JP2007091870A - Polymerizable composition and cured product thereof - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a polymerizable composition useful for obtaining cured products having excellent optical properties[e.g. high refractive index, high transparency(transparency to visible rays)] and also having characteristics including high adhesion to substrate, hard coatability and high heat resistance. <P>SOLUTION: The polymerizable composition comprises a specific polyfunctional (meth)acrylate having a fluorene skeleton[for example, 9,9-bis(4- (meth)acryloyloxyethoxyphenyl)fluorene], a hydrolytically condensable organosilicon compound having polymerizable group[for example, (meth)acryloyloxyalkyl tri-1-4C alkoxysilane], and a photoacid generator. This composition may also contain a photoradical initiator for improving its photopolymerizability. <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

  The present invention has excellent optical properties (for example, high refractive index, high transparency (transparency to visible light), etc.) and high adhesion to the substrate, hard coat properties, high heat resistance, etc. The present invention relates to a polymerizable composition (especially a photopolymerizable composition) useful for obtaining a cured product having the cured product, a cured product obtained by curing the composition (hybrid cured product), and a method for forming the cured product.

  Conventionally, a method for obtaining a cured coating film composed of a siloxane bond on the surface of a substrate by utilizing a condensation reaction by hydrolysis of alkoxysilane is known. For example, an alkoxysilane such as tetraethyl silicate or tetramethyl silicate can be subjected to a condensation reaction by hydrolysis in the presence of an acid or base, and then applied to the substrate, followed by heat treatment to form a silica thin film on the substrate. .

  This method is generally called a sol-gel method, and has recently attracted attention as a method for producing glass or ceramic materials having a new composition controlled on a molecular order. On the other hand, alkoxysilanes partially having an organic functional group are not only used as glass substrate and fiber surface treatment agents as silane coupling agents, but also relatively with respect to plastics and the like by condensation reaction by hydrolysis. Since a coating film having a high surface hardness can be obtained, it is used as a high-hardness paint (hard coating) for imparting scratch resistance of films such as methacrylic resin, polycarbonate resin and diallyl carbonate resin.

  Many coating compositions containing such alkoxysilanes are thermosetting and have problems with storage stability, curing time, setting of heating conditions during curing, etc., during curing, bath management, heating temperature・ Care must be taken for process management such as heating time.

  On the other hand, a method of photocuring photocurable alkoxysilane has also been proposed. For example, JP-A-8-302284 (Patent Document 1) contains a specific alkoxysilane compound having a 3- (meth) acryloxypropyl group, a vinyl group, a phenyl group, or a methyl group and a photoacid generator. A photocurable coating composition is disclosed. In this document, a cured film can be formed by irradiating a photocurable coating composition with ultraviolet rays without providing a heating step. Moreover, with the photocurable coating composition of this literature, a comparatively high cured film can be obtained in the adhesiveness with respect to a base material, and surface hardness.

However, in recent years, there has been a demand for a coating film having characteristics (for example, high refractive index, high transparency, etc.) that cannot be imparted by conventional methods such as the method described in this document for use in electronic materials. Development of further materials that can impart properties is desired.
JP-A-8-302284 (Claims)

  Therefore, the object of the present invention is to produce a cured product having excellent properties such as high adhesion to the substrate, hard coat properties, heat resistance and high transparency and high refractive index (optical properties). An object of the present invention is to provide a polymerizable composition, a cured product obtained by curing the polymerizable composition (hybrid cured product), and a method for producing the cured product.

  As a result of earnest studies to achieve the above-mentioned problems, the present inventors combined a specific polyfunctional (meth) acrylate having a fluorene skeleton, an alkoxysilane having a polymerizable group, and a photoacid generator, By co-polymerizing the polyfunctional (meth) acrylate and the alkoxysilanes and causing a sol-gel reaction of the alkoxysilanes with the acid generated, characteristics such as high adhesion to the substrate, and optical The inventors have found that a cured product or a cured coating film (hybrid film) capable of achieving both properties (high transparency, high refractive index, etc.) can be formed, and the present invention has been completed.

  That is, the polymerizable composition (photopolymerizable composition) of the present invention includes a polyfunctional (meth) acrylate represented by the following formula (1), a hydrolytic condensable organosilicon compound having a polymerizable group, and light. It consists of an acid generator.

(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 to 4, m1 and m2 are the same or different and represent an integer of 0 to 3, n1 and n2 are the same or different and represent an integer of 0 or 1 and p1 and p2 are the same Or it is different and represents an integer of 1 to 4, where m1 + p1 and m2 + p2 are each an integer of 1 to 5)
In the composition, the polyfunctional (meth) acrylate is, for example, in the formula (1), wherein R ^3a and R ^3b are C _2-4 alkylene groups, n1 and n2 are each an integer of 1 or more, and p1 and Compounds in which p2 is 1 to 3, particularly R ^3a and R ^3b are C _2-3 alkylene groups, n1 and n2 are each 1 or 2, and p1 and p2 are each 1 to 3 (especially 1) It may be.

  In the composition, the hydrolytic condensable organosilicon compound having a polymerizable group may be a compound represented by the following formula (2) or a partial condensate thereof.

_{X- (A) c -Si (OR} 4) a (R 5) 3-a (2)
[Wherein, X represents a polymerizable group, A represents a linking group, R ⁴ represents a hydrocarbon group or a group — [(R ⁶ O) _b —R ⁷ ] (wherein R ⁶ represents an alkylene group) R ⁷ is a hydrocarbon group, b is an integer of 1 or more, and R ⁵ is a hydrogen atom, a hydroxyl group, a halogen atom or a hydrocarbon group. a represents an integer of 1 to 3, and c represents 0 or 1. ]
In the formula (2), the polymerizable group may be a (meth) acryloyl group, and the compound represented by the formula (2) is, for example, (meth) acryloyloxyalkyltri-C _1-4 alkoxysilane, (meth) acryloyloxy alkyl tri (C _1-4 alkoxy C _2-4 alkoxy) silane, (meth) acryloyloxy alkyl amino alkyl tri C _1-4 alkoxysilane, and (meth) acryloyloxy alkyl tri C _6-10 aryl It may be at least one selected from oxysilane.

  In the composition, the photoacid generator may be at least one selected from a triarylsulfonium salt, a bis (alkylaryl) iodonium salt, and a compound represented by the following formula (6).

(Wherein R ¹⁷ , R ¹⁸ and R ¹⁹ are substituents, p, q and r are the same or different and each represents an integer of 0 to 4, Y represents a hydrogen atom, a halogen atom, a nitro group or an alkyl group.)
Moreover, in the said composition, the ratio of the hydrolytic condensable organosilicon compound which has a polymeric group is 50-700 with respect to 100 weight part of polyfunctional (meth) acrylate represented by Formula (1), for example. The proportion of the photoacid generator may be about 0.5 to 5 parts by weight with respect to 100 parts by weight of the polyfunctional (meth) acrylate represented by the formula (1). Also good.

  The composition of the present invention may further contain a hydrolytic condensable organosilicon compound having no polymerizable group. Such an organosilicon compound is, for example, a compound represented by the following formula (3), an oligomer of a compound represented by the following formula (3), or a partial condensate of a compound represented by the following formula (3). It may be configured.

Si (OR ⁸ ) _d (R ⁹ ) _4-d (3)
[Wherein R ⁸ is a hydrocarbon group or group — [(R ¹⁰ O) _e —R ¹¹ ] (wherein R ¹⁰ is an alkylene group, R ¹¹ is a hydrocarbon group, and e is 1 R ⁹ represents a hydrogen atom, a hydroxyl group, a halogen atom or a hydrocarbon group. d shows the integer of 1-4. ]
Wherein no hydrolytic condensable organic silicon compound a polymerizable group, for example, C _6-8 Arirutori C _1-4 alkoxysilane, tetra C _1-4 alkoxy silanes, tetra C _6-8 aryloxy silane and tetra C, You may comprise at least 1 type of compound selected from the oligomer of _1-4 alkoxysilane, or its partial condensate.

  The composition may further contain a non-silicon hydrolytic condensable organometallic compound, for example, an alkoxide of a non-silicon metal selected from titanium, zirconium, aluminum, and zinc (metal alkoxide). Such a non-silicon hydrolytic condensable organometallic compound may constitute the composition of the present invention in combination with the hydrolytic condensable organosilicon compound having a polymerizable group.

  The composition of the present invention may further contain a photo radical initiator.

  The present invention includes a method for producing a cured product of the polymerizable composition by applying the polymerizable composition on a base material (for example, a substrate) to form a coating film and then irradiating with light. In this method, heating may be performed after the light irradiation. In this method, a polymerizable composition in which a hydrolytic condensable organosilicon compound having a polymerizable group is partially condensed may be applied on a substrate for efficient hydrolysis and condensation. Furthermore, this invention contains the hardened | cured material (cured coating film etc.) which the said polymeric composition hardened | cured.

  In the present specification, “fluorenes” includes “fluorene having no substituent” and “fluorene having a substituent”, and means “fluorene which may have a substituent”. .

  Since the polymerizable composition of the present invention combines a polyfunctional (meth) acrylate having a fluorene skeleton, an alkoxysilane having a polymerizable group, and a photoacid generator, it has high adhesion to the substrate, hard coat properties, and heat resistance. It is possible to produce or form a cured product that is excellent in properties such as properties and excellent in properties (optical properties) such as high transparency and high refractive index.

  The polymerizable composition of the present invention (in particular, a photopolymerizable composition, hereinafter sometimes simply referred to as a composition or the like) is a polyfunctional (meth) acrylate having a fluorene skeleton, hydrolytic condensability having a polymerizable group. It comprises at least an organosilicon compound and a photoacid generator.

(Polyfunctional (meth) acrylate having a fluorene skeleton)
A polyfunctional (meth) acrylate resin having a fluorene skeleton (hereinafter sometimes simply referred to as fluorene (meth) acrylate) is a polyfunctional compound having a fluorene skeleton (9,9-bisphenylfluorene skeleton) in a compound ( It may be a (meth) acrylate, and is usually a compound represented by the following formula (1). Since the composition of the present invention is composed of such a polyfunctional (meth) acrylate having a fluorene skeleton, it provides a cured product (hybrid cured product) with high transparency and high refractive index efficiently. it can.

(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 to 4, m1 and m2 are the same or different and represent an integer of 0 to 3, n1 and n2 are the same or different and represent an integer of 0 or 1 and p1 and p2 are the same Or it is different and represents an integer of 1 to 4, where m1 + p1 and m2 + p2 are each an integer of 1 to 5)
The substituent represented by R ^1a and R ^1b is not particularly limited, but is usually an alkyl group 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. When a plurality of groups R ^1a (or R ^1b ) are present on the same benzene ring, the groups may be different from each other or the same. In addition, 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 etc. C _5-6 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 hydrocarbon group, such as (a benzyl group, C _6-10 and aryl -C _1-4 alkyl group such as a phenethyl group); alkoxy (Such as C _1-4 alkoxy group such as methoxy group); a hydroxyl group; hydroxy (poly) alkyleneoxy group (such as hydroxy (poly) C _2-4 alkyleneoxy group); C _1-6, such as acyl groups (acetyl group An acyl group); an alkoxycarbonyl group (C _1-4 alkoxycarbonyl group such as a methoxycarbonyl group); a halogen atom (fluorine atom, chlorine atom, etc.); a nitro group; a cyano group and the like. The hydroxyl group or hydroxy (poly) alkyleneoxy group may be a residue of a polyhydric alcohol (a group that has not reacted with (meth) acrylic acid or a derivative thereof) as a raw material in the production method described later. Many.

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). Of these, C _1-4 alkyl groups (particularly methyl groups) and C _6-8 aryl groups (particularly phenyl groups) are particularly preferred. The groups R ^2a and R ^2b may be the same or different from each other but are usually the same. When a plurality of groups R ^2a (or R ^2b ) are present in the same benzene ring, the groups may be different from each other or the same.

In addition, the substitution position of the substituent R ^2a (or R ^2b ) is not particularly limited, and it depends on the number of substitutions p1 (or p2), which will be described later, etc. 5), 6th position, 3,5-position, etc.).

  The preferred substitution numbers m1 and m2 are 0 to 3, more preferably 0 to 2. The substitution numbers m1 and m2 may be different but are usually the same in many cases.

Examples of the alkylene group (or alkylidene group) represented by R ^3a and R ^3b include, but are not limited to, for example, a C _1-6 alkylene group (eg, methylene group, ethylene group, trimethylene group, propylene group, butane-1, 2-diyl group, etc.) can be exemplified, and a C _2-4 alkylene group, particularly a C _2-3 alkylene group (particularly an ethylene group, 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 number of repetitions (addition number) n1 and n2 of the oxyalkylene group (or alkoxy group) is not particularly limited, but is the same or different and can be selected from the range of about 0 to 15, for example, 0 to 12 (for example, 1-12), preferably 0-8 (eg, 1-8), more preferably 0-6 (eg, 1-6), usually 1 or more [eg, 1-4 (eg, 1-3), especially about 1 or 2]. When n1 (or n2) is 2 or more, the polyalkoxy (polyalkyleneoxy) group may be composed of the same alkoxy group (oxyalkylene group), and different alkoxy groups (for example, ethoxy group and Propyleneoxy group) may be mixed, but usually it is often composed of the same alkoxy group.

  The number of substitution p1 and p2 of the (meth) acryloyloxy group or (meth) acryloyloxy (poly) alkoxy group (hereinafter sometimes referred to as (meth) acryloyloxy group-containing group) is preferably 1 to 3, respectively. 1 or 2 is preferred. The sum of p1 and p2 (p1 + p2) may be, for example, 2 to 6, preferably 2 to 4 (particularly 2 or 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 2 to 6 positions of the phenyl group substituted at the 9 position of fluorene according to the number of p1 (or p2), for example, p1 When (or p2) is 1, it may be, for example, 2-6 position (preferably 2 or 4 position, especially 4 position), and when p1 (or p2) is 2, for example, 3,4-position , 3,5-position, etc., and when p1 (or p2) is 3, for example, 3,4,5-position, 2,3,4-position, 2,3,5-position, 2 , 3,6-position, etc.

  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) n1 = 0 (n2 = 0) alone (meth) acryloyloxy group, 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). It is composed of 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, (meth) acrylates of 9,9-bis (mono to trihydroxyphenyl) fluorenes, 9,9-bis ( And (meth) acrylates of alkylene oxide (C _2-4 alkylene oxide) adducts of mono to trihydroxyphenyl) fluorenes.

  As (meth) acrylates of 9,9-bis (mono to trihydroxyphenyl) fluorenes, 9,9-bis (mono (meth) acryloyloxyphenyl) fluorenes, 9,9-bis (di (meth) acryloyl) And oxyphenyl) fluorenes and 9,9-bis (tri (meth) acryloyloxyphenyl) fluorenes.

9,9-bis (mono (meth) acryloyloxyphenyl) fluorenes include 9,9-bis ((meth) acryloyloxyphenyl) fluorene [e.g., 9,9-bis (4- (meth) acryloyloxyphenyl). ) Fluorene, substituted 9,9-bis ((meth) acryloyloxyphenyl) fluorene {e.g., 9,9-bis (alkyl- (meth) acryloyloxyphenyl) fluorene [9,9-bis (4- ( (Meth) acryloyloxy-2-methylphenyl) fluorene, 9,9-bis (4- (meth) acryloyloxy-3-methylphenyl) fluorene, 9,9-bis (4- (meth) acryloyloxy-3-ethyl) Phenyl) fluorene, 9,9-bis (3- (meth) acryloyloxy-6-methylphenyl) phenyl Oren, 9,9-bis (2- (meth) acryloyloxy-4-methylphenyl) 9,9-bis fluorene (C _1-4 alkyl - (meth) acryloyloxy phenyl) fluorene, etc.], 9,9 -Bis (dialkyl- (meth) acryloyloxyphenyl) fluorene [9,9-bis (4- (meth) acryloyloxy-3,5-dimethylphenyl) fluorene, 9,9-bis (4- (meth) acryloyloxy) 9,9-bis (diC _1-4 alkyl) such as -2,6-dimethylphenyl) fluorene, 9,9-bis (4- (meth) acryloyloxy-3,5-di-t-butylphenyl) fluorene -(Meth) acryloyloxyphenyl) fluorene, etc.], 9,9-bis (cycloalkyl- (meth) acryloyloxyphenyl) fluoro 9,9-bis (C _5-8 cycloalkyl- (meth) acryloyloxyphenyl) fluorene such as len [9,9-bis (4- (meth) acryloyloxy-3-cyclohexylphenyl) fluorene], 9,9-bis (C _6-8 aryl- (meta) such as 9-bis (aryl (meth) acryloyloxyphenyl) fluorene [9,9-bis (4- (meth) acryloyloxy-3-phenylphenyl) fluorene ] Acryloyloxyphenyl) fluorene etc.] etc.}.

The 9,9-bis (di (meth) acryloyloxyphenyl) fluorenes include fluorenes corresponding to the 9,9-bis (mono (meth) acryloyloxyphenyl) fluorenes such as 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 (3,5-di (meth) acryloyloxyphenyl) fluorene, 9,9-bis (2,3-di (meth) acryloyloxyphenyl) fluorene, 9,9-bis (2,6- Di (meth) acryloyloxyphenyl) fluorene, 9,9-bis (2,5-di (meth) acryloyloxyphenyl) fluorene ], 9,9-bis (di (meth) acryloyloxyphenyl) fluorene having a substituent {for example, 9,9-bis (alkyl-di (meth) acryloyloxyphenyl) fluorene [9,9-bis (3 9,9-bis (C ₁ ) such as 1,4-di (meth) acryloyloxy-5-methylphenyl) fluorene, 9,9-bis (3,4-di (meth) acryloyloxy-6-methylphenyl) fluorene _-4 alkyl - di (meth) acryloyloxy phenyl) fluorene, 9,9-bis (2,4-di (meth) acryloyloxy 3,6-dimethylphenyl) fluorene such as 9,9-bis (di C _{1- 4} alkyl-di (meth) acryloyloxyphenyl) fluorene, etc.], 9,9-bis (alkoxy-di (meth) acryloyloxyphenyl) fluoro [For example, 9,9-bis (C _1-4 alkoxy-di (meth) acryloyloxyphenyl) fluorene such as 9,9-bis (3,4-di (meth) acryloyloxy5-methoxyphenyl) fluorene] 9,9-bis (aryl-di (meth) acryloyloxyphenyl) fluorene [e.g., 9,9- such as 9,9-bis (3,4-di (meth) acryloyloxy5-phenylphenyl) fluorene] Bis (C _6-8 aryl-di (meth) acryloyloxyphenyl) fluorene and the like] and the like}.

  The 9,9-bis (tri (meth) acryloyloxyphenyl) fluorenes include fluorenes corresponding to the 9,9-bis (mono or 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 (meth) acryloyloxyphenyl) fluorene, 9,9-bis (2,3,4-tri (meth) acryloyloxyphenyl) fluorene, 9,9-bis (2,3,5-tri (meth) acryloyl) 9,9-bis (tri) such as oxyphenyl) fluorene, 9,9-bis (2,3,6-tri (meth) acryloyloxyphenyl) fluorene Meth) acryloyloxy phenyl) contains fluorene and the like.

The (meth) acrylate of an alkylene oxide adduct of 9,9-bis (mono to trihydroxyphenyl) fluorenes includes a (meth) acrylate of an alkylene oxide adduct of 9,9-bis (monohydroxyphenyl) fluorenes ( In particular, di (meth) acrylate), for example 9,9-bis ((meth) acryloyloxyalkoxyphenyl) fluorene [for example 9,9 such as 9,9-bis (4- (meth) acryloyloxyethoxyphenyl) fluorene. 9-bis ((meth) acryloyloxy C _2-4 alkoxyphenyl) fluorene and the like], 9,9-bis ((meth) acryloyloxyalkoxyphenyl) fluorene having a substituent {for example, 9,9-bis (alkyl- (Meth) acryloyloxyalkoxyphenyl) fluorene [For example, 9,9-bis (4- (meth) acryloyloxyethoxy-3-methylphenyl) fluorene, 9,9-bis (4- (meth) acryloyloxyethoxy-3-ethylphenyl) fluorene, etc. 9 such as 9-bis (C _1-4 alkyl- (meth) acryloyloxy C _2-4 alkoxyphenyl) fluorene, 9,9-bis (4- (meth) acryloyloxyethoxy-3,5-dimethylphenyl) fluorene , 9-bis (diC _1-4 alkyl- (meth) acryloyloxy C _2-4 alkoxyphenyl) fluorene and the like], 9,9-bis (cycloalkyl- (meth) acryloyloxyalkoxyphenyl) fluorene [9,9 -9,9- such as bis (4- (meth) acryloyloxyethoxy-3-cyclohexylphenyl) fluorene Bis (C _5-8 cycloalkyl- (meth) acryloyloxy C _2-4 alkoxyphenyl) fluorene], 9,9-bis (aryl- (meth) acryloyloxyalkoxyphenyl) fluorene [9,9-bis (4- 9,9-bis (C _6-8 aryl- (meth) acryloyloxy C _2-4 alkoxyphenyl) fluorene, etc.] such as (meth) acryloyloxyethoxy-3-phenylphenyl) fluorene, 9 corresponding to these compounds , 9-bis ((meth) acryloyloxypolyalkoxyphenyl) fluorenes [e.g., 9,9 such as 9,9-bis {4- [2- (2- (2- (meth) acryloyloxyethoxy) ethoxy] phenyl} fluorene) - bis {((meth) acryloyloxy C _2-4 alkoxy) C _2-4 alkoxyphenyl} fluorene Etc.] and the like; these correspond to the compound 9,9-bis [di (hydroxy) phenyl] alkylene oxide adducts of fluorenes of (C _2-4 alkylene oxide adducts) (meth) acrylate (di- to tetra (meth ) acrylates, especially tetra (meth) acrylate) {e.g., 9,9-bis [3,4-di (2- (meth) acryloyloxy C _2-4 alkoxy) phenyl] fluorene such as 9,9-bis [di (Hydroxyalkoxy) phenyl] fluorene di- to tetra (meth) acrylate, 9,9-bis {3,4-di [2- (2- (meth) acryloyloxy C _2-4 alkoxy) C _2-4 alkoxy ] 9} -bis [di (hydroxypolyalkoxy) phenyl] fluorene such as phenyl} fluorene }; These correspond to the compound 9,9-bis [tri (hydroxymethyl) phenyl] alkylene oxide adducts of fluorenes of (C _2-4 alkylene oxide adducts) (meth) acrylate (di- to hexa (meth) acrylate , in particular hexa (meth) acrylate) {e.g., 9,9-bis [3,4,5-tri (2- (meth) acryloyloxy C _2-4 alkoxy) phenyl] fluorene such as 9,9-bis [tri (Hydroxyalkoxy) phenyl] fluorene di to hexa (meth) acrylate, 9,9-bis {3,4,5-tri [2- (2- (meth) acryloyloxy C _2-4alkoxy ) C _{2- 4} alkoxy] phenyl} fluorene 9,9-bis [tri (hydroxy polyalkoxy) phenyl] di- to hexa (meth) acrylate fluorene Rate, etc.} and the like.

  Polyfunctional (meth) acrylates having a fluorene skeleton may be used alone or in combination of two or more.

In addition, the polyfunctional (meth) acrylate which has a fluorene skeleton may use a commercial item, and may use what was manufactured. Such polyfunctional (meth) acrylates have the corresponding 9,9-bis (hydroxyphenyl) fluorenes [ie, 9,9-bis (monohydroxyphenyl) fluorenes, 9,9-bis (dihydroxyphenyl) Fluorenes, or 9,9-bis (trihydroxyphenyl) fluorenes] or an alkylene oxide adduct thereof, and (meth) acrylic acid or a derivative thereof [for example, (meth) acrylic acid lower alkyl ester (for example, (meth) Methyl acrylate, ethyl (meth) acrylate, C _1-4 alkyl (meth) acrylate such as butyl (meth) acrylate), (meth) acrylic acid halide (such as (meth) acrylic acid chloride), etc.] It can manufacture by making it react.

Representative 9,9-bis (hydroxyphenyl) fluorenes include 9,9-bis (monohydroxyphenyl) fluorenes {eg, 9,9-bis (hydroxyphenyl) fluorene [9,9-bis (4 -Hydroxyphenyl) fluorene and the like], 9,9-bis (alkyl-hydroxyphenyl) fluorene [9,9-bis (4-hydroxy-3-methylphenyl) fluorene, 9,9-bis (4-hydroxy-3- Ethylphenyl) fluorene, 9,9-bis (4-hydroxy-2-methylphenyl) fluorene, 9,9-bis (3-hydroxy-6-methylphenyl) fluorene, 9,9-bis (2-hydroxy-4) -Methylphenyl) fluorene, 9,9-bis (4-hydroxy-3,5-dimethylphenyl) fluorene, 9,9-bi (4-hydroxy-2,6-dimethylphenyl) fluorene, 9,9-bis (4-hydroxy-3,5-di -t- butyl phenyl) fluorene such as 9,9-bis (mono- or di-C _{1- 4} alkyl-hydroxyphenyl) fluorene and the like], 9,9-bis (cycloalkyl-hydroxyphenyl) fluorene [9,9-bis (4-hydroxy-3-cyclohexylphenyl) fluorene and other 9,9-bis (C _{5 -8} cycloalkyl-monohydroxyphenyl) fluorene and the like], 9,9-bis (aryl-hydroxyphenyl) fluorene [for example, 9,9- such as 9,9-bis (4-hydroxy-3-phenylphenyl) fluorene. bis (C _6-8 aryl - hydroxyphenyl) fluorene, etc.], etc.}; 9,9-bis (dihydroxyphenyl) Luolenes {for example, 9,9-bis (dihydroxyphenyl) fluorene [9,9-bis (3,4-dihydroxyphenyl) fluorene, 9,9-bis (2,4-dihydroxyphenyl) fluorene, 9,9- Bis (2,5-dihydroxyphenyl) fluorene, 9,9-bis (3,5-dihydroxyphenyl) fluorene, 9,9-bis (2,3-dihydroxyphenyl) fluorene, 9,9-bis (2,6 -Dihydroxyphenyl) fluorene and the like], 9,9-bis (alkyl-dihydroxyphenyl) fluorene [9,9-bis (3,4-dihydroxy-5-methylphenyl) fluorene, 9,9-bis (2,4- dihydroxy-3,6-dimethylphenyl) fluorene such as 9,9-bis (mono- or di-C _1-4 alkyl - dihydroxy Eniru) fluorene, etc.], 9,9-bis (aryl - dihydroxyphenyl) fluorene [e.g., 9,9-bis (3,4-dihydroxy-5-phenylphenyl) fluorene such as 9,9-bis (C _{6- 8} aryl-dihydroxyphenyl) fluorene and the like]; 9,9-bis (trihydroxyphenyl) fluorenes [eg, 9,9-bis (3,4,5-trihydroxyphenyl) fluorene, 9,9-bis (2,4,6-trihydroxyphenyl) fluorene, 9,9-bis (2,4,5-trihydroxyphenyl) fluorene, 9,9-bis (2,3,4-trihydroxyphenyl) fluorene, 9 , 9-bis (2,3,5-trihydroxyphenyl) fluorene, 9,9-bis (2,3,6-trihydroxyphenyl) fluorene 9,9-bis such Ren (trihydroxyphenyl) fluorene, etc.] is included.

  Note that bis (monohydroxyphenyl) fluorenes can be prepared by various synthesis methods, for example, (a) a method of reacting a fluorenone with a phenol in the presence of hydrogen chloride gas and mercaptocarboxylic acid (reference [J. Appl. Polym. Sci., 27 (9), 3289, 1982], JP-A-6-145087, JP-A-8-217713), (b) 9-fluorenone in the presence of an acid catalyst (and alkyl mercaptan) A method of reacting alkylphenols (JP 2000-26349 A), (c) a method of reacting fluorenones and phenols in the presence of hydrochloric acid and thiols (such as mercaptocarboxylic acid) (JP 2002-47227 A). (D), (d) in the presence of sulfuric acid and thiols (such as mercaptocarboxylic acid), fluorenones and phenols are reacted to form hydrocarbons It can be produced by using a method of producing bisphenolfluorene by crystallization with a crystallization solvent composed of a kind and a polar solvent (Japanese Patent Laid-Open No. 2003-221352).

  In addition, 9,9-bis (di- or trihydroxyphenyl) fluorenes can be obtained by using the corresponding polyhydric alcohols (dihydroxy) instead of phenols in the above-mentioned 9,9-bis (monohydroxyphenyl) fluorenes production method. Phenols and trihydroxyphenols).

Furthermore, although the manufacturing method of the alkylene oxide adduct of 9,9-bis (monohydroxyphenyl) fluorene is not specifically limited, For example, 9,9-bis (hydroxyphenyl) fluorene and corresponding alkylene oxide (C _2-4 alkylene oxide) or alkylene carbonate (C _2-4 alkylene carbonate), if necessary, in the presence of a catalyst (such as a base catalyst) or a phenoxy C _2-4 alcohol corresponding to fluorenone It may be produced by a method of reacting with (for example, JP-A-11-349657). Moreover, the alkylene oxide adduct of 9,9-bis (di or trihydroxyphenyl) fluorenes is replaced with 9,9-bis (hydroxyphenyl) fluorenes or phenoxy C _2-4 alcohols in the above production method. The corresponding alcohols [9,9-bis (di or trihydroxyphenyl) fluorenes, di or tri (hydroxy C _2-4 alkoxy) benzenes, etc.] can be used.

(Hydrolytic condensable organosilicon compound having a polymerizable group)
A hydrolyzable condensable organosilicon compound having a polymerizable group (polymerizable functional group, radical polymerizable group, photopolymerizable group) (hereinafter sometimes simply referred to as an organosilicon compound) is a polymerizable group (in detail). Is a hydrolytic condensable group (for example, an alkoxy group, an aryloxy group, a halogen atom such as a chlorine atom) having a polyfunctional (meth) acrylate copolymerizable group) and directly bonded to a silicon atom. Although it will not specifically limit if it is a compound which has at least 1 atom), For example, the compound etc. which are represented by following formula (2) are mentioned.

_{X- (A) c -Si (OR} 4) a (R 5) 3-a (2)
[Wherein, X represents a polymerizable group, A represents a linking group, R ⁴ represents a hydrocarbon group or a group — [(R ⁶ O) _b —R ⁷ ] (wherein R ⁶ represents an alkylene group) R ⁷ is a hydrocarbon group, b is an integer of 1 or more, and R ⁵ is a hydrogen atom, a hydroxyl group, a halogen atom or a hydrocarbon group. a represents an integer of 1 to 3, and c represents 0 or 1. ]
In the above formula (2), examples of the polymerizable group (or a group containing a polymerizable group) include alkenyl groups (for example, C _2-6 alkenyl groups such as vinyl groups and allyl groups, preferably C _2-4 alkenyl groups). Group, more preferably C _2-3 alkenyl group), (meth) acryloyl group and the like. From the viewpoint of polymerizability, a (meth) acryloyl group, particularly an acryloyloxy group is preferred.

The polymerizable group may be bonded to a silicon atom via a linking group. In the formula (2), the linking group A is a divalent hydrocarbon group [for example, an alkylene group (including an alkylene group such as a methylene group, the same applies hereinafter) (for example, a methylene group, an ethylene group, a propylene group, a trimethylene group). A C _1-10 alkylene group such as a butylene group, preferably a C _1-6 alkylene group, more preferably a C _2-4 alkylene group, and a cycloalkylene group (eg, a C _5-8 cycloalkylene such as a cyclohexylene group). Group), arylene group (for example, C _6-10 arylene group such as phenylene group)], oxyalkylene group [for example, oxymethylene group, oxyethylene group, oxypropylene group (oxytrimethylene group), oxybutylene oxy C _1-10 alkylene group such group, preferably oxy C _1-6 alkylene group, more preferably oxy C _2-4 a Such Killen group], an imino group (-NH-), iminoalkylene group (iminomethylene group, Iminoechiren group, imino C _1-10 alkylene group such as imino trimethylene group, preferably imino C _1-6 alkylene group, further preferably such imino C _2-4 alkylene group), an oxyalkylene imino alkylene group (e.g., oxy-C _2-6 alkylene such as oxytrimethylene imino trimethylene group - imino -C _2-6 alkylene group, preferably oxy C _{2 -4} alkylene-imino-C _2-4 alkylene group, etc.). These linking groups may have a substituent such as a hydroxyl group. The number c of linking groups may be 0 or 1, and can be appropriately selected according to the type of the linking group. When the polymerizable group is a (meth) acryloyl group, c is usually 1 in many cases.

In the above formula (2), representative units [X— (A) _c ] — include alkenyl groups (for example, vinyl group, allyl group, etc.), (meth) acryloyloxyalkyl groups, (meth) acryloyloxyalkyls. Examples include aminoalkyl groups, and particularly include (meth) acryloyl groups such as (meth) acryloyloxyalkyl groups (for example, (meth) acryloyloxy C _2-4 alkyl groups such as (meth) acryloyloxypropyl groups). Groups are preferred.

In the formula (2), examples of the hydrocarbon group represented by the group R ⁴ (and the group R ⁷ ) include C _1-6 such as an alkyl group (for example, a methyl group, an ethyl group, a propyl group, a butyl group). An alkyl group, preferably a C _1-4 alkyl group, more preferably a C _1-2 alkyl group, etc., an aryl group (eg, a C _6-10 aryl group such as a phenyl group, a tolyl group, preferably a C _6-8 aryl group) Group) and the like. In the group —O — [(R ⁶ O) _b —R ⁷ ], the alkylene group represented by the group R ⁶ is not limited, and examples thereof include a C _2-4 alkylene group (ethylene group, trimethylene group, Propylene group, butane-1,2-diyl group, etc.) can be exemplified, and C _2-3 alkylene groups (particularly ethylene groups, propylene groups) are particularly preferable. The addition number b of the alkyleneoxy (R ⁶ O) unit may be 1 or more, and may be, for example, 1 to 4, preferably 1 to 2, and more preferably 1. Preferred groups -O-[(R ⁶ O) _b -R ⁷ ] include C _1-4 alkoxy C _2-4 alkoxy groups such as 2-methoxyethoxy group and 2-ethoxyethoxy group (particularly C _{1 -2} alkoxyethoxy group) and the like.

Moreover, the preferable substitution number a is 2-3, More preferably, it is 3. In addition, when the substitution number a is plural, the plural groups R ⁴ may be the same or different.

Examples of the halogen atom represented by the group R ⁵ include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom. Examples of the hydrocarbon group represented by the group R ⁵ include an alkyl group (for example, a C _1-8 alkyl group such as a methyl group, an ethyl group, and a propyl group, preferably a C _1-6 alkyl group, more preferably Is a C _1-4 alkyl group), an alkenyl group (for example, a C _2-6 alkenyl group such as a vinyl group or an allyl group, preferably a C _2-4 alkenyl group, more preferably a C _2-3 alkenyl group), cycloalkyl Group (for example, C _5-8 cycloalkyl group such as cyclohexyl group), aryl group (for example, C _6-15 aryl group such as phenyl group, tolyl group, xylyl group, preferably C _6-10 aryl group, more preferably Is a C _6-8 aryl group). Among these, preferred hydrocarbon groups (hydrocarbon groups which may have a substituent) include alkyl groups (C _1-6 alkyl groups, etc.), aryl groups (C _6-10 aryl groups, etc.) and the like. included.

Note that the hydrocarbon group represented by the group R ⁵ may have a substituent. Examples of the substituent substituted on the hydrocarbon group (such as the hydrocarbon group exemplified above) include, for example, a halogen atom (chlorine atom, bromine atom, etc., particularly chlorine atom), an amino group, or an N-substituted amino group [for example, amino Alkylamino groups (such as amino C _2-4 alkylamino groups such as 2-aminoethylamino group), alkenylamino groups (such as C _2-4 alkenylamino groups such as allylamino group), alkenylaminoalkyl groups (allylaminopropyl group) Etc.], mercapto group (or substituted mercapto group), epoxy group-containing group [epoxy cycloalkyl group (epoxy C _3-8 cyclohexyl group such as 3,4-epoxy cyclohexyl group, preferably epoxy C _5-8 cycloalkyl group) group, more preferably an epoxy C _5-6 cycloalkyl group), glycidyl group, (meth) Such as Riroiruokishi group, and the like. These substituents may be substituted alone or in combination of two or more with a hydrocarbon group. Among these substituents, when the number of substitutions (3-a) is plural, the plural groups R ⁵ may be the same or different.

As a typical organosilicon compound represented by the formula (2), for example, monoalkoxysilanes having a polymerizable group {for example, monoalkoxysilane having an alkenyl group [for example, alkenyldialkylalkoxysilane (for example, vinyl C _2-4 alkenyl-diC _1-4 alkyl-C _1-4 alkoxysilane, etc.)], etc.], dialkoxysilanes having a polymerizable group {eg, dialkoxysilanes having an alkenyl group [For example, alkenyl alkyl dialkoxy silane (eg, C _2-4 alkenyl C _1-4 alkyl di C _1-4 alkoxy silane such as vinyl dimethoxymethyl silane, vinyl diethoxymethyl silane), dialkenyl dialkoxy silane (eg, divinyl Dimethoxysilane, divinyldiethoxysilane, etc. Di C _2-4 Arukeniruji C _1-4 alkoxysilane), etc.], (meth) acrylate dialkoxysilane having acryloyloxy group [for example, (meth) acryloyloxy alkyl dialkoxy silanes (e.g., 3- (meth) acryloyloxy Propylmethyldimethoxysilane, (meth) acryloyloxy C _2-4 alkyl C _1-4 alkyldi C _1-4 alkoxysilane, etc.) such as 3- (meth) acryloyloxypropylmethyldiethoxysilane], etc.], polymerizable group And trialkoxysilanes having a polymerizable group, triaryloxysilanes having a polymerizable group, and mono- to trihalosilanes corresponding to these.

Trialkoxysilanes having a polymerizable group include trialkoxysilanes having an alkenyl group {for example, alkenyltrialkoxysilane [for example, vinyltrimethoxysilane, vinyltriethoxysilane, vinyltripropoxysilane, vinyltriisopropoxysilane, vinyl tri (t-butoxy) silane, allyl trimethoxy silane, C _2-4 Arukenirutori C _1-4 alkoxysilane such as allyl triethoxysilane, Arukenirutori (alkoxyalkoxy) silane [e.g., vinyl tri (2-methoxyethoxy) C _2-4 Arukenirutori such as a silane (C _1-4 alkoxy C _2-4 alkoxy) silane], etc.}, (meth) trialkoxysilane having an acryloyloxy group {e.g., (meth) acryloyloxy alkyl trialkoxy Lan [e.g., 2- (meth) acryloyloxyethyltrimethoxysilane, 2- (meth) acryloyloxyethyltriethoxysilane, 3- (meth) acryloyloxypropyltrimethoxysilane, 3- (meth) acryloyloxypropyltriethoxy (Meth) acryloyloxyalkyltri C _1-4 alkoxysilanes such as silane, 3- (meth) acryloyloxypropyltripropoxysilane, preferably (meth) acryloyloxy C _2-4 alkyltri C _1-4 alkoxysilane, preferably (meth) acryloyloxy C _2-4 alkyl tri C _1-2 alkoxysilane, etc.], (meth) acryloyloxy alkyl tri (alkoxyalkoxy) silane [e.g., 3- (meth) acryloyloxy propyl tris (2-methoxy Butoxy) such as silane, preferably (meth) acryloyloxy C _2-4 alkyl tri (C _1-4 alkoxy C _2-4 alkoxy) silane, more preferably (meth) acryloyloxy C _2-4 alkyl tri (C _{1 -2} alkoxy C _2-4 alkoxy) silane, etc.], (meth) acryloyloxy alkyl aminoalkyl trialkoxysilane [e.g., N-(3- (meth) acryloyloxy 2-hydroxypropyl) -3-aminopropyltriethoxysilane (Meth) acryloyloxyalkylaminoalkyltri-C _1-4 alkoxysilane, such as [(meth) acryloyloxy C _2-4 alkyl] amino C _2-4 alkyltri-C _1-4 alkoxysilane, etc.], more preferably the [(meth) acryloyloxy C _2-4 alkyl] amino C _2-4 alkyl tri _1-2 alkoxysilane, etc.], etc.} and the like.

Examples of the triaryloxysilane having a polymerizable group include triaryloxysilane having an alkenyl group [for example, C _2-4 alkenyltri C _6-10 such as alkenyltriaryloxysilane (for example, vinyltriphenoxysilane). Aryloxysilane)], triaryloxysilane having a (meth) acryloyloxy group {e.g. (meth) acryloyloxyalkyltriaryloxysilane [e.g. 3- (meth) acryloyloxypropyltriphenoxy silane ( Meth) acryloyloxyalkyltri-C _6-10 aryloxysilane, preferably (meth) acryloyloxy C _2-4 alkyltri-C _6-8 aryloxysilane, etc.].

  These organosilicon compounds may be used alone or in combination of two or more.

Among these organosilicon compounds, from the viewpoint of polymerizability, a hydrolytic condensable organosilicon compound having a (meth) acryloyl group [for example, (meth) acryloyloxyalkyltri-C _1-4 alkoxysilane, (meth) acryloyloxy Trialkoxysilanes having a (meth) acryloyl group such as alkyltri (C _1-4 alkoxyC _2-4 alkoxy) silane, (meth) acryloyloxyalkylaminoalkyltriC _1-4 alkoxysilane; (meth) acryloyloxyalkyl _{Triaryloxysilane} having a (meth) acryloyl group such as tri-C _{6-10 aryloxysilane} ] is preferable.

  As described above, the organosilicon compound having a polymerizable group includes a partial condensate in which a hydrolytic condensable group is partially condensed. That is, in the composition of the present invention, the organosilicon compound having a polymerizable group is in the form of a partial condensate (condensate, oligomer) obtained by partially condensing the organosilicon compound (the organosilicon compound illustrated above). You may comprise the composition of invention. Such a partial condensate may be a partial condensate of an organosilicon compound having a polymerizable group, and an organosilicon compound having a polymerizable group and other hydrolyzable compounds (polymerizable groups described later). The composition may be configured in the form of a partial condensate that is partially condensed with an organosilicon compound that is not present, a non-silicon hydrolytic condensable organometallic compound, and the like.

  The degree of condensation (partial condensation) is not particularly limited as long as such a partial condensate can maintain a sol state (or a hydrolysis-condensable group remains) before curing. The partial condensate may be a network-like partial condensate (or partial condensate), or may be a linear or linear partial condensate. Usually, a partial condensate such as a trialkoxysilane having a polymerizable group or a triaryloxysilane having a polymerizable group may be a network (or three-dimensional network) condensate.

  The proportion of the hydrolyzable condensable organosilicon compound having a polymerizable group [in the case of a partial condensate, converted into a monomer or oligomer before hydrolysis, hereinafter the same for the proportion of the partial condensate] is a polyfunctional having a fluorene skeleton. Can be selected from the range of about 10 to 2000 parts by weight, for example, 30 to 1000 parts by weight, preferably 40 to 800 parts by weight (for example, 50 to 700 parts by weight) Preferably, it may be about 50 to 500 parts by weight (for example, 100 to 450 parts by weight).

  The composition of the present invention may further contain a hydrolysis-condensable organometallic compound that is not included in the hydrolysis-condensable organosilicon compound having a polymerizable group, if necessary. Examples of such an organometallic compound include a hydrolytic condensable organosilicon compound having no polymerizable group, a non-silicon hydrolytic condensable organometallic compound, and the like. The composition of the present invention may contain a combination of a hydrolytic condensable organosilicon compound having no polymerizable group and a non-silicon hydrolytic condensable organometallic compound.

(Hydrolytic condensable organosilicon compound having no polymerizable group)
Hydrolytic condensable organosilicon compounds having no polymerizable group (or non-radical polymerizable) (hereinafter sometimes simply referred to as organosilicon compounds having no polymerizable group) are hydrolyzed directly bonded to silicon atoms. Any compound having at least one condensable group may be used. Usually, a compound represented by the following formula (3), an oligomer of a compound represented by the following formula (3), a compound represented by the following formula (3) These partial condensates can be preferably used.

Si (OR ⁸ ) _d (R ⁹ ) _4-d (3)
[Wherein R ⁸ is a hydrocarbon group or group — [(R ¹⁰ O) _e —R ¹¹ ] (wherein R ¹⁰ is an alkylene group, R ¹¹ is a hydrocarbon group, and e is 1 R ⁹ represents a hydrogen atom, a hydroxyl group, a halogen atom or a hydrocarbon group. d shows the integer of 1-4. ]
In the above formula (3), examples of the hydrocarbon group represented by the group R ⁸ (and the group R ¹¹ ) include the hydrocarbon groups exemplified in the section of the compound represented by the formula (2) (for example, C _{1- 6} alkyl group, C _6-10 aryl group, etc.). In the group —O — [(R ¹⁰ O) _e —R ¹¹ ], the alkylene group R ¹⁰ is the same as the alkylene group exemplified in the section of the compound represented by the formula (2), and e is It is the same as b in Formula (2).

In the formula (3), the halogen atom and hydrocarbon group represented by the group R ⁹ are also the same as the halogen atom and hydrocarbon group exemplified in the section of the compound represented by the formula (2). However, when the group R ⁹ is a hydrocarbon group, the hydrocarbon group does not have a polymerizable group (such as an alkenylamino group or a (meth) acryloyloxy group) as a substituent. The preferred substitution number d is 2 to 4, more preferably 3 or 4. In addition, when the substitution number d is plural, the plural groups R ⁹ may be the same or different.

  Typical organosilicon compounds represented by the formula (3) include monoalkoxysilanes (eg, alkenyldialkylalkoxysilanes such as vinyldimethylethoxysilane), dialkoxysilanes, trialkoxysilanes, tetraalkoxys. Examples thereof include silanes and tetraaryloxysilanes.

The dialkoxysilane, for example, dialkyl dialkoxy silanes (e.g., dimethyldimethoxysilane, and di C _1-4 alkyl di C _1-4 alkoxysilane such as dimethyl diethoxy silane); diaryl dialkoxy silanes (e.g., diphenyldimethoxysilane Silane, di-C _6-10 aryl di-C _1-4 alkoxy silane such as diphenyldiethoxy silane); dialkoxy silane having an epoxy group {eg (glycidyloxyalkyl) alkyl dialkoxy silane [eg 3-glycidyloxypropyl amino, such as etc. (glycidyloxy C _2-4 alkyl) C _1-4 alkyl di C _1-4 alkoxysilane]}, dialkoxysilane having an amino group (e.g., 3-aminopropyl methyl dimethoxy silane, methyl dimethoxy silane _2-4 alkyl C _1-4 alkyl di C _1-4 alkoxysilane; 3- [N- (2- aminoethyl) amino] (amino C _2-4 alkylamino), such as methyldimethoxysilane C _1-4 alkyl - C _1-4 alkyldiC _1-4 alkoxysilane), dialkoxysilane having a mercapto group (for example, mercapto C _2-4 alkyl C _1-4 alkyldiC _1-4 alkoxysilane such as 3-mercaptopropylmethyldimethoxysilane) Dialkoxysilane having a substituent (for example, at least one substituent selected from an epoxy group, an amino group, a mercapto group, and a halogen atom).

Examples of trialkoxysilanes include trialkoxysilanes (eg, tri-C _1-4 alkoxysilanes such as trimethoxysilane, triethoxysilane, and tripropoxysilane); alkyltrialkoxysilanes (eg, methyltrimethoxysilane, C _1-4 alkyl tri C _1-4 alkoxy silane such as ethyl trimethoxy silane, propyl trimethoxy silane, isopropyl trimethoxy silane, methyl triethoxy silane, ethyl triethoxy silane, propyl triethoxy silane, isopropyl triethoxy silane, etc.) Aryltrialkoxysilanes (eg C _6-10 aryltriC _1-4 alkoxysilanes such as phenyltrimethoxysilane, phenyltriethoxysilane, phenyltripropoxysilane, preferably C _6-8 aliquots); Rutori C _1-4 alkoxysilane, more preferably such C _6-8 Arirutori C _1-2 alkoxysilane); haloalkyl trialkoxysilane (e.g., 2-chloroethyl trimethoxysilane, 2-chloroethyl triethoxy silane, 3- Chloro C _2-4 alkyl tri C _1-4 alkoxysilanes such as chloropropyltrimethoxysilane, 3-chloropropyltriethoxysilane), trialkoxysilanes having an epoxy group {for example, (glycidyloxyalkyl) trialkoxysilane ( for example, 2-glycidyloxy ethyltrimethoxysilane, 2- glycidyloxy triethoxysilane, 3-glycidyloxypropyltrimethoxysilane, 3-glycidyloxy C _2-4 Arukiruto such glycidyloxypropyltriethoxysilane Such as C _1-4 alkoxysilane), epoxy cycloalkyl trimethoxysilane [e.g., 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyl triethoxysilane, 3- (Epoxy C _5-8 cycloalkyl C _2-4 alkyl tri-C _1-4 alkoxysilane etc. such as 3,4-epoxycyclohexyl) propyltrimethoxysilane etc.]}, trialkoxysilane having an amino group (for example, 2- Amino C _2-4 alkyltri C _1-4 alkoxysilanes such as aminoethyltrimethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane; 2- [N- (2-aminoethyl) amino] Ethyltrimethoxysilane, 3- [N- (2-aminoethyl) amino] B pills trimethoxysilane such as N- (amino C _2-4 alkyl) such as amino C _2-4 alkyl tri C _1-4 alkoxy silane), trialkoxysilane having a mercapto group (e.g., 2-mercaptoethyl trimethoxysilane Substituents such as, for example, epoxy groups, amino groups, mercapto groups, and halogens such as mercapto C _2-4 alkyltri C _1-4 alkoxysilanes such as 3-mercaptopropyltrimethoxysilane and 3-mercaptopropyltriethoxysilane And trialkoxysilane having at least one substituent selected from atoms.

Tetraalkoxysilanes include tetraalkoxysilanes corresponding to the above-exemplified di- or trialkoxysilanes, for example, tetra-C _1-4 alkoxysilanes such as tetramethoxysilane, tetraethoxysilane, tetrapropoxysilane, and tetrabutoxysilane Is mentioned. Examples of the tetraaryloxysilane include tetraaryloxysilane [eg, tetra C _6-10 aryloxy silane such as tetraphenoxy silane, preferably tetra C _6-8 aryloxy silane].

  As an oligomer of the compound represented by the formula (3), an oligomer of an alkoxysilane represented by the formula (3) (for example, dialkoxysilanes, trialkoxysilanes, tetraalkoxysilanes exemplified above). (Or a condensate). Such an oligomer may be an oligomer of a single organosilicon compound, or a condensate of a plurality of organosilicon compounds (for example, an oligomer of trialkoxysilanes and tetraalkoxysilanes, different tetraalkoxysilanes) And the like. The oligomer may be a condensate of an organosilicon compound usually composed of at least one selected from trialkoxysilanes, tetraalkoxysilanes, and tetraaryloxysilanes.

  The number average degree of polymerization of the oligomer may be, for example, 2 to 10, preferably 2 to 8, and more preferably about 3 to 6.

  The oligomer may be a linear or linear condensate (or partial condensate).

  Representative oligomers include trialkoxysilanes, tetraalkoxysilanes (tetraalkoxysilanes exemplified above), condensates (partial condensates) of tetraaryloxysilanes, and the like. The tetraalkoxysilane condensate (oligomer) includes a linear alkoxysilane condensate represented by the following formula (4).

(Wherein R ¹² represents an alkyl group, and f represents an integer of 2 or more)
In the above formula (4), examples of the group R ¹² include the alkyl groups exemplified above, and preferred groups R ¹² include C _1-4 alkyl groups such as a methyl group, an ethyl group, and a propyl group (particularly C _{1- 2} alkyl group) and the like. As described above, the plurality of groups R ¹² may be the same group or different groups. Further, the preferable degree of condensation (degree of polymerization) f may be, for example, about 2 to 8, preferably about 2 to 6, and more preferably about 3 to 5.

Examples of the hydrolytic condensable organosilicon compound having no polymerizable group include trialkoxysilane [eg, aryltrialkoxysilane (eg, C _6-8 aryltri C _1-4 alkoxysilane etc.)], tetraalkoxysilane [ For example, tetraalkoxy silane (tetra C _1-4 alkoxy silane etc.), tetraaryloxy silane (eg tetra C _6-8 aryloxy silane such as tetraphenoxy silane), oligomers of these compounds [eg tetra alkoxy Silane (eg, oligomers of tetra C _1-4 alkoxysilane)] and the like.

  As in the case of the organosilicon compound having a polymerizable group, the organosilicon compound having no polymerizable group includes a partial condensate in which a hydrolytic condensable group is partially condensed. That is, in the composition of the present invention, the organosilicon compound having no polymerizable group is in the form of a partial condensate (condensate or oligomer) obtained by partially condensing the organosilicon compound (the exemplified organosilicon compound). You may comprise the composition of this invention. Such a partial condensate may be a partial condensate of an organosilicon compound having no polymerizable group, and an organosilicon compound having no polymerizable group and another hydrolyzable compound (the polymerizable compound described above). The composition may be configured in the form of a partial condensate obtained by partially condensing an organosilicon compound having a group and a non-silicon hydrolytic condensable organometallic compound described later.

  The degree of condensation (partial condensation) is not particularly limited as long as such a partial condensate can maintain a sol state (or a hydrolysis-condensable group remains) before curing.

  The organosilicon compounds having no polymerizable group may be used alone or in combination of two or more.

  When the composition of the present invention contains a hydrolyzable condensable organosilicon compound having no polymerizable group, the proportion of the hydrolyzable condensable organosilicon compound having no polymerizable group is a polyfunctional (meta-functional) compound having a fluorene skeleton. ) It can be selected from the range of about 10 to 2000 parts by weight with respect to 100 parts by weight of acrylate, for example, 30 to 1000 parts by weight, preferably 40 to 800 parts by weight (for example, 50 to 700 parts by weight), and more preferably 50 About 500 parts by weight (for example, 100 to 450 parts by weight) may be used.

(Non-silicon hydrolytic condensable organometallic compound)
Examples of the non-silicon hydrolytic condensable organometallic compound (hereinafter sometimes simply referred to as non-silicon based organometallic compound) include non-silicon based metal alkoxides or partial condensates thereof. Examples of the non-silicon metal alkoxide include metal alkoxides of non-silicon metals selected from titanium, zirconium, aluminum, and zinc, for example, metal alkoxides represented by the following formula (5).

M (OR ¹³ ) _m (R ¹⁴ ) _n (5)
[Wherein M represents titanium, zirconium, aluminum or zinc. R ¹³ is an alkyl group or a group _{^{- [(R 15 O) g}} -R 16] ( wherein, R ¹⁵ is an alkylene group, R ¹⁶ is an alkyl group, g is an integer of 1 or more) , R ¹⁴ represents a hydrogen atom, a hydroxyl group, a halogen atom or an optionally substituted hydrocarbon group, m represents an integer of 1 or more, and n represents 0 or an integer of 1 or more. ]
In the formula (5), examples of the alkyl group represented by the group R ¹³ (and the group R ¹⁶ ) include C _1-18 alkyl groups such as methyl group, ethyl group, propyl group, and butyl group, preferably C Examples thereof include a _1-10 alkyl group, more preferably a C _1-6 alkyl group (for example, a C _1-4 alkyl group). Examples of the halogen atom represented by the group R ¹⁴ include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. Further, in the polyalkoxy group represented by the group —O — [(R ¹⁵ O) _g —R ¹⁶ ], the alkylene group represented by the group R ¹⁵ is not limited, but for example, a C _2-4 alkylene group. (Ethylene group, trimethylene group, propylene group, butane-1,2-diyl group, etc.) can be exemplified, and C _2-3 alkylene groups (particularly ethylene groups, propylene groups) are particularly preferable. The addition number g of alkyleneoxy (R ¹⁵ O) units may be 1 or more, and may be, for example, 1 to 4, preferably 1 to 2, and more preferably 1. Preferred polyalkoxy groups include C _1-4 alkoxy C _2-4 alkoxy groups (particularly C _1-2 alkoxyethoxy groups) such as 2-methoxyethoxy group and 2-ethoxyethoxy group.

Moreover, the preferable substitution number m of an alkoxy group is about 2-4 according to the kind of metal atom M, for example. In addition, when the substitution number m is plural, the plural groups R ¹³ may be the same or different.

Examples of the hydrocarbon group represented by the group R ¹⁴ include the same hydrocarbon groups as the group R ⁵ exemplified in the section of the compound represented by the formula (2), for example, an alkyl group (for example, C _1-6 Alkyl group, etc.), aryl groups (eg C _6-10 aryl group, etc.) and the like. In addition, the hydrocarbon group represented by the group R ¹⁴ may have the same substituent as the group R ⁵ . In addition, the preferable substitution number n is 0-2. When the number of substitutions n is plural, the plural groups R ¹⁴ may be the same or different.

Typical non-silicon metal alkoxides include aluminum alkoxides [for example, trialkoxyaluminum (trimethoxyaluminum, triethoxyaluminum, tripropoxyaluminum, tri-n-butoxyaluminum, tris-butoxyaluminum, tri-t-butoxyaluminum). tri C _1-4 alkoxy aluminum, etc.), etc.], such as titanium alkoxides [e.g., dialkoxy titanium dialkyl dialkoxy titanium (Jiarukiruji C _1-4 alkoxy titanium such as diethyl diethoxy titanium); trialkoxy titanium (e.g. , Tri-C _1-4 alkoxy titanium such as trimethoxy titanium), alkyl trialkoxy titanium (eg, alkyl tri-C _1-4 alkoxy titanium such as ethyl trimethoxy titanium), Trialkoxytitanium such as reeltrialkoxytitanium (eg aryltri C _1-4 alkoxytitanium such as phenyltrimethoxytitanium); tetraalkoxytitanium (eg tetramethoxytitanium, tetraethoxytitanium, tetrapropoxytitanium, tetraisopropoxytitanium, Tetraisobutoxy titanium, tetra n-butoxy titanium, tetra t-butoxy titanium, tetranonyloxy titanium, tetrakis (2-ethylhexyloxy) titanium, tetrakis (methoxypropoxy) titanium, tetrastearyloxy titanium, tetraisostearyloxy titanium, etc. tetra C _1-18 alkoxy, such as titanium), etc.], zirconium alkoxides [e.g., tetraalkoxy zirconium (e.g., tetramethoxysilane zirconium, tetra Butoxy zirconium, tetra-iso-propoxy zirconium, tetraisobutoxy zirconium, tetra-n- butoxy zirconium, tetra-t- butoxy zirconium, tetrakis (2-ethylhexyl oxy) zirconium, tetra C ₁ such as tetrakis (2-methyl-2-butoxy) zirconium _-18 alkoxyzirconium etc.)], zinc alkoxides (eg bismethoxyethoxyzinc etc.) and the like.

  Note that the non-silicon metal alkoxide may form a complex (metal complex). In the complex, the ligand (or the compound forming the ligand) is not particularly limited, but in particular, an organic compound [a chelate-forming organic compound (for example, having a β-diketone structure such as acetylacetone or acetoacetate). And the like. Since such a metal complex is excellent in solubility in a solvent, it can be suitably used.

  In addition, the non-silicon-type organometallic compound may comprise the composition of this invention with the form of the partial condensate which the hydrolytic condensable group partially condensed like the above. Such a partial condensate may be a partial condensate of the silicon-based organometallic compound, the non-silicon-based organometallic compound, and other hydrolyzable compounds (the organosilicon compound having the polymerizable group, The composition may be configured in the form of a partial condensate obtained by partial condensation with an organosilicon compound having no polymerizable group.

  The degree of condensation (partial condensation) is not particularly limited as long as such a partial condensate can maintain a sol state (or a hydrolysis-condensable group remains) before curing.

  Non-silicon-based organometallic compounds may be used alone or in combination of two or more.

  When the composition of the present invention contains a non-silicon hydrolytic condensable organometallic compound, the ratio of the non-silicon hydrocondensable organometallic compound is 100 parts by weight of a polyfunctional (meth) acrylate having a fluorene skeleton. On the other hand, it can be selected from the range of about 50 to 5000 parts by weight, for example, 100 to 4000 parts by weight, preferably 150 to 3000 parts by weight, more preferably 200 to 2000 parts by weight (for example, 300 to 1000 parts by weight). There may be.

  In addition, when a hydrolytic condensable organosilicon compound having no polymerizable group and a non-silicon hydrolytic condensable organometallic compound are combined, the hydrolytic condensable organosilicon compound having no polymerizable group and a non-silicon based The ratio with the hydrolytic condensable organometallic compound is the former / the latter = 90/10/1/99, preferably 80 / 20-3 / 97, more preferably 60 / 40-5 / 95 (for example, 40/60 ~ 7/93), in particular about 30 / 70-8 / 92.

(Photoacid generator)
The photoacid generator is not particularly limited as long as it is a compound (component) that generates an acid by the action of light, and a conventional compound can be used. For example, an onium salt, a metallocene complex, and the like can be preferably used. Examples of the onium salts include diazonium salts, sulfonium salts, iodonium salts, phosphonium salts, selenium salts, and the counter ions include CF ₃ SO ₃ ⁻ , BF ₄ ⁻ , PF ₆ ⁻ , AsF ₆ ⁻ and SbF. ₆ ^- anion, such as is used.

Typical photoacid generators include sulfonium salts {for example, triarylsulfonium salts [triphenylsulfonium triflate, triphenylsulfonium hexafluoroantimonate, triphenylsulfonium hexafluorophosphate, (4-phenylthiophenyl) diphenylsulfonium Hexafluoroantimonate, triphenylsulfonium salts such as (4-phenylthiophenyl) diphenylsulfonium hexafluorophosphate], bis [4- (diphenylsulfonio) phenyl] sulfide-bis-hexafluoroantimonate, bis [4- (Diphenylsulfonio) phenyl] sulfide-bis-hexafluorophosphate, (4-methoxyphenyl) diphenylsulfonium hexafluoroan Monate), etc., diazonium salts (such as 4-chlorobenzenediazonium hexafluorophosphate), iodonium salts {eg, bis (alkylaryl) iodonium salts [eg, bis (4-t-butylphenyl) iodonium hexafluorophosphate, etc. Alkylphenyl) iodonium salts], alkoxycarbonylalkoxy-trialkylaryliodonium salts [e.g. 4-[(1-ethoxycarbonyl-ethoxy) phenyl]-(2,4,6-trimethylphenyl) -iodonium hexafluorophosphate, etc. ], Bis (alkoxyaryl) iodonium salts [for example, bis (alkoxyphenyl) iodonium such as (4-methoxyphenyl) phenyliodonium hexafluoroantimonate Such unsalted] etc.}, (such as benzyl triphenyl phosphonium hexafluoroantimonate) phosphonium salts, (such as triphenyl selenium hexafluorophosphate) selenium salts, metallocene complexes [e.g., (eta ⁵ or eta ⁶ - isopropylbenzene) (eta ⁵ -cyclopentadienyl) iron (II) hexafluorophosphate etc.].

  The photoacid generator also includes a compound having the function of a photoradical initiator. Examples of such a photoacid generator include a compound represented by the following formula (6).

(Wherein R ¹⁷ , R ¹⁸ and R ¹⁹ are substituents, p, q and r are the same or different and each represents an integer of 0 to 5, Y represents a hydrogen atom, a halogen atom, a nitro group or an alkyl group.)
In the above formula (6), examples of the substituent represented by R ¹⁷ , R ¹⁸ and R ¹⁹ include a hydrocarbon group [for example, an alkyl group (for example, a C _1-4 alkyl group such as a methyl group), etc. ], An alkoxy group (for example, a C _1-4 alkoxy group such as a methoxy group), a halogen atom (such as a chlorine atom), a functional group (such as a hydroxyl group, an amino group, and a substituted amino group). R ¹⁷ , R ¹⁸ and R ¹⁹ may be the same or different. Note that p, q and r are each preferably 0 to 3, more preferably 0 or 1, particularly 0.

In the group Y of the formula (6), examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom, and a chlorine atom is particularly preferable. In the group Y, examples of the alkyl group include a C _1-10 alkyl group such as a methyl group, an ethyl group, a propyl group, and an isopropyl group, preferably a C _1-6 alkyl group, and more preferably a C _1-4 alkyl group. Groups and the like. Particularly preferred groups Y include methyl groups.

  Among these photoacid generators, onium salts [especially sulfonium salts (such as triarylsulfonium salts), iodonium salts (such as bis (alkylaryl) iodonium salts)], compounds represented by the above formula (6), and the like. preferable. You may use a photo-acid generator individually or in combination of 2 or more types.

  The ratio of the photoacid generator can be selected from the range of about 0.1 to 10 parts by weight with respect to 100 parts by weight of the polyfunctional (meth) acrylate having a fluorene skeleton. For example, it may be about 1 to 10 parts by weight), preferably about 0.5 to 5 parts by weight, and more preferably about 1 to 5 parts by weight (for example, 1 to 3 parts by weight). Moreover, the ratio of a photo-acid generator can be selected from the range of about 0.01-8 weight part with respect to 100 weight part of hydrolysis-condensable organosilicon compounds which have a polymeric group, for example, 0.02-5 Even if it is a weight part (for example, 0.03-3 weight part), Preferably it is 0.05-3 weight part, More preferably, it is about 0.08-2 weight part (for example, 0.1-1 weight part). Good. Furthermore, when the composition contains a hydrolytic condensable organometallic compound other than the hydrolytic condensable organosilicon compound having a polymerizable group, the ratio of the photoacid generator is the total amount of the hydrolytic condensable organometallic compound (for example, , The total amount of the hydrolytic condensable organosilicon compound having a polymerizable group and the hydrolytic condensable organosilicon compound and / or the non-silicon hydrolytic condensable organometallic compound having no polymerizable group) to 100 parts by weight For example, it may be about 0.001 to 5 parts by weight, preferably about 0.005 to 3 parts by weight, and more preferably about 0.001 to 2 parts by weight. In addition, the usage-amount of the said photo-acid generator may be 10 weight% or less of the whole said composition (coating liquid) containing a solvent, Preferably it may be 1-5 weight%.

  In the present invention, the polyfunctional (meth) acrylate, the organosilicon compound having a polymerizable group (radical polymerizable group), and the photoacid generator are combined, so that the cured product is obtained by hydrolysis condensation and radical polymerization by sol-gel reaction. Can be obtained. Therefore, the composition of the present invention may contain a polymerization initiator (radical polymerization initiator) in order to promote the radical polymerization.

  Such a polymerization initiator includes a photo radical initiator, a thermal polymerization initiator, and the like. In particular, the composition of the present invention is preferably a composition (photopolymerizable composition) containing at least a photoradical initiator from the viewpoint of causing hydrolytic condensation with a photoacid generator. By combining a photo radical generator and a photo acid generator, hydrolytic condensation and radical polymerization can be caused by irradiation with light. Efficient optical properties (high transparency, etc.) and mechanical properties ( A cured product having high hardness or the like can be obtained.

(Photo radical initiator)
Examples of the photo radical initiator (photo polymerization initiator, photo radical generator) include benzoins (benzoin alkyl ethers such as benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, and benzoin isobutyl ether), acetophenone (Acetophenone, p-dimethylacetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 2,2-dimethoxy-2-phenylacetophenone, 2,2-diethoxy-2-phenylacetophenone, 1, 1-dichloroacetophenone, 1-hydroxycyclohexyl phenyl ketone, etc.), aminoacetophenones {2-methyl-2-morpholino (4-thiomethylphenyl) propan-1-one, 2-benzyl-2-dimethyl Ruamino-1- (4-morpholinophenyl) -butanone-1}, anthraquinones (anthraquinone, 2-methylanthraquinone, 2-ethylanthraquinone, 2-t-butylanthraquinone, 1-chloroanthraquinone, etc.), (thio) xanthone (Thioxanthone, 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone, 2-chlorothioxanthone, 2,4-diisopropylthioxanthone, etc.), ketals (acetophenone dimethyl ketal, benzyldimethyl ketal, etc.), benzophenones (benzophenone, etc.) ), Benzoates (methyl o-benzoylbenzoate, p-dimethylaminobenzoate, etc.), sulfides (benzyldiphenyl sulfide), acylphosphine oxides S, camphor quinone, and others. These photo radical initiators can be used alone or in combination of two or more according to the desired performance.

  The ratio of the photo radical initiator can be selected from the range of about 0.1 to 10 parts by weight, for example, 0.5 to 10 parts by weight with respect to 100 parts by weight of the polyfunctional (meth) acrylate having a fluorene skeleton. Part (for example, 1 to 10 parts by weight), preferably 0.5 to 5 parts by weight, more preferably about 1 to 5 parts by weight (for example, 1 to 3 parts by weight). The ratio of the photo radical initiator is 0.01 to 8 parts by weight with respect to 100 parts by weight of the total amount of the polyfunctional (meth) acrylate having a fluorene skeleton and the hydrolytic condensable organosilicon compound having a polymerizable group. For example, 0.02 to 5 parts by weight (for example, 0.03 to 3 parts by weight), preferably 0.05 to 3 parts by weight, and more preferably 0.08 to 2 parts by weight (for example, 0.1-1 part by weight). In addition, the usage-amount of the said photoradical initiator may be 10 weight% or less of the whole said composition (coating liquid) containing a solvent, Preferably it may be 1-5 weight%.

  The photo radical initiator may be combined with a photo sensitizer. 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.

  In addition, as the thermal polymerization initiator, dialkyl peroxides (di-t-butyl peroxide, dicumyl peroxide, etc.), diacyl peroxides [dialkanoyl peroxide (lauroyl peroxide, etc.), dialoyl peroxide ( Benzoyl peroxide, benzoyl toluyl peroxide, toluyl peroxide, etc.)], peracid esters [percarboxylic acid alkyl esters such as t-butyl peracetate, t-butyl peroxy octoate, t-butyl peroxybenzoate, etc.] ], Peroxides such as ketone peroxides, peroxycarbonates, peroxyketals; azonitrile compounds [2,2′-azobis (2,4-dimethylvaleronitrile), 2,2′-azobis (isobutyronitrite) ), 2,2′-azobis (2-methylbutyronitrile), 2,2′-azobis (4-methoxy-2,4-dimethylvaleronitrile)], azoamide compound {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 compound [2,2′-azobis (2,4,4-trimethylpentane), 4,4′-azobis ( 4-cyanopentanoic acid), etc.], and azo compounds having an oxime skeleton [2,2′-azobis (2-methylpropionamidooxime), etc.] . You may use a thermal-polymerization initiator individually or in combination of 2 or more types.

  In addition, the composition of this invention may contain the additive as needed. Such additives include, for example, pigments, colorants, thickeners, sensitizers, antifoaming agents, leveling agents, coatability improvers, lubricants, stabilizers (antioxidants, heat stabilizers, light-resistant stability). Agents, light stabilizers, etc.), ultraviolet absorbers, plasticizers, surfactants, dissolution accelerators, fillers, antistatic agents, curing agents, polysilanes (polysilanes described in JP-A-2002-348357, etc.), etc. Can be mentioned. These additives may be used alone or in combination of two or more.

  The composition may contain a solvent. The composition containing such a solvent can be suitably used as, for example, a coating liquid for forming a coating film (cured coating film) on a substrate. The solvent constituting such a coating solution is not particularly limited, and is a conventional solvent, for example, hydrocarbons (aliphatic hydrocarbons such as pentane and hexane, alicyclic hydrocarbons such as cyclohexane, toluene, Aromatic hydrocarbons such as xylene), halogenated solvents (haloalkanes such as dichloromethane, haloarenes such as monochlorobenzene), alcohols (such as alkyl alcohols such as methanol, ethanol, propanol), diols (ethylene glycol, Alkanediols such as propylene glycol, (poly) oxyalkylene glycols such as diethylene glycol and polyoxyethylene glycol), ethers (chain ethers such as diethyl ether, cyclic ethers such as tetrahydrofuran), Steal (acetic esters such as ethyl acetate, ethyl lactate, etc.), ketones (dialkyl ketones such as acetone, ethyl methyl ketone, 2-butanone, cyclic ketones such as cyclopentanone, cyclohexanone, etc.), glycol ether esters (Ethylene glycol monomethyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol methyl acetate, cellosolve acetate, etc.), glycol ethers [eg, methyl cellosolve, ethyl cellosolve, diethylene glycol methyl ethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, Propylene glycol monomethyl ether, diglyme, dimethoxyethane, etc.) And the like. These solvents may be used alone or in combination of two or more. In the composition containing a solvent, each solid component (polyfunctional (meth) acrylate, organosilicon compound having a polymerizable group, photoacid generator, etc.) may be dissolved or dispersed in the solvent. Moreover, the ratio of a solvent can be suitably adjusted according to the viscosity of a coating liquid.

  The composition of the present invention may be prepared by a conventional method, for example, the polyfunctional (meth) acrylate having the fluorene skeleton, the organosilicon compound having the polymerizable group, the photoacid generator, and the other as necessary. The above components (organic silicon compound having no polymerizable group, non-silicon hydrolytic condensable organometallic compound, solvent, etc.) can be mixed.

  For example, when the composition of the present invention is used as a coating solution, the polyfunctional (meth) acrylate having the fluorene skeleton, the organosilicon compound having the polymerizable group, and the photoacid generator (if necessary) And other components) may be mixed (or dissolved or dispersed) in a solvent.

  Further, partial condensation in which a hydrolytic condensable organometallic compound such as an organosilicon compound having a polymerizable group, an organosilicon compound not having the polymerizable group, or a non-silicon hydrolytic condensable organometallic compound is partially condensed. For example, the product (partial condensation sol) is obtained by dispersing or dissolving the monomer and / or oligomer corresponding to the partial condensate in an appropriate solvent (for example, the above-mentioned solvents such as tetrahydrofuran, propylene glycol monomethyl ether acetate, and ethyl lactate). And heated (heat treatment) in the presence of an acid catalyst (an inorganic acid such as hydrochloric acid, or an organic acid such as formic acid or oxalic acid). In the heat treatment, the heating temperature and the heating time can be appropriately selected, and the heating temperature may be, for example, about 40 ° C to 100 ° C, preferably about 60 to 80 ° C. In the preparation of such a partial condensate, if necessary, water or the like may be mixed to promote hydrolysis condensation.

  When using a partial condensate, the composition of the present invention can be prepared by mixing the partial condensate prepared in advance as described above with other components (polyfunctional (meth) acrylate, etc.). Well, after mixing each component (polyfunctional (meth) acrylate, photoacid generator, organosilicon compound having a polymerizable group that is not partially condensed, and solvent, etc.), it is then partially condensed as described above. Also good.

[Hardened product and production method thereof]
The cured product of the present invention (cured product obtained by curing (or crosslinking) the polymerizable composition) is produced by irradiating the composition with light and curing (or crosslinking) by curing reaction (or crosslinking reaction). Can be prepared. In a practical method, the polymerizable composition is applied onto a substrate to form a coating film, and then light-irradiated (or further heated after light irradiation as necessary) to cure the present invention. Products (cured films, cured patterns, etc.) may be prepared. That is, in the present invention, an acid (or acid catalyst) (and radical) generated by light irradiation is used to hydrolyze and condense an organosilicon compound having a polymerizable group, and a polyfunctional (meth) acrylate and an organosilicon compound Is cured to produce a cured product (hybrid cured product).

  The cured product (organic-inorganic hybrid cured product) is not particularly limited, and may be a three-dimensional cured product, a one-dimensional or two-dimensional cured product such as a cured film or a cured pattern, or a dot or dot-shaped cured product. . The polymerizable composition of the present invention is particularly suitable for producing a thin film on a substrate. As described above, the cured product obtained by such a method is excellent in adhesion to the substrate, hard coat property (or hardness), heat resistance, visible light transparency, etc., solvent resistance, low shrinkage, low It has water absorption, and has a high refractive index and good water repellency.

  For example, the refractive index of the cured product of the present invention is 1.50 or more (for example, about 1.51 to 1.9), preferably 1.52 or more (for example, about 1.53 to 1.87), and more preferably. Is 1.54 or more (for example, about 1.55 to 1.85), and 1.6 or more [for example, 1.62 to 1.84, preferably 1.63 to 1.83, more preferably 1. 64 to 1.82].

  In the composition used for coating the substrate, the hydrolytic condensable organometallic compound (at least the hydrolytic condensable organosilicon compound having a polymerizable group) may be a compound that is not partially condensed. In order to make the hydrolysis condensation in the material proceed more efficiently, as described above, it was a partially condensed hydrolysis-condensable organometallic compound (hydrolyzable-condensable organosilicon compound having at least a polymerizable group). May be. Such a partial condensate (partial condensate sol) may be a partial condensate of the organosilicon compound having the polymerizable group, and the organosilicon compound having the polymerizable group and other hydrolytic condensable organic metal. It may be a partial cocondensate with a compound (for example, an organosilicon compound having no polymerizable group and / or a non-silicon hydrolytic condensable organometallic compound).

  Examples of the coating method include flow coating method, spin coating method, spray coating method, screen printing method, cast method, bar coating method, curtain coating method, roll coating method, gravure coating method, dipping method, slit method and the like. be able to.

  The thickness of the coating film can be selected from a range of about 0.01 μm to 10 mm depending on the use of the cured product. For example, in the case of a photoresist, the thickness is about 0.05 to 10 μm (particularly 0.1 to 5 μm). In the case of a printed circuit board, it may be about 10 μm to 5 mm (particularly 100 μm to 1 mm), and in the case of an optical thin film, it may be about 0.1 to 100 μm (particularly 0.3 to 50 μm).

The light to be irradiated or exposed may be, for example, gamma rays, X-rays, ultraviolet rays, visible rays, etc., and is usually visible rays or ultraviolet rays, particularly ultraviolet rays in many cases. The wavelength of light is, for example, about 150 to 800 nm, preferably 150 to 600 nm, more preferably about 200 to 400 nm (particularly 300 to 400 nm). Irradiation dose may vary depending on the thickness of the coating film, for example, 100~10000mJ / cm ^2, preferably 500~5000mJ / cm ^2, more preferably about 1000~3000mJ / cm ^2. The light source can be selected according to the type of light beam to be exposed. For example, in the case of ultraviolet rays, a low pressure mercury lamp, a high pressure mercury lamp, an ultrahigh pressure mercury lamp, a deuterium lamp, a halogen lamp, a laser beam (helium-cadmium laser, Excimer laser etc.) can be used. By such light irradiation, the curing (and polymerization) reaction of the composition proceeds.

  When the coating film (or coating film) is heated (heat treatment) by a heating step, curing or crosslinking reaction (and sol-gel reaction) and radical polymerization reaction are promoted, and high degree of three-dimensional crosslinking occurs, and the hardness of the coating film becomes higher. A cured product (cured coating film) can be obtained. Heating of the coating film is usually performed after light irradiation or with light irradiation, and is usually performed after light irradiation (after-cure) in many cases. The heating temperature may be, for example, about 60 to 250 ° C, preferably about 100 to 200 ° C. The heating time may be, for example, 5 seconds or more (for example, about 10 seconds to 5 hours), 1 minute to 4 hours, preferably about 10 minutes to 3 hours, and usually 20 minutes to 2.5 hours ( For example, it may be about 30 minutes to 2 hours.

  Furthermore, when forming a pattern or an image (for example, when manufacturing a printed wiring board etc.), the coating film formed on the base material may be subjected to pattern exposure, and this pattern exposure is performed by scanning with a laser beam. Alternatively, light irradiation may be performed through a photomask. A pattern or an image can be formed by developing (or dissolving) a non-irradiated region (unexposed portion) generated by such pattern exposure with a developer. Developers include water, alkaline aqueous solutions, hydrophilic solvents (for example, alcohols such as methanol, ethanol and isopropanol, ketones such as acetone, ethers such as dioxane and tetrahydrofuran, cellosolves, cellosolve acetates, etc.) A mixture of these can be used.

  When the coating is heated after the exposure, the development step may be performed before the heating step or after the heating step. In such a method, a fine and highly accurate pattern can be formed on a substrate even with a small exposure amount. Therefore, the resin composition of the present invention is suitable for applications requiring a precise pattern, for example, the production of printed wiring boards for electronic devices.

  When forming an optical thin film, a plurality of layers of the photopolymerizable resin composition may be formed on a substrate. Moreover, after forming another functional layer etc. on a base material, you may form the layer formed with the said photopolymerizable resin composition on the functional layer. The cured product of the present invention is excellent in visible light transmittance and hard coat properties, has a high refractive index, and is excellent in optical properties. Suitable for optical thin films such as plates.

  The material of the base material is selected according to the application. For example, in the case of a printed wiring board or an optical thin film, a semiconductor such as silicon, gallium arsenide, gallium nitride, or silicon carbide, a metal such as aluminum or copper, zirconium oxide, Ceramics such as titanium oxide and PZT, transparent inorganic materials (such as glass, quartz, magnesium fluoride, and calcium fluoride), transparent resins (such as polymethyl methacrylate, polymethyl acrylate, and polystyrene) are used.

  The polymerizable composition of the present invention is a paint, an insulating material for electrical equipment, a wire coating material, a sealing material for electronic equipment, a printed wiring board, a protective film, a photoresist, a printing plate making material, an ink, an adhesive, an adhesive, It can be used for a wide range of applications such as a high refractive index layer of an antireflection film such as a liquid crystal display, a reflection plate, and the like.

  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
Acrylic ester of 9,9-bis [4- (2-hydroxyethoxy) phenyl] fluorene [ie, 9,9-bis (4-acryloyloxyethoxyphenyl) fluorene] 0.1 g, acryloyloxypropyltrimethoxysilane 0 .4 g, tetrahydrofuran (THF) 1 g, photoradical initiator (2-hydroxy-2-methyl-1-phenylpropan-1-one, manufactured by Ciba Specialty Chemicals, trade name “Darocur 1173”) 2 mg, And a photo acid generator [4- (1-ethoxycarbonylethoxy) phenyl-2 ′, 4 ′, 6′-trimethylphenyliodonium hexafluorophosphate, manufactured by Nippon Soda Co., Ltd.] 2 mg, A glass substrate was spin coated to form a film. The obtained coating film was irradiated with ultraviolet rays (1300 mJ / cm ² ) to produce a hybrid film by curing of acrylate and sol-gel reaction. Further, the obtained hybrid film was after-cured at 150 ° C. for 1.5 hours to obtain a strong and transparent film. The resulting film had a refractive index of 1.55 and high heat resistance.

(Example 2)
9,9-bis [4- (2-hydroxyethoxy) phenyl] fluorene acrylate ester 0.1 g, acryloyloxypropyltrimethoxysilane 0.2 g, phenyltrimethoxysilane 0.2 g, THF 1 g, photoradical initiator ( 2-hydroxy-2-methyl-1-phenylpropan-1-one, manufactured by Ciba Specialty Chemicals Co., Ltd., trade name “Darocur 1173”) 2 mg, and photoacid generator [4- (1-ethoxycarbonylethoxy ) Phenyl-2 ′, 4 ′, 6′-trimethylphenyliodonium hexafluorophosphate, manufactured by Nippon Soda Co., Ltd.] A coating solution prepared by adding 2 mg was spin-coated on a glass substrate to form a film. The obtained coating film was irradiated with ultraviolet rays (1300 mJ / cm ² ), and a hybrid film was prepared by curing of acrylate and sol-gel reaction. Further, the obtained hybrid film was after-cured at 150 ° C. for 1.5 hours to obtain a strong and transparent film. The obtained film had a refractive index of 1.57 and high heat resistance.

(Example 3)
Acrylic ester of 9,9-bis [4- (2-hydroxyethoxy) phenyl] fluorene 0.1 g, 0.2 g of acryloyloxypropyltrimethoxysilane, 0.2 g of phenyltrimethoxysilane, 1 g of THF, 2 g of tetraisopropoxytitanium , And photo radical initiator (2-hydroxy-2-methyl-1-phenylpropan-1-one, manufactured by Ciba Specialty Chemicals, trade name “Darocur 1173”), 2 mg of photoacid generator [4- (1-Ethoxycarbonylethoxy) phenyl-2 ′, 4 ′, 6′-trimethylphenyliodonium hexafluorophosphate, Nippon Soda Co., Ltd.] 2 mg of the coating solution prepared by spin coating on a glass substrate Filmed. The obtained coating film was irradiated with ultraviolet rays (1300 mJ / cm ² ), and a hybrid film was prepared by curing of acrylate and sol-gel reaction. Further, the obtained hybrid film was after-cured at 150 ° C. for 1.5 hours to obtain a strong and transparent film. The obtained film had a refractive index of 1.65 and high heat resistance.

Example 4
-Preparation of partially condensed sol 1 g of acrylic acid ester of 9,9-bis [4- (2-hydroxyethoxy) phenyl] fluorene and 4 g of 3-acryloyloxypropyltrimethoxysilane (APTMS) were dissolved in 5 ml of tetrahydrofuran (THF). After adding 0.5 g of water and 40.5 mg of formic acid, the mixture was stirred at 60 ° C. for 2 hours, cooled, and then partially condensed silica sol (solid content 25%) was prepared.

-Preparation of cured film 0.4 g of the above partial condensation sol (0.1 g in terms of solid content), 10 g of THF, photo radical initiator (2-hydroxy-2-methyl-1-phenylpropan-1-one, Ciba Specialty Chemicals) 2 mg, photo acid generator [4- (1-ethoxycarbonylethoxy) phenyl-2 ′, 4 ′, 6′-trimethylphenyliodonium hexafluorophosphate, Nippon Soda Co., Ltd. )] A coating solution prepared by adding 2 mg was spin-coated on a glass substrate to form a film. The obtained coating film was irradiated with ultraviolet rays (1300 mJ / cm ² ), and a hybrid film was prepared by curing of acrylate and sol-gel reaction. The obtained hybrid film was after-cured at 150 ° C. for 1.5 hours to obtain a strong and transparent film (film thickness: 86 nm). The obtained film had a refractive index of 1.56 and high heat resistance.

(Example 5)
Preparation of partially condensed sol 3-acryloyloxypropyltrimethoxysilane (APTMS) 4 g was dissolved in tetrahydrofuran (THF) 5 ml, water 0.5 g and formic acid 40.5 mg were added, and the mixture was stirred at 60 ° C. for 2 hours. After cooling, a partially condensed silica sol (solid content 25%) was prepared.

-Preparation of cured film 9,9-bis [4- (2-hydroxyethoxy) phenyl] fluorene acrylic ester 0.1 g, partial condensation sol 0.4 g (0.1 g in terms of solid content), THF 10 g, photoradical 2 mg of initiator (2-hydroxy-2-methyl-1-phenylpropan-1-one, manufactured by Ciba Specialty Chemicals, trade name “Darocur 1173”), and photoacid generator [4- (1- [Ethoxycarbonylethoxy) phenyl-2 ′, 4 ′, 6′-trimethylphenyliodonium hexafluorophosphate, Nippon Soda Co., Ltd.] 2 mg of the coating solution prepared by spin coating on a glass substrate to form a film. The obtained coating film was irradiated with ultraviolet rays (1300 mJ / cm ² ), and a hybrid film was prepared by curing of acrylate and sol-gel reaction. The obtained hybrid film was after-cured at 150 ° C. for 1.5 hours to obtain a strong and transparent film (film thickness: 86 nm). The obtained film had a refractive index of 1.56 and high heat resistance.

(Example 6)
-Preparation of partially condensed sol 3-acryloyloxypropyltrimethoxysilane (APTMS) 2.07g, phenyltrimethoxysilane (PTMS) 1.98g was dissolved in tetrahydrofuran (THF) 5ml, water 0.5g and formic acid 40.5mg. Then, the mixture was stirred at 60 ° C. for 2 hours, cooled, and partially condensed silica sol (solid content: 27.2%) was prepared.

Preparation of cured film 9,9-bis [4- (2-hydroxyethoxy) phenyl] fluorene acrylate ester 0.1 g, partial condensation sol 0.37 (0.1 g in terms of solid content), THF 10 g, photoradical 2 mg of initiator (2-hydroxy-2-methyl-1-phenylpropan-1-one, manufactured by Ciba Specialty Chemicals, trade name “Darocur 1173”), and photoacid generator [4- (1- [Ethoxycarbonylethoxy) phenyl-2 ′, 4 ′, 6′-trimethylphenyliodonium hexafluorophosphate, Nippon Soda Co., Ltd.] 2 mg of the coating solution prepared by spin coating on a glass substrate to form a film. The obtained coating film was irradiated with ultraviolet rays (1300 mJ / cm ² ), and a hybrid film was prepared by curing of acrylate and sol-gel reaction. The obtained hybrid film was after-cured at 150 ° C. for 1.5 hours to obtain a strong and transparent film (film thickness: 86 nm). The obtained film had a refractive index of 1.58 and high heat resistance.

(Example 7)
-Preparation of partially condensed sol 3-acryloyloxypropyltrimethoxysilane (APTMS) 2g, phenyltrimethoxysilane (PTMS) 2g and tetraisopropoxytitanium 20g were dissolved in tetrahydrofuran (THF) 10ml, formic acid 60mg was added, After stirring at 60 ° C. for 2 hours and cooling, a partially condensed sol was prepared (solid content about 17%).

-Preparation of cured film 9,9-bis [4- (2-hydroxyethoxy) phenyl] fluorene acrylate ester 0.1 g, partial condensation sol 0.56 g (solid content conversion 0.1 g), propylene glycol monomethyl ether 4 g of acetate (PGMEA), 2 mg of photo radical initiator (2-hydroxy-2-methyl-1-phenylpropan-1-one, manufactured by Ciba Specialty Chemicals, Inc., trade name “Darocur 1173”), and photoacid A coating solution prepared by adding 2 mg of a generator [4- (1-ethoxycarbonylethoxy) phenyl-2 ′, 4 ′, 6′-trimethylphenyliodonium hexafluorophosphate, manufactured by Nippon Soda Co., Ltd.] onto a glass substrate A film was formed by spin coating. The obtained coating film was irradiated with ultraviolet rays (1300 mJ / cm ² ), and a hybrid film was prepared by curing of acrylate and sol-gel reaction. The obtained hybrid film was after-cured at 150 ° C. for 1.5 hours to obtain a strong and transparent film (film thickness: 280 nm). The obtained film had a refractive index of 1.65 and high heat resistance.

(Example 8)
Acrylic ester of 9,9-bis [4- (2-hydroxyethoxy) phenyl] fluorene 0.1 g, 1.38 g partially condensed sol prepared in Example 7 (solid content 0.23 g), PGMEA 4 g, photoradical 4 mg of initiator (2-hydroxy-2-methyl-1-phenylpropan-1-one, manufactured by Ciba Specialty Chemicals, trade name “Darocur 1173”), and photoacid generator [4- (1- [Ethoxycarbonylethoxy) phenyl-2 ′, 4 ′, 6′-trimethylphenyliodonium hexafluorophosphate, Nippon Soda Co., Ltd.] 4 mg was added, and the coating solution obtained by diluting 10 times with THF was added to a glass substrate. The film was formed by spin coating. The obtained coating film was irradiated with ultraviolet rays (1300 mJ / cm ² ), and a hybrid film was prepared by curing of acrylate and sol-gel reaction. The obtained hybrid film was after-cured at 150 ° C. for 1.5 hours to obtain a strong and transparent film (film thickness 55 nm). The obtained film had a refractive index of 1.81 and high heat resistance.

(Comparative Example 1)
0.1 g of pentaerythritol triacrylate, 0.4 g of partially condensed sol prepared in Example 5 (0.1 g in terms of solid content), 10 g of THF, photoradical initiator (2-hydroxy-2-methyl-1-phenylpropane-1) -ON, 2 mg of Ciba Specialty Chemicals Co., Ltd., trade name "Darocur 1173"), and photoacid generator [4- (1-ethoxycarbonylethoxy) phenyl-2 ', 4', 6'-trimethylphenyl A coating solution prepared by adding 2 mg of iodonium hexafluorophosphate, manufactured by Nippon Soda Co., Ltd. was spin-coated onto a glass substrate to form a film. The obtained coating film was irradiated with ultraviolet rays (1300 mJ / cm ² ) to prepare a hybrid film by curing of acrylate and sol-gel reaction. The obtained hybrid film was after-cured at 150 ° C. for 1.5 hours to obtain a transparent film (film thickness: 86 nm). The refractive index of the obtained film was 1.48.

Claims (16)

A polymerizable composition comprising a polyfunctional (meth) acrylate represented by the following formula (1), a hydrolytic condensable organosilicon compound having a polymerizable group, and a photoacid generator.

(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 to 4, m1 and m2 are the same or different and represent an integer of 0 to 3, n1 and n2 are the same or different and represent an integer of 0 or 1 and p1 and p2 are the same Or it is different and represents an integer of 1 to 4, where m1 + p1 and m2 + p2 are each an integer of 1 to 5) The polymerizable composition according to claim 1, wherein, in formula (1), R ^3a and R ^3b are C _2-3 alkylene groups, n1 and n2 are each 1 or 2, and p1 and p2 are each 1 to 3. The polymerizable composition according to claim 1, wherein the hydrolytic condensable organosilicon compound having a polymerizable group is a compound represented by the following formula (2) or a partial condensate thereof.
_{X- (A) c -Si (OR} 4) a (R 5) 3-a (2)
[Wherein, X represents a polymerizable group, A represents a linking group, R ⁴ represents a hydrocarbon group or a group — [(R ⁶ O) _b —R ⁷ ] (wherein R ⁶ represents an alkylene group) R ⁷ is a hydrocarbon group, b is an integer of 1 or more, and R ⁵ is a hydrogen atom, a hydroxyl group, a halogen atom or a hydrocarbon group. a represents an integer of 1 to 3, and c represents 0 or 1. ]   The polymerizable composition according to claim 3, wherein in the formula (2), the polymerizable group is a (meth) acryloyl group. The compound represented by the formula (2) is (meth) acryloyloxyalkyltri-C _1-4 alkoxysilane, (meth) acryloyloxyalkyltri (C _1-4 alkoxyC _2-4 alkoxy) silane, (meth) acryloyl. The polymerizable composition according to claim 3, which is at least one selected from oxyalkylaminoalkyltri-C _1-4 alkoxysilane and (meth) acryloyloxyalkyltri-C _{6-10 aryloxysilane} . The polymerizable composition according to claim 1, wherein the photoacid generator is at least one selected from a triarylsulfonium salt, a bis (alkylaryl) iodonium salt, and a compound represented by the following formula (6).

(Wherein R ¹⁷ , R ¹⁸ and R ¹⁹ are substituents, p, q and r are the same or different and each represents an integer of 0 to 4, Y represents a hydrogen atom, a halogen atom, a nitro group or an alkyl group.)   The ratio of the hydrolytic condensable organosilicon compound having a polymerizable group is 50 to 700 parts by weight with respect to 100 parts by weight of the polyfunctional (meth) acrylate represented by the formula (1). The polymerizable composition according to claim 1, wherein the ratio is 0.5 to 5 parts by weight with respect to 100 parts by weight of the polyfunctional (meth) acrylate represented by the formula (1).   The polymerizable composition according to claim 1, further comprising a hydrolytic condensable organosilicon compound having no polymerizable group. Hydrolytic condensable organosilicon compound having no polymerizable group is a compound represented by the following formula (3), an oligomer of a compound represented by the following formula (3), or a compound represented by the following formula (3) The polymerizable composition according to claim 8, comprising a partial condensate of
Si (OR ⁸ ) _d (R ⁹ ) _4-d (3)
[Wherein R ⁸ is a hydrocarbon group or group — [(R ¹⁰ O) _e —R ¹¹ ] (wherein R ¹⁰ is an alkylene group, R ¹¹ is a hydrocarbon group, and e is 1 R ⁹ represents a hydrogen atom, a hydroxyl group, a halogen atom or a hydrocarbon group. d shows the integer of 1-4. ] No hydrolytic condensable organic silicon compound polymerizable group, C _6-8 Arirutori C _1-4 alkoxysilane, tetra C _1-4 alkoxy silanes, tetra C _6-8 aryloxy silane and tetra C _1-4, The polymerizable composition according to claim 8, comprising at least one compound selected from oligomers of alkoxysilanes or a partial condensate thereof.   The polymerizable composition according to claim 1, further comprising an alkoxide of a non-silicon metal selected from titanium, zirconium, aluminum, and zinc.   Furthermore, the polymeric composition of Claim 1 containing a photoradical initiator.   A method for producing a cured product of the polymerizable composition by applying the polymerizable composition according to claim 1 on a substrate to form a coating film and then irradiating with light.   The method of Claim 13 which heats after light irradiation.   The method according to claim 13, wherein a polymerizable composition obtained by partially condensing a hydrolytic condensable organosilicon compound having a polymerizable group is applied onto a substrate.   A cured product obtained by curing the polymerizable composition according to claim 1.