JP5091407B2 - Multifunctional (meth) acrylate and method for producing the same - Google Patents

Description

  The present invention can form materials for optical materials (optical overcoat agent, hard coat agent, antireflection film, spectacle lens, optical fiber, optical waveguide, hologram, etc.), etc., and improve heat resistance, refractive index, etc. The present invention relates to a polyfunctional (meth) acrylate useful for the above, a production method thereof, and a polymerizable composition (and a cured product thereof) composed of the polyfunctional (meth) acrylate.

  For optical materials such as optical overcoat agent, hard coat agent, antireflection film, spectacle lens, optical fiber, optical waveguide, hologram, etc., thermoplastic resin (polycarbonate etc.) and thermosetting resin (diethylene glycol bisallyl carbonate (CR Cured products of polyfunctional aliphatic acrylates such as -39) are used. Such optical materials are required to have improved characteristics such as moisture resistance, heat resistance, and high refractive index, and development of various optical materials has been studied.

  JP-A-4-325508 (Patent Document 1) discloses a compound obtained by reacting 9,9-bis (4-hydroxyphenyl) fluorene with (meth) acrylic acid chloride as a plastic lens material, or 9,9- A copolymer containing as a main component a compound obtained by adding ethylene oxide or propylene oxide to bis (4-hydroxyphenyl) fluorene and then reacting with (meth) acrylic acid is disclosed.

However, with such a bisacrylate fluorene compound, the crosslinking density cannot be increased, and the properties (eg, hardness, heat resistance, etc.) required for optical materials and coating films cannot be sufficiently improved.
JP-A-4-325508 (Claim 1, paragraph number [0010])

  Accordingly, an object of the present invention is to provide a polyfunctional (meth) acrylate capable of remarkably improving properties such as hardness, heat resistance and moisture resistance, and a method for producing the same.

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

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

  As a result of intensive studies to achieve the above-mentioned problems, the present inventors have found that when a polyfunctional (meth) acrylate of a compound (or an alkylene oxide adduct thereof) in which a polyhydric phenol is substituted at the 9-position of fluorene is used, crosslinking occurs. It was found that the density can be improved and the properties such as hardness and heat resistance of the material (optical material, etc.) can be remarkably improved, and the present invention has been completed.

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

（式中、Ｒ^１ａ、Ｒ^１ｂ、Ｒ^２ａおよびＲ^２ｂは置換基を示し、Ｒ^３ａおよびＲ^３ｂはアルキレン基を示し、Ｒ^４ａおよびＲ^４ｂは水素原子又はメチル基を示す。ｋ１及びｋ２は同一又は異なって０又は１〜４の整数を示し、ｍ１及びｍ２は同一又は異なって０又は１〜３の整数を示し、ｎ１およびｎ２は同一又は異なって０又は１以上の整数を示し、ｐ１およびｐ２は同一又は異なって２〜４の整数を示す。ただし、ｍ１＋ｐ１及びｍ２＋ｐ２は、２〜５の整数である）
前記式（１）において、Ｒ^３ａおよびＲ^３ｂがＣ_２−４アルキレン基であり、ｎ１およびｎ２が０〜１２程度であり、ｎ１＋ｎ２が０〜２４程度であってもよく、特に、式（１）において、Ｒ^１ａおよびＲ^１ｂがＣ_１−４アルキル基、ｋ１およびｋ２が０又は１であり、Ｒ^２ａおよびＲ^２ｂが、Ｃ_１−４アルキル基、Ｃ_１−４アルコキシ基又はＣ_６−８アリール基、ｍ１およびｍ２が０〜２であり、Ｒ^３ａおよびＲ^３ｂがＣ_２−４アルキレン基、ｎ１およびｎ２が０〜６、ｎ１＋ｎ２が０〜１２であってもよい。ｐ１およびｐ２は、それぞれ２又は３である場合が多い。また、前記式（１）において、ｎ１およびｎ２が１以上の好ましい多官能性（メタ）アクリレートには、Ｒ^３ａおよびＲ^３ｂがＣ_２−４アルキレン基であり、ｎ１およびｎ２が１〜４程度であり、ｎ１＋ｎ２が２〜８程度であり、ｐ１およびｐ２がそれぞれ２である多官能性（メタ）アクリレートなどが含まれる。

(In the formula, R ^1a , R ^1b , R ^2a and R ^2b represent a substituent, R ^3a and R ^3b represent an alkylene group, R ^4a and R ^4b represent a hydrogen atom or a methyl group, and k 1 and k 2 represent Same or different and represents 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 are the same or different and represent 0 or an integer of 1 or more, p1 And p2 are the same or different and each represents an integer of 2 to 4, provided that m1 + p1 and m2 + p2 are integers of 2 to 5)
In the formula (1), R ^3a and R ^3b may be a C _2-4 alkylene group, n1 and n2 may be about 0 to 12, and n1 + n2 may be about 0 to 24. In particular, the formula (1 ) In which R ^1a and R ^1b are a C _1-4 alkyl group, k1 and k2 are 0 or 1, and R ^2a and R ^2b are a C _1-4 alkyl group, a C _1-4 alkoxy group, or C _{6- 8} aryl group, m1 and m2 are 0 to ^{2, R 3a} and ^{R 3b} are _{C 2-4} alkylene groups, n1 and n2 are Less than six, n1 + n2 may be 0-12. In many cases, p1 and p2 are 2 or 3, respectively. Further, in the formula (1), the n1 and n2 is 1 or more preferably multifunctional (meth) ^{acrylate, R 3a} and ^{R 3b} are _{C 2-4} alkylene groups, n1 and n2 are about 1-4 N1 + n2 is about 2 to 8, and polyfunctional (meth) acrylates in which p1 and p2 are each 2 are included.

Representative multifunctional (meth) acrylates represented by the formula (1) include (meth) acrylates of C _9-4 alkylene oxide adducts of 9,9-bis (dihydroxyphenyl) fluorenes, And (meth) acrylates of C _2-4 alkylene oxide adducts of 9-bis (trihydroxyphenyl) fluorenes.

  The polyfunctional (meth) acrylate represented by the formula (1) is not particularly limited, but usually a polyhydric alcohol having a fluorene skeleton represented by the following formula (2) and (meth) acrylic acid or its It can be produced by reacting with a derivative.

（式中、Ｒ^１ａ、Ｒ^１ｂ、Ｒ^２ａ、Ｒ^２ｂ、Ｒ^３ａ、Ｒ^３ｂ、ｋ１、ｋ２、ｍ１、ｍ２、ｎ１、ｎ２、ｐ１およびｐ２は前記に同じ）
本発明は、前記式（１）で表される多官能性（メタ）アクリレートと、重合開始剤（例えば、光重合開始剤）とで構成された重合性組成物を含む。重合開始剤の割合は、前記式（１）で表される多官能性（メタ）アクリレート１００重量部に対して０．１〜３０重量部程度であってもよい。また、前記重合性組成物は、さらに、ポリシランを含んでいてもよい。このようなポリシランには、下記式（３）〜（５）で表される構造単位のうち少なくとも１つの構造単位を有するポリシランなどが含まれ、ポリシランの割合は、前記式（１）で表される多官能性（メタ）アクリレート１００重量部に対して、例えば、０．１〜５０重量部程度であってもよい。

(In the formula, 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 by the polyfunctionality (meth) acrylate represented by the said Formula (1), and a polymerization initiator (for example, photoinitiator). The proportion of the polymerization initiator may be about 0.1 to 30 parts by weight with respect to 100 parts by weight of the polyfunctional (meth) acrylate represented by the formula (1). The polymerizable composition may further contain polysilane. Such polysilane includes polysilane having at least one structural unit among the structural units represented by the following formulas (3) to (5), and the ratio of polysilane is represented by the formula (1). For example, it may be about 0.1 to 50 parts by weight with respect to 100 parts by weight of the multifunctional (meth) acrylate.

（式中、Ｒ^５〜Ｒ^７は、同一又は異なって、水素原子、ヒドロキシル基、アルキル基、アルコキシ基、アルケニル基、シクロアルキル基、シクロアルキルオキシ基、シクロアルケニル基、アリール基、アリールオキシ基、アラルキル基、アラルキルオキシ基又はシリル基を示し、ｘ、ｙ及びｚはそれぞれ０又は１以上の整数を示し、ｘ、ｙ及びｚの合計は５〜４００である。）
本発明は、前記重合性組成物（又は前記式（１）で表される多官能性（メタ）アクリレート）が、重合又は硬化した硬化物、およびこの硬化物で構成された材料（光学材料など）も含む。

Wherein R ^{5 to} R ⁷ are the same or different and are a hydrogen atom, hydroxyl group, alkyl group, alkoxy group, alkenyl group, cycloalkyl group, cycloalkyloxy group, cycloalkenyl group, aryl group, aryloxy group , An aralkyl group, an aralkyloxy group or a silyl group, x, y and z each represent 0 or an integer of 1 or more, and the total of x, y and z is 5 to 400.)
The present invention provides a cured product obtained by polymerizing or curing the polymerizable composition (or the polyfunctional (meth) acrylate represented by the formula (1)), and a material (such as an optical material) composed of the cured product. ) Is also included.

  In the present specification, “(meth) acrylate” means acrylate or methacrylate. “(Meth) acryloyloxy” means acryloyloxy or methacryloyloxy.

The polyfunctional (meth) acrylate of the present invention has a fluorene skeleton and a large number of highly polymerizable (meth) acryloyl groups, so that the crosslinking density can be improved and the hardness of the material (such as an optical material) can be improved. Characteristics such as heat resistance can be remarkably improved. Moreover, in this invention, many (meth) acryloyl groups can be introduce | transduced and the novel polyfunctional (meth) acrylate which has a fluorene skeleton can be manufactured simply and with a high yield.
Detailed Description of the Invention

  The polyfunctional (meth) acrylate of the present invention is represented by the following formula (1), and a polyol is a polyhydric alcohol (or an alkylene oxide adduct thereof) in which two polyhydric phenols are substituted at the 9-position of fluorenes. It is a polyfunctional (meth) acrylate as a component.

（式中、Ｒ^１ａ、Ｒ^１ｂ、Ｒ^２ａおよびＲ^２ｂは置換基を示し、Ｒ^３ａおよびＲ^３ｂはアルキレン基を示し、Ｒ^４ａおよびＲ^４ｂは水素原子又はメチル基を示す。ｋ１及びｋ２は同一又は異なって０又は１〜４の整数を示し、ｍ１及びｍ２は同一又は異なって０又は１〜３の整数を示し、ｎ１およびｎ２は同一又は異なって０又は１以上の整数を示し、ｐ１およびｐ２は同一又は異なって２〜４の整数を示す。ただし、ｍ１＋ｐ１及びｍ２＋ｐ２は、２〜５の整数である）
基Ｒ^１ａおよびＲ^１ｂで表される置換基としては、特に限定されないが、通常、アルキル基である場合が多い。アルキル基としては、メチル基、エチル基、プロピル基、イソプロピル基、ブチル基、ｔ−ブチル基などのＣ_１−６アルキル基（例えば、Ｃ_１−４アルキル基、特にメチル基）などが例示できる。基Ｒ^１ａおよびＲ^１ｂは互いに異なっていてもよく、同一であってもよい。また、基Ｒ^１ａ（又はＲ^１ｂ）は、同一のベンゼン環において、異なっていてもよく、同一であってもよい。なお、フルオレン骨格を構成するベンゼン環に対する基Ｒ^１ａ（又はＲ^１ｂ）の結合位置（置換位置）は、特に限定されない。好ましい置換数ｋ１およびｋ２は、０又は１、特に、０である。なお、置換数ｋ１及びｋ２は、異なっていてもよいが、通常、同一である。

(In the formula, R ^1a , R ^1b , R ^2a and R ^2b represent a substituent, R ^3a and R ^3b represent an alkylene group, R ^4a and R ^4b represent a hydrogen atom or a methyl group, and k 1 and k 2 represent Same or different and represents 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 are the same or different and represent 0 or an integer of 1 or more, p1 And p2 are the same or different and each represents an integer of 2 to 4, provided that m1 + p1 and m2 + p2 are integers of 2 to 5)
The substituents represented by the groups R ^1a and R ^1b are not particularly limited, but are usually alkyl groups in many cases. Examples of the alkyl group include C _1-6 alkyl groups such as a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, and a t-butyl group (for example, a C _1-4 alkyl group, particularly a methyl group). . The groups R ^1a and R ^1b may be different from each other or the same. Moreover, group R ^<1a> (or R ^<1b> ) may differ in the same benzene ring, and may be the same. Note that the bonding position (substitution position) of the group R ^1a (or R ^1b ) with respect to the benzene ring constituting the fluorene skeleton is not particularly limited. Preferred substitution numbers k1 and k2 are 0 or 1, in particular 0. The substitution numbers k1 and k2 may be different but are usually the same.

As the substituents R ^2a and R ^2b , an alkyl group (a C _1-20 alkyl group such as methyl group, ethyl group, propyl group, isopropyl group, butyl group, s-butyl group, t-butyl group, preferably C _{1 -8} alkyl group, more preferably C _1-6 alkyl group, etc., cycloalkyl group (C _5-10 cycloalkyl group such as cyclopentyl group, cyclohexyl group, etc., preferably C _5-8 cycloalkyl group, more preferably C _5-6, such as a cycloalkyl group), an aryl group [phenyl group, alkylphenyl group (methylphenyl group (tolyl group), _{C 6-10} aryl group such as a dimethylphenyl group (xylyl), etc.), preferably _{C 6- 8} aryl group, especially phenyl group, an aralkyl group (benzyl group, _{C 6-10} aryl -C such phenethyl Alkoxy groups; _-4 hydrocarbon group such as an alkyl group, etc.) (such as _{C 1-4} alkoxy group such as methoxy group); a hydroxyl group; hydroxy (poly) alkyleneoxy group (hydroxy _{(poly) C 2-4} alkyleneoxy group Acyl group (C _1-6 acyl group such as acetyl group); Alkoxycarbonyl group (C _1-4 alkoxycarbonyl group such as methoxycarbonyl group); Halogen atom (fluorine atom, chlorine atom etc.); Nitro Group; a cyano group, etc. are mentioned.

  The hydroxyl group or hydroxy (poly) alkyleneoxy group reacts with the residue of polyhydric alcohol ((meth) acrylic acid or a derivative thereof as a raw material in the method for producing a polyfunctional (meth) acrylate described later. In many cases, the group is not.

Preferred substituents R ^2a (or R ^2b ) are an alkyl group (C _1-6 alkyl group), a cycloalkyl group (C _5-8 cycloalkyl group), an aryl group (C _6-10 aryl group), an aralkyl group ( C _6-8 aryl-C _1-2 alkyl group), hydroxyl group, hydroxy (poly) alkyleneoxy group (hydroxy (poly) C _2-4 alkyleneoxy group). Among these, a C _1-4 alkyl group, a C _1-4 alkoxy group, and a C _6-8 aryl group are particularly preferable. The substituent R ^2a (or R ^2b ) may be substituted on the benzene ring alone or in combination of two or more. The groups R ^2a and R ^2b may be the same or different from each other, but are usually the same. Further, the groups R ^2a (or R ^2b ) may be different or the same in the same benzene ring.

The substitution position of the substituent R ^2a (or R ^2b ) is not particularly limited, and is a (meth) acryloyloxy group or a (meth) acryloyloxy (poly) alkoxy group (hereinafter referred to as a (meth) acryloyloxy group-containing group). Depending on the substitution position (which may be collectively referred to), the phenyl group can be substituted at the 2-6 position (for example, the 2-position, 5-position, 2,5-position).

  The preferred substitution numbers m1 and m2 are 0 to 2, more preferably 0 to 1 (particularly 0), although depending on the number of substitutions of the (meth) acryloyloxy group-containing group. The substitution numbers m1 and m2 may be different but are usually the same in many cases.

Examples of the alkylene group represented by R ^3a and R ^3b include, but are not limited to, C _2-4 alkylene groups (ethylene group, trimethylene group, propylene group, butane-1,2-diyl group, etc.). In particular, a C _2-3 alkylene group (particularly an ethylene group or a propylene group) is preferable. R ^3a and R ^3b may be the same or different alkylene groups, but are usually the same alkylene group.

  The substitution number (addition number) n1 and n2 of the alkoxy group is the same or different and can be selected from the range of about 0 to 15, for example, 0 to 12 (for example, 1 to 12), preferably 0 to 8 (for example, 1 to 8), more preferably 0 to 6 (for example, 1 to 6), particularly about 0 to 4 (for example, 1 to 4). Moreover, 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 it is 0-16 (for example, 2-12), More preferably 0 to 12 (for example, 2 to 10), particularly about 0 to 8 (for example, 2 to 8) may be used. When n1 (or n2) is 2 or more, the polyalkoxy (polyalkyleneoxy) group may be composed of the same alkoxy group, and different alkoxy groups (for example, ethoxy group and propyleneoxy group) Although they may be mixed, they are usually composed of the same alkoxy group in many cases.

  The substitution number p1 and p2 of the (meth) acryloyloxy group-containing group is preferably 2 to 3, and particularly preferably 2. The sum of p1 and p2 (p1 + p2) may be, for example, 4 to 8, preferably about 4 to 6 (particularly 4). The substitution numbers p1 and p2 may be different but are usually the same in many cases. The substitution position of the (meth) acryloyloxy group-containing group is not particularly limited, and can be selected from the 2 to 6 positions of the phenyl group substituted at the 9 position of fluorene according to the number of p1 (or p2), and p1 (or When p2) is 2, it may be, for example, 3,4-position, 3,5-position, etc. One (meth) acryloyloxy group-containing group may usually be substituted at the 4-position.

  In addition, the several (meth) acryloyloxy group containing group substituted by the same benzene ring may be the same, and may differ. For example, a plurality of (meth) acryloyloxy group-containing groups may be composed of (i) a (meth) acryloyloxy group alone with n1 = 0 (n2 = 0), and (ii) n1 = 0 (n2 = 0) and a (meth) acryloyloxy (poly) alkoxy group (such as a 2- (meth) acryloyloxyethoxy group) where n1 ≠ 0 (n2 ≠ 0) (Iii) It may be composed of the same (meth) acryloyloxy (poly) alkoxy group alone where n1 ≠ 0 (n2 ≠ 0), and (iv) n1 ≠ 0 (n2 ≠ 0) Different (meth) acryloyloxy (poly) alkoxy groups [for example, 2- (meth) acryloyloxyethoxy group and 2- (2- (meth) acryloyloxyethoxy) ethoxy group]. It may be.

Typical polyfunctional (meth) acrylates represented by the formula (1) include, for example, 9,9-bis (di (meth) acryloyloxyphenyl) fluorenes, 9,9-bis (tri (meta) ) Acryloyloxyphenyl) fluorenes, (meth) acrylates of alkylene oxide ( _C2-4 alkylene oxide) adducts of the corresponding polyhydric alcohols [9,9-bis (di or trihydroxyphenyl) fluorenes], etc. Is mentioned.

The 9,9-bis (di (meth) acryloyloxyphenyl) fluorenes include, 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.], substitution 9,9-bis (di (meth) acryloyloxyphenyl) fluorene having a group {eg, 9,9-bis (alkyl-di (meth) acryloyloxyphenyl) fluorene [9,9-bis (3,4-di (Meth) acryloyloxy 5-methylphenyl) fluorene, 9,9-bis (3,4-di (meth) acryloyloxy 6-methyl Eniru) fluorene such as 9,9-bis _{(C 1-4} alkyl - di (meth) acryloyloxy phenyl) fluorene, 9,9-bis (2,4-di (meth) acryloyloxy 3,6-dimethylphenyl) 9,9-bis (diC _1-4 alkyl-di (meth) acryloyloxyphenyl) fluorene and the like] such as fluorene], 9,9-bis (alkoxy-di (meth) acryloyloxyphenyl) fluorene [for example, 9, 9,9-bis (C _1-4 alkoxy-di (meth) acryloyloxyphenyl) fluorene etc.] such as 9-bis (3,4-di (meth) acryloyloxy-5-methoxyphenyl) fluorene], 9,9 -Bis (aryl-di (meth) acryloyloxyphenyl) fluorene [eg 9,9-bis (3,4-di (me ) Acryloyloxy-5-phenylphenyl) fluorene such as 9,9-bis _{(C 6-8} aryl -, and the like di (meth) acryloyloxy phenyl) fluorene, etc.], etc.}.

  The 9,9-bis (tri (meth) acryloyloxyphenyl) fluorenes include fluorenes corresponding to the 9,9-bis (di (meth) acryloyloxyphenyl) fluorenes such as 9,9-bis ( 2,4,6- (meth) acryloyloxyphenyl) fluorene, 9,9-bis (2,4,5-tri (meth) acryloyloxyphenyl) fluorene, 9,9-bis (3,4,5-tri 9,9-bis (tri (meth) acryloyloxyphenyl) fluorene such as (meth) acryloyloxyphenyl) fluorene is included.

Examples of the (meth) acrylate of an alkylene oxide adduct of 9,9-bis (dihydroxyphenyl) fluorene include 9,9-bis [3,4-di (2- (meth) acryloyloxyethoxy) phenyl] fluorene. 9,9-bis [di (2- (meth) acryloyloxy C _2-4 alkoxy) phenyl] fluorene (n1 = n2 = 1), 9,9-bis {3,4-di [2- (2 - (meth) acryloyloxy) ethoxy] phenyl} fluorene such as 9,9-bis {di [2- (2- (meth) acryloyloxy _{C 2-4 alkoxy) C 2-4} alkoxyphenyl] fluorene} (n1 = N2 = 2) and the like.

Examples of the (meth) acrylate of an alkylene oxide adduct of 9,9-bis (trihydroxyphenyl) fluorene include 9,9-bis [3,4,5-tri (2- (meth) acryloyloxyethoxy). 9,9-bis [di (2- (meth) acryloyloxy C _2-4alkoxy ) phenyl] fluorene (n1 = n2 = 1), 9,9-bis {3,4,5-tri, such as phenyl] fluorene [2- (2- (meth) acryloyloxy) ethoxy] phenyl} fluorene such as 9,9-bis {tri [2- (2- (meth) acryloyloxy _{C 2-4 alkoxy) C 2-4} alkoxyphenyl ] Fluorene} (n1 = n2 = 2) and the like.

Among these polyfunctional (meth) acrylates, in particular, (meth) acrylates of C _9-4 alkylene oxide adducts of 9,9-bis (dihydroxyphenyl) fluorenes {for example, 9,9-bis [di ( 2- (meth) acryloyloxy oxy- _{(C 2-3)} alkoxy) phenyl] fluorene, 9,9-bis {di [2- (2- (meth) acryloyloxy oxy- _{(C 2-3) alkoxy) C 2-3} alkoxy] phenyl} fluorene }, (Meth) acrylates of C _2-4 alkylene oxide adducts of 9,9-bis (trihydroxyphenyl) fluorenes {for example, 9,9-bis [tri (2- (meth) acryloyloxy C _{2− 3} alkoxy) phenyl] fluorene, 9,9-bis {tri [2- (2- (meth) acryloyloxy oxy- _{(C 2-3)} alkoxy ) C _2-3 alkoxy] phenyl} fluorene, etc.} is preferred.

The polyfunctional (meth) acrylate of the present invention has a fluorene skeleton and a large number of (meth) acryloyloxy group-containing groups (in particular, (meth) acryloyloxy (poly) C _2-4 alkoxy groups) having high reactivity. ) To provide various excellent characteristics (particularly characteristics required for optical applications such as high refractive index, light transmission, high hardness, weather resistance, flexibility, strength, etc.) Useful for. In addition, since it has a large number of highly reactive (meth) acryloyloxy group-containing groups, the polymerization rate can be improved, the crosslinking density of the cured product can be remarkably increased, and a hardened cured product can be obtained efficiently. it can.

[Production method of polyfunctional (meth) acrylate]
The polyfunctional (meth) acrylate of the present invention is not particularly limited, but is produced by reacting a polyhydric alcohol having a fluorene skeleton represented by the following formula (2) with (meth) acrylic acid or a derivative thereof. it can.

（式中、Ｒ^１ａ、Ｒ^１ｂ、Ｒ^２ａ、Ｒ^２ｂ、Ｒ^３ａ、Ｒ^３ｂ、ｍ１、ｍ２、ｋ１、ｋ２、ｎ１、ｎ２、ｐ１およびｐ２は前記に同じ）
上記式（２）で表される多価アルコールにおいて、好ましい基および置換数（Ｒ、ｋ、ｍ、ｎ、ｐ）は前記と同様である。代表的な多価アルコールとしては、例えば、９，９−ビス（ジヒドロキシフェニル）フルオレン［９，９−ビス（３，４−ジヒドロキシフェニル）フルオレン（ビスカテコールフルオレン（ＢＣＡＦ））、９，９−ビス（２，４−ジヒドロキシフェニル）フルオレン、９，９−ビス（２，５−ジヒドロキシフェニル）フルオレン］、置換基を有する９，９−ビス（ジヒドロキシフェニル）フルオレン｛例えば、９，９−ビス（モノ又はジＣ_１−４アルキル−ジヒドロキシフェニル）フルオレン［９，９−ビス（３，４−ジヒドロキシ−５−メチルフェニル）フルオレンなど］、９，９−ビス（Ｃ_１−４アルコキシ−ジヒドロキシフェニル）フルオレン［９，９−ビス（３，４−ジヒドロキシ−５−メトキシフェニル）フルオレンなど］、９，９−ビス（Ｃ_６−８アリール−ジヒドロキシフェニル）フルオレン［９，９−ビス（３，４−ジヒドロキシ−５−フェニルフェニル）フルオレンなど］など｝などの９，９−ビス（ジヒドロキシフェニル）フルオレン類；これらに対応する９，９−ビス（トリヒドロキシフェニル）フルオレン類［９，９−ビス（２，４，６−トリヒドロキシフェニル）フルオレン、９，９−ビス（２，４，５−トリヒドロキシフェニル）フルオレン、９，９−ビス（３，４，５−トリヒドロキシフェニル）フルオレンなど］；これらのアルキレンオキシド付加体｛例えば、９，９−ビス［３，４−ジ（２−ヒドロキシエトキシ）フェニル］フルオレンなどの９，９−ビス［ジ（２−ヒドロキシＣ_２−４アルコキシ）フェニル］フルオレン、９，９−ビス｛３，４−ジ［２−（２−ヒドロキシエトキシ）エトキシ］フェニル｝フルオレンなどの９，９−ビス｛ジ［２−（２−ヒドロキシＣ_２−４アルコキシ）Ｃ_２−４アルコキシフェニル］フルオレン｝など｝などが含まれる。

(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 the above formula (2), preferred groups and substitution numbers (R, k, m, n, p) are the same as described above. As typical polyhydric alcohols, for example, 9,9-bis (dihydroxyphenyl) fluorene [9,9-bis (3,4-dihydroxyphenyl) fluorene (biscatecholfluorene (BCAF)), 9,9-bis (2,4-dihydroxyphenyl) fluorene, 9,9-bis (2,5-dihydroxyphenyl) fluorene], 9,9-bis (dihydroxyphenyl) fluorene having a substituent {for example, 9,9-bis (mono Or diC _1-4 alkyl-dihydroxyphenyl) fluorene [9,9-bis (3,4-dihydroxy-5-methylphenyl) fluorene and the like], 9,9-bis (C _1-4 alkoxy-dihydroxyphenyl) fluorene [9,9-bis (3,4-dihydroxy-5-methoxyphenyl) fluorene and the like], 9 9- bis _{(C 6-8} aryl - dihydroxyphenyl) fluorene [9,9-bis (3,4-dihydroxy-5-phenylphenyl) fluorene, etc.], etc.}, etc. of 9,9-bis (dihydroxyphenyl) fluorenes Corresponding 9,9-bis (trihydroxyphenyl) fluorenes [9,9-bis (2,4,6-trihydroxyphenyl) fluorene, 9,9-bis (2,4,5-trihydroxy); Phenyl) fluorene, 9,9-bis (3,4,5-trihydroxyphenyl) fluorene and the like]; these alkylene oxide adducts {for example, 9,9-bis [3,4-di (2-hydroxyethoxy) phenyl] fluorene such as 9,9-bis [di _{(2-hydroxy-C 2-4} alkoxy) phenyl] fluorene, 9,9-bis { , 4-di [2- (2-hydroxyethoxy) ethoxy] phenyl} fluorene such as 9,9-bis {di [2- _{(2-hydroxy-C 2-4 alkoxy) C 2-4} alkoxyphenyl] fluorene} etc. } Etc. are included.

  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 the said Formula (2) is a novel compound, and can usually be simply manufactured with the following method. Although the manufacturing method of the polyhydric alcohol represented by the said Formula (2) is not specifically limited, Usually, in presence of an acid catalyst, fluorenone represented by the following formula (2a), and the following formula (2b) At least a step of reacting the represented polyhydric phenols.

（式中、Ｒ^２は置換基を示し、ｍは０又は１〜３の整数、ｐは２〜４の整数を示す。ただし、ｍ＋ｐは、２〜５の整数である。Ｒ^１ａ、Ｒ^１ｂ、ｋ１、およびｋ２は前記に同じ）
すなわち、（ｉ）ｎ１及びｎ２が０である多価アルコール（９，９−ビス（ポリヒドロキシフェニル）フルオレン類）は、酸触媒の存在下で、前記式（２ａ）で表されるフルオレノン類と、前記式（２ｂ）で表される多価フェノール類とを反応させることにより製造できる。そして、（ｉｉ）ｎ１及び／又はｎ２が１以上の多価アルコールは、酸触媒の存在下で、前記式（２ａ）で表されるフルオレノン類と、前記式（２ｂ）で表される多価フェノール類とを反応させた後、生成した９，９−ビス（ポリヒドロキシフェニル）フルオレン類に、さらに、アルキレンオキサイド又はアルキレンカーボネートを反応させることにより製造できる。

(In the formula, R ² represents a substituent, m represents an integer of 0 or 1 to 3, p represents an integer of 2 to 4. However, m + p is an integer of 2 to 5. R ^1a and R ^1b , K1 and k2 are the same as above)
That is, (i) a polyhydric alcohol (9,9-bis (polyhydroxyphenyl) fluorenes) in which n1 and n2 are 0 is a fluorenone represented by the formula (2a) in the presence of an acid catalyst. , And can be produced by reacting with the polyhydric phenol represented by the formula (2b). And (ii) a polyhydric alcohol having n1 and / or n2 of 1 or more is a polyhydric compound represented by the formula (2a) and a polyvalent alcohol represented by the formula (2b) in the presence of an acid catalyst. After reacting with phenols, the produced 9,9-bis (polyhydroxyphenyl) fluorenes can be further reacted with alkylene oxide or alkylene carbonate.

In the formula (2b), R ² corresponds to R ^2a or R ^2b , m corresponds to m1 or m2, and p corresponds to p1 or p2, which is preferable. The aspect and the like are as described above.

(Method for producing polyhydric alcohol in which n1 and n2 are 0)
The fluorenones represented by the formula (2a) (hereinafter sometimes simply referred to as fluorenones) correspond to the fluorene skeleton of the polyhydric alcohol represented by the formula (2), and are representative fluorenones. Is 9-fluorenone. The purity of the fluorenones used is not particularly limited, but is usually 95% by weight or more, preferably 99% by weight or more.

The polyhydric phenols represented by the formula (2b) (hereinafter may be simply referred to as polyhydric phenols) correspond to the polyhydroxyphenyl group substituted at the 9-position in the formula (1). Examples of typical polyphenols (polyhydroxybenzene) include dihydroxybenzene (catechol, resorcinol, hydroquinone), alkyl-dihydroxybenzene [dihydroxytoluene (3,5-dihydroxytoluene (orcinol), 3-methylcatechol, 4 Mono- or di-C _1-6 alkyl-dihydroxybenzene, tetrahydrourushiol (2,3-dihydroxy) such as 4-methyl catechol), 4-t-butylcatechol, dihydroxyxylene (2,6-dihydroxy-p-xylene, etc.) -1-pentadecylbenzene) Etc.], aryl-dihydroxybenzene (C _6-8 aryl-dihydroxybenzene such as 2,3-dihydroxybiphenyl, 3,4-dihydroxybiphenyl), halo-dihydroxybenzene (chlorocatechol, 2,4-difluorohydroquinone, etc.) Mono- or di-C ₁ such as mono- or dihalo-dihydroxybenzene), nitro-dihydroxybenzene (such as nitrocatechol), alkoxy-dihydroxybenzene (3-methoxycatechol, 4,6-di-t-butyl-3-methoxycatechol) _-6 alkoxy - such as dihydroxybenzene), acyl - _{C 2-6} acyl such as dihydroxybenzene (2,4-dihydroxy acetophenone - such as dihydroxybenzene) dihydroxybenzenes such as; these dihydroxy Trihydroxy benzenes corresponding to benzene compounds [e.g., trihydroxybenzene (pyrogallol, hydroxyhydroquinone, phloroglucinol), trihydroxy acetophenone, etc.] and the like. Polyhydric phenols may be reacted with fluorenones alone or in combination of two or more.

  The amount of polyhydric phenol used may be, for example, 2 to 20 moles, preferably 2.5 to 10 moles, and more preferably about 3 to 5 moles per mole of fluorenones.

  The reaction (condensation reaction) between the polyhydric phenols and the fluorenones is not particularly limited, but can usually be performed in the presence of an acid catalyst. Examples of the acid catalyst include inorganic acids [such as sulfuric acid, hydrogen chloride, hydrochloric acid, and phosphoric acid], organic acids [such as sulfonic acids (such as alkanesulfonic acids such as methanesulfonic acid), 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. A preferred acid catalyst is hydrochloric acid or sulfuric acid.

The amount of the acid catalyst used can be selected according to the type of the acid catalyst. For example, 0.001 to 150 parts by weight, preferably 0.005 to 100 parts by weight, and more preferably 0 to 100 parts by weight of fluorenones. It may be about 0.01 to 50 parts by weight. In particular, when sulfuric acid is used as the catalyst, the amount of sulfuric acid (in terms of H ₂ SO ₄ ) may be very small, and is usually 0.001 to 0.5 parts by weight (1 part by weight of fluorenone ( For example, 0.005 to 0.5 parts by weight), preferably 0.01 to 0.5 parts by weight, more preferably 0.05 to 0.5 parts by weight (for example, 0.1 to 0.3 parts by weight). It may be a degree. Moreover, when using hydrochloric acid as a catalyst, the usage-amount of hydrochloric acid is 1-100 weight part with respect to 100 weight part of fluorenone in conversion of hydrogen chloride, Preferably it is 5-50 weight part, More preferably, it is 10-30 weight part. It may be about a part.

The condensation reaction may be performed in combination with a thiol as a cocatalyst in addition to the acid catalyst. By combining with thiols, the condensation reaction can proceed effectively and the yield can often be improved. Examples of thiols include conventional thiols that function as a co-catalyst, such as mercaptocarboxylic acid (mercaptoacetic acid, β-mercaptopropionic acid, α-mercaptopropionic acid, thioglycolic acid, mercaptosuccinic acid, mercaptobenzoic acid, etc.) Thiocarboxylic acid (thioacetic acid, thiooxalic acid, etc.), alkyl mercaptan (methyl mercaptan, ethyl mercaptan, propyl mercaptan, isopropyl mercaptan, n-butyl mercaptan, dodecyl mercaptan, etc., C _1-16 alkyl mercaptan (especially C _1-4 alkyl mercaptan) Etc.), aralkyl mercaptan (such as benzyl mercaptan) or a salt thereof. Examples of the salt include alkali metal salts (sodium salt and the like). Among these thiols, mercapto C _2-6 carboxylic acid (for example, β-mercaptopropionic acid) is preferable. Thiols can be used alone or in combination of two or more.

  The amount of thiols used can be selected from the range of about 0 to 0.2 parts by weight with respect to 1 part by weight of fluorenone, for example, 0.001 to 0.1 parts by weight, preferably 0.003 to 0.03. Part by weight, more preferably about 0.005 to 0.015 part by weight.

  Moreover, the usage-amount of thiols can be selected from the range of about 0-10 weight part with respect to 1 weight part of acid catalysts, for example, 0.001-10 weight part, Preferably 0.01-10 weight part ( For example, it may be about 0.01 to 5 parts by weight), more preferably about 0.01 to 2 parts by weight. In particular, when sulfuric acid is used, 0.001 to 1 part by weight of thiols, preferably 0.01 to 0.5 parts by weight, more preferably 0.01 to 0.3 parts by weight per 1 part by weight of sulfuric acid. It may be about parts by weight. When hydrochloric acid is used, 0.1 to 3 parts by weight, preferably 0.3 to 1 part by weight, more preferably 0.5 to 1 part by weight per 1 part by weight of hydrochloric acid (in terms of hydrogen chloride). It may be about 5 parts by weight.

  The condensation reaction may be performed in the absence of a solvent or in a solvent. The solvent is not particularly limited as long as it is non-reactive with the acidic catalyst and can dissolve fluorenones and polyhydric phenols, and can be used in a wide range. Typical solvents (organic solvents) include ether solvents (dialkyl ethers such as diethyl ether, cyclic ethers such as tetrahydrofuran and dioxane), halogenated solvents (halogenated such as methylene chloride, chloroform, carbon tetrachloride). Hydrocarbons), aromatic solvents (aromatic hydrocarbons such as benzene, toluene and xylene, anisole and the like). An excess of polyhydric phenols may be used as a solvent. Of 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.

  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 it is 1-8 weight part, More preferably, it is 2- It may be about 5 parts by weight.

  The condensation reaction varies depending on the type of polyhydric phenol, acid catalyst, thiol and the like used, but is usually 10 to 150 ° C., preferably 20 to 120 ° C., more preferably about 30 to 100 ° C. There are many. Moreover, reaction time can be adjusted according to the kind of raw material, reaction temperature, the density | concentration in a solvent, etc., for example, 30 minutes-48 hours, Usually, 1 to 24 hours, Preferably it is about 1 to 10 hours.

  The reaction may be performed with stirring, may be performed in air or in an inert atmosphere (nitrogen, rare gas, etc.), or may be performed at normal pressure or under pressure.

  The reaction mixture after completion of the reaction usually contains unreacted fluorenones, unreacted polyhydric phenols, catalysts (acids) in addition to the produced polyhydric alcohol (9,9-bis (polyhydroxyphenyl) fluorenes). Catalyst, thiols), side reaction products and the like. Therefore, it can be separated and purified by a conventional method, for example, separation means such as filtration, concentration, extraction, crystallization, recrystallization, column chromatography, etc., or a separation means combining these. For example, it may be purified by removing the acid catalyst (and thiols) by a conventional method, adding a crystallization solvent, cooling to crystallize, and then separating by filtration.

  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-propyl ketone, alkyl ketones such as diisopropyl ketone, cyclohexanone, etc.), ethers (dialkyl ethers such as diethyl ether, diisopropyl ether, etc.), nitriles, cellosolves, amides (dimethylphenol) Muamido etc.), and the like sulfoxides. The crystallization solvents may be used alone or in combination of two or more. Moreover, the usage-amount of a crystallization solvent is not specifically limited, It is 0.5-50 weight part with respect to 1 weight part of reaction mixtures (solid content conversion), Preferably it is 1-10 weight part, More preferably, it is 1-1 weight part. It may be about 5 parts by weight.

  The method for producing 9,9-bis (polyhydroxyphenyl) fluorenes is a method for producing bis (hydroxylphenyl) fluorenes (compounds corresponding to n = 0 and p = 1 in the formula (1)). You may refer to the following documents regarding: For example, (a) literature [J. Appl. Polym. Sci. , 27 (9), 3289, 1982], JP-A-6-145087, JP-A-8-217713 (method of reacting fluorenones with phenols in the presence of hydrogen chloride gas and mercaptocarboxylic acid), (B) JP 2000-26349 A [Method of reacting 9-fluorenone with alkylphenols in the presence of an acid catalyst (and alkyl mercaptan)], (c) JP 2002-47227 A (hydrochloric acid and thiols) (D) Japanese Patent Application Laid-Open No. 2003-221352 (reacting fluorenones and phenols in the presence of sulfuric acid and thiols to react hydrocarbons and polar) Crystallizing with a crystallization solvent composed of a solvent) and the like.

  That is, in the methods of these documents, instead of phenols, the polyhydric phenols (compound represented by the formula (3)) are used, and the synthesis method (purification method, component addition ratio, etc.) is referred to. Thus, polyhydric alcohols [9,9-bis (polyhydroxyphenyl) fluorenes] may be produced. Of these methods, in particular, when a method using hydrochloric acid or sulfuric acid (the methods (c), (d), etc.) is applied, a product with higher yield and higher purity is often obtained.

(Method for producing a polyhydric alcohol in which n1 and / or n2 is 1 or more)
As an alkylene oxide, _C2-4 alkylene oxide (especially _C2-3 alkylene oxide), such as ethylene oxide, a propylene oxide, butylene oxide, can be illustrated, for example. Moreover, as alkylene carbonate (alkylene carbonate), _C2-4 alkylene carbonate (especially _C2-3 alkylene carbonate), such as ethylene carbonate, propylene carbonate, butylene carbonate, etc. can be illustrated. These alkylene oxides and alkylene carbonates may be used alone or in combination of two or more. In addition, when using alkylene carbonate, an alkylene oxide unit (alkoxy unit) is introduce | transduced by decarboxylation reaction after addition of alkylene carbonate.

  The amount of alkylene oxide or alkylene carbonate used can be adjusted according to the number of alkylene oxide units to be added, and is, for example, 1 to 50 mol, preferably 1 to 20 mol, per 1 mol of hydroxyl group constituting the polyhydric alcohol. More preferably, it may be about 1 to 10 moles.

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

  The reaction with alkylene oxide or alkylene carbonate may be carried out in the absence of a catalyst, but can usually be carried out in the presence of a catalyst. Examples of the catalyst include a base catalyst and an acid catalyst, and usually a base catalyst can be used. Base catalysts 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, sodium hydrogen carbonate, etc.) Inorganic bases such as alkali metals or alkaline earth metal hydrogen carbonates; amines [for example, tertiary amines (trialkylamines such as triethylamine, aromatic tertiary amines such as N, N-dimethylaniline) , Heterocyclic tertiary amines such as 1-methylimidazole, etc.], and organic bases such as carboxylic acid metal salts (such as alkali metal acetates or alkaline earth metal salts such as sodium acetate and calcium acetate). The catalyst (base catalyst) may be used alone or in combination of two or more.

  The amount of the catalyst used can be adjusted according to the type of the catalyst, and ranges from 0 to 1 part by weight with respect to 1 part by weight of the polyhydric alcohol (bis (polyhydroxyphenyl) fluorenes) produced by the method (i). For example, 0.001-1 part by weight, usually 0.003-0.5 part by weight, preferably 0.005-0.3 part by weight, more preferably 0.01-0.1 part by weight It may be a degree.

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, According to the raw material to be used, it can select. For example, when using alkylene oxide, the above-exemplified solvents can be used, and when using alkylene carbonate, alcohols (C _1-4 alcohols such as methanol and ethanol, C _2-3 alkylene glycol such as ethylene glycol, oxy C _2-3 alkylene glycol such as diethylene glycol, etc.) may be used. The amount of the solvent used is 1 to 20 parts by weight, preferably 1.5 to 10 parts by weight, more preferably about 2 to 5 parts by weight, based on 1 part by weight of the polyhydric alcohol produced by the method (i). There may be.

  The reaction can be adjusted according to the type of compound to be added (alkylene oxide, alkylene carbonate) and the like. For example, the reaction is often performed at 0 to 170 ° C., preferably 10 to 150 ° C., more preferably about 20 to 130 ° C. In particular, when alkylene carbonate is used, in order to efficiently perform the decarboxylation reaction, for example, the reaction is often performed at 70 to 150 ° C, preferably about 80 to 120 ° C. 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 with stirring, may be performed in air or in an inert atmosphere (such as nitrogen or a rare gas), or may be performed under normal pressure or under pressure. Moreover, you may react, removing the gas (carbon dioxide etc.) generated as needed. Furthermore, as described above, an alkylene oxide adduct of a polyhydric alcohol may be obtained by purifying the reaction mixture after completion of the reaction using a conventional purification method (extraction, crystallization, etc.).

(Meth) acrylic acid lower alkyl ester (for example, methyl (meth) acrylate, (meth) acrylic acid) is used as a (meth) acrylic acid derivative to be reacted with a polyhydric alcohol (polyhydric alcohol obtained by the above method). _C1-4 alkyl (meth) acrylates such as ethyl and butyl (meth) acrylate), (meth) acrylic acid halides ((meth) acrylic acid chloride and the like), and the like. In addition, (meth) acrylic acid halide may use a commercial item, and may use what was synthesize | combined. For example, (meth) acrylic acid chloride can be prepared by reacting thionyl chloride with (meth) acrylic acid.

  The amount of (meth) acrylic acid or its derivative used is, for example, 1 to 10 mol, preferably 1 to 5 mol, more preferably 1 mol with respect to 1 mol of the hydroxyl group of the polyhydric alcohol (hydroxyl group corresponding to p). May be about 1 to 3 moles.

  In the reaction (reaction with (meth) acrylic acid or a derivative thereof), a catalyst (such as an acid catalyst or a base catalyst) may be used as appropriate. For example, when (meth) acrylic acid or (meth) acrylic acid lower alkyl ester is used, an acid catalyst may be preferably used, and when (meth) acrylic acid halide is used, it is by-produced. In order to capture (trap) hydrogen halide (such as hydrogen chloride), a base may be preferably used.

The acid catalyst is not particularly limited as long as it is an esterification acid catalyst. For example, inorganic acid (sulfuric acid, hydrochloric acid, phosphoric acid, etc.), organic acid [sulfonic acid (methanesulfonic acid, ethanesulfonic acid, trifluoromethanesulfonic acid, etc.) And alkanesulfonic acid, and arenesulfonic acid such as p-toluenesulfonic acid), etc.], and solidified acid [supporting acid (inorganic acid such as sulfuric acid, phosphoric acid, heteropoly acid, organic acid) on a carrier] Solid acid (such as solid phosphoric acid)], cation exchange resin, metal oxide (such as ZnO), metal halide (such as CuCl ₂ ), metal salt catalyst [metal sulfate (such as NiSO ₄ ), metal phosphorus salt (Zr, as phosphates of transition metals such as Ti), metal nitrate _{(Zn (NO 3) 2 ·} 6H 2 O , etc.), etc.], natural minerals (acid clay, bentonite, kaolin Also included are solid acid catalysts such as phosphorus and montmorillonite). The acid catalysts may be used alone or in combination of two or more.

  The base is not particularly limited as long as it is an inert base with respect to (meth) acrylic acid or a derivative thereof ((meth) acrylic acid halide, etc.). Metal carbonate (alkali metal such as sodium carbonate or alkaline earth) Metal carbonate, alkali metal such as sodium hydrogen carbonate or alkaline earth metal hydrogen carbonate), carboxylate metal salt (such as alkali acetate or alkaline earth metal salt such as sodium acetate and calcium acetate), metal hydroxide Inorganic bases such as alkali metal hydroxides such as sodium hydroxide and alkaline earth metal hydroxides such as calcium hydroxide; amines [eg tertiary amines (triethylamine, triisopropylamine, tributylamine, etc.) Such as trialkylamines, N, N-dimethylaniline and other aromatic tertiary amines, Etc. can be exemplified organic bases such as heterocyclic tertiary amines), etc.], such as gin. The bases may be used alone or in combination of two or more.

  The amount of the catalyst (acid catalyst, base) used depends on the type of catalyst, but is, for example, 0.01 to 10 parts by weight, preferably 0 with respect to 100 parts by weight of (meth) acrylic acid or a derivative thereof. It may be about 0.05 to 5 parts by weight, more preferably about 0.1 to 3 parts by weight.

  Moreover, you may perform reaction in presence of a polymerization inhibitor (thermal polymerization inhibitor) as needed. Polymerization inhibitors include hydroxyphenols (hydroquinones such as hydroquinone and hydroquinone monomethyl ether, catechols such as t-butylcatechol), amines (such as diphenylamine), and 2,2-diphenyl-1-picrylhydrazyl. 4-hydroxy-2,2,6,6-tetramethylpiperazine-1-oxyl and the like. The polymerization inhibitors may be used alone or in combination of two or more. The amount of the polymerization inhibitor used may be very small, for example, 0.001 to 5 parts by weight, preferably 0.005 to 3 parts by weight, more preferably 100 parts by weight of (meth) acrylic acid or a derivative thereof. May be about 0.01 to 1 part by weight.

  The reaction may be performed in the absence of a solvent, but can usually be performed in a solvent. Solvents (organic solvents) include hydrocarbons (aliphatic hydrocarbons such as hexane, heptane, and octane, aromatic hydrocarbons such as benzene, toluene, and xylene), halogenated hydrocarbons (methylene chloride, chloroform, etc.) And carbon tetrachloride), ether solvents (dialkyl ethers such as diethyl ether, cyclic ethers such as tetrahydrofuran and dioxane, anisole and the like), ketones (dialkyl ketones such as acetone and methyl ethyl ketone), and the like. The solvents may be used alone or in combination of two or more. The amount of the solvent used is, for example, 10 to 500 parts by weight, preferably 30 to 300 parts per 100 parts by weight of the total amount of the polyhydric alcohol represented by the formula (2) and (meth) acrylic acid (or a derivative thereof). It may be about 50 parts by weight, more preferably about 50 to 200 parts by weight.

  The reaction temperature varies depending on the type of (meth) acrylic acid or its derivative to be used, but is usually 30 to 180 ° C, preferably 40 to 150 ° C, more preferably about 50 to 130 ° C. Moreover, reaction time can be adjusted according to the kind of raw material, reaction temperature, the density | concentration in a solvent, etc., for example, 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 and alcohols. The reaction may be performed with stirring, may be performed in air or in an inert atmosphere (nitrogen, rare gas, etc.), or may be performed at normal pressure or under pressure.

  The produced polyfunctional (meth) acrylate is separated and purified by a conventional method, for example, separation means such as filtration, concentration, extraction, crystallization, recrystallization, column chromatography, or a combination means combining these. May be.

[Polymerizable composition]
The present invention includes a polymerizable composition composed of a polyfunctional (meth) acrylate (a compound represented by the formula (1)). The polymerizable composition can usually be composed of at least a polyfunctional (meth) acrylate (a compound represented by the formula (1)) and a polymerization initiator. In addition, a polyfunctional (meth) acrylate may comprise a polymeric composition individually or in combination of 2 or more types.

(Polymerization initiator)
The polymerization initiator includes a thermal polymerization initiator and a photopolymerization initiator. Examples of thermal polymerization initiators include dialkyl peroxides (di-t-butyl peroxide, dicumyl peroxide, etc.), diacyl peroxides [dialkanoyl peroxide (such as lauroyl peroxide), and dialoyl peroxide (benzoyl peroxide). Oxide, benzoyl toluyl peroxide, toluyl peroxide, etc.)], peracid esters (percarboxylic acid alkyl esters such as t-butyl peracetate, t-butyl peroxyoctate, t-butyl peroxybenzoate, etc.), Organic peroxides such as ketone peroxides, peroxycarbonates, peroxyketals; azonitrile compounds [2,2′-azobis (2,4-dimethylvaleronitrile), 2,2′-azobis (isobutyro) Nitrile), , 2′-azobis (2-methylbutyronitrile), 2,2′-azobis (4-methoxy-2,4-dimethylvaleronitrile), etc.], azoamide compounds {2,2′-azobis {2-methyl- N- [1,1-bis (hydroxymethyl) -2-hydroxyethyl] propionamide} and the like}, azoamidine compounds {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-cyanopentane) Acid) and the like, and azo compounds having an oxime skeleton [2,2′-azobis (2-methylpropionamidooxime) 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. Examples of the photopolymerization initiator include various known photopolymerization initiators such as benzoins (benzoin alkyl ethers such as benzoin, benzoin methyl ether, benzoin ethyl ether, and benzoin isopropyl ether), 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-morpholinoaminopropanone-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-dimethylthioxanthone, 2,4-diethylthioxanthone, 2-chlorothioxanthone, 2,4-diisopropylthioxanthone Etc.), ketals (acetophenone dimethyl ketal, benzyl dimethyl ketal, etc.), benzophenones (benzophenone, etc.), xanthones and the like. These photopolymerization initiators may be used alone or in combination of two or more.

  Moreover, you may combine a photoinitiator with a photosensitizer. As photosensitizers, tertiary amines {eg, trialkylamines, trialkanolamines (such as triethanolamine), ethyl N, N-dimethylaminobenzoate [such as ethyl p- (dimethylamino) benzoate] , N, N-dimethylaminobenzoic acid amyl [p- (dimethylamino) benzoic acid amyl etc.] and other dialkylaminobenzoic acid alkyl esters, 4,4-bis (diethylamino) benzophenone (Michler's ketone) and other bis (dialkylamino) Conventional photosensitizers such as benzophenone, dialkylaminobenzophenone such as 4- (dimethylamino) benzophenone} and the like. The photosensitizers may be used alone or in combination of two or more.

  The amount of the polymerization initiator (and the total amount of the photosensitizer) used is 0.1 to 30 parts by weight (for example, 1 to 30 parts by weight), preferably 1 with respect to 100 parts by weight of the polyfunctional (meth) acrylate. It may be about 20 to 20 parts by weight (for example, 5 to 25 parts by weight), more preferably about 1.5 to 10 parts by weight. If the amount of the photopolymerization initiator used is too small, the polymerizability (or photocuring property) of the composition will be reduced. May decrease.

  Moreover, the usage-amount of a photosensitizer is 5-200 weight part with respect to 100 weight part of polymerization initiators (photoinitiator), Preferably it is 10-150 weight part, More preferably, it is about 20-100 weight part. It may be.

  The polymerization initiator may be composed of a thermal polymerization initiator and a photopolymerization initiator. Although a polymerization initiator can be selected according to the use of a polymerizable composition, when used for an optical material, it is usually composed of at least a photopolymerization initiator.

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

Examples of the reactive diluent (polymerizable diluent) include a monofunctional monomer and a polyfunctional monomer. Monofunctional monomers include alkyl (meth) acrylate [such as C _1-6 alkyl (meth) acrylate such as methyl (meth) acrylate], cycloalkyl (meth) acrylate [cyclohexyl (meth) acrylate, etc. (Meth) acrylic acid C _5-8 cycloalkyl, (meth) acrylic acid di to tetracycloalkyl esters such as isobornyl (meth) acrylate], aryl (meth) acrylate [phenyl (meth) acrylate, etc.] , Hydroxyalkyl (meth) acrylate [(2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, hydroxy C _2-10 alkyl (meth) acrylate such as 2-hydroxybutyl (meth) acrylate)], (Poly) oxyalkylene glycol (Meth) acrylate (diethylene glycol mono (meth) acrylate, methoxy tetraethylene glycol mono (meth) acrylate, such as polyethylene glycol mono (meth) acrylate (poly) oxy-C _2-6 alkylene glycol mono (meth) acrylate), alkoxyalkyl (Meth) acrylate [(meth) acrylic acid 2-methoxyethyl, (meth) acrylic acid 3-methoxybutyl (meth) acrylic acid C _1-4 alkoxyalkyl etc.], N-substituted (meth) acrylamide (N, N- dimethyl (meth) N, such as acrylamide, N- di _{C 1-4} alkyl (meth) acrylamide, N- methylol (meth) N- hydroxy _{C 1-4} alkyl, such as acrylamide (meth) acrylamide), aminoalkyl Meth) acrylate (N, N-dimethylaminoethyl acrylate), such as glycidyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate such as (meth) acrylic monomers can be exemplified.

  Polyfunctional monomers include difunctional (meth) acrylates, polyfunctional (meth) acrylates, epoxy group-containing compounds (glyceryl diglycidyl ether, trimethylolpropane triglycidyl ether, polyglycidyl ethers such as triglycidyl isocyanurate) Etc.) (for example, di to penta) (meth) acrylate, melamine acrylate, and the like.

Difunctional (meth) acrylates include alkylene glycol di (meth) acrylate [ethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, 1,4-butanediol di (meth) acrylate, hexanediol di ( C _2-10 alkylene glycol di (meth) acrylate such as meth) acrylate and neopentyl glycol di (meth) acrylate], (poly) oxyalkylene glycol di (meth) acrylate [diethylene 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 (Poly) oxy C _2-6 alkylene glycol di (meth) acrylate such as glycol di (meth) acrylate and polytetramethylene glycol di (meth) acrylate], bisphenol A (or its C _2-3 alkylene oxide adduct) Di (meth) acrylate, di (meth) acrylate of polyhydric alcohol (or its C _2-3 alkylene oxide adduct) [for example, glycerin di (meth) acrylate, trimethylolpropane di (meth) acrylate, tris (hydroxy) Examples include triol di (meth) acrylates such as ethyl) isocyanurate di (meth) acrylate, tetraol di (meth) acrylates such as pentaerythritol di (meth) acrylate, and the like.

As the polyfunctional (meth) acrylate, a trifunctional or polyfunctional (meth) acrylate of a polyhydric alcohol (or its C _2-3 alkylene oxide adduct), for example, glycerin tri (meth) acrylate, trimethylolethane tri Tri (meth) acrylates of triols such as (meth) acrylate, trimethylolpropane tri (meth) acrylate, trimethylolpropane ethoxytri (meth) acrylate, tris (hydroxyethyl) isocyanurate tri (meth) acrylate; pentaerythritol tri ( Tri) of tetraols such as meth) acrylate and pentaerythritol tetra (meth) acrylate; tetra (meth) acrylate; ditrimethylolpropane tetra (meth) acrylate; dipentaerythritol te Examples include tiger (meth) acrylate; dipentaerythritol hexa (meth) acrylate and the like.

  The reactive diluent may be used alone or in combination of two or more. 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) acrylate, for example, 1-100 weight part, Preferably it is 1-50 weight part, More preferably, it may be about 1 to 30 parts by weight.

  Diluents also include non-reactive diluents. When a non-reactive diluent is used, the applicability of the polymerizable composition can be improved. Non-reactive diluents (or solvents) include organic solvents such as aliphatic hydrocarbons such as hexane, heptane, octane and decane; ketones such as ethyl methyl ketone and cyclohexanone; toluene, xylene, tetramethylbenzene and the like Aromatic hydrocarbons: glycols such as 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 Ethers; carboxylate esters (methyl acetate, ethyl acetate, butyl acetate, cellosolve acetate, butyl cellosolve acetate, carbitol acetate, butyl carbide Ether acetate, propylene glycol monomethyl ether acetate, acetate esters such as dipropylene glycol monomethyl ether acetate, butyl lactate, etc.), esters such as carbonate esters (propylene carbonate, etc.); petroleum solvents such as petroleum ether, petroleum naphtha, solvent naphtha, etc. Can be illustrated. A non-reactive diluent can be used individually or in combination of 2 or more types.

  The amount (addition amount) of the non-reactive diluent varies depending on the coating method and the like, but can be selected from the range of 0 to 500 parts by weight with respect to 100 parts by weight of the polyfunctional (meth) acrylate. It may be 400 parts by weight, preferably 20 to 300 parts by weight, more preferably about 30 to 200 parts by weight.

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

  The polysilane is not particularly limited as long as it is a linear, cyclic, branched or network compound having a Si—Si bond. For example, among the structural units represented by the following formulas (3) to (5) Examples include polysilane (including oligosilane and copolysilane) having at least one structural unit.

（式中、Ｒ^５〜Ｒ^７は、同一又は異なって、水素原子、ヒドロキシル基、アルキル基、アルコキシ基、アルケニル基、シクロアルキル基、シクロアルキルオキシ基、シクロアルケニル基、アリール基、アリールオキシ基、アラルキル基、アラルキルオキシ基又はシリル基を示し、ｘ、ｙ及びｚはそれぞれ０又は１以上の整数を示し、ｘ、ｙ及びｚの合計は５〜４００である。）
このようなポリシランとしては、例えば、式（３）で表される構造単位を有する直鎖状又は環状ポリシラン、前記式（４）又は（５）で表される構造単位を有する分岐鎖状又は網目状ポリシラン、前記式（３）〜（５）で表される構造単位を組み合わせて有するポリシラン（環状、分岐鎖状又は網目状ポリシラン、例えば、前記式（３）と（４）で表される構造を有するポリシランなど）などが挙げられる。

Wherein R ^{5 to} R ⁷ are the same or different and are a hydrogen atom, hydroxyl group, alkyl group, alkoxy group, alkenyl group, cycloalkyl group, cycloalkyloxy group, cycloalkenyl group, aryl group, aryloxy group , An aralkyl group, an aralkyloxy group or a silyl group, x, y and z each represent 0 or an integer of 1 or more, and the total of x, y and z is 5 to 400.)
Examples of such a polysilane include a linear or cyclic polysilane having a structural unit represented by the formula (3), and a branched or network having a structural unit represented by the formula (4) or (5). Polysilane, polysilane having a combination of structural units represented by the above formulas (3) to (5) (cyclic, branched or network polysilane, for example, structures represented by the above formulas (3) and (4) And the like.

In the substituents R ^{5 to} R ⁷ , the alkyl group may be a C _1-14 alkyl group such as methyl, ethyl, propyl, isopropyl, butyl, t-butyl (preferably a C _1-10 alkyl group, particularly C _1-6 Alkyl group). Examples of the alkoxy group include C _1-14 alkoxy groups such as methoxy and ethoxy (preferably C _1-10 alkoxy groups, particularly C _1-6 alkoxy groups). Examples of the alkenyl group include C _2-14 alkenyl groups such as vinyl and allyl (preferably C _2-10 alkenyl groups). Examples of the cycloalkyl group include C _5-14 cycloalkyl groups such as cyclohexyl and methylcyclohexyl (preferably a C _5-10 cycloalkyl group, more preferably a C _5-8 cycloalkyl group). _{Examples of the} cycloalkyloxy group include C _5-14 cycloalkyloxy groups (preferably C _5-10 cycloalkyloxy groups) such as cyclohexyloxy. Examples of the cycloalkenyl group include C _5-14 cycloalkenyl groups such as cyclohexenyl (preferably a C _5-10 cycloalkenyl group). Examples of the aryl group include C _6-20 aryl groups such as phenyl, methylphenyl and dimethylphenyl (preferably a C _6-15 aryl group, more preferably a C _6-12 aryl group). Examples of the aryloxy group include C _6-20 aryloxy groups (preferably C _6-15 aryloxy groups) such as phenoxy. Examples of the aralkyl group include C _6-20 aryl-C _1-4 alkyl groups (preferably C _6-10 aryl-C _1-2 alkyl groups) such as benzyl and phenethyl. Examples of the aralkyloxy group include C _6-20 aryl-C _1-4 alkyloxy groups such as benzyloxy (preferably C _6-10 aryl-C _1-2 alkyloxy groups). Examples of the silyl group include Si _1-10 silanyl groups (preferably Si _1-6 silanyl groups) such as a silyl group and a disilanyl group.

Moreover, when R < ⁵ > -R < ⁷ > is the said organic substituent or a silyl group, at least 1 of the hydrogen atom may be substituted by substituents, such as an alkyl group, an aryl group, and an alkoxy group. Examples of such a substituent include the same groups as described above. The hydrogen atom, hydroxyl group, alkoxy group and silyl group are often substituted with terminal groups.

Of these, the substituents R ^{5 to} R ⁷ are usually hydrocarbon groups such as alkyl groups, alkenyl groups, cycloalkyl groups, aryl groups, and aralkyl groups. _1-6 alkyl groups) and aryl groups (C _6-8 aryl groups such as phenyl) are preferred.

  When the polysilane has an acyclic structure (straight, branched, or network), the terminal substituent is usually a hydrogen atom, a hydroxyl group, an alkyl group, an alkoxy group, a silyl group, or a halogen atom (such as a chlorine atom). And it is preferably composed of at least a hydroxyl group.

Specific examples of the structural unit of polysilane include a structural unit (3) in which both R ⁵ and R ⁶ are aryl groups, and a structural unit (3) in which 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 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, A structural unit (3) which is at least one group selected from an aralkyloxy group and a silyl group, a structural unit (4) wherein R ⁷ is an alkyl group, a structural unit (4) wherein R ⁷ is an aryl group, and a structural unit (5).

Preferable polysilanes include a structural unit (3) in which at least one of R ⁵ and R ⁶ is an aryl group, or a polysilane containing a structural unit (4) in which R ⁷ is an aryl group, and in particular, any of R ⁵ and R ⁶ Is a structural unit (3) which is an aryl group (particularly a phenyl group), a structural unit (3) wherein R ⁵ is an aryl group (particularly a phenyl group), and R ⁶ is an alkyl group (particularly a methyl group), or R ⁷ Is a polysilane composed of a structural unit (4) in which is an aryl group (particularly a phenyl group). The structure of polysilane is preferably cyclic, branched, or network, and particularly preferably branched.

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

  Typical polysilanes include cyclic polydiarylsilanes (cyclic polydiphenylsilane (5- to 8-membered ring)), linear polyalkylarylsilanes (such as linear polymethylphenylsilane), and linear polydiarylsilanes. -Polyalkylarylsilane copolymer (such as linear polydiphenylsilane-polymethylphenylsilane copolymer), polyarylsilin (such as polyphenylsilin), polydiarylsilane-polyarylsilin copolymer (polydiphenylsilane) -Polyphenylsilin copolymer), polyalkylarylsilane-polyarylsilin copolymer (polymethylphenylsilane-polyphenylsilin copolymer, etc.) and the like. “Polycillin” means a branched polysilane composed of the structural unit (4).

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

  The molecular weight of the polysilane may be about 300 to 100,000, preferably 400 to 50,000, and more preferably about 500 to 20,000 in terms of number average molecular weight.

  The polysilane can be prepared using various known methods. In order to produce these polysilanes, for example, a silicon-containing monomer having a specific structural unit (mono to tetrahalosilanes, etc.) is used as a raw material, and (a) a method of dehalogenating polycondensation of halosilanes using magnesium as a reducing agent ("Magnesium reduction method", methods described in WO98 / 29476, JP-A-2001-48987, and JP-A-2002-226586), (b) Dehalogenation of halosilanes in the presence of an alkali metal Polymerization method (“Kipping method”, J. Am. Chem. Soc., 110, 124 (1988), Macromolecules, 23, 3423 (1990), etc.), (c) Dehalogenation condensation polymerization of halosilanes by electrode reduction Method (J. Chem. Soc., Chem. Commun., 11 1 (1990), J. Chem. Soc., Chem. Commun. 897 (1992), etc.), (d) a method of dehydrogenating polycondensation of hydrazines in the presence of a metal catalyst (JP-A-4-334551, etc.) ), (E) a method by anionic polymerization of disilene crosslinked with biphenyl or the like (Macromolecules, 23, 4494 (1990), etc.), and (e) a method by ring-opening polymerization of cyclic silanes.

  Of these methods, the purity and molecular weight distribution of the resulting polysilane, the excellent compatibility with the resin, the low sodium and chlorine content, and the industrial aspects such as manufacturing cost and safety, the magnesium reduction method (In particular, the method described in JP-A No. 2001-48987 and JP-A No. 2002-226586) is most preferable. The method for introducing the silanol group (terminal hydroxyl group) is not particularly limited. For example, it can be introduced simply by adding water to the polysilane obtained by the above method.

  The proportion of the polysilane can be selected from the range of 0 to 100 parts by weight with respect to 100 parts by weight of the polyfunctional (meth) acrylate, and usually 0.1 to 50 parts by weight, preferably 0.5 to 20 parts by weight, More preferably, it may be about 1 to 20 parts by weight.

  In addition, the polymerizable composition may be filled with conventional additives such as colorants, stabilizers (thermal stabilizers, antioxidants, ultraviolet absorbers, etc.), and the like, as long as the original properties are not impaired. Agents, antistatic agents, flame retardants (phosphorus-containing compounds such as organic phosphorus compounds and inorganic phosphorus compounds, halogen-containing flame retardants, metal oxides, metal hydroxides, metal sulfides, etc.), flame retardant aids, leveling agents, A silane coupling agent, a polymerization inhibitor (or a thermal polymerization inhibitor), and the like may be included. You may use an additive individually or in combination of 2 or more types.

  The proportion of the additive (such as a flame retardant) can be appropriately selected depending on the type of the additive. It may be about 50 parts by weight, more preferably about 1 to 20 parts by weight.

  The polymerizable composition can be prepared by blending or mixing a polyfunctional (meth) acrylate and at least a polymerization initiator. The blending method (mixing method) is not particularly limited, and a conventional method can be used. In particular, when the polymerizable composition is formed as a coating film, the multifunctional (meth) acrylate and the polymerization initiator (and other components such as polysilane) are mixed with the diluent (especially a non-reactive diluent). The polymerizable composition (a coating composition or a coating composition) may be prepared by dissolving (or suspending) in a diluent containing the same.

  The polymerizable composition of the present invention (particularly the photopolymerizable composition) (or the polyfunctional (meth) acrylate) is useful for obtaining a cured product (molded product) that has been polymerized or cured (or crosslinked). . Such a cured product (a cured product of a polymerizable composition composed of the polyfunctional (meth) acrylate and a polymerization initiator, a cured product of the polyfunctional (meth) acrylate) is in the form of a molded body. Accordingly, it can be obtained by subjecting the polymerizable composition to curing treatment (heating treatment or light irradiation treatment) during the molding process or after molding. For example, a film-like cured product may be obtained by applying a polymerizable composition to a substrate to form a coating film (or thin film) and then performing a curing treatment. For the formation of such a coating film (or thin film), conventional methods such as flow coating method, spin coating method, spray coating method, screen printing method, casting method, bar coating method, curtain coating method, roll coating method are used. A dip method or the like can be used. Moreover, after application of the polymerizable composition (after application), a drying process may be performed by a conventional method, and drying may be performed by heating as necessary. The heating temperature in drying can be appropriately selected according to the type of polymerization initiator and diluent (non-reactive diluent), and is usually about 40 to 250 ° C. The drying treatment may be performed in an inert gas atmosphere such as nitrogen or argon or in the air, or may be performed under normal pressure or reduced pressure.

  The thickness of the coating film (or thin film) may be, for example, about 0.01 to 100 μm, preferably 0.1 to 10 μm, and more preferably about 0.1 to 1 μm.

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

  In the heat treatment, the heating temperature is, for example, about 50 to 250 ° C., preferably 60 to 150 ° C., and more preferably about 70 to 120 ° C., depending on the type of polymerization initiator.

In the light irradiation treatment, as the light irradiation source, for example, a low pressure mercury lamp, a high pressure mercury lamp, an ultrahigh pressure mercury lamp, a hydrogen lamp, a deuterium lamp, a fluorescent lamp, a halogen lamp, an excimer laser, a nitrogen laser, a dye laser, A helium-cadmium laser can be exemplified. Moreover, although the amount of light irradiation energy changes with uses, the film thickness of a coating film, etc., it is about 0.1-10000 mJ / cm < ² > normally, Preferably it is about 0.5-2000 mJ / cm < ² >. The exposure time is, for example, about 1 second to 3 hours, preferably about 5 seconds to 2 hours, and more preferably about 10 seconds to 1 hour. The light irradiation may be performed in an atmosphere of an inert gas such as nitrogen or argon or in the air, and may be performed under normal pressure, increased pressure, or reduced pressure.

  Note that heat treatment and light irradiation treatment may be combined. For example, a polymerizable composition containing a photopolymerization initiator may be further heated after light irradiation (or while light irradiation) in order to promote curing or crosslinking.

  The shape of the cured product (molded product) is not particularly limited, and for example, a two-dimensional structure (film shape, sheet shape, plate shape, etc.), a three-dimensional structure (tubular, rod shape, tube shape, hollow shape, etc.) Etc.

  The cured product of the present invention has a high refractive index and is excellent in optical properties. For example, the refractive index of the cured product (or the cured product of the polyfunctional (meth) acrylate) is 1.55 or more (for example, about 1.59 to 1.7), preferably 1.60 or more (for example, 1.60 to about 1.7). In particular, when the cured product is a cured product of a polymerizable composition containing a polysilane compound, the refractive index is, for example, about 1.60 to 1.7, preferably about 1.62 to 1.7.

  Therefore, the cured product of the present invention can be suitably used particularly as an optical material (a coating agent such as an optical overcoat agent or hard coat agent, an antireflection film, a spectacle lens, an optical fiber, an optical waveguide, a hologram, etc.). Examples of the shape of the optical material include a film or sheet shape, a plate shape, a lens shape, and a tubular shape.

  The polyfunctional (meth) acrylate (and its polymerizable composition) of the present invention has a high refractive index, light transmittance, hardness, weather resistance, flexibility, mechanical strength, dimensional stability, workability and the like. And is useful as a plastic raw material satisfying various required performances. In particular, it is excellent in heat resistance and moisture resistance, and has a high refractive index and high hardness, so that it can be used for optical materials, for example, optical overcoat agent, hard coat agent, antireflection film, spectacle lens, optical fiber, optical fiber It can be used effectively in waveguides, holograms, etc.

  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 heated at 80 ° C. 5 ml of 98% sulfuric acid was added dropwise. After completion of the reaction, 200 ml of MIBK (methyl isobutyl ketone) and 100 ml of water were added for extraction. Excess sulfuric acid was removed by performing the same operation three times. After concentration of the solvent, 100 ml of MIBK and 200 ml of toluene were added, and then cooled to 10 ° C. to obtain 65 g of biscatecholfluorene [9,9-bis (3,4-dihydroxyphenyl) fluorene]. The ¹ H-NMR spectrum data of the obtained biscatechol fluorene is shown below.

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 the obtained biscatechol fluorene, 100 g of diethylene glycol, 1 g of 1-methylimidazole, and 150 g (about 1.7 mol) of ethylene carbonate were placed in a reactor and heated to 100 ° C. for reaction. It was. After completion of the reaction, 500 ml of IPA (isopropanol) was added and cooled to 10 ° C. to obtain 40 g of a polyhydric alcohol to which an ethylene oxide unit was added as white crystals. As a result of analyzing the obtained polyhydric alcohol, it was found that it was a polyhydric alcohol in which 4.5 mol of an ethoxy group was added to 1 mol of biscatechol fluorene used as a raw material.

  A reactor equipped with 40 g (0.06 mol) of the obtained polyhydric alcohol, 43 g (0.6 mol) of acrylic acid, 1 g of 70% by weight methanesulfonic acid aqueous solution, 0.01 g of hydroquinone and 100 mL of toluene, with a Dean-Stark trap attached. The esterification reaction was performed for 5 hours under toluene reflux. The water produced during the esterification reaction was removed by a Dean-Stark trap to obtain 45 g of the polyhydric alcohol tetraacrylate. When analyzed by high performance liquid chromatography, the purity of tetraacrylate was 98%.

Synthesis example 1
Polysilane was synthesized by the magnesium reduction method of 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 of the reaction, extraction with toluene was performed to convert the unreacted terminal chlorine group (chlorine atom) into a hydroxyl group to obtain polysilane (polymethylphenylsilane-polyphenylsilin copolymer) having an average polymerization degree of 25.

Example 2 (Photo-curing of tetraacrylate)
To 40 g of the tetraacrylate obtained in Example 1, 0.6 g of 2-hydroxy-2-methyl-1-phenylpropan-1-one was added, photocured by irradiating with UV (ultraviolet light), and further 80 ° C. And cured for 1 hour to obtain a cured product as a transparent film. The obtained cured product had a glass transition temperature Tg of 225 ° C. and a refractive index of 1.630 (D line).

Example 3 (Photocuring of tetraacrylate containing polysilane)
In addition to 40 g of the tetraacrylic acid ester obtained in Example 1, 8 g of the polysilane obtained in Synthesis Example 1 is added, and the cured product is cured as a transparent film by photocuring and thermosetting in the same manner as in Example 2. Got. The obtained cured product had a Tg of 220 ° C. and a refractive index of 1.645 (D line).

Claims (12)

A polyfunctional (meth) acrylate having a fluorene skeleton represented by the following formula (1).

(In the formula, R ^1a , R ^1b , R ^2a and R ^2b represent a substituent, R ^3a and R ^3b represent an alkylene group, R ^4a and R ^4b represent a hydrogen atom or a methyl group, and k 1 and k 2 represent The same or different and 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 are the same or different and represent an integer of 1 or more, p1 and p2 Represents 2, where m1 + p1 and m2 + p2 are integers of 2 to 5) The polyfunctional (meth) acrylate according to claim 1, wherein in formula (1), R ^3a and R ^3b are C _2-4 alkylene groups, n1 and n2 are 1 to 12, and n1 + n2 is 2 to 24. . In formula (1), R ^1a and R ^1b are C _1-4 alkyl groups, k 1 and k 2 are 0 or 1, and R ^2a and R ^2b are C _1-4 alkyl groups, C _1-4 alkoxy groups or The C _6-8 aryl group, m1 and m2 are 0 to 2, R ^3a and R ^3b are C _2-4 alkylene groups, n1 and n2 are 1 to 6, and n1 + n2 is 2 to 12. Multifunctional (meth) acrylate. The polyfunctional (meth) acrylate according to claim 1, wherein in formula (1), R ^3a and R ^3b are C _2-4 alkylene groups, n1 and n2 are 1 to 4, and n1 + n2 is 2 to 8. . The polyfunctionality (meth) represented by Formula (1) of Claim 1 by making the polyhydric alcohol which has a fluorene skeleton represented by following formula (2) react with (meth) acrylic acid or its derivative (s). A method for producing acrylates.

(In the formula, 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)   A polymerizable composition comprising the polyfunctional (meth) acrylate according to claim 1 and a polymerization initiator.   The polymerizable composition according to claim 6, wherein the ratio of the polymerization initiator is 0.1 to 30 parts by weight with respect to 100 parts by weight of the polyfunctional (meth) acrylate according to claim 1.   Furthermore, the polymeric composition of Claim 6 containing polysilane. The polymerizable composition according to claim 8, wherein the polysilane has at least one structural unit among the structural units represented by the following formulas (3) to (5).

Wherein R ^{5 to} R ⁷ are the same or different and are a hydrogen atom, hydroxyl group, alkyl group, alkoxy group, alkenyl group, cycloalkyl group, cycloalkyloxy group, cycloalkenyl group, aryl group, aryloxy group , An aralkyl group, an aralkyloxy group or a silyl group, x, y and z each represent 0 or an integer of 1 or more, and the total of x, y and z is 5 to 400.)   The polymerizable composition according to claim 8, wherein the proportion of polysilane is 0.1 to 50 parts by weight with respect to 100 parts by weight of the polyfunctional (meth) acrylate according to claim 1.   A cured product obtained by polymerizing or curing the polymerizable composition according to claim 6.   The optical material comprised with the hardened | cured material of Claim 11.