JP2012062398A - Curable composite composition and cured material thereof - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a curable composite composition and a cured material thereof which have excellent optical characteristics such as low color dispersion and high light transmittance, have heat resistance, hardness and processability, and additionally is improved in the heat-resistive retention property of a molded article under a severe mounting condition including a reflow condition.SOLUTION: The curable composite composition includes (A) component, which is a copolymer obtained from a monofunctional (meth)acrylate (a), a monofunctional (meth)acrylate (b) having an alcoholic hydroxyl group, a bifunctional (meth)acrylate (c), and 2,4-diphenyl-4-methyl-1-pentene (d), and having reactive (meth)acrylate groups originated from the bifunctional (meth)acrylate (c) on the side chains and structural units originated from the 2,4-diphenyl-4-methyl-1-pentene (d) on terminals; (B) component, which is a monomer having one or more functional groups having an unsaturated double bond; and (C) component, which is a silica particle having an average particle diameter of 1 to 100 nm.

Description

  The present invention has excellent optical properties such as low color dispersion and high light transmittance, heat resistance, hardness, and processability, and in addition, maintains the heat resistance of the shape of the molded product under severe mounting conditions such as reflow conditions. The present invention relates to a curable composite composition having improved properties and a cured product thereof.

  Thermosetting resin compositions are useful as, for example, mechanical component materials, electrical / electronic component materials, automotive component materials, civil engineering and building materials, molding materials, etc., and also used as materials for paints and adhesives It is. Furthermore, when a hybrid member is combined with an inorganic base material, not only can the thermal expansion coefficient be lowered, but also the appearance of the resin composition and its cured product can be controlled by combining the refractive index of the inorganic substance and the resin. Since transparency can also be expressed, it is particularly useful as a material in electrical / electronic component materials and optical applications. For example, digital camera modules are being miniaturized, such as being mounted on mobile phones, and cost reduction is also required. Furthermore, needs for new applications such as in-vehicle cameras and barcode readers for home delivery companies are increasing. When applying to these applications, not only is heat resistance required to maintain the shape so that the shape of the molded product does not change during solder reflow during manufacturing, but in consideration of high temperature exposure in summer, etc. during actual use, High reliability such as long-term heat resistance and low water absorption is required.

  In response to such technical requirements, Patent Document 1 contains (a) colloidal silica dispersed in an organic solvent, (b) an alicyclic polyepoxy compound, and (c) a metal chelate compound as essential components, and The blending ratio of the component (a) and the component (b) is a solid content ratio of (a) component 5 to 85% by weight and (b) component 95 to 15% by weight, and (c) component is the component (a) and An organic solvent-based thermosetting composition containing 0.01 to 30 parts by weight per 100 parts by weight of the total solid content of the component (b) is disclosed. Patent Documents 2 to 4 are epoxy resin moldings molded by curing a composition comprising at least an epoxy resin and inorganic oxide particles, and the average particle size in the molding is 50 nm or less. An epoxy resin molded body in which inorganic oxide particles are dispersed is disclosed. When the material obtained by the technique disclosed in these documents is subjected to a severe thermal history during reflow at a temperature of 280 ° C. or higher, the material is not resistant to heat discoloration and is subject to the thermal history. After that, it was necessary to improve the optical characteristics.

  On the other hand, in Patent Document 5, at least one (meth) acrylate (a) having a bifunctional condensed polycyclic alicyclic structure and silica fine particles (b) having an average particle diameter of 1 to 100 nm are organic. In the composite composition obtained by removing the organic solvent of the composition containing colloidal silica dispersed in a solvent, the composite composition having a silica fine particle (b) content of 30 to 90% by weight is crosslinked. A molded cured product is disclosed. However, the molded cured product obtained according to the technique of this document does not have the moldability necessary for continuously molding a highly accurate shape such as an optical lens or a prism.

Further, Patent Document 6 discloses an optical material containing a vinyl polymer having a repeating structural unit derived from a heteropolymerizable monomer having a specific structure and zirconium oxide particles having an average particle diameter of 1 nm to 100 nm. A curable resin composition is disclosed.
Here, zirconium oxide particles having an average particle diameter of 1 nm to 100 nm are used as the inorganic fine particles. When such a material is used as an optical lens for an imaging system, it becomes a highly dispersed material. Therefore, it is necessary to improve the optical characteristics in order to reduce light bleeding and a material having a high Abbe number. It was. In addition, when a severe thermal history is received during high-temperature reflow, the heat resistance related to shape maintenance is insufficient, and it is necessary to improve the optical characteristics after receiving the thermal history.

  When a curable composite composition produced according to the techniques disclosed in these documents is used, the properties such as low water absorption, moldability, heat resistance, and high transparency required in advanced optical lens / prism application fields. In addition to balance, it also has basic performance such as high heat resistance, shape accuracy, and heat-resistant shape retention stability. It has high optical properties and is suitable for continuous molding of various optical members. No curable composite composition as obtained has been obtained.

Japanese Patent No. 2865741 Japanese Patent Laid-Open No. 2004-250521 JP 2008-133439 A JP 2008-156625 A Japanese Patent No. 4008246 JP 2009-92598 A

  The present invention has excellent optical properties such as low color dispersion and high light transmittance, heat resistance, hardness, and processability, and in addition, maintains the heat resistance of the shape of the molded product under severe mounting conditions such as reflow conditions. An object of the present invention is to provide a curable composite composition having improved properties and a cured product thereof.

The present invention comprises (A) component: monofunctional (meth) acrylic acid ester (a) having an alicyclic structure, monofunctional (meth) acrylic acid ester (b) having an alcoholic hydroxyl group, and bifunctional (meth) acrylic. A copolymer obtained by copolymerizing an acid ester (c) and a component containing 2,4-diphenyl-4-methyl-1-pentene (d), wherein the side chain is bifunctional (meth) acrylic acid A copolymer having a reactive (meth) acrylate group derived from ester (c) and having a structural unit derived from 2,4-diphenyl-4-methyl-1-pentene (d) at the terminal, and having a weight average A soluble polyfunctional (meth) acrylic acid ester copolymer having a molecular weight of 2000 to 20000 and further soluble in toluene, xylene, tetrahydrofuran, dichloroethane or chloroform,
(B) component: a monomer having one or more functional groups having an unsaturated double bond and a molecular weight of 1000 or less, and (C) component: silica fine particles having an average particle diameter of 1 to 100 nm,
The compounding amount of the component (A) with respect to the sum of the components (A) and (B) is 2 to 83 wt%, the compounding amount of the component (B) is 83 to 2 wt%, (C ) A curable composite composition characterized in that the compounding amount of the component is 15 to 90 wt%.

The amount of 2,4-diphenyl-4-methyl-1-pentene (d) introduced into the component (A) is 0.02 to 0.35 as the molar fraction M _d represented by the following formula (1). Preferably there is. In addition, the amount of the reactive (meth) acrylate group derived from the bifunctional (meth) acrylic acid ester (c) in the component (A) introduced into the side chain is a mole fraction M represented by the following formula (2). _c1 is preferably 0.05 to 0.5.
M _d = (d) / [(a) + (b) + (c) + (d)] (1)
M _c1 = (c1) / [(a) + (b) + (c)] (2)
Here, (a), (b), (c) and (d) are structural units derived from monofunctional (meth) acrylic acid ester (a) having an alicyclic structure, and monofunctional having an alcoholic hydroxyl group. A structural unit derived from (meth) acrylic acid ester (b), a structural unit derived from bifunctional (meth) acrylic acid ester (c), and 2,4-diphenyl-4-methyl-1-pentene (d) The number of moles of the derived structural unit is shown. (C1) indicates the number of moles of the structural unit (c1) containing a bifunctional (meth) acrylate group in the side chain. The number of moles is calculated as the number of moles of the soluble polyfunctional (meth) acrylic acid ester copolymer per fixed weight (for example, mole / 100 g).

  Examples of the monofunctional (meth) acrylic acid ester (a) having an alicyclic structure include isobornyl methacrylate, isobornyl acrylate, cyclohexyl methacrylate, cyclohexyl acrylate, dicyclopentenyl acrylate, and dicyclopentenyloxyethyl. One or more alicyclic structures selected from the group consisting of acrylate, dicyclopentanyl acrylate, dicyclopentenyloxyethyl methacrylate, dicyclopentenyloxyethyl methacrylate, and dicyclopentanyl methacrylate A monofunctional (meth) acrylic acid ester having the above is preferred.

  The monofunctional (meth) acrylic acid ester (b) having an alcoholic hydroxyl group is selected from the group consisting of 2-hydroxypropyl methacrylate, 2-hydroxyethyl methacrylate and partially ethoxylated 2-tobyloxy methacrylate. Monofunctional (meth) acrylic acid esters are preferred.

  Examples of the bifunctional (meth) acrylic acid ester (c) include 1,4-butanediyl diacrylate, 1,6-hexanediyl diacrylate, 1,9-nonanediol diacrylate, and dimethylol tricyclodecane diacrylate. One or more bifunctional (meth) acrylic acid esters selected from the group are preferably mentioned.

  Monomers (meth) acrylates and bifunctional (meth) acrylates having an alicyclic structure as monomers having a molecular weight of 1000 or less and having one or more functional groups having an unsaturated double bond as component B One or more (meth) acrylic acid esters selected from are preferably mentioned.

  The curable composite composition of the present invention preferably further contains a photopolymerization initiator as the component (D).

  In addition, the present invention is a cured product obtained by curing the above curable composite composition. Furthermore, the present invention is an optical material formed from the above cured product. As the optical material, an optical plastic lens or a prism is preferably mentioned.

  According to the present invention, it has excellent optical properties such as low color dispersion and high light transmittance, heat resistance, hardness, and workability, and in addition, heat resistance of the shape of the molded product under severe mounting conditions such as reflow conditions. A curable composite composition having improved properties and a cured product thereof can be provided.

  Hereinafter, the curable composite composition of the present invention will be described in detail. Since the curable composite composition of this invention contains (A) component, (B) component, and (C) component as an essential component, it demonstrates from an essential component.

  The soluble polyfunctional (meth) acrylic acid ester copolymer (hereinafter sometimes abbreviated as copolymer) which is the component (A) of the present invention is a monofunctional (meth) acrylic acid ester having an alicyclic structure. (A) a monomer containing a monofunctional (meth) acrylic acid ester (b) having an alcoholic hydroxyl group and a bifunctional (meth) acrylic acid ester (c), and 2,4-diphenyl-4-methyl-1 A copolymer obtained by copolymerization in the presence of pentene (d), having a reactive (meth) acrylate group derived from a bifunctional (meth) acrylic acid ester (c) in the side chain; Furthermore, it is a soluble polyfunctional (meth) acrylate copolymer having a structural unit derived from 2,4-diphenyl-4-methyl-1-pentene (d) at the terminal. Here, soluble means that it is soluble in toluene, xylene, tetrahydrofuran, dichloroethane or chloroform. The solubility test is performed under the conditions shown in the synthesis examples. In addition, the monofunctional (meth) acrylic acid ester has one ethylenic double bond existing in the molecule, and the bifunctional (meth) acrylic acid ester is an ethylenic double bond existing in the molecule. It is understood that the number is two and the polyfunctional (meth) acrylic acid ester copolymer has two or more ethylenic double bonds present in the molecule. Moreover, monofunctional (meth) acrylic acid ester (a) having an alicyclic structure (a) component, monofunctional (meth) acrylic acid ester (b) having an alcoholic hydroxyl group (b) component, bifunctional ( The (meth) acrylic acid ester (c) is also referred to as component (c), and 2,4-diphenyl-4-methyl-1-pentene (d) is also referred to as component (d) or DMP. Here, when the monofunctional (meth) acrylic acid ester (a) having an alicyclic structure has an alcoholic hydroxyl group, or the monofunctional (meth) acrylic acid ester (b) having an alcoholic hydroxyl group is alicyclic. When it has a structure, it is understood that both are the component (a) and the component (b) at the same time. In addition, it is preferable that (a) component does not have an alcoholic hydroxyl group, and it is preferable that (b) component does not have an alicyclic structure.

  Since the copolymer is obtained by copolymerizing a monofunctional (meth) acrylic acid ester and a bifunctional (meth) acrylic acid ester, it has a branched structure or a crosslinked structure. Limited to the extent that it is soluble. Accordingly, the copolymer has a structural unit (c1) containing an unreacted (meth) acryl group derived from the bifunctional (meth) acrylic acid ester (c) in the side chain. This unreacted (meth) acrylic group is also referred to as a pendant (meth) acrylic group, and since this exhibits polymerizability, it can be polymerized by a further polymerization treatment to give a solvent-insoluble cured resin.

  Moreover, a copolymer has the structural unit derived from (d) component at the terminal. By introducing this structural unit at the terminal of the copolymer, a cured product having improved moldability such as releasability can be obtained.

  The copolymer has a structural unit derived from the component (a), a unit derived from the component (b), a structural unit derived from the component (c), and a structural unit derived from the component (d). Here, in the structural unit derived from the component (c), both of the polymerizable double bonds (referred to as vinyl groups) contained in the two (meth) acrylic acid esters are involved in the polymerization to form a branched structure or a crosslinked structure. There is a structural unit (c2) that forms, and a structural unit (c1) that contains an unreacted (meth) acrylic group in which only one vinyl group is involved in the polymerization and the other vinyl groups remain unreacted. Component (d), DMP, acts as a chain transfer agent to prevent an increase in molecular weight and exists at the end of the copolymer.

The introduction amount of the component (d) into the copolymer, as a molar fraction M _d represented by the following formula (1), 0.02 to 0.35, preferably 0.03 to 0.30, particularly preferably Is 0.05 to 0.15.
M _d = (d) / [(a) + (b) + (c) + (d)] (1)
Here, (a), (b), (c) and (d) are the numbers of moles or mole ratios of structural units derived from the components (a), (b), (c) and (d). Show. By introducing the structural unit derived from the component (d) into the above range at the end of the copolymer, the releasability and low water absorption can be improved.

  The bifunctional (meth) acrylic acid ester (c) causes the copolymer to be branched or cross-linked, as well as to generate a pendant vinyl group, impart curability to the copolymer, and develop heat resistance during curing. It plays an important role as an ingredient.

  Bifunctional (meth) acrylic acid esters include cyclohexane dimethanol diacrylate, dimethylol tricyclodecane diacrylate, cyclohexane dimethanol dimethacrylate, dimethylol tricyclodecane dimethacrylate, ethylene glycol diacrylate, propylene glycol diacrylate, 1 , 4-butanediol diacrylate, hexanediol diacrylate, diethylene glycol diacrylate, ethylene glycol diacrylate, propylene glycol diacrylate, 1,4-butanediol dimethacrylate, hexanediol dimethacrylate, diethylene glycol dimethacrylate, etc. ) Acrylic acid esters can be used, but are not limited thereto.

  Preferred examples of the bifunctional (meth) acrylic acid ester are cyclohexane dimethanol diacrylate and dimethylol tricyclodecane diacrylate in view of cost, ease of polymerization control and heat resistance of the obtained polymer. It is done.

The copolymer has a structural unit (c1) containing a reactive (meth) acrylate group derived from a bifunctional (meth) acrylic acid ester (c) in the side chain, but the structural unit represented by the formula (2) The molar fraction M _c1 of (c1) is preferably 0.05 or more and 0.4 or less, and preferably 0.1 to 0.3.
M _c1 = (c1) / [(a) + (b) + (c)] (2)
Here, (c1) in the formula indicates the number of moles of the structural unit (c1) containing a (meth) acrylate group. By satisfying the molar fraction, a molded article having excellent curability with light and heat and excellent in heat resistance and mechanical properties after curing can be obtained.

  The monofunctional (meth) acrylic acid ester (a) having an alicyclic structure is important for improving the solvent solubility, low water absorption, heat resistance, optical properties and processability of the copolymer. Monofunctional (meth) acrylic acid esters having such an alicyclic structure include isobornyl methacrylate, isobornyl acrylate, cyclohexyl methacrylate, cyclohexyl acrylate, dicyclopentenyl acrylate, dicyclopentenyloxyethyl acrylate. It has one or more alicyclic structures selected from the group consisting of a rate, dicyclopentanyl acrylate, dicyclopentenyloxyethyl methacrylate, dicyclopentenyloxyethyl methacrylate, and dicyclopentanyl methacrylate. Although monofunctional (meth) acrylic acid ester can be mentioned, it is not restricted to these. By introducing structural units derived from these components into a copolymer having an alicyclic structure, not only can the gelation of the polymer be prevented and the solubility in a solvent can be increased, Optical properties such as low color dispersibility of the coalescence, low water absorption, and heat resistance can be improved.

Examples of the monofunctional (meth) acrylic acid ester (a) having a preferred alicyclic structure include compounds represented by the following formula (a1).
A-R-C- (R ') n (a1)
Here, A is a (meth) acryloxy group, R is a single bond, an alkylene group having 1 to 10 carbon atoms or a polyalkylene oxide group, C is an aliphatic ring, and R ′ is substituted with an aliphatic ring. And an alkyl group having 1 to 10 carbon atoms, and n is 0 to 5.

ここで、Ｒ¹は水素原子またはメチル基を表し、Ｒ²は炭素数６〜１５の脂環式構造を含む炭化水素基を表し、Ｒ³は炭素数２〜４のアルキレン基を表し、ｍは０〜１０の整数を表す。 Examples of the monofunctional (meth) acrylic acid ester (a) having another preferred alicyclic structure include compounds represented by the following formula (a2).

Here, R ¹ represents a hydrogen atom or a methyl group, R ² represents a hydrocarbon group containing an alicyclic structure having 6 to 15 carbon atoms, R ³ represents an alkylene group having 2 to 4 carbon atoms, m Represents an integer of 0 to 10.

  Preferable specific examples include isobornyl methacrylate, isobornyl acrylate, cyclohexyl methacrylate, cyclohexyl acrylate, dicyclopentenyl acrylate, dicyclopropylene in terms of cost, prevention of gelation and moldability of the resulting polymer. One or more alicyclic rings selected from the group consisting of pentenyloxyethyl acrylate, dicyclopentanyl acrylate, dicyclopentenyloxyethyl methacrylate, dicyclopentenyloxyethyl methacrylate, dicyclopentanyl methacrylate Mention may be made of monofunctional (meth) acrylic acid esters having the formula structure.

  The monofunctional (meth) acrylic acid ester (b) having an alcoholic hydroxyl group is important for improving the adhesion to an inorganic material under severe actual use conditions such as wet heat conditions of the copolymer. Examples of such monofunctional (meth) acrylic acid ester having an alcoholic hydroxyl group include 2-hydroxypropyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, and 4-hydroxybutyl. (Meth) acrylate, partially ethoxylated 2-hydroxypropyl (meth) acrylate, partially ethoxylated 2-hydroxyethyl (meth) acrylate, and the like can be mentioned, but 2-hydroxyethyl methacrylate is preferable. is there. These (meth) acrylic acid ester monomers having an alcoholic hydroxyl group may be used alone or in combination of two or more.

ここで、Ｒ¹は水素原子またはメチル基を表し、Ｒ⁴は水酸基を一つ有する炭素数２〜４の炭化水素基を表す。 Preferred monofunctional (meth) acrylic acid ester (b) having an alcoholic hydroxyl group includes a compound represented by the following formula (b1).

Here, R ¹ represents a hydrogen atom or a methyl group, and R ⁴ represents a C 2-4 hydrocarbon group having one hydroxyl group.

The monofunctional (meth) acrylic acid ester (b) containing an alcoholic hydroxyl group is a monofunctional containing a molar fraction of the components (a), (b) and (c) and an alcoholic hydroxyl group in the copolymer. (meth) and the mole fraction of the structural unit derived from acrylic acid ester (c) (3) formula M _b which is expressed by 0.05 or more, often 0.60 or less, preferably 0.1 ~ 0.3.
M _b = (b) / [(a) + (b) + (c)] (3)
Here, (a), (b) and (c) in the formula indicate the number of moles of structural units derived from the respective components (a), (b) and (c). By satisfying the above molar fraction, a well-balanced copolymer capable of improving the optical properties under severe use conditions such as wet heat conditions and the adhesion between inorganic materials can be obtained.

  DMP functions as a chain transfer agent and controls the molecular weight of the copolymer. The molecular weight of the copolymer is in the range of 2000 to 20000, preferably 3000 to 10,000, as the weight average molecular weight Mw. By using a copolymer having a relatively low molecular weight, the moldability and releasability of the cured resin are enhanced.

  Furthermore, a monofunctional (meth) acrylic acid ester having no alicyclic structure and no hydroxyl group can be added as the component (e) for the purpose of improving the solvent solubility and processability of the copolymer. Examples of such (meth) acrylic acid esters include methyl methacrylate, ethyl methacrylate, methyl acrylate, ethyl acrylate, n-butyl acrylate, 2-methylhexyl acrylate, 2-ethylhexyl acrylate, octyl acrylate, etc. , Methyl methacrylate and n-butyl acrylate. These (meth) acrylic acid ester monomers may be used alone or in combination of two or more, but are one or more selected from the group consisting of methyl methacrylate, methyl acrylate, and n-butyl acrylate. Most preferred is a (meth) acrylic acid ester.

  Moreover, the structural unit derived from these other monomer components (e) includes a structural unit derived from the monomer component (a), a structural unit derived from the monomer component (b), and a monomer component (c ) It is good to be in the range of less than 30 mol% with respect to the total amount of the derived structural units.

Moreover, from another viewpoint, the soluble polyfunctional (meth) acrylic acid ester copolymer is 20 to 55 mol% of structural units derived from the component (a), 20 to 35 mol% of structural units derived from the component (b), And (c) 60 to 10 mol%, preferably 50 to 12 mol%, more preferably 40 to 15 mol% of structural units derived from the component. The mol% is calculated with the total of structural units derived from the components (a), (b) and (c) as 100 mol%. If the structural unit derived from the bifunctional (meth) acrylic acid ester (c) is less than 10 mol%, the heat resistance of the cured product is insufficient, and this is not preferable. If the structural unit exceeds 60 mol%, molding is performed. It is not preferable because processability is lowered and the strength of the molded product is remarkably lowered.
Moreover, the structural unit derived from the other monomer (e) component is preferably within a range of less than 30 mol% with respect to the total amount of the structural unit derived from the component (a) and the component (b).

  (A) Although it does not specifically limit as a manufacturing method of the copolymer used as a component, DMP, a monofunctional acrylate ester aromatic compound, and a bifunctional (meth) acrylic acid ester are adjusted so that it may become desired content. If necessary, it is produced by polymerizing at a temperature of 20 to 200 ° C. using a radical polymerization initiator and a solvent, and recovered by a commonly used method such as a steam stripping method or precipitation with a poor solvent. .

Next, the component (B) will be described.
As the component (B), a (meth) acrylate monomer having one or more functional groups having an unsaturated double bond (hereinafter sometimes abbreviated as (meth) acrylate monomer) is used. The (meth) acrylate monomer has one or more (meth) acryloyl groups in the molecule, and one or more are used. These (meth) acrylates used as the component (B) can be used in combination with the component (A) to adjust the viscosity of the composition without degrading curability, and synergistically, heat resistant In addition, optical characteristics such as low color dispersion and high light transmittance are simultaneously improved.

  The (meth) acrylate monomer is a monomer having a molecular weight of 1000 or less, but can also be a monomer having a molecular weight distribution such as polyethylene glycol di (meth) acrylate. In this case, Mw is 1000 or less. Preference is given to monomers or mixtures thereof consisting of compounds having no molecular weight distribution.

  As said (meth) acrylate monomer, what is copolymerizable with (A) component is good, for example, although monofunctional (meth) acrylic acid ester (a) which has alicyclic structure is used preferably, others For example, acryloylmorpholine, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, polyethylene glycol mono (meth) acrylate, polypropylene glycol mono (meth) acrylate, cyclohexane -1,4-dimethanol mono (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, phenoxyethyl (meth) acrylate, phenyl polyethoxy (meth) acrylate, 2-hydroxy-3-phenyloxypropyl (meth) Acrylate, o-phenylphenol monoethoxy (meth) acrylate, o-phenylphenol polyethoxy (meth) acrylate, p-cumylphenoxyethyl (meth) acrylate, isobornyl (meth) acrylate, tribromophenyloxyethyl (meth) acrylate , Dicyclopentanyl (meth) acrylate, dicyclopentenyl (meth) acrylate, dicyclopentenyloxyethyl (meth) acrylate, 1,4-butanediol di (meth) acrylate, 1,6-hexanediol di (meth) Acrylate, 1,9-nonanediol di (meth) acrylate, tricyclodecane dimethanol (meth) acrylate, bisphenol A polyethoxydi (meth) acrylate, bisphenol A polypropoxy (Meth) acrylate, bisphenol F polyethoxydi (meth) acrylate, ethylene glycol di (meth) acrylate, trimethylolpropane trioxyethyl (meth) acrylate, tris (2-hydroxyethyl) isocyanurate tri (meth) acrylate, pentaerythritol tri ( (Meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol hexa (meth) acrylate, polyethylene glycol di (meth) acrylate, tris (acryloxyethyl) isocyanurate, pentaerythritol tetra (meth) acrylate, dipentaerythritol hexa (Meth) acrylate, dipentaerythritol penta (meth) acrylate, tripentaerythritol hexa (meta ) Acrylate, tripentaerythritol penta (meth) acrylate, di (meth) acrylate of ε-caprolactone adduct of hydroxybivalic acid neopenglycol di (meth) acrylate, hydroxybivalic acid neopenglycol (eg Nippon Kayaku) KAYARAD HX-220, HX-620, etc.), trimethylolpropane tri (meth) acrylate, trimethylolpropane polyethoxytri (meth) acrylate, ditrimethylolpropane tetra (meth) acrylate, and other monomers be able to. Particularly preferred are 1,6-hexanediol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, trimethylolpropane trioxyethyl (meth) acrylate, and pentaerythritol tri (meth) acrylate.

Next, the component (C) will be described.
The silica fine particles (d) having an average particle diameter of 1 to 100 nm used as the component (C) of the present invention may be a metal oxide containing silicon and having an average particle diameter in the range of 1 to 100 nm. There is no particular limitation. As the silica fine particles, dried powdery silica fine particles and colloidal silica (silica sol) dispersed in an organic solvent can be used. From the viewpoint of dispersibility, it is preferable to use colloidal silica (silica sol) dispersed in an organic solvent. In the case of using colloidal silica (silica sol) dispersed in an organic solvent, it is preferable to use an organic solvent in which an organic component used in the composite composition is dissolved. For example, alcohols, ketones, esters And glycol ethers. Colloidal silica, silica sol, silica fine particles dispersed in alcoholic solvents such as methanol, ethanol, isopropyl alcohol, butyl alcohol and n-propyl alcohol, and ketone organic solvents such as methyl ethyl ketone and methyl isobutyl ketone for ease of solvent removal Is preferable, and colloidal silica dispersed in isopropyl alcohol is more preferable. In particular, when colloidal silica dispersed in isopropyl alcohol is used, it is suitable for stably producing a composite composition having a low viscosity after solvent removal compared to other solvent systems and a low viscosity. Colloidal silica (silica sol) and silica fine particles dispersed in these organic solvents are surface-treated with coupling agents such as silane coupling agents and titanate coupling agents as long as the required properties are not significantly impaired. In order to disperse in an organic solvent, a dispersant such as a surfactant may be used.

  The average particle size of the silica fine particles is preferably 1 to 100 nm, and more preferably 1 to 50 nm, more preferably 5 to 50 nm, and most preferably 5 to 40 nm in terms of the balance between transparency and fluidity. If the thickness is less than 1 nm, the viscosity of the prepared composite composition is extremely increased, so that the amount of silica fine particles is limited, the dispersibility is deteriorated, and sufficient transparency and linear expansion coefficient cannot be obtained. . On the other hand, if the thickness exceeds 100 nm, the transparency may be remarkably deteriorated.

Here, the average particle diameter of the silica fine particles is calculated from the specific surface area S (m ² / g) obtained by the nitrogen adsorption method (BET method) by the formula of D (nm) = 2720 / S.

  In order not to reduce the light transmittance at a wavelength of 400 to 500 nm, it is preferable to use silica fine particles in which silica fine particles having a primary particle size of 200 nm or more are present at a ratio of 5% or less, and the ratio is 0%. More preferred. In order to increase the filling amount of the silica fine particles, silica fine particles having different average particle diameters may be mixed and used. As silica fine particles, porous silica sol as disclosed in JP-A-7-48117, or a composite metal oxide of aluminum, magnesium, zinc or the like and silicon may be used.

  The content of the silica fine particles in the curable composite composition is preferably 15 to 90 wt%, more preferably 25 to 80 wt%, more preferably 25 to 70 wt%, in terms of the balance between the linear expansion coefficient and weight reduction. Most preferably, it is 30-70 wt%. If it is this range, since fluidity | liquidity and a dispersibility are favorable, manufacture is easy, and a molded article with sufficient intensity | strength and a low linear expansion coefficient can be manufactured.

  The curable composite composition of the present invention comprises the above component (A), component (B) and component (C) as essential components, and the content ratios thereof are as follows. In the composite composition, the blending amount of the component (A) with respect to the sum of the components (A) and (B) is 2 to 83 wt%, the blending amount of the component (B) is 83 to 2 wt%, and the blending of the component (C) The amount is 15 to 90 wt%. More preferably, the amount of component (A) is 5 to 75 wt%, the amount of component (B) is 80 to 10 wt%, and the amount of component (C) is 15 to 80 wt%. Most preferably, the blending amount of component (A) is 10 to 65 wt%, the blending amount of component (B) is 75 to 15 wt%, and the blending amount of component (C) is 15 to 70 wt%.

  The curable composite composition of the present invention may contain a polymerization initiator, preferably a photopolymerization initiator, as the component (D). The curable resin composition of the present invention can be molded and cured even by thermal polymerization. However, when molding and curing an optical material such as a lens, photocuring capable of strictly controlling the shape is advantageous. Therefore, it is preferable to add a photopolymerization initiator.

  Examples of the photopolymerization initiator used as the component (D) include benzoins such as benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin propyl ether, and benzoin isobutyl ether; acetophenone, 2,2-diethoxy-2-phenylacetophenone 2,2-diethoxy-2-phenylacetophenone, 1,1-dichloroacetophenone, 2-hydroxy-2-methyl-phenylpropan-1-one, diethoxyacetophenone, 1-hydroxycyclohexyl phenyl ketone, 2-methyl-1 Acetophenones such as-[4- (methylthio) phenyl] -2-morpholinopropan-1-one; 2-ethylanthraquinone, 2-tertiarybutylanthraquinone, 2-chloroanthraquinone, 2-amyl Anthraquinones such as nthraquinone; thioxanthones such as 2,4-diethylthioxanthone, 2-isopropylthioxanthone, 2-chlorothioxanthone; ketals such as acetophenone dimethyl ketal and benzyldimethyl ketal; benzophenone, 4-benzoyl-4'- Benzophenones such as methyldiphenyl sulfide and 4,4′-bismethylaminobenzophenone; phosphine oxides such as 2,4,6-trimethylbenzoyldiphenylphosphine oxide and bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide Etc.

  These can be used alone or as a mixture of two or more thereof, and further, tertiary amines such as triethanolamine and methyldiethanolamine, N, N-dimethylaminobenzoic acid ethyl ester, N, N-dimethylaminobenzoic acid isoamyl ester Can be used in combination with an accelerator such as a benzoic acid derivative.

  On the other hand, examples of the thermal polymerization initiator used as the component (D) include ketone peroxides such as cyclohexanone peroxide, 3,3,5-trimethylcyclohexanone peroxide, and methylcyclohexanone peroxide; 1,1-bis ( tert-butylperoxy) -3,3,5-trimethylcyclohexane, 1,1-bis (tert-butylperoxy) cyclohexane, n-butyl-4,4-bis (tert-butylperoxy) valerate and the like Oxyketals; hydroperoxides such as cumene hydroperoxide and 2,5-dimethylhexane-2,5-dihydroperoxide; 1,3-bis (tert-butylperoxy-m-isopropyl) benzene, 2 , 5-Dimethyl-2,5-di (tert-butylperoxy) hexa Dialkyl peroxides such as diisopropylbenzene peroxide and tert-butylcumyl peroxide; diacyl peroxides such as decanoyl peroxide, lauroyl peroxide, benzoyl peroxide and 2,4-dichlorobenzoyl peroxide; bis (tert -Peroxycarbonates such as butylcyclohexyl) peroxydicarbonate; organic peroxidation such as peroxyesters such as tert-butylperoxybenzoate and 2,5-dimethyl-2,5-di (benzoylperoxy) hexane -Based polymerization initiators, 2,2'-azobisisobutyronitrile, 1,1-azobis (cyclohexane-1-carbonitrile), azocumene 2,2'-azobismethylvaleronitrile, 4,4'-azobis (4-Cyanovaleric acid An azo polymerization initiator such as

  The amount of these polymerization initiators used is not particularly limited, but is usually 0.01 to 25 parts by weight based on 100 parts by weight of the total amount of the polymerizable components including the component (A). Is preferable, and it is more desirable to be in the range of 0.05 to 20 parts by weight. Most preferably, it is in the range of 0.1 to 15 parts by weight.

  When the curable composite composition of the present invention contains the above component (A), component (B), component (C) and component (D), the preferred content ratios are as follows. (B) The compounding quantity of a component is 5-250 weight part with respect to 100 weight part of (A) component, Preferably it is 20-100 weight part. The amount of component (C) is 0.1 to 10 parts by weight, preferably 1.0 to 5 parts by weight, based on 100 parts by weight of the total amount of components (B) and (A).

  From another viewpoint, the curable composite composition contains (D) component: 0.1 to 10 wt% with respect to a total of 100 wt% of the (A) component, the (B) component, and the (D) component. It is good. Formability found synergistically in mold release and curability when the blending ratio of component (D) is within the above range with respect to the sum of component (A), component (B) and component (D). And the balance between heat resistance and optical properties is improved. Moreover, when there are too few (D) components, it will be easy to produce insufficient hardening, heat resistance and light resistance will fall, and when too large, mechanical strength will fall or heat resistance will fall. In addition, when an organic solvent and a filler are included in a curable composite composition, the said content is calculated excluding these.

The curable composite composition of the present invention may contain a polymerization inhibitor for the purpose of preventing the polymerization reaction from proceeding at the time of preparing the composite composition and increasing the viscosity. The curable composite composition of the present invention contains a hydrophobizing agent such as trimethylmethoxysilane, hexamethyldisilazane, trimethylchlorosilane, and octamethylcyclotetrasiloxane for the purpose of reducing water absorption. Also good.
In the curable composite composition of the present invention, if necessary, a thermoplastic or thermosetting oligomer or polymer is used as long as the properties such as transparency, solvent resistance, liquid crystal resistance, and heat resistance are not impaired. Can be used in combination. In this case, it is preferable to use an oligomer or polymer having an alicyclic structure or a cardo skeleton for the purpose of reducing water absorption or further reducing the linear expansion coefficient.
Further, in the curable composite composition of the present invention, if necessary, a small amount of an antioxidant and an ultraviolet absorber can be used as long as the properties such as transparency, solvent resistance, liquid crystal resistance and heat resistance are not impaired. A filler such as an agent, a dye and pigment, and other inorganic fillers may be included.

  As a method for producing the curable composite composition of the present invention, for example, colloidal silica (silica sol) dispersed in an organic solvent and other blends are mixed and, if necessary, reduced in pressure while stirring. A method of removing organic solvent, a method of mixing colloidal silica (silica sol) dispersed in an organic solvent and other compounds, removing the solvent if necessary, and then further removing the solvent, and a high dispersion ability Examples thereof include a method of dispersing powdered silica fine particles dried using a mixing apparatus. Examples of the apparatus having a high dispersion ability include a film mix manufactured by Tokushu Kika Kogyo Co., Ltd. and various bead mills. When using a device with high dispersion capacity, care must be taken not to raise the temperature too much during mixing or kneading so that the reaction does not proceed rapidly. The temperature of the composition when preparing the curable composite composition is preferably maintained at 30 to 100 ° C, more preferably 35 to 70 ° C, and most preferably 35 to 70 ° C in balance with the solvent removal speed. 60 ° C. If the temperature is raised too much, the fluidity will be extremely lowered or gelled, making it impossible to form a sheet. In addition, when using a device having a high dispersion capacity, it is necessary to pay attention to contamination of impurities due to wear of the device. When using colloidal silica dispersed in an organic solvent, the organic solvent may be left in the curable composite composition. When the organic solvent is contained, a post-treatment step such as heat treatment is provided, and finally the organic solvent may be detached from the coating layer made of the curable composite composition of the present invention, for example, in the form of an optical film or sheet. The content of the organic solvent in the curable composite composition is a step of removing volatile components by a crosslinking step or heat treatment, etc., in order to avoid problems such as foaming, sheet waviness, and coloring. The content of the curable composite composition is preferably 0 to 10 wt%, more preferably 0 to 5 wt%, and most preferably 0 to 3 wt%.

The curable composite composition of the present invention can obtain a cured product by irradiation with active energy rays such as ultraviolet rays. Here, specific examples of the light source used for curing by irradiating with active energy rays include, for example, a xenon lamp, a carbon arc, a germicidal lamp, a fluorescent lamp for ultraviolet rays, a high pressure mercury lamp for copying, a medium pressure mercury lamp, and a high pressure mercury lamp. An ultra high pressure mercury lamp, an electrodeless lamp, a metal halide lamp, or an electron beam using a scanning type or curtain type electron beam acceleration path can be used. Moreover, when hardening the curable composite composition of this invention by ultraviolet irradiation, the ultraviolet irradiation amount required for hardening may be about 300-20000 mJ / cm < ² >. In order to sufficiently cure the curable composite composition, it is desirable to irradiate active energy rays such as ultraviolet rays in an inert gas atmosphere such as nitrogen gas.

  In addition, the curable composite composition of the present invention can be cured by heating. As curing temperature, 70-200 degreeC is preferable. More preferably, it is 80-180 degreeC. The curing time is preferably 1 minute to 15 hours. More preferably, it is 3 minutes to 10 hours.

  When heat treatment is performed at a high temperature after curing by active energy rays and / or crosslinking by thermal polymerization, 150 ° C. to 300 ° C. in a nitrogen atmosphere or in a vacuum state for the purpose of reducing the linear expansion coefficient during the heat treatment step. It is preferable to include a heat treatment step at 1 ° C. for 1 to 24 hours.

  Furthermore, the curable composite composition of the present invention can be prepared by using a silane coupling agent, a polymerization inhibitor, a leveling agent, a surface lubricant, an antifoaming agent, a light stabilizer, an antioxidant, a plasticizer, and an antistatic agent. Additives such as agents and fillers can be used in combination.

  The hardened | cured material of the curable composite composition of this invention can be obtained by irradiating active energy rays, such as an ultraviolet-ray and a visible light laser, according to a conventional method. When ultraviolet rays are used, irradiation is performed using a low-pressure or high-pressure mercury lamp, an ultra-high pressure mercury lamp, a metal halide lamp, a xenon lamp, or the like. In particular, a lamp having a high energy intensity at 350 to 450 nm is preferable as the light source.

The refractive index of the cured product of the curable composite composition of the present invention obtained by curing with active energy rays such as ultraviolet rays or heat is preferably 1.45 or more at 25 ° C, more preferably at 25 ° C. 1.48 or more. In particular, when an optical lens is produced with the resin composition for optical materials of the present invention, if the refractive index of the cured product is less than 1.45 at 25 ° C., there is a problem that a sufficient lens module cannot be made compact. is there.
Further, the Abbe number of the cured product (a numerical value specific to a substance that defines the property of changing the refractive index depending on the wavelength of light) is preferably 40.0 or more, and more preferably 45.0 or more. If the Abbe number of the cured product is less than 40.0, chromatic aberration is large and color blurring occurs, which is not preferable.

A composite cured product obtained by molding and curing the curable composite composition of the present invention is excellent as an optical material such as a lens or a prism. In particular, it is useful as an optical plastic lens such as an aspherical lens, a Fresnel lens, a lenticular lens, and a spectacle lens, as well as a coating material for an optical film and an optical adhesive material. And the optical lens obtained from the curable composite composition of this invention is used advantageously for an imaging device. In addition, the curable composite composition or the composite cured product can also be used for optical electronics, optical fiber, optical waveguide and other optoelectronic applications, printing inks, paints, clear coating agents, glossy varnishes, and the like.
Further, the curable composite composition of the present invention can also be used as an adhesive, and examples of articles having a cured product resulting from curing as an adhesive layer include mobile phones, portable game machines, and digital cameras. is there.

  When the polarizing film and the protective plate are bonded together using the curable composite composition of the present invention, for example, the protective plate is not limited to a protective plate made of non-alkali glass or quartz glass having excellent active energy ray permeability. A protective plate such as an acrylic plate or polycarbonate that absorbs a large amount of ultraviolet rays can also be used because of the good reaction curability of the composition.

  The curable composite composition of the present invention is applied to a base material such as a polarizing film using a roll coater, a spin coater, a screen printing method or the like so that the adhesive film thickness is 1 to 100 μm. The protective plates can be bonded together, and can be bonded by irradiating with ultraviolet rays from the protective plate and curing.

  EXAMPLES Next, the present invention will be described with reference to examples, but the present invention is not limited thereto. In addition, all the parts in each example are parts by weight. In addition, each physical property in the examples was prepared and measured by the following method.

1) Molecular weight and molecular weight distribution of polymer GPC (manufactured by Tosoh Corporation, HLC-8120GPC) was used for measuring the molecular weight and molecular weight distribution of the soluble polyfunctional (meth) acrylic acid ester copolymer, solvent: tetrahydrofuran (THF), flow rate: 1 0.0 ml / min, column temperature: 40 ° C. The molecular weight of the copolymer was measured as a molecular weight in terms of polystyrene using a calibration curve with monodisperse polystyrene.

2) Polymer structure It was determined by 13C-NMR and 1H-NMR analysis and elemental analysis using a JNM-LA600 type nuclear magnetic resonance spectrometer manufactured by JEOL. Chloroform-d1 was used as a solvent, and the tetramethylsilane resonance line was used as an internal standard.

3) Solubility test 1 g of the copolymer was added to 100 ml of various organic solvents (toluene, xylene, tetrahydrofuran, dichloroethane and chloroform) at 25 ° C., and after 30 minutes of stirring using a magnetic stirrer, the solubility was visually confirmed. . When all of the above organic solvents were dissolved and no gel was formed, the solubility was evaluated as ◯.

4) Creation of test pieces for measuring physical properties Glass mold in which a gap of 0.2 to 1.0 mm is opened between two glass plates having a width of 50 mm, a length of 50 mm, and a thickness of 1.0 mm, and the outer periphery is fixed with a polyimide tape. 1) Irradiate ultraviolet rays from one side of the glass mold for 5 seconds with the high-pressure mercury lamp, or 2) Put the glass mold in an inert gas oven under a nitrogen gas stream. And cured by heating at 180 ° C. for 1 hour. The cured resin plate was removed from the glass mold and used for measuring various physical properties.

5) Measurement of refractive index The refractive index and Abbe number at 589 nm were measured with an Abbe refractometer (manufactured by Atago Co., Ltd.).

6) Hue (YI): A flat plate having a thickness of 1.0 mm was measured with a color difference meter (trade name “MODEL TC-8600”, manufactured by Tokyo Denshoku Co., Ltd.), and the YI value was shown.
7) Haze (turbidity) and total light transmittance A test piece having a thickness of 0.2 mm was prepared, and the sample Haze (turbidity) and total light transmittance were measured using an integrating sphere light transmittance measuring device (Nippon Denshoku Co., Ltd.). Manufactured by SZ-Σ90).

8) Releasability: Evaluated based on the degree of difficulty when the cured resin was released from the mold.
○ ············································································································ 9 The shape and the surface shape of the mold were observed.
○ ・ ・ ・ ・ Reproducibility is good △ ・ ・ ・ ・ Reproducibility is good depending on curing conditions (light, heat) × ・ ・ ・ ・ Reproducibility is poor

10) Burr, More: Evaluation was made based on the size of the burrs generated outside the product portion of the molded product and the degree of resin leakage into the mold clearance when the cured resin was released from the mold.
B: The amount of burrs produced is less than 0.05 mm, and resin leakage into the mold clearance is less than 1.0 mm.
Δ: The amount of burrs generated is 0.05 mm or more and less than 0.2 mm. The resin leakage into the mold clearance is 1.0mm or more and less than 3.0mm.
× ··· Burr generation amount is 0.2 mm or more, and resin leakage into the mold clearance is 3.0 mm or more.

11) Reflow heat resistance: Using a parallel plate having a thickness of 1 mm as a test piece, spectral transmittance at a wavelength of 400 nm was measured with a spectrocolorimeter CM-3700d (manufactured by Konica Minolta). The measurement timing was before the heat resistance test after post-cure at 190 ° C. for 60 minutes and after the heat resistance test at 260 ° C. for 8 minutes in an air oven.

12) Water absorption rate Using a parallel flat plate with a thickness of 1 mm as a test piece, the weight of a test sample vacuum-dried at 60 ° C. for 24 hours is defined as Wo, and weighed with a scale capable of measuring up to ± 0.1 mg, temperature: 85 ° C. Humidification was performed for 1 week in a constant temperature and humidity chamber of 85% relative humidity. After humidification, water attached to the test sample was wiped off, and the sample was weighed with a scale capable of measuring up to ± 0.1 mg. The water absorption was calculated by the following formula. Three identical test samples were prepared and tested in the same manner.
Wo / W × 100 = water absorption

13) Heat cycle resistance A sample obtained by adhering a non-alkali glass (thickness: 0.7 mm) and a 2 mm thick acrylic plate to a thickness of 25 μm with an energy of 3000 mJ using an ultrahigh pressure mercury lamp of 157 mW for one cycle, After 100 cycles under conditions of 35 ° C. for 30 minutes and 85 ° C. for 30 minutes, the state of peeling of the two substrates was observed, and no peeling was evaluated as “good” and peeling was evaluated as “poor”.

14) Moisture resistance A sample obtained by adhering an alkali-free glass (thickness: 0.7 mm) and a 2 mm thick acrylic plate to a thickness of 25 μm with an energy of 3000 mJ using an ultrahigh pressure mercury lamp of 157 mW, 60 ° C., 90% RH Then, the state of peeling of the two substrates after being allowed to stand for 100 hours was observed.

15) Shape maintenance heat resistance Hardened and post-cured composite lens surface shape of spherical lens (shape 1) and composite cured product layer after passing through 280 ° C solder reflow furnace three times The surface shape (shape 2) of the spherical lens was measured with a non-contact three-dimensional shape measuring device manufactured by Mitaka Kogyo Co., Ltd., and the maximum value of the difference between shape 1 and shape 2 was calculated as shape maintenance heat resistance.

Synthesis example 1
Dimethylol tricyclodecane diacrylate 3.2 mol (926.5 ml), isobornyl methacrylate 8.0 mol (1814.1 ml), 2-hydroxypropyl methacrylate 4.8 mol (645.5 ml), 2,4- 4.8 mol (1145.9 ml) of diphenyl-4-methyl-1-pentene and 2400 ml of toluene were put into a 10.0 L reactor, 240 mmol of benzoyl peroxide was added at 90 ° C., and reacted for 6 hours. . After stopping the polymerization reaction by cooling, the reaction mixture was poured into a large amount of hexane at room temperature to precipitate a polymer. The obtained polymer was washed with hexane, filtered, dried and weighed to obtain 1392.6 g of copolymer A (yield: 40.5 wt%).

Mw of the obtained copolymer A was 8950, Mn was 3470, and Mw / Mn was 2.58. By performing ¹³ C-NMR, ¹ H-NMR analysis and elemental analysis, copolymer A has a total of 18.2 mol% of structural units derived from dimethylol tricyclodecane diacrylate, and a structure derived from isobornyl methacrylate. A total of 51.1 mol% of units and 30.7 mol% of structural units derived from 2-hydroxypropyl methacrylate were contained. Moreover, the terminal group of the structure derived from 2,4-diphenyl-4-methyl-1-pentene includes dimethylol tricyclodecane diacrylate, isobornyl methacrylate, 2-hydroxypropyl methacrylate, and 2,4-diphenyl-4. -It was 8.3 mol% with respect to the total amount of methyl-1-pentene. Furthermore, the ratio of the pendant acrylate was 12.10 mol%.
Copolymer A was soluble in toluene, xylene, THF, dichloroethane, dichloromethane, and chloroform, and no gel was formed. The cast film of copolymer A was a transparent film without fogging.

Synthesis example 2
1,4-butanediol diacrylate 4.8 mol (950.4 g), dicyclopentanyl methacrylate 6.4 mol (922.7 g), 2-hydroxypropyl methacrylate 4.8 mol (692.2 g), 2, 4.8 mol (1135 g) of 4-diphenyl-4-methyl-1-pentene and 2400 ml of toluene were put into a 10.0 L reactor, 240 mmol of benzoyl peroxide was added at 90 ° C., and reacted for 6 hours. . After stopping the polymerization reaction by cooling, the reaction mixture was poured into a large amount of hexane at room temperature to precipitate a polymer. The obtained polymer was washed with hexane, filtered, dried and weighed to obtain a copolymer B.

Mw of the obtained copolymer B was 12500, Mn was 3640, and Mw / Mn was 3.43. By performing ¹³ C-NMR, ¹ H-NMR analysis and elemental analysis, the copolymer B is derived from a total of 27.8 mol% of structural units derived from 1,4-butanediol diacrylate and derived from dicyclopentanyl methacrylate. 27.8 mol% in total, and 41.6 mol% of structural units derived from 2-hydroxypropyl methacrylate. Moreover, the terminal group of the structure derived from 2,4-diphenyl-4-methyl-1-pentene is 1,4-butanediol diacrylate, dicyclopentanyl methacrylate, 2-hydroxypropyl methacrylate, and 2,4-diphenyl. 10.1 mol% was present with respect to the total amount of -4-methyl-1-pentene. Furthermore, the ratio of the pendant acrylate was 20.4 mol%.
Copolymer B was soluble in toluene, xylene, THF, dichloroethane, dichloromethane, and chloroform, and no gel was formed. Further, the cast film of the copolymer B was a transparent film without fogging.

Synthesis example 3
1,4-butanediol diacrylate 5 mol (990 g), dicyclopentanyl methacrylate 1 mol (144.2 g), 2-hydroxypropyl methacrylate 4 mol (576.8 g), 2,4-diphenyl-4-methyl- 1 mol of pentane (1182 g) and 2400 ml of toluene were put into a 10.0 L reactor, 240 mmol of benzoyl peroxide was added at 90 ° C., and the mixture was reacted for 6 hours. After stopping the polymerization reaction by cooling, the reaction mixture was poured into a large amount of hexane at room temperature to precipitate a polymer. The obtained polymer was washed with hexane, filtered, dried and weighed to obtain a copolymer C.

Mw of the obtained copolymer C was 9230, Mn was 3210, and Mw / Mn was 2.88. By performing ¹³ C-NMR, ¹ H-NMR analysis and elemental analysis, the copolymer C is derived from a total of 45.6 mol% of structural units derived from 1,4-butanediol diacrylate, derived from dicyclopentanyl methacrylate. The total of 12.3 mol% of structural units and 42.1 mol% of structural units derived from 2-hydroxypropyl methacrylate were contained. Moreover, the terminal group of the structure derived from 2,4-diphenyl-4-methyl-1-pentene is 1,4-butanediol diacrylate, dicyclopentanyl methacrylate, 2-hydroxypropyl methacrylate, and 2,4-diphenyl. 14.6 mol% was present with respect to the total amount of -4-methyl-1-pentene. Furthermore, the ratio of the pendant acrylate was 32.6 mol%.
Copolymer C was soluble in toluene, xylene, THF, dichloroethane, dichloromethane, and chloroform, and no gel was formed. The cast film of copolymer C was a transparent film without cloudiness.

Synthesis Examples 4-15 and Synthesis Examples 16-20
Using the same method as in Synthesis Example 1, the types and amounts of acrylates were changed according to the formulations shown in Tables 1 and 2, and various copolymers were synthesized. Synthesis examples 16 to 20 are synthesis examples for comparison. The results are summarized in Tables 1-2.

Examples 1-25 and Comparative Examples 1-8
Various copolymers synthesized in the synthesis examples at the ratios shown in Tables 3 to 5 and (meth) acrylates, silica fine particles, a polymerization initiator, and other additives were mixed to obtain a curable composition. Next, this curable resin composition was cured by the various test methods described above, and performance evaluation was performed. The performance evaluation results are shown in Tables 3-5.

Explanation of symbols in the table: IBOMA; isobornyl methacrylate DCPM; dicyclopentanyl methacrylate DCPA; dicyclopentanyl acrylate HOP; 2-hydroxypropyl methacrylate HO; 2-hydroxyethyl methacrylate CD570; partially ethoxylated 2-hydroxyethyl methacrylate DMTCD; dimethylol tricyclodecane diacrylate 14BDDA; 1,4-butanediol diacrylate MMA; methyl methacrylate DCP-A; tricyclodecane dimethanol diacrylate (manufactured by Kyoeisha Chemical Co., Ltd.)
M-600A; 2-hydroxy-3-phenoxypropyl acrylate (epoxy ester M-600A: manufactured by Kyoeisha Chemical Co., Ltd.)
3EG-A; triethylene glycol diacrylate (light acrylate 3EG-A: manufactured by Kyoeisha Chemical Co., Ltd.)
FA-513AS; dicyclopentanyl acrylate (manufactured by Hitachi Chemical Co., Ltd.)
FA-129AS; Nonanediol diacrylate (manufactured by Hitachi Chemical Co., Ltd.)
SR205; triethylene glycol dimethacrylate (Sartomer-SR205: manufactured by Sartomer)
EG; ethylene glycol dimethacrylate (light ester EG; manufactured by Kyoeisha Chemical Co., Ltd.)
MEK-SD: methyl ethyl ketone-dispersed colloidal silica (silica content 30% by weight, average particle size 10-20 nm, Snowtech MEK-SD- (1); manufactured by Nissan Chemical Co., Ltd.)
MEK-ST-MS; methyl ethyl ketone-dispersed colloidal silica (silica content 35 wt%, average particle size 17-23 nm, MEK solvent, Snowtex MEK-ST-MS; manufactured by Nissan Chemical Co., Ltd.)
MEK-ST-L; methyl ethyl ketone-dispersed colloidal silica (silica content 30 wt%, average particle size 40-50 nm, MEK solvent, Snowtex MEK-ST-L; manufactured by Nissan Chemical Co., Ltd.)
SC1050: Methyl ethyl ketone-dispersed colloidal silica (average particle size 0.2 to 0.3 μm, MEK solvent, silica content 65 wt%, SC1050-MMA; manufactured by Admatechs Co., Ltd.)
AO-60; antioxidant (ADK STAB AO-60; manufactured by ADEKA CORPORATION)
Perbutyl O; t-butyl peroxy-2-ethylhexanate (manufactured by NOF Corporation)
Irgacure 184; 1-hydroxy-cyclohexyl-phenyl-ketone (Ciba Specialty Chemicals)

In Tables 1 and 2, the numbers of components (a) to (c) indicate the amount used (mol), the numbers in parentheses are the mol% in the acrylates, and the DMP number indicates the amount used (mol). The numbers in parentheses are mol% with respect to the total amount of acrylates. In addition, when using MMA as another monomer component, this is calculated as acrylates. Moreover, although content of each component is abundance ratio (molar ratio) of the structural unit originating in each component which exists in a copolymer, it is each calculated by said formula (1)-(5). In addition, when using MMA as another monomer component, this is calculated as a structural unit derived from acrylates.
Moreover, in Tables 3-5, the weight of the silica of (C) component is a solid content weight except a solvent component.

Claims (11)

Component (A): monofunctional (meth) acrylic acid ester (a) having an alicyclic structure, monofunctional (meth) acrylic acid ester (b) having an alcoholic hydroxyl group, bifunctional (meth) acrylic acid ester (c) ) And 2,4-diphenyl-4-methyl-1-pentene (d), and a bifunctional (meth) acrylic acid ester (c) in the side chain. It is a copolymer having a reactive (meth) acrylate group derived from and having a structural unit derived from 2,4-diphenyl-4-methyl-1-pentene (d) at the terminal, and has a weight average molecular weight of 2000 to 2000 A soluble polyfunctional (meth) acrylic acid ester copolymer that is 20000 and is soluble in toluene, xylene, tetrahydrofuran, dichloroethane or chloroform;
(B) component: a monomer having one or more functional groups having an unsaturated double bond and a molecular weight of 1000 or less, and (C) component: silica fine particles having an average particle diameter of 1 to 100 nm,
The compounding amount of the component (A) with respect to the sum of the components (A) and (B) is 2 to 83 wt%, the compounding amount of the component (B) is 83 to 2 wt%, (C ) A curable composite composition, wherein the compounding amount of the component is 15 to 90 wt%. The amount of 2,4-diphenyl-4-methyl-1-pentene (d) introduced into the component (A) is 0.02 to 0.35 as the molar fraction M _d represented by the following formula (1). The curable composite composition according to claim 1.
M _d = (d) / [(a) + (b) + (c) + (d)] (1)
Here, (a), (b), (c) and (d) are a structural unit derived from a monofunctional (meth) acrylic acid ester (a) having an alicyclic structure, and a single unit having an alcoholic hydroxyl group. Structural unit derived from functional (meth) acrylic acid ester (b), structural unit derived from bifunctional (meth) acrylic acid ester (c), and 2,4-diphenyl-4-methyl-1-pentene (d) The number of moles of the structural unit derived from is shown. The amount of the reactive (meth) acrylate group derived from the bifunctional (meth) acrylic acid ester (c) in the component (A) introduced into the side chain is expressed as a mole fraction M _c1 represented by the following formula (2). The curable composite composition according to claim 2, which is 0.05 to 0.5.
M _c1 = (c1) / [(a) + (b) + (c)] (2)
Here, (c1) in the formula represents the number of moles of the structural unit (c1) containing a bifunctional (meth) acrylate group in the side chain.   The monofunctional (meth) acrylic acid ester (a) having an alicyclic structure in the component (A) is an isobornyl methacrylate, isobornyl acrylate, cyclohexyl methacrylate, cyclohexyl acrylate, dicyclopentenyl acrylate, di One or more selected from the group consisting of cyclopentenyloxyethyl acrylate, dicyclopentanyl acrylate, dicyclopentenyloxyethyl methacrylate, dicyclopentenyloxyethyl methacrylate, and dicyclopentanyl methacrylate It is monofunctional (meth) acrylic acid ester which has an alicyclic structure, The curable composite composition in any one of Claims 1-3 characterized by the above-mentioned.   The monofunctional (meth) acrylic acid ester (b) having an alcoholic hydroxyl group in the component (A) is 2-hydroxypropyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, partially ethoxylated 2 The monofunctional (meth) acrylic acid ester selected from the group consisting of -hydroxypropyl (meth) acrylate and partially ethoxylated 2-hydroxyethyl (meth) acrylate. The curable composite composition according to any one of the above.   The bifunctional (meth) acrylic acid ester (c) in the component (A) is 1,4-butanediyl diacrylate, 1,6-hexanediyl diacrylate, 1,9-nonanediol diacrylate and dimethylol tricyclo. The curable composite composition according to claim 1, wherein the curable composite composition is one or more bifunctional (meth) acrylic acid esters selected from the group consisting of decanediacrylate.   The monomer having a molecular weight of 1000 or less in the component B is at least one (meth) acrylate selected from monofunctional (meth) acrylic acid esters and bifunctional (meth) acrylic acid esters having an alicyclic structure. The curable composite composition according to any one of claims 1 to 6.   Furthermore, a photoinitiator is included as (D) component, The curable composite composition in any one of 1-7 characterized by the above-mentioned.   A cured product obtained by curing the curable composite composition according to claim 1.   An optical material formed from the cured product according to claim 9.   The optical material according to claim 10, wherein the optical material is an optical plastic lens or a prism.