, optical fiber, optical waveguide, hologram, and the like), and is useful for improving heat resistance, refractive index and the like. It relates to a functional (meth) acrylate, a method for producing the same, and a polymerizable composition (and a cured product thereof) composed of the polyfunctional (meth) acrylate.

Optical materials such as optical overcoats, hard coats, antireflection films, spectacle lenses, optical fibers, optical waveguides, holograms, and the like, such as thermoplastic resins (polycarbonates) and thermosetting resins (diethylene glycol bisallylcarbonates (CR-39). And hardened | cured material of polyfunctional aliphatic acrylates, such as), etc. are used. Such optical materials are required to improve properties such as moisture resistance, heat resistance, and high refractive index, and development of various optical materials has been studied.

Japanese Patent Application Laid-Open No. 4-325508 (Patent Document 1) discloses a compound in which 9,9-bis (4-hydroxyphenyl) fluorene is reacted with (meth) acrylic acid chloride as a plastic material, or 9,9- Disclosed is a copolymer having as its main component a compound in which ethylene oxide or propylene oxide is added to bis (4-hydroxyphenyl) fluorene and then reacted with (meth) acrylic acid.

However, in such a bisacrylate fluorene compound, a crosslinking density cannot be raised and the characteristic (for example, hardness, heat resistance, etc.) calculated | required by an optical material, a coating film, etc. cannot fully be improved.

Patent Document 1: Japanese Patent Application Laid-Open No. 4-325508 (claim 1, paragraph No.)

Problems to be solved by the invention

Therefore, the objective of this invention is providing the polyfunctional (meth) acrylate which can remarkably improve characteristics, such as hardness, heat resistance, and moisture resistance, and its manufacturing method.

Another object of the present invention is to provide a polyfunctional (meth) acrylate capable of improving the crosslinking density.

It is still another object of the present invention to provide a method for producing a novel multifunctional (meth) acrylate having a fluorene skeleton in a simple and high yield.

Means for solving the problem

MEANS TO SOLVE THE PROBLEM As a result of earnestly examining in order to achieve the said subject, when the polyfunctional (meth) acrylate of the compound (or its alkylene oxide adduct) substituted with polyhydric phenol in the 9-position of fluorene is used, a crosslinking density The present invention was found to be able to improve the properties of the material (such as an optical material) and to significantly improve the properties such as hardness and heat resistance.

That is, the polyfunctional (meth) acrylate of this invention is (meth) acrylate which has a fluorene skeleton represented by following formula (1).

Wherein R ^1a , R ^1b , R ^2a and R ^2b represent a substituent, R ^3a and R ^3b represent an alkylene group, and R ^4a and R ^4b represent a hydrogen atom or a methyl group. K1 and k2 are the same or Different and represent an integer of 0 or 1 to 4, m1 and m2 are the same or different and represent an integer of 0 or 1 to 3, n1 and n2 represent the same or different and represent an integer of 0 or 1, p1 and p2 is the same or different and represents an integer of 2 to 4. However, m1 + p1 and m2 + p2 are integers of 2-5.)

In the formula (1), R ^3a and R ^3b is a C ₂₄ alkylene group, n1 and n2 are 0 to 12 degree and, n1 + n2 is 0 to 24 degree from the even and, particularly formula (1), R ^1a and R ^1b is C _{1 - 4} alkyl group, k1 and R k2 is 0 or 1, R ^2a and R ^2b are, C _{1 - 4} alkyl, C _{1 - 4} alkoxy group or a C _{6 - 8} aryl group, m1 and m2 that is 0 ~ 2, R ^3a and R ^3b is C _{2 - 4} alkylene group, n1 and n2 are 0 ~ 6, n1 + n2 is or may be 0-12. p1 and p2 are 2 or 3, respectively. Further, in the formula (1), n1 and preferred multi-functional (meth) acrylate, n2 is 1 or more, R ^3a and R ^3b is C _{2 -} and ₄ alkylene group, n1, and a degree n2 is 1 ~ 4, n1 The polyfunctional (meth) acrylate etc. which + n2 is about 2-8 and p1 and p2 are 2 are contained.

In typical multi-functional (meth) acrylate represented by the formula (1), 9, 9-bis (di-hydroxyphenyl) fluorene flow of C _{2 - 4} (meth) acrylates of the alkylene oxide adduct, 9 , 9-bis (tri-hydroxyphenyl) fluorene flow of C _{2 - 4,} and the like (meth) acrylates of the alkylene oxide adduct.

Although the polyfunctional (meth) acrylate represented by said Formula (1) is not specifically limited, Usually, the polyhydric alcohol which has a fluorene skeleton represented by following formula (2), and (meth) acrylic acid or its derivatives are reacted. It can manufacture by making it.

(Wherein R ^1a , R ^1b , R ^2a , R ^2b , R ^3a , R ^3b , k1, k2, m1, m2, n1, n2, p1 and p2 are the same as above)

This invention contains the polymeric composition comprised from the polyfunctional (meth) acrylate represented by said Formula (1), and a polymerization initiator (for example, a photoinitiator). The ratio of a polymerization initiator may be about 0.1-30 weight part with respect to 100 weight part of polyfunctional (meth) acrylates represented by said formula (1). Moreover, the said polymeric composition may contain polysilane further. Such polysilane contains the polysilane etc. which have at least one structural unit among the structural units represented by following formula (3)-(5), and the ratio of polysilane is the polytube represented by said formula (1). 0.1-100 weight part may be sufficient with respect to 100 weight part of functional (meth) acrylates, for example.

(In formula, R <^5> -R <^7> is the same or different, and is a hydrogen atom, a hydroxyl group, an alkyl group, an alkoxy group, an alkenyl group, a cycloalkyl group, a cycloalkyloxy group, a cycloalkenyl group, an aryl group, an aryloxy group, An aralkyl group, an aralkyloxy group or a silyl group, x, y and z each represent an integer of 0 or 1 or more, and the sum of x, y and z is 5 to 400.)

This invention also includes the hardened | cured material which the said polymerizable composition (or the polyfunctional (meth) acrylate) represented by said Formula (1) superposed | polymerized or hardened | cured, and the material (optical material etc.) which consisted of this hardened | cured material. .

In addition, in this specification, "(meth) acrylate" means an acrylate or a methacrylate. In addition, "(meth) acryloyloxy" means acryloyloxy or methacryloyloxy.

Effects of the Invention

Since the polyfunctional (meth) acrylate of this invention has a fluorene skeleton and has many (meth) acryloyl groups which have many high polymerizability, a crosslinking density can be improved and a material (optical Properties such as hardness and heat resistance of the material) can be remarkably improved. In addition, in this invention, many (meth) acryloyl groups can be introduce | transduced and novel polyfunctional (meth) acrylate which has a fluorene skeleton can be manufactured in a simple and high yield.

DETAILED DESCRIPTION OF THE INVENTION

The polyfunctional (meth) acrylate of this invention is represented by following formula (1), The polyol component which the polyhydric alcohol (or its alkylene oxide adduct) substituted with two polyhydric phenols in the 9 position of fluorene is substituted. It is polyfunctional (meth) acrylate to be.

&Lt; Formula 1 >

Wherein R ^1a , R ^1b , R ^2a and R ^2b represent a substituent, R ^3a and R ^3b represent an alkylene group, and R ^4a and R ^4b represent a hydrogen atom or a methyl group. K1 and k2 are the same or Different and represent an integer of 0 or 1 to 4, m1 and m2 are the same or different and represent an integer of 0 or 1 to 3, n1 and n2 represent the same or different and represent an integer of 0 or 1, p1 and p2 is the same or different and represents an integer of 2 to 4. However, m1 + p1 and m2 + p2 are integers of 2-5.)

Although it does not specifically limit as a substituent represented by group R <^1a> and R <^1b> , Usually, it is an alkyl group in many cases. As the alkyl group, methyl group, ethyl group, propyl group, isopropyl group, butyl group, C _1, such as t- butyl group _- can be exemplified ₍₄ alkyl, especially a methyl group, for example, C ₁₎ such as ₆ alkyl group. The groups R ^1a and R ^1b may be different from each other or may be the same. In addition, the group R ^1a (or R ^1b ) may be different or the same in the same benzene ring. In addition, the bonding position (substitution position) of group R <^1a> (or R < ^1b ) with respect to the benzene ring which comprises a fluorene skeleton is not specifically limited. Preferred substitution numbers k1 and k2 are 0 or 1, in particular, 0. In addition, although substitution number k1 and k2 may differ, it is the same normally.

The substituent R ^2a and R ^2b, an alkyl group (a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, a s- butyl group, a t- butyl group, such as C _{1 - 20} alkyl group, preferably a C _{1 - 8} alkyl group, more preferably C _{1 - 6} alkyl group), cycloalkyl (cyclopentyl, cyclohexyl, etc. of C _{5 - 10} cycloalkyl group, preferably a C _{5 - 8} cycloalkyl group, more preferably C _{5 - 6} cycloalkyl _[- such as ₈ aryl group, especially a phenyl group, an alkylphenyl group (methylphenyl group (tolyl), dimethylphenyl group (group-xylene), and so on), C _6-10 aryl group, preferably a C _6, such as; the alkyl group and the like), an aryl group, , an aralkyl group such as a hydrocarbon group (benzyl group, phenethyl group and so on of the C _{6 - - 10} aryl -C _{1 4} alkyl and the like); Alkoxy groups (such as C _1-4 alkoxy groups such as methoxy groups); Hydroxyl group; Hydroxy (poly) alkyleneoxy group (hydroxy (poly) C _{2 - 4} alkylene group); An acyl group (an acetyl group or the like of the C _{1 - 6} acyl group and the like); Alkoxycarbonyl group (such as methoxycarbonyl group C _{1 - 4} alkoxycarbonyl group and the like); Halogen atoms (fluorine atoms, chlorine atoms, etc.); A nitro group; Cyano group etc. are mentioned.

In addition, in the manufacturing method of the polyfunctional (meth) acrylate mentioned later, the said hydroxyl group or the hydroxy (poly) alkyleneoxy group does not react with the residue ((meth) acrylic acid or its derivative (s) of the polyhydric alcohol used as a raw material. In many cases.

Preferred substituents R ^2a (or R ^2b) is an alkyl (C _{1 - 6} alkyl group), a cycloalkyl group (C _{5 - 8} cycloalkyl group), aryl group (C _{6 - 10} aryl group), aralkyl group (C _{6 - 8} aryl -C _{1 - 2} is an alkyl group), a hydroxyl group, a hydroxy (poly) alkyleneoxy group (hydroxy (poly) C _2-4 alkyleneoxy group). Of these, in particular, C _{1 - 4} alkyl, C _{1 - 4} alkoxy groups, C _{6 - 8} aryl groups are preferred. The substituent R ^2a (or R ^2b ) may be substituted with the benzene ring alone or in combination of two or more thereof. Further, the groups R ^2a and R ^2b may be the same as or different from each other, but are usually the same. In addition, group R <^2a> (or R < ^2b ) may be different and may be the same in the same benzene ring.

In addition, the substitution position of substituent ^R2a (or ^R2b ) is not specifically limited, A (meth) acryloyloxy group or (meth) acryloyloxy (poly) alkoxy group (hereinafter, (meth) acryloyloxy group According to the substitution position of the containing group may be generically mentioned, it can substitute in 2-6 positions (for example, 2 position, 5 position, 2, 5-position etc.) of a phenyl group.

Preferable substitution numbers m1 and m2 vary depending on the number of substitution of the (meth) acryloyloxy group-containing group, but are 0 to 2, and more preferably 0 to 1 (particularly 0). In addition, although the substitution numbers m1 and m2 may be different, they are usually the same.

R ^3a and R ^3b alkylene group represented by, but not limited to, for example, C _{2 -4} illustrating an alkylene group such as (an ethylene group, a trimethylene group, a propylene group, butane-1,2-diyl, etc.) may, in particular, C _{2 - 3} alkylene groups are preferred (particularly, ethylene, propylene). In addition, although R <^3a> and R <^3b> may be the same or different alkylene groups, they are usually the same alkylene group.

Substitution number (addition number) n1 and n2 of an alkoxy group are the same or different, and it can select from the range of about 0-15, For example, 0-12 (for example, 1-12), Preferably May be 0-8 (for example, 1-8), More preferably, it is 0-6 (for example, 1-6), Especially 0-4 (for example, 1-4) may be sufficient. In addition, the sum (n1 + n2) of n1 and n2 can be selected from the range of about 0-30, for example, 0-24 (for example, 2-24), Preferably 0-16 (for example) For example, 2-12, More preferably, it is 0-12 (for example, 2-10), Especially 0-8 (for example, 2-8) may be sufficient. In addition, when n1 (or n2) is two or more, the polyalkoxy (polyalkyleneoxy) group may be comprised by the same alkoxy group, and heterogeneous alkoxy groups (for example, an ethoxy group and a propyleneoxy group) are mixed. Although it may be, it is usually comprised by the same alkoxy group in many cases.

2-3 are preferable and, as for the substitution numbers p1 and p2 of a (meth) acryloyloxy group containing group, 2 is especially preferable. In addition, the sum (p1 + p2) of p1 and p2 may be 4-8, for example, about 4-6 (especially 4) may be sufficient. In addition, although the substitution numbers p1 and p2 may differ, they are usually the same. Substitution position of a (meth) acryloyloxy group containing group is not specifically limited, According to the number of p1 (or p2), it can select from 2-6 positions of the phenyl group substituted by 9-position of fluorene, and p1 (Or p2) is 2, for example, 3, 4-position, 3, 5-position may be sufficient. One (meth) acryloyloxy group containing group may substitute in 4 position normally.

In addition, the some (meth) acryloyloxy group containing group substituted by the same benzene ring may be the same, and may differ. For example, the some (meth) acryloyloxy group containing group may be comprised by the (meth) acryloyloxy group which is (iii) n1 = 0 (n2 = 0) independently, (ii) n1 = 0 (n2 (Meth) acryloyloxy group (2- (meth) acryloyloxyethoxy group etc.) which is (meth) acryloyloxy group which is = 0) and n1 ≠ 0 (n2 ≠ 0) (B) may be composed of the same (meth) acryloyloxy (poly) alkoxy group alone, which is n1 ≠ 0 (n2 ≠ 0), or (b) different from n1 ≠ 0 (n2 ≠ 0) Meth) acryloyloxy (poly) alkoxy group [eg, 2- (meth) acryloyloxyethoxy group and 2- (2- (meth) acryloyloxyethoxy) ethoxy group] You may be.

As typical polyfunctional (meth) acrylate represented by said formula (1), for example, 9, 9-bis (di (meth) acryloyloxyphenyl) fluorene, 9, 9-bis (tri ( meth) fluorene yl oxyphenyl) acryloyl fluorene acids, polyhydric alcohols corresponding to these 9, 9-bis (di or tri-hydroxyphenyl) fluorene acids] of the alkylene oxide (C _{2 - 4} alkylene oxide) portion Sieve (meth) acrylate etc. are mentioned.

As 9, 9-bis (di (meth) acryloyloxyphenyl) fluorenes, for example, 9, 9-bis (di (meth) acryloyloxyphenyl) fluorene [9, 9-bis ( 3, 4-di (meth) acryloyloxyphenyl) fluorene, 9, 9-bis (2, 4-di (meth) acryloyloxyphenyl) fluorene, 9, 9-bis (2, 5- Di (meth) acryloyloxyphenyl) fluorene, etc.], 9, 9-bis (di (meth) acryloyloxyphenyl) fluorene which has a substituent (for example, 9, 9-bis (alkyl-di) (Meth) acryloyloxyphenyl) fluorene [9,9-bis (3,4-di (meth) acryloyloxy5-methylphenyl) fluorene, 9,9-bis (3,4-di (meth) ) acryloyloxy-6-methylphenyl) fluorene such as a 9, 9-bis (C _{1 - 4} alkyl-di (meth) acryloyloxyethyl phenyl) fluorene, 9, 9-bis (2,4-di ( meth) acryloyloxy 3, 6-dimethylphenyl) fluorene such as a 9, 9-bis (di-C _{1 - 4} alkyl-di (meth) acryloyloxyethyl phenyl) fluorene, etc.], 9, 9-bis (Alkoxy-di (meth) arc Roil oxyphenyl) fluorene [for example, 9, 9-bis (3,4-di (meth) such as acryloyloxy-5-methoxyphenyl) fluorene 9, 9-bis (C _{1 -4} Alkoxy-di (meth) acryloyloxyphenyl) fluorene, etc.], 9, 9-bis (aryl-di (meth) acryloyloxyphenyl) fluorene [eg, 9, 9-bis (3, include one oxyphenyl) fluorene, etc.], etc.} acryloyl 4-di (meth) acryloyloxy-5-phenylphenyl) fluorene such as a 9, 9-bis (di (meth C _{6 - - 8} aryl) Included.

Examples of the 9,9-bis (tri (meth) acryloyloxyphenyl) fluorene include fluorenes corresponding to the 9,9-bis (di (meth) acryloyloxyphenyl) fluorenes; For example, 9, 9-bis (2, 4, 6- (meth) acryloyloxyphenyl) fluorene, 9, 9-bis (2, 4, 5-tri (meth) acryloyloxyphenyl) fluorene 9, 9-bis (tri (meth) acryloyloxyphenyl) fluorene, such as 9, 9-bis (3, 4, 5-tri (meth) acryloyloxyphenyl) fluorene, etc. are contained.

As a (meth) arcrelate of the alkylene oxide adduct of 9, 9-bis (dihydroxyphenyl) fluorene, for example, 9, 9-bis [3, 4-di (2- (meth)) to an acryloyl oxy) phenyl] fluorene, etc. at the time of yloxy 9, 9-bis [di (2- (meth) acrylic C _{2 - 4} alkoxy) phenyl] fluorene (n1 = n2 = 1), 9, 9,9-bis {di [2- (2- (meth), such as 9-bis [3,4-di [2- (2- (meth) acryloyloxyethoxy) ethoxy] phenyl} fluorene acryloyloxy-C _{2 - 4} and the like alkoxy phenyl] fluorene} (n1 = n2 = 2) - 4 alkoxy) C _2.

As the (meth) acrylate of the alkylene oxide adduct of 9, 9-bis (trihydroxyphenyl) fluorene, for example, 9, 9-bis [3, 4, 5-tri (2- (meth) ) with an oxy-acryloyl) phenyl] fluorene when yloxy 9, 9-bis [di (2- (meth) acrylate, such as fluoren-C _{2 - 4} alkoxy) phenyl] fluorene (n1 = n2 = 1), 9 9,9-bis {tri [2- (2-, such as 9-bis [3, 4, 5-tri [2- (2- (meth) acryloyloxyethoxy) ethoxy] phenyl] fluorene meth) acryloyloxy-C _{2 - 4} and the like alkoxy phenyl] fluorene} (n1 = n2 = 2) - 4 alkoxy) C _2.

Of these polyfunctional (meth) acrylate, particularly, 9, 9-bis (di-hydroxyphenyl) fluorene flow of C _{2 - 4} g. (Meth) acrylate {for example, an alkylene oxide adduct, 9, 9 -Bis [di (2- (meth) acryloyloxyC _2-3 alkoxy) phenyl] fluorene, 9, 9-bis {di [2- (2- (meth) acryloyloxyC _2-3 alkoxy ) C _2-3 alkoxy] phenyl} fluorene}, etc., 9, 9-bis (tri-hydroxyphenyl) fluorene flow of C _{2 - 4} alkylene oxides, for (meth) acrylate {for example the adduct, 9 , 9-bis [tri (2- (meth) acryloyloxyC _2-3 alkoxy) phenyl] fluorene, 9, 9-bis {tri [2- (2- (meth) acryloyloxyC _{2- 3} alkoxy) C _2-3 alkoxy] phenyl} fluorene etc. are preferable.

The polyfunctional (meth) acrylate of the present invention has a fluorene skeleton and a number of (meth) acryloyloxy group-containing groups (especially (meth) acryloyloxy (poly) C ₂ having high reactivity) Since it has a _-4 alkoxy group, it is useful in providing various outstanding characteristics (especially the characteristic calculated | required for optical uses, such as high refractive index, light transmittance, high hardness, weather resistance, flexibility, and intensity | strength). Moreover, since it has many highly reactive (meth) acryloyloxy-group containing groups, while the superposition | polymerization rate can be improved, the crosslinking density of hardened | cured material can be made remarkably large, and high hardened | cured material can be obtained efficiently. Can be.

[Method for producing polyfunctional (meth) acrylate]

Although the polyfunctional (meth) acrylate of this invention is not specifically limited, It can manufacture by making the polyhydric alcohol which has a fluorene skeleton represented by following formula (2), (meth) acrylic acid or its derivative (s) react.

<Formula 2>

(Wherein R ^1a , R ^1b , R ^2a , R ^2b , R ^3a , R ^3b , m1, m2, k1, k2, n1, n2, p1 and p2 are the same as above)

In the polyhydric alcohol represented by said formula (2), preferable group and substitution number (R, k, m, n, p) are the same as the above. As typical polyhydric alcohol, for example, 9, 9-bis (dihydroxyphenyl) fluorene [9, 9-bis (3, 4-dihydroxyphenyl) fluorene (biscatechol fluorene (BCAF)) , 9, 9-bis (2, 4-dihydroxyphenyl) fluorene, 9, 9-bis (2, 5-dihydroxyphenyl) fluorene], 9, 9-bis (dihydroxy) having a substituent phenyl) fluorene {e.g., 9, 9-bis (mono- or di-C _{1 - 4} alkyl-di-hydroxyphenyl) fluorene 9, 9-bis (3, 4-hydroxy-5-methylphenyl) fluorene, etc.], 9, 9-bis such as (C _{1 - - 4} alkoxy-di-hydroxyphenyl) fluorene 9, 9-bis (3,4-dihydroxy-5-methoxyphenyl) fluorene], 9, 9-bis (C _{6 - 8} aryl-di-hydroxyphenyl) fluorene 9, 9 such as a 9, 9-bis (3, 4-hydroxy-5-phenylphenyl) fluorene, etc.], etc.} -Bis (dihydroxyphenyl) fluorene; 9, 9-bis (trihydroxyphenyl) fluorene [9, 9-bis (2, 4, 6- trihydroxyphenyl) fluorene, 9, 9-bis (2, 4, 5) corresponding to these -Trihydroxyphenyl) fluorene, 9, 9-bis (3, 4, 5-trihydroxyphenyl) fluorene, etc .; 9, 9-bis [di (2-hydroxy C), such as these alkylene oxide adducts {for example, 9, 9-bis [3, 4-di (2-hydroxyethoxy) phenyl] fluorene _{2 - 4} alkoxy) phenyl] fluorene, 9, 9-bis {3,4-di [2- (2-hydroxy-ethoxy) ethoxy] phenyl} fluorene 9, 9-bis {di, such as fluoren-2 -(2-hydroxyC _2-4 alkoxy) C _2-4 alkoxyphenyl] fluorene} and the like} and the like.

In the production of the polyfunctional (meth) acrylate, the purity of the polyhydric alcohol is not particularly limited, but is usually 95% by weight or more, preferably 96% by weight or more, and more preferably 98% by weight or more.

In addition, the polyhydric alcohol represented by said formula (2) is a novel compound, and can usually manufacture simply by the following method. Although the manufacturing method of the polyhydric alcohol represented by said Formula (2) is not specifically limited, Usually, in the presence of an acid catalyst, fluorene represented by following formula (2a) and polyhydric phenol represented by following formula (2b) Reacting at least.

(Wherein R ² represents a substituent, m represents 0 or an integer of 1 to 3, p represents an integer of 2 to 4, except that m + p is an integer of 2 to 5. R ^1a , R ^1b , k1 and k2 are the same as above)

That is, (iii) polyhydric alcohols (9, 9-bis (polyhydroxyphenyl) fluorenes) in which n1 and n2 are 0 include fluorenones represented by the above formula (2a) in the presence of an acid catalyst, and It can manufacture by making polyhydric alcohol represented by Formula (2b) react. And (ii) the polyhydric alcohol having n1 and / or n2 of 1 or more reacts the fluorenones represented by the formula (2a) with the polyhydric alcohols represented by the formula (2b) in the presence of an acid catalyst. In addition, the produced 9, 9-bis (polyhydroxyphenyl) fluorene can be produced by reacting an alkylene oxide or an alkylene carbonate.

In formula (2b), R ² corresponds to R ^2a or R ^2b , m corresponds to m 1 or m 2, p corresponds to p 1 or p 2, and preferred embodiments and the like. As exemplified above.

(Method for producing polyhydric alcohol wherein n1 and n2 are 0)

The fluorenones (hereinafter sometimes referred to simply as fluorenones) represented by the above formula (2a) correspond to the fluorene skeleton of the polyhydric alcohol represented by the above formula (2), and representative fluorenones , 9-fluorenone. In addition, the purity of the fluorenones to be used is not particularly limited, but is usually 95% by weight or more, preferably 99% by weight or more.

The polyhydric phenols (hereinafter sometimes referred to simply as polyhydric phenols) represented by the formula (2b) correspond to the polyhydroxyphenyl group substituted at the 9 position in the formula (1), and are representative polyhydric phenols (poly As hydroxybenzene), for example, dihydroxybenzene (catechol, resorcinol, hydroquinone), alkyl-dihydroxybenzene [dihydroxytoluene (3, 5-dihydroxytoluene (orcinol)) , 3-methylcatechol, 4-methylcatechol, etc.), 4-t-butylcatechol, dihydroxyxylene (2, 6-dihydroxy-p-xylene, etc.) such as mono or di C _{1 - 6} alkyl-dihydroxybenzene, tetrahydro urushiol (2, 3-dihydroxy-1-pentadecyl benzene), etc.], aryl-dihydroxybenzene (2, 3-hydroxybiphenyl-phenyl, 3, 4 - di-hydroxybiphenyl phenyl such as C _{6 - 8} aryl-dihydroxybenzene, etc.), halo-dihydroxybenzene (catechol-chloro, 2, a mono- or dihalo, such as hydroquinone, 4-difluoro-dihydroxydiphenyl Cybenzene, etc.), nitro-dihydroxybenzene (such as nitrocatechol), alkoxy-dihydroxybenzene (3-methoxycatechol, 4, 6-di-t-butyl-3-methoxycatechol, etc. mono- or di-C _{1 - 6} alkoxy-dihydroxybenzene and the like), acyl-dihydroxybenzene (2, 4-hydroxy-acetophenone such as C _{2 - 6} acyl-dihydroxybenzene and so on) such as a dihydric Oxybenzenes; Trihydroxybenzenes corresponding to these dihydroxybenzenes (for example, trihydroxybenzene (pyrogarol, hydroxyhydroquinone, phloroglucinol), trihydroxyacetophenone, etc.); . You may make polyhydric alcohol react with fluorenone individually or in combination of 2 or more types.

The usage-amount of polyhydric alcohols may be 2-20 mol, Preferably it is 2.5-10 mol, More preferably, about 3-5 mol with respect to 1 mol of fluorenones.

Although reaction (condensation reaction) of polyhydric alcohols and fluorenones is not specifically limited, Usually, it can carry out in presence of an acidic catalyst. Examples of the acid catalyst include inorganic acids [sulfuric acid, hydrogen chloride, hydrochloric acid, phosphoric acid, and the like], organic acids [sulfonic acid (alkanesulfonic acid such as methanesulfonic acid, etc.), and the like. The sulfuric acid includes dilute sulfuric acid, concentrated sulfuric acid, fuming sulfuric acid and the like, and sulfur trioxide may be used as the sulfuric acid precursor as long as it can be converted into sulfuric acid in the reaction system. The acid catalysts may be used alone or in combination of two or more thereof. Preferred acid catalysts are hydrochloric acid or sulfuric acid.

The amount of acid catalyst to be used can be selected according to the type of acid catalyst, and for example, 0.001 to 150 parts by weight, preferably 0.005 to 100 parts by weight, more preferably 0.01 to 50 parts by weight based on 100 parts by weight of fluorenones. It may be about a weight part. In particular, when sulfuric acid is used as the catalyst, the amount of sulfuric acid (equivalent to H ₂ SO ₄ ) may be very small, and usually 0.001 to 0.5 parts by weight (for example, 0.005 to 1 part by weight) of pullulenone. 0.5 weight part), Preferably it is 0.01-0.5 weight part, More preferably, it may be about 0.05-0.5 weight part (for example, 0.1-0.3 weight part). When hydrochloric acid is used as a catalyst, the amount of hydrochloric acid used is 1 to 100 parts by weight, preferably 5 to 50 parts by weight, more preferably 10 to 30 parts by weight, based on 100 parts by weight of fluorenone in terms of hydrogen chloride. It may be negative.

The condensation reaction may be performed in addition to the acid catalyst, using thiols as cocatalysts in combination. By combining with thiols, a condensation reaction can be advanced effectively and a yield can be improved in many cases. As the thiols, conventional thiols that function as co-catalysts, for example, mercaptocarboxylic acid (mercaptoacetic acid, β-mercaptopropionic acid, α-mercaptopropionic acid, thioglycolic acid, mercaptosuccinic acid, mercapto Benzoic acid, etc.), thiocarboxylic acids (thioacetic acid, thiooxalic acid, etc.), alkyl mercaptans (methyl mercaptan, ethyl mercaptan, propyl mercaptan, isopropyl mercaptan, n-butyl mercaptan, dodecyl mercaptan, etc.) and the like ₍₄ alkyl mercaptans, especially C ₁₎ and the like), aralkyl mercaptan (benzyl mercaptan or the like) or salts thereof, C _1-16 alkyl mercaptans. As a salt, an alkali metal salt (sodium salt etc.) can be illustrated, for example. Among these thiols, mercapto-C _{2 -6-carboxylic} acid (for example, β- mercaptopropionic acid) are preferred. Thiols can be used individually or in combination of 2 or more types.

The amount of thiols to be used can be selected from the range of about 0 to 0.2 part by weight based on 1 part by weight of fluorenone, for example, 0.001 to 0.1 part by weight, preferably 0.003 to 0.03 part by weight, more preferably It is about 0.005-0.015 weight part.

In addition, the usage-amount of thiols can be selected from the range of about 0-10 weight part with respect to 1 weight part of acidic catalysts, For example, 0.001-10 weight part, Preferably it is 0.01-10 weight part (for example, 0.01 to 5 parts by weight), more preferably about 0.01 to 2 parts by weight. In particular, in the case of using sulfuric acid, 0.001 to 1 part by weight of thiols, preferably 0.01 to 0.5 part by weight, and more preferably about 0.01 to 0.3 part by weight based on 1 part by weight of sulfuric acid. In addition, when using hydrochloric acid, 0.1-3 weight part, Preferably it is 0.3-1 weight part, More preferably, about 0.5-1.5 weight part with respect to 1 weight part of hydrochloric acid (hydrogen chloride conversion).

Condensation reaction may be performed in the absence of a solvent, and may be performed in a solvent. The solvent is not particularly limited as long as it is nonreactive with respect to the acidic catalyst and can dissolve fluorenones and polyhydric phenols, and can be used in a wide range. Representative solvents (organic solvents) include ether solvents (dialkyl ethers such as diethyl ether, cyclic ethers such as tetrahydrofuran, dioxane and the like), halogen crab solvents (halogenated hydrocarbons such as methylene chloride, chloroform and carbon tetrachloride). And aromatic solvents (aromatic hydrocarbons such as benzene, toluene, xylene, anisole, etc.) and the like. Moreover, you may use excess polyhydric alcohol as a solvent. Among these solvents, cyclic ethers (tetrahydrofuran, 1, 4-dioxane and the like) are preferable. The solvents may be used alone or in combination of two or more thereof.

The usage-amount of a solvent can be selected from the range of about 0-20 weight part with respect to 1 weight part of fluorenones, For example, 0.5-10 weight part, Preferably 1-8 weight part, More preferably, 2 It may be about 5 parts by weight.

Although condensation reaction changes with kinds of polyhydric alcohol, acid catalyst, thiol, etc. to be used, it is usually 10-150 degreeC, Preferably it is 20-120 degreeC, More preferably, it carries out about 30-100 degreeC in many cases. . Moreover, reaction time can be adjusted with the kind of raw material, reaction temperature, the density | concentration in a solvent, etc., For example, it is 30 minutes-48 hours, Usually, 1 to 24 hours, Preferably it is about 1 to 10 hours.

In addition, reaction may be performed while stirring, may be performed in air or in an inert atmosphere (nitrogen, a rare gas, etc.), and may be performed under normal pressure or pressurization.

In the reaction mixture after completion of the reaction, in addition to the polyhydric alcohols (9, 9-bis (polyhydroxyphenyl) fluorenes) usually produced, unreacted fluorenones, unreacted polyhydric alcohols, catalysts (acid catalysts, thiols) ), Side reaction products and the like. For this reason, it can isolate | separate and refine by conventional means, for example, separation means, such as filtration, concentration, extraction, crystallization, recrystallization, column chromatography, and the like. For example, after removing an acid catalyst (and thiols) by the conventional method, it refine | purifies by adding crystallization solvent, cooling and crystallizing, and then filtering and isolate | separating.

Examples of the crystallization solvent include hydrocarbons [aliphatic hydrocarbons (hexane, heptane, etc.), alicyclic hydrocarbons (cyclohexane, etc.), aromatic hydrocarbons (toluene, xylene, etc.), halogenated hydrocarbons (dichloromethane, etc.), water, Alcohols (alkyl alcohols such as methanol, ethanol, n-propanol, isopropanol, butanol, cyclohexanol, etc.), ketones (acetone, methyl ethyl ketone, methyl isobutyl ketone, diethyl ketone, ethyl propyl ketone, di-n- Alkyl ketones, such as propyl ketone and diisopropyl ketone, cyclohexanone, etc., Ethers (dialkyl ether, such as diethyl ether and diisopropyl ether, etc.), nitriles, cellosolves, and amides (dimethylformamide) And sulfoxides. A crystallization solvent may be independent or it may combine it 2 or more types. In addition, the usage-amount of a crystallization solvent is not specifically limited, 0.5-50 weight part, Preferably it is 1-10 weight part, More preferably, about 1-5 weight part with respect to 1 weight part of reaction mixtures (solid content conversion). It may be.

In addition, about the manufacturing method of 9, 9-bis (polyhydroxyphenyl) fluorene, bis (hydroxylphenyl) fluorene (compound corresponding to n = 0 and p = 1 in said Formula (1)). You may refer to the following literature about the manufacturing method of the). For example, (a) J. Appl. Polym. Sci., 27 (9), 3289, 1982], Japanese Patent Laid-Open No. 6-145087, and Japanese Patent Laid-Open No. 8-217713 (in the presence of hydrogen chloride gas and mercaptocarboxylic acid, fluorenones and phenols) Reaction method), (b) Japanese Patent Laid-Open No. 2000-26349 [Method for reacting 9-fluorenone and alkylphenols in the presence of an acid catalyst (and alkyl mercaptan)], (c) Japanese Patent Laid-Open No. 2002- 47227 (method of reacting fluorenones and phenols in the presence of hydrochloric acid and thiols), (d) JP 2003-221352 (Reacting fluorenones and phenols in the presence of hydrochloric acid and thiols) And crystallization with a crystallization solvent composed of hydrocarbons and a polar solvent).

That is, in the method of these documents, instead of phenols, the polyhydric alcohols [the compound represented by the above formula (3)) are used, and a polyhydric alcohol [ 9, 9-bis (polyhydroxyphenyl) fluorene] may be produced. Among these methods, in particular, when a method using hydrochloric acid or sulfuric acid (the above methods (c), (d) and the like) is applied, products with higher yields and high purity are often obtained.

(Method for producing polyhydric alcohol wherein n1 and / or n2 is 1 or more)

As the alkylene oxide, e.g., ethylene oxide, propylene oxide, butylene oxide, etc. of C _{2 -} can be given a _{- (3} alkylene oxide, especially C _{2) 4} alkylene oxide. In addition, the alkylene carbonate (carbonate-alkylene) include ethylene carbonate, propylene carbonate, butylene carbonate, and the like of C _{2 -} and the like can be given ₍₃ alkylene carbonate, especially C _{2) 4} alkylene carbonate. These alkylene oxides and alkylene carbonates may be used alone or in combination of two or more thereof. In addition, when using an alkylene carbonate, after adding an alkylene carbonate, a decarbonate reaction arises and an alkylene oxide unit (alkoxy unit) is introduce | transduced.

The amount of the alkylene oxide or the alkylene carbonate can be adjusted in accordance with the number of alkylene oxide units to be added, and is preferably 1 to 50 mol, for example, to 1 mol of the hydroxyl group constituting the polyhydric alcohol. 1-20 mol, More preferably, about 1-10 mol may be sufficient.

The purity of the polyhydric alcohols (9, 9-bis (polyhydroxyphenyl) fluorenes) in which n1 and n2 are 0 to be reacted is not particularly limited, but is usually 95% by weight or more, preferably 99% by weight. The above may be sufficient.

Although reaction with alkylene oxide or alkylene carbonate may be performed in absence of a catalyst, it can usually be performed in presence of a catalyst. As a catalyst, a base catalyst and an acid catalyst can be illustrated, and a base catalyst can be used normally. Examples of the base catalyst include metal hydroxides (alkali metals such as sodium hydroxide or alkaline earth metal hydroxides), metal carbonates (alkali metals such as sodium carbonate or alkaline earth metal carbonates, alkali metals such as sodium hydrogen carbonate or alkaline earth metal carbonates, etc.) Inorganic bases such as these; Amines [for example, tertiary amines (trialkylamines such as triethylamine, aromatic tertiary amines such as N and N-dimethylaniline, heterocyclic tertiary amines such as 1-methylimidazole), etc. ], And organic bases, such as a carboxylic acid metal salt (alkali acetate metal salts, such as sodium acetate and a calcium acetate, or alkaline-earth metal salt, etc.), etc. can be illustrated. The catalysts (base catalysts) may be used alone or in combination of two or more thereof.

The usage-amount of a catalyst can be adjusted according to the kind of catalyst, and it is 0 to 1 weight part with respect to 1 weight part of polyhydric alcohols (bis (polyhydroxyphenyl) fluorenes) produced by the said method (i). It can select, For example, 0.001- 1 weight part, Usually, 0.003-0.5 weight part, Preferably it is 0.005-0.3 weight part, More preferably, about 0.01-0.1 weight part may be sufficient.

The reaction (addition reaction with alkylene oxide or alkylene carbonate) may be carried out in a solvent. It does not specifically limit as a solvent, It can select according to the raw material to be used. For example, in the case of using an alkylene oxide, in the case where it is possible to use such a solvent in the above examples, the use of an alkylene carbonate, in addition to the solvents exemplified above, alcohols (such as methanol, ethanol, C _{1 - 4} It may be used, such as the ₃ alkylene glycol), such as _- alcohol, ethylene glycol, and the like of C _{2 - 3} alkylene glycol, _2-deoxy-C, such as ethylene glycol. The usage-amount of a solvent may be 1-20 weight part, Preferably it is 1.5-10 weight part, More preferably, about 2-5 weight part with respect to 1 weight part of polyhydric alcohol produced by the said method (i).

Reaction can be adjusted according to the kind of compound (alkylene oxide, alkylene carbonate) etc. to add, for example, 0-170 degreeC, Preferably it is 10-150 degreeC, More preferably, it is 20-130 degreeC It is often done in precision. In particular, in the case of using an alkylene carbonate, in order to perform decarbonation reaction efficiently, it is made to react at 70-150 degreeC, Preferably it is about 80-120 degreeC in many cases. The reaction time is, for example, 30 minutes to 48 hours, usually 1 to 24 hours, preferably about 1 to 10 hours.

The reaction may be performed while stirring, may be performed in air or in an inert atmosphere (nitrogen, rare gas, etc.), or may be performed under normal pressure or under pressure. Moreover, you may react, removing the gas (carbon dioxide etc.) which generate | occur | produce as needed. In addition, the alkylene oxide adduct of polyhydric alcohol may be obtained by refine | purifying the reaction mixture after completion | finish of reaction using usual purification methods (extraction, crystallization, etc.).

As a (meth) acrylic-acid derivative made to react with polyhydric alcohol (polyhydric alcohol etc. obtained by the said method), (meth) acrylic-acid lower alkyl ester (for example, methyl (meth) acrylate, ethyl (meth) acrylate, (meth) and the like can be given ₄ alkyl (meth) acrylate), (meth) acrylic acid halides ((meth) acrylic acid chloride or the like) _- C _1, such as butyl acrylate. In addition, a commercial item may be used for the (meth) acrylic acid halide, and what synthesize | combined may be used. For example, (meth) acrylic acid chloride can be prepared by making thionyl chloride and (meth) acrylic acid react.

The usage-amount of (meth) acrylic acid or its derivative (s) is 1-10 mol, Preferably 1-5 mol, Furthermore, with respect to 1 mol of hydroxyl groups (hydroxyl group corresponding to said p) of polyhydric alcohol, for example. Preferably, about 1-3 mol may be sufficient.

In reaction (reaction with (meth) acrylic acid or its derivative), you may use a catalyst (acid catalyst, a base catalyst, etc.) suitably. For example, when using (meth) acrylic acid or (meth) acrylic acid lower alkyl ester, an acid catalyst may be used preferably, and when using (meth) acrylic acid halide, by-product hydrogen halide (hydrogen chloride etc.) In order to trap (trap), a base may be preferably used.

The acid catalyst is not particularly limited as long as it is an esterified acid catalyst, and examples thereof include inorganic acids (sulfuric acid, hydrochloric acid, phosphoric acid, and the like), organic acids [sulfonic acids (alkanesulfonic acids such as methanesulfonic acid, ethanesulfonic acid, trifluoromethanesulfonic acid, and p-toluenesulfonic acid). Arensulfonic acid, etc.); and the like, and a solidified acid (solidified acid (solid phosphoric acid, etc.) supported on an acid (an inorganic acid such as sulfuric acid, phosphoric acid, heteropoly acid, or organic acid) on a carrier), cation exchange resin, metal Oxides (such as ZnO), metal halides (such as CuCl ₂ ), metal salt catalysts (such as metal sulfates (NiSO ₄ ), metal phosphates (such as phosphates of transition metals such as Zr and Ti), and metal nitrates (Zn (NO ₃ ) _2? 6H ₂ O, etc.), etc.], also includes a solid acid catalyst such as natural minerals (acid clay, bentonite, kaolin, montmorillonite, etc.). The acid catalysts may be used alone or in combination of two or more thereof.

The base is not particularly limited as long as it is an inert base with respect to (meth) acrylic acid or its derivative (such as (meth) acrylic acid halide), and may be a metal carbonate (alkali metal such as sodium carbonate or alkali earth metal carbonate, alkali metal such as sodium hydrogencarbonate). Or alkaline earth metal carbonate salts), carboxylate metal salts (alkali acetate metals such as sodium acetate or calcium acetate or alkaline earth metal salts), metal hydroxides (alkali metal hydroxides such as sodium hydroxide, alkaline earth metal hydroxides such as calcium hydroxide, etc.) Inorganic bases such as; Amines [For example, tertiary amines (trialkylamines such as triethylamine, triisopropylamine, tributylamine, etc.), aromatic tertiary amines such as N, N-dimethylaniline, and heterocyclic thirds such as pyridine Organic amines], and the like. Bases may be used alone or in combination of two or more.

Although the usage-amount of a catalyst (acid catalyst, a base) changes with kinds of catalyst, For example, with respect to 100 weight part of (meth) acrylic acid or its derivatives, it is 0.01-10 weight part, Preferably it is 0.05-5 A weight part, More preferably, about 0.1-3 weight part may be sufficient.

In addition, you may perform reaction in presence of a polymerization inhibitor (thermal polymerization inhibitor) as needed. Examples of the polymerization inhibitor include hydroxyphenols (hydroquinones such as hydroquinone and hydroquinone monomethyl ether, catechols such as t-butylcatechol), amines (such as diphenylamine), 2, 2-diphenyl-1-pi Krill hydrazyl, 4-hydroxy-2, 2, 6, 6-tetramethylperazine- 1-oxyl, etc. can be illustrated. The polymerization inhibitors may be used alone or in combination of two or more thereof. The amount of the polymerization inhibitor may be extremely small and may be, for example, 0.001 to 5 parts by weight, preferably 0.005 to 3 parts by weight, and more preferably 0.01 to 5 parts by weight of (meth) acrylic acid or its derivatives. 1 part by weight may be sufficient.

Although reaction may be performed in a solvent-free, it can usually be performed in a solvent. As a solvent (organic solvent), hydrocarbons (aliphatic hydrocarbons, such as hexane, heptane, and octane, aromatic hydrocarbons, such as benzene, toluene, and xylene), halogenated hydrocarbons (methylene chloride, chloroform, carbon tetrachloride, etc.), ether type Solvents (dialkyl ethers such as diethyl ether, cyclic ethers such as tetrahydrofuran, dioxane, anisole and the like), ketones (dialkyl ketones such as acetone, methyl ethyl ketone and the like) and the like. The solvent may be used alone or in combination of two or more thereof. The usage-amount of a solvent is 10-500 weight part, Preferably it is 30-300 weight part with respect to 100 weight part of total amounts of the polyhydric alcohol and (meth) acrylic acid (or its derivative) represented by Formula (2). More preferably, about 50-200 weight part may be sufficient.

Although reaction temperature changes with kinds of (meth) acrylic acid or its derivative (s) used, it is usually performed at 30-180 degreeC, Preferably it is 40-150 degreeC, More preferably, it is about 50-130 degreeC. Moreover, reaction time can be adjusted according to the kind of raw material, reaction temperature, the density | concentration in a solvent, etc., For example, it is 30 minutes-48 hours, Usually, 1 to 24 hours, Preferably it is about 1 to 10 hours.

The reaction may be performed while refluxing, or may be performed while removing by-product water or alcohols. In addition, reaction may be performed while stirring, may be performed in air or in an inert atmosphere (nitrogen, a rare gas, etc.), and may be performed under normal pressure or pressurization.

In addition, the produced polyfunctional (meth) acrylate is separated and purified by conventional methods, for example, separation means such as filtration, concentration, extraction, crystallization, recrystallization, column chromatography, or a combination thereof. You may also

[Polymerizable Composition]

This invention contains the polymeric composition comprised from polyfunctional (meth) acrylate (compound represented by said Formula (1)). The polymerizable composition can usually be composed of at least a polyfunctional (meth) acrylate (compound represented by the formula (1)) and a polymerization initiator. In addition, you may comprise a polymeric composition individually or in combination of 2 or more types of polyfunctional (meth) acrylates.

(Polymerization initiator)

The polymerization initiator includes a thermal polymerization initiator and a photopolymerization initiator. Examples of the thermal polymerization initiator include dialkyl peroxides (di-t-butyl peroxide, dicumyl peroxide, etc.), diacyl peroxides (dialkanoyl peroxide (lauroyl peroxide, etc.), dialloyl peroxide (benzoyl peroxide, Benzoyl toluyl peroxide, toluyl peroxide, etc.)], peracid esters (percarboxylic acid alkyl esters such as t-butyl peroxide, t-butyl peroxy octoate, t-butyl peroxy benzoate, etc.), ketones Organic peroxides such as peroxides, peroxycarbonates, and peroxyketals; Azonitrile compound [2, 2'- azobis (2, 4-dimethylvaleronitrile), 2, 2'- azobis (isobutylonitrile), 2, 2'- azobis (2-methylbutylonitrile ), 2, 2'-azobis (4-methoxy-2, 4-dimethylvaleronitrile), etc.], azoamide compound {2, 2'-azobis {2-methyl-N- [1, 1- Bis (hydroxymethyl) -2-hydroxyethyl] propionamide} and the like}, azoamidine compound {2, 2'-azobis (2-amidinopropane) dihydrochloride, 2, 2'-azobis [2 -(2-imidazolin-2-yl) propane] dihydrochloride etc.}, azoalkane compounds [2, 2'- azobis (2, 4, 4-trimethylpentane), 4, 4'- azobis (4 -Cyanopentanoic acid); and azo compounds such as azo compounds having an oxime skeleton [2, 2'-azobis (2-methylpropionamide oxime)] and the like. You may use a thermal polymerization initiator individually or in combination of 2 or more types.

In this invention, a photopolymerizable composition can be comprised by combining with a photoinitiator. As a photoinitiator, various well-known conventional photoinitiators, for example, benzoin (benzoin alkyl ether, such as benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, etc.), acetophenones ( Acetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 2, 2-dimethoxy-2-phenylacetophenone, 2, 2-diethoxy-2-phenylacetophenone, 1, 1 -Dichloroacetophenone, etc.), aminoacetophenones {2-methyl-1- [4- (methylthio) phenyl] -2-morpholinoaminopropaneone-1, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1, etc.}, anthraquinones (anthraquinone, 2-methylanthraquinone, 2-ethylanthraquinone, 2-t-butylanthraquinone, 1-chloroanthraquinone, etc.) , Thioxanthones (2, 4-dimethyl thioxanthone, 2, 4-diethyl thioxanthone, 2-chlorothioxanthone, 2, 4-diisopropyl thioxanthone, etc.), ketals (acetophenonedimethyl Ketal, benzyl dimethyl ketal, etc.), benzophenone (Benzophenone etc.), xanthones, etc. can be illustrated. You may use these photoinitiators individually or in combination of 2 or more types.

In addition, you may combine a photoinitiator with a photosensitizer. As a photosensitizer, tertiary amines (for example, trialkylamine, trialkanolamine (triethanolamine etc.), N, N-dimethylamino benzoate ethyl [p- (dimethylamino) benzoate, etc.], N, Dialkylaminobenzoic acid alkyl esters such as amyl N-dimethylaminobenzoic acid [am] such as p- (dimethylamino) benzoic acid, and bis (dialkylamino) such as 4,4-bis (diethylamino) benzophenone (mihilerketone) Common photosensitizers, such as dialkylamino benzophenone, such as) benzophenone and 4- (dimethylamino) benzophenone, etc. are mentioned. The photosensitizers may be used alone or in combination of two or more thereof.

The usage-amount of a polymerization initiator (and the total amount of a photosensitizer) is 0.1-30 weight part (for example, 1-30 weight part) with respect to 100 weight part of polyfunctional (meth) acrylates, Preferably it is 1-20 weight A part (for example, 5-25 weight part), More preferably, about 1.5-10 weight part may be sufficient. When the usage-amount of a photoinitiator is too small, the polymerizability (or photocurability) of a composition will fall, and when too large, there exists a possibility that the photocurability in a thick film may fall by absorption of a photoinitiator itself.

The amount of the photosensitizer may be 5 to 200 parts by weight, preferably 10 to 150 parts by weight, and more preferably about 20 to 100 parts by weight based on 100 parts by weight of the polymerization initiator (photopolymerization initiator).

Moreover, you may comprise a polymerization initiator with a thermal polymerization initiator and a photoinitiator. Although a polymerization initiator can be selected according to the use of a polymeric composition, when using for an optical material use, it is usually comprised by the photoinitiator at least.

(diluent)

The polymerizable composition may contain a diluent (reactive diluent, non-reactive diluent).

As a reactive diluent (polymerizable diluent), a monofunctional monomer, a polyfunctional monomer, etc. are mentioned. Monofunctional monomer As the (meth) acrylic acid alkyl - (meth) acrylate, (meth) acrylic acid C _1, such as _methyl-, such as ₆ alkyl], (meth) acrylic acid cycloalkyl [(meth) acrylate, cyclohexyl, etc. (meth) acrylic acid C _5-8 cycloalkyl (meth) acrylate, isobornyl, etc. of (meth) acrylate, di to tetra-cycloalkyl ester, etc.], (meth) acrylic acid aryl [(meth) acrylic acid phenyl, etc.], hydroxy alkyl (meth) acrylate [Hydroxy C _2-10 alkyl (meth) acrylates such as (2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate and 2-hydroxybutyl (meth) acrylate)] (Poly) s such as (poly) oxyalkylene glycol mono (meth) acrylate (diethylene glycol mono (meth) acrylate, methoxytetraethylene glycol mono (meth) acrylate, polyethylene glycol mono (meth) acrylate oxy-C _{2 -6} alkylene glycol mono (meth) Acrylate), alkoxyalkyl (meth) acrylate [(meth) acrylate, 2-methoxyethyl (meth) acrylate, 3-methoxybutyl, etc. of (meth) acrylic acid C _{1 - 4} alkoxy, such as alkyl], N- substituted ( meth) acrylamide (N, N- dimethyl (meth) acrylamide such as N, N- di-C _{1 -4} alkyl (meth) acrylamide, N- hydroxy such as N- methylol (meth) acrylamide, C _{1 - 4} alkyl (meth) acrylamide and the like), aminoalkyl (meth) acrylate, (N, N- dimethylaminoethyl acrylate and the like), glycidyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, etc. (Meth) acrylic-type monomer etc. can be illustrated.

Examples of the polyfunctional monomers include polyfunctional (meth) acrylates, polyfunctional (meth) acrylates, and epoxy group-containing compounds (glycerin diglycidyl ether, trimethylolpropane triglycidyl ether, triglycidyl isocyanurate, etc.). Poly (for example, di-penta) (meth) acrylate, melamine acrylate, etc. of glycidyl ether, etc. are contained.

As a bifunctional (meth) acrylate, alkylene glycol di (meth) acrylate [ethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, 1, 4- butanediol di (meth) acrylate, hexane diol di (meth) acrylate, neopentyl glycol di (meth) acrylate such as a C _{2 - 10} alkylene glycol di (meth) acrylate], (poly) oxyalkylene glycol di (meth) acrylate [D. Ethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, dipropylene glycol di (meth) acrylate, tripropylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, polytetramethylene glycol di (meth) acrylate such as a (poly) oxy-C _2-6 alkylene glycol di (meth) acrylate and so on], bisphenol a (or C _{2 - 3} alkyl Lenoxy D. adduct) (meth) acrylate, polyhydric alcohol (or a C _{2 -} a ₃ alkylene oxide adduct) Synthesis of di (meth) acrylate [for example, glycerin di (meth) acrylate, trimethylolpropane di Di (meth) acrylates of triols such as (meth) acrylate and tris (hydroxyethyl) isocyanurate di (meth) acrylate, and di (tetraol) such as pentaerythritol di (meth) acrylate. Meth) acrylate etc.] etc. can be illustrated.

Polyfunctional (meth) acrylate, polyhydric alcohol (or a C _{2 - 3} alkylene oxide adduct), tri-functional or multi-functional (meth) acrylate of, e.g., glycerol tri (meth) acrylate, trimethylolpropane Of triols such as ethane tri (meth) acrylate, trimethylolpropane tri (meth) acrylate, trimethylolpropaneethoxy (meth) acrylate and tris (hydroxyethyl) isocyanurate tri (meth) acrylate Tri (meth) acrylates; Tri or tetra (meth) acrylates of tetraols such as pentaerythritol tri (meth) acrylate and pentaerythritol tetra (meth) acrylate; Ditrimethylolpropane tetra (meth) acrylate; Dipentaerythritol tetra (meth) acrylate; Dipentaerythritol hexa (meth) acrylate and the like can be exemplified.

The reactive diluents may be used alone or in combination of two or more thereof. The usage-amount of a reactive diluent can be selected from the range of 0-100 weight part with respect to 100 weight part of polyfunctional (meth) acrylates, For example, 1-100 weight part, Preferably 1-50 weight part, More Preferably, about 1-30 weight part may be sufficient.

Diluents include non-reactive diluents. By using a non-reactive diluent, the coatability of a polymeric composition, etc. can be improved. Examples of the non-reactive diluent (or solvent) include organic solvents such as aliphatic hydrocarbons such as hexane, heptane, octane and decane; Ketones such as ethyl methyl ketone and cyclohexanone; Aromatic hydrocarbons such as toluene, xylene and tetramethylbenzene; Cellosolve, methyl cellosolve, butyl cellosolve, carbitol, methyl carbitol, butyl carbitol, propylene glycol monomethyl ether, dipropylene glycol monomethyl ether, dipropylene glycol diethyl ether, tripropylene glycol monomethyl ether Glycol ethers such as these; Acetic acid, such as carboxylic acid ester (methyl acetate, ethyl acetate, butyl acetate, cellosolve acetate, butyl cellosolve acetate, carbitol acetate, butyl carbitol acetate, propylene glycol monomethyl ether acetate, dipropylene glycol monomethyl ether acetate, etc. Esters, butyl lactate and the like), esters such as carbonate esters (propylene carbonate and the like); Petroleum solvents, such as petroleum ether, petroleum naphtha, and solvent naphtha, etc. can be illustrated. A non-reactive diluent can be used individually or in combination of 2 or more types.

Although the usage-amount (addition amount) of a non-reactive diluent changes with an application | coating method etc., it can select from the range of 0-500 weight part with respect to 100 weight part of polyfunctional (meth) acrylates, Usually, 10-400 weight part, Preferably 20-300 weight part, More preferably, it may be about 30-200 weight part.

(Polysilane)

The polymerizable composition may further contain polysilane. Polysilane is useful in polymerizable compositions used for optical or electrical applications (particularly optical applications) because the addition of the polysilane can effectively lower the dielectric constant and improve the refractive index. Moreover, although it depends also on the kind of polysilane (linear, branched, mesh-like, three-dimensional structure, such as a cyclic structure, the kind of terminal group, etc.), flame retardance and water repellency can also be improved.

The polysilane is not particularly limited as long as it is a linear, cyclic, branched or meshed compound having a Si—Si bond. For example, at least one structural unit among the structural units represented by the following formulas (3) to (5): Polysilanes (including oligosilanes, copolysilanes) and the like can be exemplified.

(In formula, R <^5> -R <^7> is the same or different, and is a hydrogen atom, a hydroxyl group, an alkyl group, an alkoxy group, an alkenyl group, a cycloalkyl group, a cycloalkyloxy group, a cycloalkenyl group, an aryl group, an aryloxy group, An aralkyl group, an aralkyloxy group or a silyl group, x, y and z each represent an integer of 0 or 1 or more, and the sum of x, y and z is 5 to 400.)

As such a polysilane, linear or cyclic polysilane which has a structural unit represented by Formula (3), for example, a branched chain or mesh-shaped poly which has a structural unit represented by said Formula (4) or (5) Polysilane (cyclic, branched or meshed polysilane, which has a combination of the structural units represented by said Formula (3)-(5), for example, the structure represented by said Formula (3) and (4) Polysilane and the like); and the like.

The substituent R ⁵ in R ~ ^7, examples of the alkyl group, C _1, such as methyl, ethyl, propyl, isopropyl, butyl, t- butyl _{- (6} alkyl preferably C _{1 - - 10} alkyl groups, especially C _{1) 14} alkyl group Can be mentioned. As the alkoxy group, such as methoxy, ethoxy, C _{1 - 14} alkoxy groups (preferably C _{1 - 6 alkoxy-10} alkoxy groups, especially C ₁₎ can be given. _{14 alkenyl-alkenyl} group, C _2, such as vinyl, allyl _As-can be a (preferably C _{2 10} alkenyl group). As the cycloalkyl groups, cyclohexyl, methylcyclohexyl, etc. of C _{5 -} may be mentioned ₍₈ cycloalkyl group preferably C _{5 - - 10} cycloalkyl group, more preferably C _{5) 14} cycloalkyl group. As the cycloalkyloxy groups, cyclohexyloxy, etc. of C _{5 - 14} cycloalkyloxy groups _- can be given (preferably C _{5 10} cycloalkyl group). As the cycloalkenyl group, cyclohexenyl group, etc. C _{5 -14} cycloalkenyl group _- can be given (preferably C _{5 10} cycloalkenyl group). As may be mentioned, an aryloxy group, ₂₀ aryl group ₍₁₂ aryl group, preferably a C _{6 - - - 15} aryl group, more preferably C ₆₎ aryl group, C _6, such as phenyl, methylphenyl, dimethylphenyl such as a phenoxy C _{6 - 20} aryloxy group _- can be given (preferably C _{6 15} aryl group). As the aralkyl group, benzyl, phenethyl and the like of the C _{6 -} (preferably C _{6 -10} aryl group -C _{1-2) 20} aryl -C _{1 -4} alkyl group may be mentioned. Examples are alkyloxy, benzyloxy, such as C _{6 - 20} aryl -C _1-4 alkyloxy group may be a (preferably C _{6 - 2 oxy-alkyl-10-aryl} -C _1). As the silyl group, a silyl group, a disilazane group or the like of Si _{1 - 10} silanol group (preferably Si _{1 - 6} silanol groups) may be mentioned.

In addition, when R <^5> -R <^7> is the said organic substituent or silyl group, at least one of the hydrogen atoms may be substituted by substituents, such as an alkyl group, an aryl group, and an alkoxy group. As such a substituent, the group similar to the above is mentioned. In addition, a hydrogen atom, a hydroxyl group, an alkoxy group, and a silyl group are often substituted by the terminal group.

Of these, substituents R ⁵ ~ R ⁷ are, typically, an alkyl group, an alkenyl group, a cycloalkyl group, an aryl group, in many cases a hydrocarbon group such as an aralkyl group, particularly, an alkyl group (methyl, etc. of C _{1 - 6} alkyl group), an aryl group, (C _6-8 aryl groups such as phenyl) are preferred.

When the polysilane has an acyclic structure (linear, branched, or meshed), the terminal substituent is usually a hydrogen atom, a hydroxyl group, an alkyl group, an alkoxy group, a silyl group, a halogen atom (chlorine atom, etc.), at least It is preferable that it is comprised by the hydroxyl group.

As a structural unit of a specific polysilane, For example, the structural unit (3) which R <^5> and R <^6> are both aryl groups, the structural unit (3) whose R <^5> is an aryl group, and R <^6> is an alkyl group, R <^5> is an alkyl group, or An aryl group and R ⁶ is selected from a hydrogen atom, a hydroxyl group, an alkoxy group, an alkenyl group, a cycloalkyl group, a cycloalkyloxy group, a cycloalkenyl group, an aryl group, an aryloxy group, an aralkyl group, an aralkyloxy group and a silyl group Structural unit (3) which selected at least 1 group of group, Structural unit (4) whose R <^7> is an alkyl group, Structural unit (4) whose R <^7> is an aryl group, Structural unit (5), etc. are mentioned.

As a preferable polysilane, the polysilane containing the structural unit (3) whose at least one of R <^5> and R <^6> is an aryl group, and the structural unit (4) which R <^7> is an aryl group, especially R <^5> and R <^6> are all aryl groups Structural unit (3) (particularly phenyl group), structural unit (3) in which R ⁵ is an aryl group (particularly a phenyl group) and R ⁶ is an alkyl group (particularly a methyl group), or a structural unit in which R ⁷ is an aryl group (particularly a phenyl group) The polysilane comprised by (4) is mentioned. In addition, the structure of the polysilane is preferably cyclic, branched, or meshed, and particularly preferably branched.

In addition, a polysilane copolymer (copolysilane) may be a random copolymer, a block copolymer, or a graft copolymer.

Representative polysilanes include cyclic polydiarylsilanes (such as cyclic polydiphenylsilanes (5- to 8-membered rings)), linear polyalkylarylsilanes (such as linear polymethylphenylsilanes), and linear polydiarylsilane-polyalkylaryls. Silane copolymers (linear polydiphenylsilane-polymethylphenylsilane copolymers, etc.), polyarylsilanes (polyphenylsilanes, etc.), polydiarylsilane-polyarylsilin copolymers (polydiphenylsilane-polyphenylsilin copolymers) And the like, polyalkylarylsilane-polyarylsilin copolymers (polymethylphenylsilane-polyphenylsilin copolymer, etc.) and the like. In addition, "polysilane" means the branched polysilane comprised with the said structural unit (4).

The polymerization degree of polysilane, ie, the sum of x, y and z in the structural units (3) to (5), may be 5 to 400, preferably 10 to 350, and more preferably about 20 to 300.

In addition, the molecular weight of polysilane may be 300-100000 in a number average molecular weight, Preferably 400-50000, More preferably, about 500-20000 may be sufficient.

In addition, the said polysilane can be prepared using various well-known methods. In order to manufacture these polysilanes, for example, silicon-containing monomers (mono to tetrahalosilanes, etc.) having a specific structural unit are used as raw materials, and (a) magnesium is used as a reducing agent to dehalogen halosilanes. Method of polycondensation ("Magnesium reduction method", the method of WO98 / 29476, the method of Unexamined-Japanese-Patent No. 2001-48987, 2002-226586, etc.), (b) halosilanes in presence of alkali metal Dehalogen condensation polymerization ("keeping method", J. Am. Chem. Soc., 110, 124 (1988), Macromolecules, 23, 3423 (1990), etc.), (c) halosilanes by electrode reduction Dehalogen condensation (J. Chem. Soc., Chem. Commun., 1161 (1990), J. Chem. Soc., Chem. Commun. 897 (1992, etc.), (d) in the presence of a metal catalyst Dehydrogenation polycondensation of hydrazines (Japanese Patent Laid-Open No. 4-334551, etc.), (e) acelene of crosslinked crosslinked biphenyl, etc. Method according to one polymerized (Macromolecules, 23, 4494 (1990), etc.), (f) and a method of a method based on ring-opening polymerization of cyclic silanes.

Among these methods, magnesium reduction method (especially, Japanese patent publication) from the point which is excellent in the purity and molecular weight distribution of the polysilane obtained, the compatibility with resin, the low content of sodium and chlorine, and the industrial cost, such as manufacturing cost and safety, Most preferred is 2001-48987 and the method described in Japanese Patent Laid-Open No. 2002-226586. In addition, the introduction method of a silanol group (terminal hydroxyl group) is not specifically limited, For example, it can introduce | transduce simply by adding water to the polysilane obtained by the said method.

The ratio of polysilane can be selected from the range of 0-100 weight part with respect to 100 weight part of polyfunctional (meth) acrylates, Usually, 0.1-50 weight part, Preferably 0.5-20 weight part, More preferably, May be about 1 to 20 parts by weight.

In addition, the polymerizable composition may be a conventional additive such as colorants, stabilizers (heat stabilizers, antioxidants, ultraviolet absorbers, etc.), fillers, antistatic agents, and flame retardants (as necessary) within a range that does not impair the original properties. Phosphorus-containing compounds such as organic phosphorus compounds and inorganic phosphorus compounds, halogen-containing flame retardants, metal oxides, metal hydroxides, metal sulfides, and the like, flame retardant aids, leveling agents, silane coupling agents, polymerization inhibitors (or thermal polymerization inhibitors), and the like. You may include it. You may use an additive individually or in combination of 2 or more types.

The ratio of an additive (flame retardant etc.) can be suitably selected according to the kind of additive, For example, 0.5-100 weight part with respect to 100 weight part of polyfunctional (meth) acrylates, Preferably 1-50 weight part More preferably, about 1-20 weight part may be sufficient.

A polymerizable composition can be prepared by mix | blending or mixing a polyfunctional (meth) acrylate and a polymerization initiator at least. A compounding method (mixing method) is not specifically limited, A conventional method can be used. In particular, when the polymerizable composition is formed as a coating film, a polyfunctional (meth) acrylate and a polymerization initiator (and other components such as polysilane) are dissolved in the diluent (in particular, a diluent containing a non-reactive diluent) ( Or suspension), to prepare a polymerizable composition (composition for coating, coating composition).

The polymerizable composition (particularly, a photopolymerizable composition) (or the polyfunctional (meth) acrylate) of the present invention is useful for obtaining a cured product (molded product) that has been polymerized or cured (or crosslinked). Such hardened | cured material (hardened | cured material of the polymeric composition comprised from the said polyfunctional (meth) acrylate and a polymerization initiator, and hardened | cured material of the said polyfunctional (meth) acrylate) is a shaping | molding process or shaping | molding according to the shape of a molded object. After that, it can obtain by giving hardening process (heating process or light irradiation process) to a polymeric composition. For example, a film-shaped hardened | cured material may be obtained by apply | coating a polymeric composition with respect to a base material, and forming a coating film (or a thin film), and then performing hardening process. In the formation of such a coating film (or thin film), conventional methods such as flow coating, spin coating, spray coating, screen printing, casting, bar coating, curtain coating, roll coating, The dip method can be used. In addition, after application | coating of a polymeric composition (after application | coating), you may dry-process by a conventional method, and you may dry by heating as needed. The heating temperature in drying can be suitably selected according to the kind of polymerization initiator, a diluent (non-reactive diluent), etc., and it is about 40-250 degreeC normally. In addition, a drying process may be performed in inert gas atmosphere, such as nitrogen and argon, or in air, and may be performed under normal pressure or under reduced pressure.

In addition, the thickness of a coating film (or a thin film) may be 0.01-100 micrometers, Preferably it is 0.1-10 micrometers, More preferably, about 0.1-1 micrometer may be sufficient.

The curing treatment for the polymerizable composition can be selected in accordance with the type of polymerization initiator (thermal polymerization initiator and / or photopolymerization initiator), and can be performed by heat treatment and / or light irradiation treatment.

In heat processing, although heating temperature changes with kinds of polymerization initiator, it is 50-250 degreeC, Preferably it is 60-150 degreeC, More preferably, it is about 70-120 degreeC.

In the light irradiation treatment, as a light irradiation source, for example, a low pressure mercury lamp, a high pressure mercury lamp, an ultra high pressure mercury lamp, a hydrogen lamp, a deuterium lamp, a fluorescent lamp, a halogen lamp, an excimer laser, a nitrogen laser, a dye laser, helium-cadmium Laser and the like. The amount of light irradiation energy varies depending on the use, the film thickness of the coating film and the like, but is usually about 0.1 to 10,000 mJ / cm 2, preferably about 0.5 to 2000 mJ / cm 2. The exposure time is, for example, 1 second to 3 hours, preferably 5 seconds to 2 hours, and more preferably 10 seconds to 1 hour. Light irradiation may be performed in inert gas atmosphere, such as nitrogen and argon, or in air, and may be performed under normal pressure, under pressure, or under reduced pressure.

Moreover, you may combine heat processing and light irradiation process. For example, in the polymeric composition containing a photoinitiator, after light irradiation (or light irradiation), you may further heat in order to accelerate hardening or crosslinking.

Although the shape of the said hardened | cured material (molded object) is not specifically limited, For example, two-dimensional structure (film shape, sheet shape, plate shape, etc.), three-dimensional structure (tubular shape, rod shape, tube shape, hollow shape, etc.) ), And the like.

The cured product of the present invention has a high refractive index and is excellent in optical characteristics. For example, the refractive index of the said hardened | cured material (or hardened | cured material of the said polyfunctional (meth) acrylate) is 1.55 or more (for example, about 1.59-1.7), Preferably it is 1.60 or more (for example, 1.60-) 1.7 degree). In particular, when the said hardened | cured material is a hardened | cured material of the polymeric composition containing a polysilane compound, refractive index is 1.60-1.7, for example, Preferably it is about 1.62-1.7.

For this reason, the hardened | cured material of this invention can be used suitably especially as an optical material (coating agents, such as an optical overcoat agent and a hard coat agent, an antireflection film, spectacle lens, an optical fiber, an optical waveguide, a hologram, etc.), As a shape of an optical material, a film or sheet form, plate shape, lens shape, tubular shape, etc. are mentioned, for example.

Hereinafter, the present invention will be described in more detail based on Examples, but the present invention is not limited to these Examples.

Example 1

36 g (about 0.2 mol) of 9-fluorenone, 88 g (about 0.8 mol) of catechol, 0.7 ml of β-mercaptopropionic acid, and 60 g of 1,4-dioxane were placed in a reactor, and 98% sulfuric acid was heated at 80 ° C. 5 ml was added dropwise. After completion of the reaction, 200 ml of MIBK (methyl isobutyl ketone) and 100 ml of water were added and extracted. The same operation was performed three times to remove excess sulfuric acid. After solvent concentration, 100 ml of MIBK and 200 ml of toluene were added, followed by cooling to 10 ° C to obtain 65 g of biscatechol fluorene [9, 9-bis (3, 4-dihydroxyphenyl) fluorene]. Below, ¹ H-NMR spectrum data of the obtained biscatechol fluorene is shown.

¹ H-NMR: 6.35 ppm (d, 2H), 6.58 ppm (m, 4H), 7.33 ppm (m, 6H), 7.89 ppm (d, 2H), 8.75 ppm (s, 2H), 8.80 ppm (s, 2H).

38 g (about 0.1 mol) of obtained biscatechol fluorene, 100 g of diethylene glycol, 1 g of 1-methyl imidazole, and 150 g (about 1.7 mol) of ethylene carbonate were put into a reactor, and it heated at 100 degreeC and reacted. After completion of the reaction, 500 ml of IPA (isopropanol) was added and cooled to 10 ° C, thereby obtaining 40 g of a polyhydric alcohol added by the ethylene oxide unit as white crystals. As a result of analyzing the obtained polyhydric alcohol, it turned out that it is the polyhydric alcohol which 4.5 mol of ethoxy groups added with respect to 1 mol of biscatechol fluorene used as a raw material.

40 g (0.06 mol) of the obtained polyhydric alcohol, 43 g (0.6 mol) of acrylic acid, 1 g of a 70% by weight aqueous solution of methanesulfonic acid, 0.01 g of hydroquinone and 100 ml of toluene were placed in a reactor with a Dean Stark trap, followed by ester for 5 hours under toluene reflux. The reaction was carried out. Water produced during the esterification reaction was removed by Dean Stark trap to obtain 45 g of tetraacrylate of the polyhydric alcohol. As a result of analysis by high performance liquid chromatography, the purity of the tetraacrylate was 98%.

Synthesis Example 1

Polysilane was synthesize | combined by the magnesium reduction method of the chlorosilanes described in WO98 / 29476. That is, 400 ml of THF (tetrahydrofuran), 37 g of Mg (magnesium), 10 g of iron chloride (FeCl ₃ ), and 15 g of lithium bromide were placed in a reactor, and 95 g of methylphenyldichlorosilane and 53 g of phenyltrichlorosilane were slowly added dropwise. After completion | finish of reaction, it extracted with toluene, and converted unreacted terminal chlorine group (chlorine atom) into a hydroxyl group, and obtained polysilane (polymethylphenylsilane-polyphenylsilin copolymer) of average polymerization degree 25.

Example 2 (photocuring of tetraacrylate)

0.6 g of 2-hydroxy-2-methyl-1-phenylpropan-1-one was added to 40 g of tetraacrylate obtained in Example 1, and photocured by irradiation with UV (ultraviolet) light, followed by 80 ° C. The cured product was obtained as a transparent film by thermosetting for 1 hour. The glass transition temperature (Tg) of the obtained hardened | cured material was 225 degreeC, and the refractive index was 1.630 (D line).

Example 3 (Photocuring of Tetraacrylate Containing Polysilane)

In addition to 40 g of tetraacrylic acid ester obtained in Example 1, except that 8 g of polysilane obtained in Synthesis Example 1 was added, photocuring and thermosetting were carried out similarly to Example 2, and the hardened | cured material was obtained as a transparent film. Tg of the obtained hardened | cured material was 220 degreeC, and the refractive index was 1.645 (D line).

The multifunctional (meth) acrylate (and its polymerizable composition) of the present invention has high refractive index and is excellent in light transmittance, hardness, weather resistance, flexibility, mechanical strength, dimensional stability and workability, and various performance requirements. It is useful as a plastic raw material which satisfies the requirements. In particular, since it is excellent in heat resistance and moisture resistance, and has high refractive index and high hardness, it is used in optical materials, for example, in optical overcoat agent, hard coat agent, antireflection film, spectacle lens, optical fiber, optical waveguide, hologram, etc. It can be used effectively.

Claims (14)

The polyfunctional (meth) acrylate which has a fluorene skeleton represented by following formula (1). &Lt; Formula 1 >

(Wherein R ^3a and R ^3b represent a C _2-4 alkylene group, R ^4a and R ^4b represent a hydrogen atom or a methyl group. N1 and n2 are the same or different and represent an integer of 0 to 6 and n1. + n2 is 0-12, p1 and p2 represent 2, respectively.) delete delete The polyfunctional (meth) acrylate according to claim 1, wherein in formula (1), n1 and n2 are 1-4, and n1 + n2 is 2-8. delete A method for producing a polyfunctional (meth) acrylate by reacting a polyhydric alcohol having a fluorene skeleton represented by the following formula (2) with (meth) acrylic acid or a derivative thereof. <Formula 2>

^Wherein R ^3a , R ^3b , n 1, n 2, p 1 and p 2 are as defined in claim 1 The polymerizable composition comprised of the polyfunctional (meth) acrylate of Claim 1, and a polymerization initiator. The polymeric composition of Claim 7 whose ratio of a polymerization initiator is 0.1-30 weight part with respect to 100 weight part of polyfunctional (meth) acrylates of Claim 1. The polymerizable composition according to claim 7, further comprising polysilane in a proportion of 0.1 to 50 parts by weight based on 100 parts by weight of the multifunctional (meth) acrylate of claim 1. The polymerizable composition according to claim 9, wherein the polysilane has at least one structural unit among the structural units represented by the following formulas (3) to (5).

(In formula, R <^5> -R <^7> is the same or different, and is a hydrogen atom, a hydroxyl group, an alkyl group, an alkoxy group, an alkenyl group, a cycloalkyl group, a cycloalkyloxy group, a cycloalkenyl group, an aryl group, an aryloxy group, An aralkyl group, an aralkyloxy group or a silyl group, x, y and z each represent an integer of 0 or 1 or more, and the sum of x, y and z is 5 to 400.) Hardened | cured material which the polymeric composition of Claim 7 superposed | polymerized or hardened | cured. An optical material composed of the cured product of claim 11. delete delete