TWI605066B - Soluble polyfunctional (meth) acrylate copolymer, its manufacturing method, curable resin composition, and hardened | cured material - Google Patents

Description

Soluble polyfunctional (meth) acrylate copolymer and its production method, curable resin composition and cured product

The present invention relates to an optical property, heat resistance and processability which are excellent in low color dispersion, high light transmittance, etc., and optical properties, low water absorption and density of inorganic materials under severe practical conditions such as moist heat conditions. An improved alicyclic structure and a soluble polyfunctional (meth) acrylate copolymer having an alcoholic hydroxyl group, a method for producing the same, and a curable resin composition and a cured product using the same.

Many of the monomers having reactive unsaturated bonds can be cleaved by unsaturated bonds to select a catalyst that causes a chain reaction and appropriate reaction conditions to produce a multi-component. In general, the types of monomers having unsaturated bonds are extremely diverse, and the variety of resins obtained is also remarkable. However, a monomer having a high molecular weight of 10,000 or more which is generally called a polymer compound is relatively small. For example, ethylene, substituted ethylene, propylene, substituted propylene, styrene, alkyl styrene, alkoxy styrene, norbornene, various acrylates, butadiene, cyclopentadiene, dicyclopentadiene, Isoprene, maleic anhydride, maleimide, fumarate, allyl compound and the like are representative monomers. A wide variety of resins are synthesized by copolymerizing these monomers separately or in this manner.

The use of these resins is mainly limited to the field of relatively inexpensive livelihood machines, and in the field of optical and electronic materials, there is almost no sophisticated technology field that requires high heat resistance, dimensional stability or micro-machining properties. The reason for this is that, for example, a polymer which is generally synthesized from the above-mentioned monomers is thermoplastic, and in order to satisfy mechanical properties, it is necessary to form a relatively high molecular weight body, so that it is sacrificed in the field of advanced technology such as heat resistance or fine processability. Required characteristics.

A method for solving the disadvantages of such a vinyl-based thermoplastic polymer is disclosed in Patent Documents 1 to 3 as a polymer having a (meth) acryloxy group or a vinyl ether group in a pendant group. For example, Patent Document 1 discloses a (meth)acryloxyl suspension-type polymer obtained by cationically polymerizing a heterogeneous polymerizable monomer such as 2-vinyloxyethyl acrylate (VEA), and photopolymerization. A photosensitive composition composed of a starting agent. Further, Patent Document 2 discloses a photosensitive composition comprising a (meth)acrylonitrile-based pendant polymer, a compound having a photoreactive unsaturated carboxyl group, and a photopolymerization initiator. Further, Patent Document 3 discloses a carboxylic acid in which a heterogeneous polymerizable monomer such as 2-vinyloxyethyl acrylate (VEA) or the like is cationically polymerized to have an inactive photoreactive unsaturated group. Among the ester solvent compounds, a polymerization method of a polymer solution is obtained by separately polymerizing or copolymerizing using a cationic polymerization catalyst.

However, according to the reactive polymer produced by the technique of the heterogeneous polymerizable monomer disclosed in the above-mentioned patent documents, it has both low water absorption and formation required in the field of advanced optical lenses and enamel applications. The properties of the properties, heat resistance, and high transparency are balanced, and the optical properties under the severe use conditions such as damp heat conditions and the adhesion to the inorganic materials are not obtained.

Further, Patent Document 4 discloses a method of copolymerizing a monovinyl aromatic compound and a bifunctional (meth) acrylate, and having a reactivity derived from a bifunctional (meth) acrylate in a side chain. A soluble polyfunctional vinyl aromatic copolymer of a (meth) acrylate-based building block. However, the soluble polyfunctional vinyl aromatic copolymer obtained by the technique disclosed in the patent document is a material which has an excellent thermal decomposition resistance even in the heat history at a high temperature and has a reaction in the side chain. The (meth) acrylate group is excellent in workability and solvent solubility, but it cannot be used in optical lens systems for low-color dispersion applications, and practically limited, and the adhesion to inorganic materials has not been improved. .

Further, Patent Document 5 discloses a composition characterized by containing a linear aliphatic divalent alcohol having a carbon number of 4 to 8 in a methyl methacrylate (MMA)-based slurry. The acrylate is 1 to 25% by weight as a constituent component. Further, the production of the MMA-based slurry composition disclosed in the patent document has revealed that MMA, or MMA, and a vinyl copolymer copolymerizable therewith, a chain shifting agent, in the presence of a polymerization initiator, an inert gas (for example) In a N ₂ gas) environment, normal temperature or heat polymerization is carried out. Further, in the publication of the patent publication, the chain-moving agent is specifically exemplified by only sulfur compounds such as lauryl mercaptan, octyl thioglycolate, thiocresol, thionaphthol, benzyl mercaptan, etc. 2, 4-Diphenyl-4-methyl-1-pentene (d) is not specifically disclosed. Even the terminal group derived from 2,4-diphenyl-4-methyl-1-pentene coexists with a structural unit derived from a monofunctional (meth) acrylate (a) having an alicyclic structure, Effectively, it is not implied that the refractive index divergence can be suppressed when the heat is wet. Further, the composition obtained by the technique disclosed in the patent document is not improved in adhesion to an inorganic material under severe use conditions such as moist heat conditions.

Further, Patent Document 6 discloses a polymerizable composition composed of a vinyl monomer and a di(meth)acrylate compound, 2,4-diphenyl-4-methyl-1-pentene ( The use of d) has also been disclosed, but its use amount is used as a general chain shifting agent to a degree of zero percent, and the product is also crosslinked gelatinized, and no solvent solubility is shown.

Further, Patent Document 7 discloses a method comprising: 1) an epoxy group-containing (meth) acrylate, 2) a hydroxyl group-containing (meth) acrylate, 3) (meth) acrylic acid, and 4) a fragrance. A self-curing copolymer of a structural unit composed of a group-based (meth) acrylate and a thermosetting resin composition for a color filter of an organic solvent. Then, the self-hardening copolymer obtained by the technique disclosed in the patent document can be used in the polymerization stage to achieve a desired molecular weight range, and thiopropionic acid, thiopropyl propionate, thioglycol can be used. A known molecular weight modifier such as thioglycerol, dodecyl mercaptan or α-methylstyrene. However, in the technique disclosed in the patent document, a vinyl compound having two or more functional groups having a plurality of vinyl groups is not added during polymerization, and only terminal groups derived from one or less molecular weight modifiers are introduced into the polymer chain, and it is not sufficiently imparted. The disadvantages of the function derived from the terminal group still exist. Further, in this patent publication, the self-curable copolymer obtained by the disclosed technology is formed into a thermosetting resin composition in a resin composition with an epoxy resin, but in combination with an acrylate resin. Since the hardening reaction is not caused, there is a disadvantage that the strength and heat resistance of the so-called resin composition are lowered.

Therefore, it has excellent optical characteristics such as low color dispersion, high light transmittance, low water absorption, moldability, and heat resistance, and optical properties under severe practical conditions such as damp heat conditions, and inorganic materials. Soluble polyfunctional (meth) acrylate copolymers with improved adhesion have not been present to date.

Further, the thermosetting resin composition can be used as a mechanical part material, an electric and electronic part material, an automobile part material, a civil construction material, a molding material, and the like, and can also be used as a material for a coating or an adhesive. Further, when a composite member is formed in combination with an inorganic substrate, not only the coefficient of thermal expansion can be lowered, but also the refractive index of the inorganic substance and the resin can be controlled, and the appearance of the resin composition and the cured product can be controlled to exhibit transparency, so that it can be used particularly as Materials for electrical or electronic parts or optical applications. For example, the digital camera module is mounted on a mobile phone to be miniaturized, and is also being reduced in cost. Further, there is a growing demand for a car camera for a novel use or a bar code reader for a home buyer. When it is used for such applications, the shape of the molded article does not change during solder reflow at the time of manufacture, and not only the heat resistance of the shape retention can be sought, but also the high-temperature exposure in the summer is considered in actual use, and heat resistance for a long period of time is required. High reliability such as water absorption.

For such a technical requirement, Patent Document 8 discloses an organic solvent-based thermosetting composition containing (a) colloidal vermiculite dispersed in an organic solvent, (b) an alicyclic polyepoxy compound, and (c) a metal chelate compound as an essential component, and the ratio of the ratio of the component (a) to the component (b) is from 5 to 85% by weight of the component (a) and from 95 to 15% by weight of the component (b). Then, the total amount of the solid component of the component (c) and the component (b) is 0.01 to 30 parts by weight per 100 parts by weight. Further, Patent Literatures 9 to 11 disclose an epoxy resin molded body in which an epoxy resin molded body obtained by curing a composition containing at least an epoxy resin and inorganic oxide particles is molded, and in the molded body. The inorganic oxide particles having an average particle diameter of 50 nm or less are dispersed. When the material obtained by the technique disclosed in the literature is subjected to a severe heat history at a temperature of 280 ° C or higher, it is insufficient in heat-resistant discoloration, and it is necessary to improve the optical characteristics after the heat history.

Further, Patent Document 12 discloses a molded cured product having at least one (meth) acrylate (a) having a bifunctional condensed polycyclic alicyclic structure and having an average particle diameter of 1 to 100 nm. The vermiculite fine particles (b) are a composite composition obtained by removing an organic solvent containing a composition of colloidal vermiculite dispersed in an organic solvent, and the content of the fine particles (b) of the vermiculite is 30 to 90% by weight. A shaped hardened product obtained by crosslinking a composite composition. However, the form-hardened material obtained by the literature technique does not have the formability required for continuous molding in the case of a high-precision shape of an optical lens or a crucible.

Further, Patent Document 13 discloses a curable resin composition for an optical material, which comprises a vinyl polymer having a repeating structural unit derived from a heterogeneous polymerizable monomer having a specific structure, and an average particle diameter of Zirconia particles of 1 nm to 100 nm.

Here, as the inorganic fine particles, zirconia particles having an average particle diameter of 1 nm to 100 nm are used. When such a material is used as an optical lens of an imaging system, it is a highly dispersed material, so that light penetration is reduced and a material having a high ABBE number is formed. Therefore, it is necessary to improve optical characteristics. In addition, when the heat history of the high-temperature reflow is excessive, the heat resistance of the shape maintenance is insufficient, and it is necessary to improve the optical characteristics after the heat history.

When using a curable composite composition manufactured by the techniques disclosed in these documents, it has a balance of low water absorption, formability, heat resistance, and high transparency which are pursued in the field of advanced optical lens applications. In addition, it has high optical properties, such as high heat resistance, shape accuracy, and heat-resistant shape stability. It is not available for a curable resin composition suitable for continuous molding of various optical members.

[Previous Technical Literature] [Patent Literature]

[Patent Document 1] Japanese Patent Publication No. Sho 49-13212

[Patent Document 2] Japanese Patent Publication No. Sho 51-34433

[Patent Document 3] Japanese Patent Publication No. 54-27394

[Patent Document 4] Japanese Patent Laid-Open Publication No. 2008-247978

[Patent Document 5] Japanese Laid-Open Patent Publication No. SHO 57-167340

[Patent Document 6] Japanese Patent Laid-Open Publication No. 2002-121228

[Patent Document 7] Japanese Patent Laid-Open Publication No. 2009-1770

[Patent Document 8] Japanese Patent No. 2856741

[Patent Document 9] Japanese Patent Laid-Open Publication No. 2004-250521

[Patent Document 10] Japanese Patent Laid-Open Publication No. 2008-133439

[Patent Document 11] Japanese Laid-Open Patent Publication No. 2008-156625

[Patent Document 12] Japanese Patent No. 4008246

[Patent Document 13] Japanese Laid-Open Patent Publication No. 2009-92598

An object of the present invention is to provide a reactive (meth) acrylate group having excellent color properties such as low color dispersion and high light transmittance, and having excellent curability in side chains, and low water absorbability, processability, and heat resistance. In the advanced technology field, the balance of various characteristics required for optical lenses and tantalum materials is excellent, and the optical properties and the adhesion of inorganic materials are improved under the strict practical conditions such as hot and humid conditions. A polyfunctional (meth) acrylate copolymer and a method for producing the copolymer by high efficiency. Further, an object of the present invention is to provide an optical property having excellent optical properties, heat resistance, hardness, and processability with low color dispersion and high light transmittance, and shape of a molded article under severe packaging conditions such as reflow conditions. A curable resin composition in which retention is improved and a cured product thereof.

The soluble polyfunctional (meth) acrylate copolymer of the present invention contains a monofunctional (meth) acrylate having an alicyclic structure (a) and a monofunctional (meth) acrylate having an alcoholic hydroxyl group. a copolymer obtained by copolymerizing an ester (b), a bifunctional (meth) acrylate (c), and a component of 2,4-diphenyl-4-methyl-1-pentene (d), and The reactive (meth) acrylate (c1) derived from the bifunctional (meth) acrylate (c) in the side chain has a terminal derived from 2,4-diphenyl-4-methyl-1 a copolymer of a structural unit of pentene (d) having a weight average molecular weight of from 2,000 to 20,000, further soluble in toluene, xylene, tetrahydrofuran, dichloroethane or chloroform.

The soluble polyfunctional (meth) acrylate copolymer of the present invention preferably satisfies the amount of introduction of the structural unit derived from 2,4-diphenyl-4-methyl-1-pentene (d) by the following formula ( 1) The molar fraction M _d shown is 0.02 to 0.35;

M _d = (d) / [(a) + (b) + (c) + (d)] (1)

Moreover, it is preferable to satisfy the introduction amount of the (meth) acrylate group (c1) derived from the reactivity of the bifunctional (meth) acrylate (c) by the (c1) molar represented by the following formula (2). The fraction M _c1 is 0.05 to 0.5;

Mc ₁ =(c1)/[(a)+(b)+(c)] (2)

In the formulas (1) and (2), (a), (b), (c), (d) and (c1) are derived from a monofunctional (meth) acrylate having an alicyclic structure (a). a structural unit, a structural unit derived from a monofunctional (meth) acrylate having an alcoholic hydroxyl group (b), a structural unit derived from a bifunctional (meth) acrylate (c), and a 2,4- The structural unit of diphenyl-4-methyl-1-pentene (d) and the molar number of the structural unit containing a bifunctional (meth) acrylate group in the side chain.

The above monofunctional (meth) acrylate (a) is preferably isodecyl (meth) acrylate, isodecyl acrylate, cyclohexyl methacrylate, cyclohexyl acrylate, dicyclopentenyl acrylate, acrylic acid. Dicyclopentenyloxyethyl ester, dicyclopentanyl acrylate, dicyclopentenyloxyethyl methacrylate, dicyclopentenyloxyethyl methacrylate, and dicyclopentanyl methacrylate One or more monofunctional (meth) acrylates selected from the group, and the monofunctional (meth) acrylate (b) having an alcoholic hydroxyl group is preferably 2-hydroxypropyl methacrylate or 2-hydroxyethyl methacrylate One or more (meth) acrylates having an alcoholic hydroxyl group selected from the group consisting of esters and partially ethoxylated 2-hydroxy methacrylate, and the bifunctional (meth) acrylate (c) is preferably One or more kinds of bifunctional (meth) acrylates selected from the group consisting of cyclohexane dimethanol diacrylate and dimethylol tricyclodecane diacrylate.

A method for producing a soluble polyfunctional (meth) acrylate copolymer of the present invention, characterized in that 2,4-diphenyl-4-methyl-1-pentene (d) is relative to a bifunctional (methyl) group 100 parts by weight of acrylate (c), 10 to 500 parts by weight, and monofunctional (meth) acrylate having an alicyclic structure (a) 2 to 55 mol%, monofunctional having an alcoholic hydroxyl group The monomer component obtained by (meth) acrylate (b) 2 to 50 mol% and bifunctional (meth) acrylate (c) 96 to 10 mol% is polymerized at a temperature of 50 to 200 °C.

The curable resin composition of the present invention is characterized in that it contains

(A) component: a soluble polyfunctional (meth) acrylate copolymer as claimed in claim 1

(B) component: a monomer having one or more functional groups containing an unsaturated double bond and having a molecular weight of 1,000 or less, and

(C) component: vermiculite particles having an average particle diameter of 1 to 100 nm.

The compounding amount of the component (A) to the component (A) and the component (B) in the curable resin composition is 2 to 83% by weight, and the amount of the component (B) is 83 to 2% by weight, and the component (C) The blending amount is 15 to 90% by weight. Further, the component B is one or more (meth) acrylates selected from monofunctional (meth) acrylates and bifunctional (meth) acrylates having an alicyclic structure. Further, the curable resin composition contains a photopolymerization initiator as the component (D). Further, the cured product of the present invention is obtained by curing the curable resin composition.

According to the present invention, a solvent-soluble polyfunctional (meth) acrylate copolymer which is excellent in optical properties such as low color dispersion and high light transmittance and excellent in photocurability in side chains can be produced with high efficiency. The (meth) acrylate group is excellent in various characteristics required for optical lenses and ruthenium materials in the advanced technical fields of low water absorption, workability, and heat resistance, and is still harsh and practical in conditions such as damp heat. The optical properties under the conditions of use are improved with the adhesion of the inorganic material. By curing the soluble polyfunctional (meth) acrylate copolymer of the present invention, it is an excellent resin for optical lenses and enamel materials. Further, it is possible to provide an optical property, heat resistance, hardness, and processability which are excellent in low color dispersion and high light transmittance, and the heat resistance retention of the shape of the molded article is improved under severe and practical conditions such as reflow conditions. A curable resin composition and a cured product thereof.

[Formation for implementing the invention]

Hereinafter, the soluble polyfunctional (meth) acrylate copolymer of the present invention and a method for producing the same will be described in detail. This soluble polyfunctional (meth) acrylate copolymer is an alicyclic structure and a hydroxyl group. Hereinafter, the soluble polyfunctional (meth) acrylate copolymer is sometimes referred to simply as a copolymer.

The copolymer of the present invention contains a monofunctional (meth) acrylate (a) having an alicyclic structure, a monofunctional (meth) acrylate having an alcoholic hydroxyl group (b), and a bifunctional (methyl) group. a monomer of acrylate (c), and 2,4-diphenyl-4-methyl-1-pentene (d) are present, copolymerized to obtain a copolymer, and have a bifunctional group derived from a side chain ( The reactive (meth)acrylic group of the methyl (meth) acrylate (c) further has a structural unit derived from 2,4-diphenyl-4-methyl-1-pentene (d) at the terminal. Here, soluble means soluble in toluene, xylene, tetrahydrofuran, dichloroethane or chloroform. The solubility test is carried out under the conditions described later.

Since the copolymer is obtained by copolymerizing a monofunctional (meth) acrylate and a bifunctional (meth) acrylate, it has a branched structure or a crosslinked structure, but the amount of such a structure is limited to exhibit solubility. Degree. Therefore, it is a copolymer which has a structural unit containing the unreacted (meth)acrylic group (c1) derived from the bifunctional (meth)acrylate (c) in a side chain. This unreacted (meth)acrylic group is also called a pendant (meth)acrylic group, and this shows the polymerizability, and polymerization is carried out by further polymerization treatment to obtain a solvent-insoluble resin cured product.

Further, the copolymer has a structural unit derived from 2,4-diphenyl-4-methyl-1-pentene (d) at the terminal. By introducing the structural unit at the end of the copolymer, a cured product having improved moldability such as release property can be obtained.

The copolymer has a structural unit derived from a monofunctional (meth) acrylate (a) having an alicyclic structure, a structural unit derived from a monofunctional (meth) acrylate having an alcoholic hydroxyl group (b), A structural unit derived from a bifunctional (meth) acrylate (c) and a structural unit derived from 2,4-diphenyl-4-methyl-1-pentene (d). Here, the structural unit derived from the bifunctional (meth) acrylate (c) is a polymerized double bond (referred to as a vinyl group) contained in two (meth) acrylate groups, and includes: a structural unit (c2) which participates in polymerization to form a branched structure or a crosslinked structure, and a structure in which only one vinyl group participates in polymerization, and other vinyl groups do not react and contain residual unreacted (meth)acrylic group Unit (c1). 2,4-Diphenyl-4-methyl-1-pentene (d) acts as a mobile agent to prevent an increase in molecular weight and is present at the end of the copolymer.

The amount of introduction of 2,4-diphenyl-4-methyl-1-pentene (d) in the copolymer is 0.02% in terms of the molar fraction M _d represented by the above formula (1). 0.35, preferably 0.03~0.30, especially 0.05~0.15.

Here, (a), (b), (c), and (d) are derived from a structural unit derived from a monofunctional (meth) acrylate (a) having an alicyclic structure, derived from an alcoholic hydroxyl group. a structural unit of a monofunctional (meth) acrylate (b), a structural unit derived from a bifunctional (meth) acrylate (c), and a 2,4-diphenyl-4-methyl-1- The number of moles (or mole fraction) of the structural unit of pentene (d). The structural unit derived from 2,4-diphenyl-4-methyl-1-pentene (d) is introduced into the above range at the end of the copolymer to improve the release property and low water absorption.

The bifunctional (meth) acrylate (c) is a branching or cross-linking of a copolymer to produce a pendant vinyl group, and the copolymer can be cured, and plays an important role as a cross-linking component for exhibiting heat resistance during curing. Character.

As the bifunctional (meth) acrylate, cyclohexane dimethanol diacrylate, dimethylol tricyclodecane diacrylate, cyclohexane dimethanol dimethacrylate, dimethylol tricyclothracene can be used. Alkyl dimethacrylate, ethylene glycol diacrylate, propylene glycol diacrylate, 1,4-butanediol diacrylate, hexanediol diacrylate, diethylene glycol diacrylate, ethylene glycol diacrylate a bifunctional (meth) acrylate such as ester, propylene glycol diacrylate, 1,4-butanediol dimethacrylate, hexanediol dimethacrylate or diethylene glycol dimethacrylate, but It is not limited to this.

A suitable specific example of the bifunctional (meth) acrylate is preferably cyclohexane dimethanol diacrylate or dimethylol in terms of cost, ease of polymerization control, and heat resistance of the obtained polymer. Tricyclodecane diacrylate.

The copolymer is a structural unit (c1) having a (meth) acrylate group derived from a reactive group derived from a bifunctional (meth) acrylate (c) in a side chain, but has a structure represented by the above formula (2) The unit fraction (c1) has a molar fraction M _c1 of 0.05 to 0.5, more preferably 0.1 to 0.3.

Here, (c1) in the formula represents the number of moles of the structural unit (c1) containing a (meth) acrylate group. By satisfying the above molar fraction, a molded article excellent in light- or heat-hardening property, heat resistance after hardening, and excellent mechanical properties can be obtained.

The monofunctional (meth) acrylate (a) having an alicyclic structure is important for improving solvent solubility, low water absorption, heat resistance, optical properties, and processability of the copolymer. The monofunctional (meth) acrylate having such an alicyclic structure may, for example, be isodecyl methacrylate, isodecyl acrylate, cyclohexyl methacrylate, cyclohexyl acrylate or dicyclopentene acrylate. Ester, dicyclopentenyloxyethyl acrylate, dicyclopentanyl acrylate, dicyclopentenyloxyethyl methacrylate, dicyclopentenyloxyethyl methacrylate, and dicyclopentanyl methacrylate One or more monofunctional (meth) acrylates having an alicyclic structure selected from the group consisting of, but not limited to, these. The structural unit derived from these components is introduced into a copolymer having an alicyclic structure, and not only prevents gelation of the polymer, but also improves solubility in a solvent, and improves low-color dispersion of the copolymer. Optical properties, low water absorption, heat resistance.

In a preferred embodiment, the cost, the prevention of gelation, and the moldability of the obtained polymer include, for example, isodecyl methacrylate, isodecyl acrylate, cyclohexyl methacrylate, and an acrylic ring. Hexyl ester, dicyclopentenyl acrylate, dicyclopentenyloxyethyl acrylate, dicyclopentanyl acrylate, dicyclopentenyloxyethyl methacrylate, dicyclopentenyloxyethyl methacrylate, One or more monofunctional (meth) acrylates having an alicyclic structure selected from the group consisting of dicyclopentanyl methacrylate.

The monofunctional (meth) acrylate (b) having an alcoholic hydroxyl group is important for improving the adhesion of an inorganic material under severe and practical conditions such as a wet heat condition of a copolymer. The monofunctional (meth) acrylate having an alcoholic hydroxyl group may, for example, be 2-hydroxypropyl methacrylate, 2-hydroxyethyl methacrylate or partially ethoxylated 2-hydroxy methacrylate. Etc., but preferably 2-hydroxyethyl methacrylate. These monofunctional (meth) acrylate type monosystems having an alcoholic hydroxyl group may be used singly or in combination of two or more kinds.

Molar fraction of (a) component, (b) component, and (c) component in a monofunctional (meth)acrylate (b) copolymer containing an alcoholic hydroxyl group and a monofunctional group derived from an alcoholic hydroxyl group mole fraction of structural units of (meth) acrylate (c) of M _b, (. 3) should be calculated by the formula M _b is 0.05 or more and 0.06 or less, should be 0.1 to 0.3.

M _b = (b) / [(a) + (b) + (c)] (3)

In the formula, (a), (b) and (c) have the same meanings as in the formula (1).

By satisfying the above molar fraction, it is possible to obtain a copolymer which is excellent in optical characteristics under severe practical use conditions such as damp heat conditions and excellent in adhesion to inorganic materials.

2,4-Diphenyl-4-methyl-1-pentene (c) functions as a chain shifting agent to control the molecular weight of the copolymer. The molecular weight of the copolymer of the present invention is in the range of 2,000 to 20,000, preferably in the range of 3,000 to 10,000, in terms of the weight average molecular weight Mw. By using a relatively low molecular weight copolymer, the formability and release property of the resin composition or cured product can be improved.

Further, for the purpose of improving the solvent solubility and processability of the copolymer, a monofunctional (meth) acrylate having no alicyclic structure and a hydroxyl group may be added as the component (e). Such (meth) acrylates may, for example, be methyl methacrylate, ethyl methacrylate, methyl acrylate, ethyl acrylate, n-butyl acrylate, 2-methylhexyl acrylate, acrylate 2-ethyl. Hexyl ester, octyl acrylate, etc., but preferably methyl methacrylate or n-butyl acrylate. These (meth) acrylate-based single systems may be used singly or in combination of two or more kinds, but are most preferably one selected from the group consisting of methyl methacrylate, methyl acrylate, and n-butyl acrylate. The above (meth) acrylate.

Further, the structural unit derived from the other monomer component (e) such as this is based on the structural unit derived from the monomer component (a), the structural unit derived from the monomer component (b), and the monomer component. The total amount of the structural unit of (c) is preferably in the range of less than 30 mol%.

The soluble polyfunctional (meth) acrylate copolymer of the present invention contains a monofunctional (meth) acrylate having an alicyclic structure (a) and a monofunctional (meth) acrylate having an alcoholic hydroxyl group ( b) a copolymer obtained by copolymerizing a bifunctional (meth) acrylate (c) and a component of 2,4-diphenyl-4-methyl-1-pentene (d), thereby having a source From the respective structural units. When the total structural unit is 100 m, when the number of moles derived from the respective tectonic elements is (a), (b), (c), and (d), (a), (b)~( d) is preferably in the following range. (a) is 10 to 55 m, (b) is 10 to 45 m, (c) is 10 to 50 m, preferably 15 to 40 m, and (d) is 2 to 35 m. 5 to 20 moles.

Further, the structural unit derived from the bifunctional (meth) acrylate (c) has a reactive (meth) acrylate (c1), but contains a structural unit of the (meth) acrylate. The number of ears (c1) is such that when the total structural unit is 100 m, it is preferably 5 to 35 m, more preferably 10 to 25 m. Further, (c1) is preferably in the range of 1/4 to 3/4 of (c). If (c) or (c1) is too small, the heat resistance of the cured product is insufficient, and if too much, the formability is lowered, and the strength of the molded article is remarkably lowered.

The method for producing a soluble polyfunctional aromatic (meth) acrylate copolymer of the present invention is to use a monofunctional (meth) acrylate (a) having an alicyclic structure and a monofunctional group having an alcoholic hydroxyl group ( Monomers of methyl)acrylate (b), bifunctional (meth)acrylate (c) and 2,4-diphenyl-4-methyl-1-pentene (d) The molar amount or the molar fraction of the structural unit of the monomer may be determined in such a manner as to be within the above range. Here, 2,4-diphenyl-4-methyl-1-pentene (d) is also a known compound as a chain shifting agent, but in the present invention, it is used in a smaller amount than a chain shifting agent. The amount is more, so it is part of the monomer component. The amount of 2,4-diphenyl-4-methyl-1-pentene (d) used is derived from 2,4 contained in the soluble polyfunctional aromatic (meth) acrylate copolymer of the present invention. - The molar fraction of the structural unit of diphenyl-4-methyl-1-pentene (d) is adjusted to be in the range of 0.02 to 0.35, but the reactivity is low and unreacted, so it is preferable to compare the theoretical amount. Use more. Therefore, it is used in the range of 2 to 60 moles with respect to the monomer 100, but it is preferably in the range of 10 to 50 moles.

In the method for producing a soluble polyfunctional aromatic (meth) acrylate copolymer of the present invention, 2,4-diphenyl-4-methyl-1-pentene (d) is compared with a bifunctional (methyl group) The acrylate (c) is present in an amount of 10 to 500 parts by weight, so that the monofunctional (meth) acrylate having an alicyclic structure (a) is 2 to 55 mol%, and the monofunctional group having an alcoholic hydroxyl group (A) The monomer component of the acrylate (b) 2 to 35 mol% and the bifunctional (meth) acrylate (c) 96 to 10 mol% is polymerized at a temperature of 50 to 200 °C.

From the viewpoint of the function of 2,4-diphenyl-4-methyl-1-pentene (d) as a chain shifting agent, the amount used is from the limitation of the crosslinking reaction, the formation of suspended (meth) acrylate, The control of the molecular weight distribution is preferably in the range of 10 to 500 parts by weight, more preferably 20 to 100 parts by weight, per 100 parts by weight of the bifunctional (meth) acrylate (c). It is most preferably in the range of 50 to 80 parts by weight.

The mono(meth)acrylate aromatic compound (a) having an alicyclic structure is used in an amount relative to a monofunctional (meth) acrylate (a) having an alicyclic structure and a monofunctional group having an alcoholic hydroxyl group. The total of (meth) acrylate (b) and bifunctional (meth) acrylate (c) is 100 moles, and is 2 to 55 moles, preferably 10 to 40 moles. The bifunctional (meth) acrylate (c) is used in an amount of from 96 to 10 mol, preferably from 20 to 50 mol%. The monofunctional (meth) acrylate (b) having an alcoholic hydroxyl group is used in an amount of 2 to 50 mol%, preferably 10 to 40 mol%.

In the production method of the present invention, a radical polymerization initiator may be added in the case where the initial reaction rate of the thermal initiation reaction is small. In this case, the radical polymerization initiator used in the present invention may, for example, be cyclohexanone peroxide, 3,3,5-trimethylcyclohexanone peroxide or methylcyclohexanone peroxide. Ketone peroxides; 1,1-bis(t-butylperoxy)-3,3,5-trimethylcyclohexane, 1,1-bis(t-butylperoxy)cyclohexane, Peroxide ketals such as n-butyl-4,4-bis(t-butylperoxy)trimethylacetate; cumyl hydroperoxide, 2,5-dimethylhexane-2 , hydroperoxides such as 5-dihydroperoxide; 1,3-bis(t-butylperoxy-m-isopropyl)benzene, 2,5-dimethyl-2,5-di (T-butyl peroxy) dialkyl peroxides such as hexane, diisopropylbenzene peroxide, and t-butyl cumyl peroxide; sulfhydryl peroxide, lauryl peroxide a bismuthinoyl peroxide such as an oxide, a benzammonium peroxide or a 2,4-dichlorobenzhydryl peroxide; a bis(t-butylcyclohexyl)peroxydicarbonate or the like Peroxycarbonates; peroxy benzoate, 2,5-dimethyl-2,5-bis(benzhydrylperoxy)hexane, etc. Peroxide polymerization initiator and 2,2'-azobisisobutyronitrile, 1,1-azobis(cyclohexane-1-carbonitrile), azobenzene 2,2'-couple An azo polymerization initiator such as nitrogen bismethylvaleronitrile or 4,4'-azobis(4-cyanomethoate). The amount of the radical polymerization initiator to be used is not particularly limited, but is usually 0.01 to 25 parts by weight, more preferably 0.05 to 20 parts by weight, based on 100 parts by weight of the total of the monomer components. . It is most preferably in the range of 0.1 to 15 parts by weight.

Further, the polymerization reaction can be carried out basically in the form of bulk polymerization without using a solvent, but it can also be carried out in one or more organic solvents in which the produced soluble polyfunctional (meth)acrylate aromatic copolymer is dissolved. The organic solvent is a compound which does not inhibit radical polymerization in nature, and if the chain shifting agent, the initiator, the monomer, and the polyfunctional (meth) acrylate aromatic copolymer of the present invention are dissolved to form a uniform solution, It can be used without special restrictions.

Examples of the organic solvent that can be used include aromatic hydrocarbons such as benzene, toluene, xylene, ethylbenzene, propylbenzene, and butylbenzene; ethane, propane, butane, pentane, hexane, and heptane. a linear aliphatic hydrocarbon such as octane, decane or decane; 2-methylpropane, 2-methylbutane, 2,3,3-trimethylpentane, 2,2,5- A branched aliphatic hydrocarbon such as trimethyl hexane; a cyclic aliphatic hydrocarbon such as cyclohexane, methylcyclohexane or ethylcyclohexane; or a paraffin oil of a hydrogenated petroleum fraction. Among them, toluene, xylene, pentane, hexane, heptane, octane, 2-methylpropane, 2-methylbutane, cyclohexane, methylcyclohexane and ethylcyclohexane are preferable. From the viewpoints of balance of polymerizability and solubility and ease of availability, it is more preferably toluene, xylene, methylcyclohexane or ethylcyclohexane.

The compound which is an organic solvent of these can be used individually or in combination of 2 or more types. The amount of the solvent to be used is not particularly limited.

In the production method of the present invention, the polymerization is carried out at a temperature ranging from 50 to 200 °C. When the polymerization reaction is carried out at a temperature of less than 50 ° C, the polymerization rate becomes low, so that it is not preferable from the viewpoint of industrial implementation. If it exceeds 200 ° C, the selectivity of the reaction is lowered, the reaction is difficult to control, and the insolubility due to crosslinking is liable to occur. The gel is formed, so it is not good.

After the polymerization reaction is stopped, the method of recovering the copolymer is not particularly limited, and any method generally used, such as a heating and pressure reduction devolatilization method, a vapor removal method, or a precipitation in a weak solvent, may be used.

The soluble polyfunctional (meth) acrylate copolymer of the present invention or the soluble polyfunctional (meth) acrylate copolymer obtained by the production method of the present invention can be processed into a molded material, a sheet or a film. This hardening is obtained by heating or the like to obtain a cured product. A soluble polyfunctional (meth) acrylate copolymer, which is processed into a molded article, a sheet or a film, or a hardened resin or molded article which is suitable for low color dispersion and low dielectric Optical materials or semiconductor-related materials, such as rate, low water absorption, high heat resistance, etc., further coatings, photosensitive materials, adhesives, sewage treatment agents, heavy metal capture agents, ion exchange resins, antistatic agents, antioxidants Antifogging agent, anti-rust agent, anti-pollution agent, medical material, aggregating agent, binder for solid fuel, conductive treatment agent, and the like. Further, examples of the optical component include a pickup lens for a CD, a pickup lens for a DVD, a lens for FAX, a lens for LBP, an oregon mirror, a crucible, and the like.

The soluble polyfunctional (meth) acrylate copolymer of the present invention is soluble in at least one selected from the group consisting of toluene, xylene, tetrahydrofuran, dichloroethane and chloroform. It is preferably soluble in all of the above solvents. Here, the soluble solution is dissolved in 100 ml of a solvent at room temperature (25 ° C) to dissolve 1 g or more, preferably 10 g or more. Then, after dissolution, it is preferred that the formation of the gel is not observed.

Next, the curable resin composition of the present invention will be described in detail. Since the curable resin composition of the present invention contains the component (A), the component (B), and the component (C) as essential components, it will be described from the essential components.

The soluble polyfunctional (meth) acrylate copolymer (hereinafter sometimes abbreviated as a copolymer) of the component (A) of the present invention is the above-described soluble polyfunctional (meth) acrylate copolymer of the present invention.

As the component (B), one or more (meth) acrylate monomers having a functional group having an unsaturated double bond (hereinafter sometimes referred to simply as a (meth) acrylate monomer) may be used. When the (meth) acrylate single system has one or more (meth) acryloxy groups in the molecule, one type or two or more types may be used. The (meth) acrylate which can be used as the component (B) can be used in combination with the component (A) to adjust the viscosity of the composition without dropping the hardenability, and at the same time, in addition to the heat resistance Moreover, the optical characteristics of low-color dispersion and high light transmittance are simultaneously improved.

The (meth) acrylate monomer alone has a molecular weight of 1,000 or less, but may be a monomer having a molecular weight distribution such as polyethylene glycol di(meth)acrylate, and Mw is 1000 or less at this time. A monomer consisting essentially of a compound having no molecular weight distribution or a mixture thereof.

The above (meth) acrylate single system is preferably copolymerizable with the component (A), and for example, a monofunctional (meth) acrylate (a) having an alicyclic structure is preferably used, but other examples include propylene oxime. Base morpholine, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, polyethylene glycol mono (meth) acrylate, poly Propylene glycol mono (meth) acrylate, cyclohexane-1,4-dimethanol mono (meth) acrylate, (meth) acrylate tetrahydrofuran ester, phenoxyethyl (meth) acrylate, (methyl) Phenyl polyethoxylate acrylate, 2-hydroxy-3-phenyloxypropyl (meth)acrylate, o-phenylphenol monoethoxylate (meth)acrylate, o-phenylphenol (meth)acrylate Oxy ester, p-cumylphenoxyethyl (meth)acrylate, isodecyl (meth)acrylate, tribromophenyloxyethyl (meth)acrylate, dicyclopentanyl (meth)acrylate, Dicyclopentenyl (meth)acrylate, dicyclopentenyloxyethyl (meth)acrylate, 1,4-butanediol di(meth)acrylate, 1,6-hexanediol di(a) Acrylate, 1,9-nonanediol di(meth)acrylate, Cyclodecane dimethanol (meth) acrylate, bis (meth) bisphenol A polyethoxylate, bis (meth) acrylate bisphenol A polypropoxylate, bis (meth) acrylate bisphenol F poly Oxy ester, ethylene glycol di(meth)acrylate, trihydroxypropane (meth)acrylate, tris(2-hydroxyethyl)trimeric isocyanate tri(meth)acrylate, pentaerythritol tris(A) Acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol hexa(meth)acrylate, polyethylene glycol di(meth)acrylate, tris(propyleneoxyethyl)trimeric isocyanate, pentaerythritol tetra ( Methyl) acrylate, dipentaerythritol hexa(meth) acrylate, dipentaerythritol penta (meth) acrylate, tripentaerythritol hexa (meth) acrylate, tripentaerythritol penta (meth) acrylate, hydroxypivalic acid Di(meth) acrylate of neopentyl glycol di(meth) acrylate, ε-caprolactone adduct of hydroxypivalic acid neopentyl glycol (for example, manufactured by Nippon Kayaku Co., Ltd., KAYARAD HX) -220, HX-620, etc.), trihydroxypropane tri(meth)acrylate, trihydroxypropane polyethoxylate tri(meth)acrylate, Trimethylolpropane tetra (meth) acrylate monomers of the class. More preferably, for example, 1,6-hexanediol di(meth)acrylate, trihydroxypropane tri(meth)acrylate, trihydroxypropane trioxyethyl (meth)acrylate, pentaerythritol tris(methyl) )Acrylate.

Next, explain the relevant component (C).

The vermiculite fine particles (d) having an average particle diameter of 1 to 100 nm which can be used as the component (C) of the present invention may be a metal oxide containing cerium and an average particle diameter of 1 to 100 nm. Special restrictions. As the vermiculite fine particle system, a dry powdery vermiculite fine particle or a colloidal vermiculite (a vermiculite sol) dispersed in an organic solvent can be used. In terms of dispersibility, colloidal vermiculite (aragonite sol) dispersed in an organic solvent is preferably used. The organic solvent in the case of using a colloidal vermiculite (the vermiculite sol) dispersed in an organic solvent is preferably used in the organic solvent used for the resin composition, and examples thereof include alcohols, ketones, esters, and glycol ethers. From the easiness of solvent removal, it is preferred to use a colloidal vermiculite which is dispersed in an organic solvent such as an alcohol, such as methanol, ethanol, isopropanol, butanol or n-propanol, or a ketone-based organic solvent such as methyl ethyl ketone or methyl isobutyl ketone. The vermiculite sol and the vermiculite fine particles are more preferably a colloidal vermiculite dispersed in isopropyl alcohol. In particular, when colloidal vermiculite dispersed in isopropyl alcohol is used, the viscosity after solvent removal is lower than that of other solvent systems, and it is suitable for making a resin composition having a low viscosity. The colloidal vermiculite (the vermiculite sol) and the vermiculite microparticles dispersed in the organic solvent may be surface-treated with a coupling agent such as a decane coupling agent or a titanate coupling agent in a range of characteristics required for extremely nondestructive properties. In order to disperse in an organic solvent, a dispersing agent such as a surfactant may be used.

The average particle diameter of the vermiculite particles is preferably from 1 to 100 nm, and in terms of the balance between transparency and fluidity, it is preferably from 1 to 50 nm, more preferably from 5 to 50 nm, and most preferably from 5 to 40 nm. When the viscosity is less than 1 nm, the viscosity of the produced resin composition is extremely increased. Therefore, the amount of the fine particles of the vermiculite is limited, and the dispersibility is deteriorated, and sufficient transparency and coefficient of linear expansion cannot be obtained. Moreover, if it exceeds 100 nm, transparency may be deteriorated remarkably, which is not preferable.

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

In order to prevent the light transmittance of the wavelength of 400 to 500 nm from being lowered, it is preferable to use the fine particles of the vermiculite having a particle diameter of 200 nm or more in a ratio of 5% or less, more preferably, the ratio is 0%. In order to increase the amount of the fine particles of the vermiculite particles, it is also possible to mix the fine particles having different average particle diameters. Further, as the fine-grained fine particles, a porous vermiculite gel as shown in JP-A-H07-48117 or a composite metal oxide such as aluminum, magnesium or zinc may be used.

The content of the vermiculite particles in the curable resin composition is preferably 15 to 90% by weight, and in terms of the balance between the linear expansion coefficient and the weight reduction, it is preferably 25 to 80% by weight, more preferably 25 to 70% by weight, most preferably 30~70wt%. In this range, since fluidity and dispersibility are good, production is easy, and a molded article having sufficient strength and a low coefficient of linear expansion can be produced.

In the curable resin composition of the present invention, the component (A), the component (B) and the component (C) are essential components, but the content ratio thereof is preferably in the following range. In the resin composition, the total amount of the component (A) to the component (A) and the component (B) is 2 to 83% by weight, and the amount of the component (B) is 83 to 2% by weight, and the component (C) is blended. The amount is 15 to 90% by weight. The blending ratio of the component (A) is preferably 5 to 75 wt%, the blending amount of the component (B) is 80 to 10 wt%, and the blending amount of the component (C) is 15 to 80 wt%. The optimum amount of the component (A) is 10 to 65 wt%, the blending amount of the component (B) is 75 to 15 wt%, and the blending amount of the component (C) is 15 to 70 wt%.

The curable resin composition of the present invention preferably contains 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 if it is thermally polymerized. However, when an optical material such as a lens is molded and cured, it is advantageous to strictly control the photohardening of the shape. Therefore, photopolymerization is added. The starting agent is better.

Examples of the photopolymerization initiator which can be used as the component (D) include benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin propyl ether, benzoin isobutyl ether, and the like. Benzocaine; acetophenone, 2,2-diethoxy-2-phenylethylbenzene, 2,2-diethoxy-2-phenylethylbenzene, 1,1-dichloro Acetylene, 2-hydroxy-2-methyl-phenylpropan-1-one, diethoxyethyl benzene, 1-hydroxycyclohexyl phenyl ketone, 2-methyl-1-[4-(A Ethyl benzene such as thiol)phenyl]-2-morpholinylpropan-1-one; 2-ethyl fluorenone, 2-tert-butyl fluorenone, 2-chlorofluorenone, 2-pentyl Anthrones such as anthrone; thioxanthone such as 2,4-diethylthianone, 2-isopropylthioxanthone or 2-chlorothiazepin; acetophenone a ketal such as a ketal or a benzyl dimethyl ketal; benzophenone, 4-benzylidene-4'-methyldiphenyl sulfide, 4,4'-bismethylamine Benzophenones such as benzophenone; 2,4,6-trimethylbenzimidyldiphenylphosphine oxide, bis(2,4,6-trimethylbenzylidene)-benzene Phosphorus oxides such as phosphorus oxides.

These may be used singly or in combination of two or more kinds, and further may be a tertiary amine such as triethanolamine or methyldiethanolamine, N,N-dimethylamino benzoic acid ethyl ester, N,N- A promoter such as a benzoic acid derivative such as isopropylamino benzoic acid isoamyl ester or the like is used in combination.

Further, the thermal polymerization initiator which can be used for the component (D) may, for example, be cyclohexanone peroxide, 3,3,5-trimethylcyclohexanone peroxide or methylcyclohexanone peroxide. Ketone peroxides; 1,1-bis(t-butylperoxy)-3,3,5-trimethylcyclohexane, 1,1-bis(t-butylperoxy)cyclohexane, Peroxide ketals such as n-butyl-4,4-bis(t-butylperoxy)trimethylacetate; cumyl hydroperoxide, 2,5-dimethylhexane-2 , hydroperoxides such as 5-dihydroperoxide; 1,3-bis(t-butylperoxy-m-isopropyl)benzene, 2,5-dimethyl-2,5-di (T-butyl peroxy) dialkyl peroxides such as hexane, diisopropylbenzene peroxide, and t-butyl cumyl peroxide; sulfhydryl peroxide, lauryl peroxide a bismuthinoyl peroxide such as an oxide, a benzammonium peroxide or a 2,4-dichlorobenzhydryl peroxide; a bis(t-butylcyclohexyl)peroxydicarbonate or the like Peroxycarbonates; organic peroxides such as tert-butyl peroxybenzoate, 2,5-dimethyl-2,5-di(benzhydryl peroxy)hexane, etc. Compound polymerization initiator and 2,2'-azobisisobutyronitrile, 1,1-azobis(cyclohexane-1-carbonitrile), azobenzene 2,2'-azo double An azo polymerization initiator such as methylvaleronitrile or 4,4'-azobis(4-cyanobenzoic acid).

The amount of the polymerization initiator to be used is not particularly limited, but is usually 0.01 to 25 parts by weight, more preferably 0.05 to 20 parts by weight, based on 100 parts by weight of the total amount of the polymerizable component containing the component (A). Within the scope of the share. It is most preferably in the range of 0.1 to 15 parts by weight.

When the curable resin composition of the present invention contains the above components (A), (B), (C) and (D), the preferred content ratio is as follows. The amount of the component (B) is 5 to 250 parts by weight, more preferably 20 to 100 parts by weight, based on 100 parts by weight of the component (A), and the amount of the component (C) is relative to the component (B) and (A) The total amount of the components to be formulated is 0.1 to 1 part by weight, more preferably 1.0 to 5 parts by weight.

From the other viewpoints, the curable resin composition contains 100% by weight of the total of the component (A), the component (B), and the component (D), and contains the component (D): 0.1 to 10% by weight. With respect to the total of the components (A), (B), and (D), the blending ratio of the component (D) is within the above range, and the moldability of the release property or the curability can be comprehensively observed. The balance of characteristics of heat resistance and optical characteristics is improved. Further, if the component (D) is too small, the curing is insufficient, and the heat resistance or the light resistance is lowered. If too much, the mechanical strength is lowered or the heat resistance is lowered. Further, when the organic solvent and the filler are contained in the curable resin composition, the above content is calculated unless otherwise excluded.

The curable resin composition of the present invention is subjected to a polymerization reaction at the time of preparation of the resin composition, and may contain a polymerization inhibitor for the purpose of preventing an increase in viscosity. Further, in the curable resin composition of the present invention, trimethyl methoxy decane, hexamethyldioxane, trimethyl chlorodecane, octamethyl ring four may be contained for the purpose of lowering the water absorption rate. A hydrophobic treatment agent such as a siloxane.

In the curable resin composition of the present invention, a thermoplastic or thermosetting oligomer or polymer may be used in combination insofar as it does not impair the properties such as transparency, solvent resistance, liquid crystal resistance, heat resistance and the like. At this time, the purpose of lowering the water absorbency or further reducing the coefficient of linear expansion is also suitable, and an oligomer or polymer having an alicyclic structure or a Cardo skeleton is preferably used.

Further, the curable resin composition of the present invention may contain a small amount of an antioxidant, an ultraviolet absorber, or a dye, as needed, insofar as it does not impair the properties such as transparency, solvent resistance, liquid crystal resistance, and heat resistance. A filler such as a pigment or other inorganic filler.

The method for producing the curable resin composition of the present invention may be, for example, a method in which a colloidal vermiculite (aragonite sol) dispersed in an organic solvent and other preparations are mixed, and if necessary, a pressure is reduced while stirring to remove an organic solvent; Mixing colloidal vermiculite (aragonite sol) dispersed in an organic solvent with other formulations, removing the solvent as needed, casting, further removing the solvent; using a mixing device with high dispersibility to make the dried powdery mash A method of dispersing stone particles and the like. The apparatus having a high dispersing ability may, for example, be a Filmix manufactured by a special machine-making industry or a ball mill of various types. When using a device with high dispersing ability, in the mixing or kneading, the reaction does not proceed rapidly, and it must be noted that the temperature does not rise too much. The temperature of the composition when the curable resin composition is formed is preferably maintained at 30 to 100 ° C, and the solvent concentration is more preferably 35 to 70 ° C, and most preferably 35 to 60 ° C. If the temperature is raised too much, the fluidity is extremely lowered and becomes gelatinous. Can't be thinned. Further, when a device having a high dispersing ability is used, it is necessary to pay attention to the incorporation of impurities such as wear of the device. When a colloidal vermiculite dispersed in an organic solvent is used, the organic solvent may remain in the curable resin composition. When the organic solvent is contained, a post-treatment step such as heat treatment is provided, and finally, the organic solvent is removed from the coating layer composed of, for example, an optical film or a sheet-like curable resin composition of the present invention. The content of the curable resin composition in the organic solvent is a step of avoiding the step of removing the volatile component by the crosslinking step, the heat treatment, or the like, and causing distortion or coloration in the sheet, and is preferably a curable resin composition. 0~10wt%, more preferably 0~5wt%, especially preferably 0~3wt%.

The curable resin composition of the present invention can be obtained by irradiating an active energy ray such as ultraviolet rays. Here, specific examples of the light source used when the active energy ray is irradiated and cured are, for example, a xenon lamp, a carbon arc, a germicidal lamp, a fluorescent lamp for ultraviolet light, a high pressure mercury lamp for photocopying, a medium pressure mercury lamp, a high pressure mercury lamp, and an ultrahigh pressure mercury lamp. , electrodeless lamps, metal halide lamps, or electron beams of scanning type, curtain type electron beam accelerating tubes, and the like. Moreover, when the curable resin composition of the present invention is cured by ultraviolet irradiation, the amount of ultraviolet rays required for curing can be about 300 to 20,000 mJ/cm ² . Further, in order to sufficiently cure the curable resin composition, it is preferred to irradiate an active energy ray such as ultraviolet rays in an inert atmosphere such as nitrogen.

Further, the curable resin composition of the present invention can obtain a cured product even by heating. The hardening temperature should be 70~200 °C. More preferably 80~180 °C. The hardening time should be from 1 minute to 15 hours. More preferably 3 minutes to 10 hours.

When the active energy line is hardened and/or heat treated at the high temperature after cross-linking, the purpose of reducing the coefficient of linear expansion in the heat treatment step is preferably 150 ° C to 300 in a nitrogen atmosphere or under vacuum. °C, 1~24 hours heat treatment step.

Further, the curable resin composition of the present invention may be used in combination with a decane coupling agent, a polymerization inhibitor, a leveling agent, a surface lubricant, an antifoaming agent, a photostabilizer, an antioxidant, a plasticizer, an antistatic agent, and the like. Additives such as fillers.

The cured product of the curable resin composition of the present invention can be obtained by irradiation with an active energy ray such as ultraviolet light or visible light laser according to a usual method. When ultraviolet rays are used, they are irradiated with a low-pressure or high-pressure mercury lamp, an ultrahigh pressure mercury lamp, a metal halide lamp, a xenon lamp, or the like. In particular, the light source is preferably a lamp having a high energy intensity of 350 to 450 nm.

The refractive index of the cured product of the curable resin composition of the present invention obtained by curing the active energy ray such as ultraviolet rays or heat is preferably 1.55 or more at 25 ° C or lower, more preferably 1.48 or more at 25 ° C. In particular, when an optical lens is produced from the resin composition for an optical material of the present invention, the refractive index of the cured product may not be 1.45 at 25 ° C, and there is a problem that a sufficient size of the lens module cannot be reduced.

Further, the number of Abbe of the cured product (the value inherent to the substance which defines the refractive index by the wavelength of light) is preferably 40.0 or more, and more preferably 45.0 or more. If the number of Abbe of the cured product is less than 40.0, the color difference is large, and the color is impregnated, which is not preferable.

The cured composite material obtained by molding and curing the curable resin composition of the present invention is excellent as an optical material such as a lens or a crucible. In particular, it can be used as an optical plastic lens such as an aspherical lens, a Fresnel lens, a long cylindrical lens, or a spectacle lens, and a coating material for an optical film or an optical bonding material. Then, an optical lens system obtained from the curable resin composition of the present invention can be advantageously used in a photographing apparatus. Further, the curable resin composition or the composite cured product may be used in applications suitable for photovoltaics such as optical disks, optical fibers, and optical waveguides, printing inks, paints, transparent layering agents, varnishes, and the like.

In addition, the curable resin composition of the present invention may be used as an adhesive, and the cured product produced by the curing may be used as an adhesive layer, and may be, for example, a mobile phone, a mobile game machine, or a digital camera.

When the polarizing film and the protective sheet are bonded to each other by using the curable resin composition of the present invention, for example, a protective sheet made of an alkali-free glass or quartz glass which is excellent in active energy ray permeability is not limited, and even a large ultraviolet absorbing acrylic acid is used. A protective sheet such as a plate or a polycarbonate can be used because of its good reaction hardenability.

The curable resin composition of the present invention is applied to a substrate such as a polarizing film, and is applied by a coating device such as a roll coater, a spin coater or a screen printing method, and has a thickness of the adhesive of 1 to 100 μm. The protective plate can be cured by irradiating ultraviolet rays from the protective plate to make it follow.

[Examples]

Next, the invention is illustrated by the examples, but the invention is not limited thereto. Moreover, any part of each of the examples is a part by weight. Further, the measurement of the softening temperature and the like in the examples was carried out by measuring and measuring the samples according to the methods shown below.

1) Molecular weight and molecular weight distribution of polymers

The molecular weight and molecular weight distribution of the copolymer were measured by using GPC (manufactured by Tosoh, HLC-8120GPC), solvent: tetrahydrofuran (THF), flow rate: 1.0 ml/min, and column temperature: 40 °C. The molecular weight of the copolymer was measured using a calibration curve of monodisperse polystyrene in terms of molecular weight in terms of polystyrene.

2) Polymer structure and solubility test

It was determined by 13C-NMR and 1H-NMR analysis using a JNM-LA600 type nuclear magnetic resonance spectroscope manufactured by JEOL Ltd. Using chloroform-d1 as a solvent, a resonance line of tetramethylnonane was used as an internal standard.

In the solubility test, 1 g of a copolymer was added to 100 ml of various organic solvents (toluene, xylene, tetrahydrofuran, dichloroethane, and chloroform) at 25 ° C, and the mixture was stirred for 30 minutes using a magnetic stir bar, and the solubility was visually confirmed. All of the above organic solvents were also dissolved, and when the formation of the gel was not observed, the solubility was ○.

3) Sample preparation and determination of glass transition temperature (Tg) and softening temperature

The thickness of the copolymer solution after drying on the glass substrate was uniformly applied to 20 μm, and then heated at 90 ° C for 30 minutes using a hot plate to be dried. The resin film on the obtained glass substrate was attached to a TMA (thermomechanical analyzer) measuring apparatus together with a glass substrate, and the temperature was raised to 220 ° C at a temperature increase rate of 10 ° C /min under a nitrogen gas flow, and further, heat treatment was performed at 220 ° C. Minutes to harden the resin. After the glass substrate was allowed to cool to room temperature, the sample in the TMA measuring apparatus was contacted with the probe for analysis, and the sample was scanned at a temperature increase rate of 10 ° C/min from 30 ° C to 360 ° C under a nitrogen gas flow, and the softening temperature was determined by a tangential method. . Depending on the heat resistance of the sample, when the probe does not penetrate the resin film and does not exhibit a probe intrusion amount smaller than the film thickness, the amount of penetration of the probe into the temperature and the film thickness is expressed as a percentage other than the softening temperature.

4) Determination of thermal weight loss and heat discoloration

The thermal decomposition temperature and the heat discoloration resistance of the copolymer were measured by mounting the sample on a TGA (thermal balance) measuring device, and measuring at a temperature increase rate of 10 ° C / min from 30 ° C to 320 ° C under a nitrogen gas flow to obtain a sample of 300 ° C. The amount of weight loss was measured, and the amount of discoloration of the sample after the measurement was visually confirmed, and classified into ◎: no thermal discoloration, ○: light yellow, Δ: brown, and X: black, and evaluation of heat discoloration resistance was performed.

5) Determination of water absorption rate

The test sample (hardened sheet) which was vacuum dried at 60 ° C for 24 hours was wo, and it was weighed in a constant temperature and humidity chamber with a scale of measurable to ±0.1 mg, temperature: 85 ° C, and relative humidity: 85%. Humidify for 1 week. After humidification, the moisture of the test sample is wiped off, and the sample is weighed to a scale of ±0.1 mg as W. The water absorption rate was calculated by the following formula (3), and three test samples were prepared in the same manner, and the test was carried out simultaneously.

Wo/W×100=Water absorption rate (3)

6) Determination of solvent resistance

The measurement of the solvent resistance of the copolymer was carried out by immersing the sample plate which was subjected to vacuum press forming at 200 ° C for one hour at room temperature for 10 minutes, and visually confirming the change of the sample after the immersion, and classifying it into ○: no change, Δ: Swelling, X: Deformation, expansion, and evaluation of solvent resistance.

7) Determination of refractive index

The synthesized soluble polyfunctional (meth) acrylate copolymer was dissolved in toluene, and 1.0 part by weight of Perbutyl O as a starter was added to 100 parts by weight of the soluble polyfunctional (meth) acrylate copolymer. A cast piece was prepared from this polymer solution, the cast piece was crushed, pelletized, filled in a press die, and hardened at 170 ° C for 1 hour by a press forming machine. The obtained hardened parallel plate was used as a test piece, and the refractive index of the d line (587.6 nm) was measured by KPR-200 (manufactured by Shimadzu Kalnew Co., Ltd.). After the measurement was performed, the machine was placed in a high-temperature and high-humidity apparatus at a humidity of 85 ° C × 85 RH for one week.

8) Adhesion test

The varnish diluted with a solvent (methyl ethyl ketone) was applied onto a glass substrate, dried at 80 ° C for 5 minutes, and then cured at 200 ° C for 1 hour in a nitrogen oven under a nitrogen atmosphere. Next, a glass substrate on which a coating film of a copolymer hardened was placed was engraved into a vertical and horizontal incision at intervals of 1 mm on the surface of the coating film in accordance with JIS K5400 to prepare 100 checkerboard eyes. After the cellophane tape was adhered to the surface, the number of quality eyes remaining without peeling off at the time of peeling was counted.

9) Preparation of test piece for measuring physical properties of a curable resin composition

A glass mold having a width of 50 mm, a length of 50 mm, and a thickness of 1.0 mm is opened between 0.2 mm and 1.0 mm, and a curable resin composition is injected into the glass mold which is crimped and fixed by a polyimide film at the outer periphery, 1) From the single side of the glass mold, the high-pressure mercury lamp was irradiated with ultraviolet rays for 5 seconds, or 2) the glass mold was placed in an inert gas oven under a nitrogen gas stream, and hardened by heating at 180 ° C for 1 hour. The cured resin sheet was peeled off from the glass mold and used for various physical properties.

10) Determination of refractive index

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

11) Hue (YI)

A plate having a thickness of 1.0 mm was measured by a color difference meter (trade name "MODEL TC-8600" or Tokyo Electric Co., Ltd.), and its YI value was shown.

12) Haze (turbidity) and total light transmittance

A 0.2 mm thick test piece was produced, and the haze (turbidity) and total light transmittance of the sample were measured using an integrating sphere type light transmittance measuring device (manufactured by Nippon Denshoku Co., Ltd., SZ-Σ90).

13) Release property: Evaluation was made by the ease with which the hardened resin was released from the mold.

○...Good release from the mold

△...It is a little difficult to release

X... It is difficult to get out of the mold or the mold is sticky.

14) Modular reproducibility: The surface shape of the hardened resin layer and the surface shape of the mold were observed.

○...reproducible

△...Reproducible according to the conditions of hardening (light, heat)

X...reproducible

15) Raw edges, color lines

The size of the burrs generated outside the product portion of the molded article when the hardened resin was released from the mold and the leakage of the resin to the gap of the mold were evaluated.

○... The amount of burrs generated was less than 0.05 mm, and the leakage of resin to the die gap was less than 1.0 mm.

△... The amount of burrs generated was 0.05 mm or more, less than 0.2 mm, and the resin was discharged to the mold gap by 1.0 mm or more and less than 3.0 mm.

X... The amount of burrs generated is 0.2 mm or more, and the resin is released to the die gap by 3.0 mm or more.

16) Reflow heat resistance: A parallel plate having a thickness of 1 mm was used as a test piece, and a spectral transmittance of a wavelength of 400 nm was measured by a spectrophotometer CM-3700d (manufactured by Konica Minolta Co., Ltd.). The measurement timing was performed after heat resistance test at 190 ° C for 60 minutes, and after heat resistance test at 260 ° C for 8 minutes in an air oven. 17) Heat cycle resistance

Using an ultra-high pressure mercury lamp of 157 mW, with an energy of 3000 mJ, the sample of the alkali-free glass (thickness: 0.7 mm) and the 2 mm-thick acrylic plate with a thickness of 25 μm was used for 1 cycle, -35 ° C for 30 minutes, and 85 ° C. After 100 cycles of the conditions of 30 minutes, the peeling of the two substrates was observed, and the peeling evaluation was ○, and the peeling evaluation was X.

18) Moisture resistance

Using a 157 mW ultra-high pressure mercury lamp, an alkali-free glass (thickness: 0.7 mm) and a 2 mm-thick acrylic plate were placed at a thickness of 25 μm with an energy of 3000 mJ, and observed at 60 ° C, 90% RH for 100 hours. The peeling of the two subsequent substrates was evaluated as ○ without peeling and X at the peeling evaluation.

19) Shape maintains heat resistance

After hardening, the spherical lens surface shape (shape 1) of the post-hardened composite cured layer was measured by a non-contact three-dimensional shape measuring apparatus manufactured by Sanying Optical Co., Ltd., and after three times of reflowing at 280 ° C. In the surface shape (shape 2) of the spherical lens of the cured body layer of the composite, the maximum value of the difference between the shape 1 and the shape 2 was calculated as the shape to maintain heat resistance.

Example 1

Dimethylol tricyclodecane diacrylate 3.2 mol (926.5 ml), isodecyl methacrylate 8.0 mol (1814.1 ml), 2-hydroxypropyl methacrylate 4.8 mol (645.5 ml), 2,4-Diphenyl-4-methyl-1-pentene 14.8 mol (1145.9 ml), 2400 ml of toluene was placed in a 10.0 liter reactor, and 240 mmol of benzoyl peroxide was added at 90 ° C. , the reaction was 6 hours. After the polymerization reaction was stopped by cooling, the reaction mixture was poured into a large amount of hexane at room temperature to precipitate a polymer, and the obtained polymer was washed with hexane, filtered, dried, and weighed to obtain a copolymer. A 1392.6 g (yield: 40.5 wt%).

The obtained copolymer A had Mw of 8,950, Mn of 3,470, and Mw/Mn of 2.58. By performing ¹³ C-NMR, ¹ H-NMR analysis and elemental analysis, the copolymer A contained 18.2 mol% of structural units derived from dimethylol tricyclodecane diacrylate, derived from methacrylic acid. The structural unit of the oxime ester was 51.1 mol% in total, and the structural unit derived from 2-hydroxypropyl methacrylate was 30.7 mol% in total. Further, the terminal group derived from the structure of 2,4-diphenyl-4-methyl-1-pentene is compared with dimethylol tricyclodecane diacrylate, isodecyl methacrylate, methacrylic acid. The total amount of 2-hydroxypropyl ester and 2,4-diphenyl-4-methyl-1-pentene was 8.3 mol%.

The copolymer A was soluble in toluene, xylene, tetrahydrofuran, dichloroethane or chloroform, and no gel formation was observed. Further, the cast film of the copolymer A is a transparent film having no fog.

The copolymer A was formed into a cured sheet according to various measurement conditions. The sample obtained by cutting out the cured sheet was subjected to measurement of optical characteristics, water absorption, thermal weight reduction, heat discoloration resistance, and solvent resistance.

As a result, the coefficient of linear expansion was 91 ppm/° C., the water absorption ratio was 0.98%, and the solvent resistance was ○.

Further, as a result of TMA measurement, the softening temperature was 300 ° C or more, and as a result of TGA measurement, the weight loss at 300 ° C was 1.8 wt%, and the heat discoloration resistance was ◎.

Further, after the refractive index measurement of the copolymer A, the refractive index after curing (589 nm): 1.520, and the refractive index after the wet heat test (589 nm): 1.514.

Further, after calculating the number of quality eyes remaining in the adhesion test, 100 mass eyes were not lacking, and it was confirmed that they remained on the substrate.

Examples 2 to 13 and Comparative Examples 1 to 6

Polymerization was carried out in the same manner as in Example 1 using various bifunctional acrylates and monofunctional (meth) acrylates in the same manner as in Example 1.

The amounts of the raw materials used for the reaction are shown in Tables 1 and 2, and the test results of the copolymer and the cured product thereof are shown in Tables 3 and 4. Other reaction conditions and measurement conditions are the same as in the first embodiment unless otherwise stated.

In Table 1, the amount of raw materials used is expressed in terms of moles and weight (g), but the description is in the form of mol/g.

The abbreviations shown in the table are indicated below.

DMTCD: Dimethylol tricyclodecane diacrylate (c)

BDDA: 1,4-butanediol diacrylate (c)

HOP: 2-hydroxypropyl methacrylate (b)

HO: 2-hydroxyethyl methacrylate (b)

CD570: Partially ethoxylated 2-hydroxyethyl methacrylate (b)

IBOMA: isodecyl methacrylate (a)

DCPM: Dicyclopentyl Methacrylate (a)

DCPA: Dicyclopentyl acrylate (a)

αMSD: 2,4-diphenyl-4-methyl-1-pentene (d)

DDME: n-dodecyl mercaptan

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 (tetraacrylate 3EG-A: manufactured by Kyoeisha Chemical Co., Ltd.)

FA-513AS: Dicyclopentyl acrylate (manufactured by Hitachi Chemical Co., Ltd.)

FA-129AS: decanediol diacrylate (manufactured by Hitachi Chemical Co., Ltd.)

SR205: Triethylene glycol dimethacrylate (Sartomer-SR205: manufactured by Sartomer Co., Ltd.)

EG: ethylene glycol dimethacrylate (lightEster EG: manufactured by Kyoeisha Chemical Co., Ltd.)

MEK-SD: methyl ethyl ketone-dispersed colloidal vermiculite (30% by weight of vermiculite, average particle size of 10 to 20 nm, and Snowtex MEK-SD-(1): manufactured by Nissan Chemical Co., Ltd.)

MEK-ST-MS: Methyl ethyl ketone-dispersed colloidal vermiculite (35% by weight of vermiculite, average particle size of 17 to 23 nm, MEK solvent, Snowtex MEK-ST-MS: manufactured by Nissan Chemical Co., Ltd.)

MEK-ST-L: methyl ethyl ketone-dispersed colloidal vermiculite (30% by weight of vermiculite, average particle size 40 to 50 nm, MEK solvent, Snowtex MEK-ST-L: manufactured by Nissan Chemical Co., Ltd.)

SC1050: Methyl ethyl ketone-dispersed colloidal vermiculite (average particle size 0.2-0.3 μm, MEK solvent, vermiculite content 65% by weight, SC 1050-MMA: manufactured by the company Adomatex)

AO-60: Antioxidant (Adekastab AO-60: manufactured by Adeka)

Perbutyl O: tert-butylperoxy-2-ethylhexanoate (manufactured by Nippon Oil & Fat Co., Ltd.)

Irgacure 184: 1-hydroxy-cyclohexyl-phenyl-ketone (manufactured by Ciba Specialty Chemicals Co., Ltd.)

In Table 4, G system indicates gelation, and in Tables 4 and 8, NM indicates that it is not measurable. In the gel formation of Tables 3 to 6, ○: indicates that there is, and X indicates no.

Synthesis Example 1

Copolymer A was obtained in the same manner as in Example 1.

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-Diphenyl-4-methyl-1-pentene 4.8 mol (1135 g) and 2400 ml of toluene were placed in a 10.0 liter reactor, and 240 mmol of benzoyl peroxide was added at 90 ° C. Reaction for 6 hours. After the polymerization reaction was stopped by cooling, the reaction mixture was poured into a large amount of hexane at room temperature to precipitate a polymer, and the obtained polymer was washed with hexane, filtered, dried, and weighed to obtain a copolymer B. .

The obtained copolymer B had Mw of 12,500, Mn of 3,640, and Mw/Mn of 3.43. By performing ¹³ C-NMR, ¹ H-NMR analysis and elemental analysis, the copolymer B contained a structural unit derived from 1,4-butanediol diacrylate in a total amount of 27.8 mol%, derived from biphenyl methacrylate. The structural unit of amyl ester totaled 27.8 mol%, and the structural unit derived from 2-hydroxypropyl methacrylate totaled 41.6 mol%. Further, the terminal group derived from the structure of 2,4-diphenyl-4-methyl-1-pentene is relative to 1,4-butanediol diacrylate, dicyclopentanyl methacrylate, methacrylic acid The total amount of 2-hydroxypropyl ester and 2,4-diphenyl-4-methyl-1-pentene was 10.1 mol%. The ratio of further suspension acrylate was 20.4 mol%.

The copolymer B was soluble in toluene, xylene, tetrahydrofuran, dichloroethane or chloroform, and no gel formation was observed. Further, the cast film of the copolymer B is a transparent film having no fog.

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-pentene 5 mol (1182 g), 2400 ml of toluene was placed in a 10.0 liter reactor, and 240 mmol of benzoyl peroxide was added at 90 ° C. hour. After the polymerization reaction was stopped by cooling, the reaction mixture was poured into a large amount of hexane at room temperature to precipitate a polymer, and the obtained polymer was washed with hexane, filtered, dried, and weighed to obtain a copolymer C. .

The obtained copolymer C had Mw of 9,230, Mn of 3210, and Mw/Mn of 2.88. By performing ¹³ C-NMR, ¹ H-NMR analysis and elemental analysis, the copolymer C contained a total of 45.6 mol% of structural units derived from 1,4-butanediol diacrylate, derived from bicyclo methacrylate. The structural unit of the amyl ester totaled 12.3 mol%, and the structural unit derived from 2-hydroxypropyl methacrylate totaled 42.1 mol%. Further, the terminal group derived from the structure of 2,4-diphenyl-4-methyl-1-pentene is relative to 1,4-butanediol diacrylate, dicyclopentanyl methacrylate, methacrylic acid The total amount of 2-hydroxypropyl ester and 2,4-diphenyl-4-methyl-1-pentene was 14.6 mol%. The ratio of further suspension acrylate was 32.6 mol%.

The copolymer C was soluble in toluene, xylene, tetrahydrofuran, dichloroethane or chloroform, and no gel formation was observed. Further, the cast film of the copolymer C is a transparent film having no fog.

Synthesis Examples 4 to 15 and Synthesis Examples 16 to 20

In the same manner as in Synthesis Example 1, various types of copolymers were synthesized by changing the types and amounts of acrylates as shown in Tables 1 and 2. Further, Synthesis Examples 1 to 15 are examples, and Synthesis Examples 16 to 20 are synthesis examples for comparison. The results are summarized in Tables 5-8.

Examples 14 to 38 and Comparative Examples 7 to 14

Additives such as various copolymers, (meth) acrylates, vermiculite fine particles, and polymerization initiators synthesized in the synthesis examples were mixed at a ratio shown in Tables 9 to 11 to obtain a curable composition. Next, the curable resin composition was hardened according to the various test methods described above, and performance evaluation was performed. The performance evaluation results are shown in Tables 9-11.

In Tables 5 to 8, the numbers of components (a) to (c) indicate the amount of use (mole), the number in parentheses is the % of moles in the acrylates, and the number of DMP indicates the amount of use (mole). The number in the bracket is the % of the mole relative to the total amount of the acrylate. Further, when MMA is used as another monomer component, it is calculated as an acrylate. Further, the content of each component is derived from the existence ratio (mole ratio) of the structural unit in which each component of the copolymer is present, but is calculated by the above formulas (1) to (5), respectively. Further, when MMA is used as another monomer component, it is calculated as a structural unit derived from an acrylate.

In Tables 9 to 11, the weight of the vermiculite of the component (C) is the solid component weight of the solvent component. In the evaluation of heat cycle resistance and moisture resistance, ○ indicates no peeling, and X indicates peeling.

Claims (9)

A soluble polyfunctional (meth) acrylate copolymer comprising: a monofunctional (meth) acrylate having an alicyclic structure (a), a monofunctional (meth) acrylate having an alcoholic hydroxyl group ( b) a copolymer obtained by copolymerizing a bifunctional (meth) acrylate (c) and a component of 2,4-diphenyl-4-methyl-1-pentene (d), and a reactive (meth) acrylate group (c1) derived from a bifunctional (meth) acrylate (c) in the side chain and having a 2,4-diphenyl-4-methyl group derived from the terminal a copolymer of a structural unit of 1-pentene (d) having a monounsity (meth) acrylate (a) having an alicyclic structure and having an alcoholic hydroxyl group when the total structural unit is 100 mol Molar number of structural units of functional (meth) acrylate (b), bifunctional (meth) acrylate (c) and 2,4-diphenyl-4-methyl-1-pentene (d) For (a), (b), (c) and (d), (a) is 10 to 55 m, (b) is 10 to 45 m, and (c) is 10 to 50 m, (d) Is 5 to 20 moles, and when the number of moieties of the structural unit containing a bifunctional (meth) acrylate group (c1) in the side chain is (c1), it is derived from a bifunctional (meth) acrylate (c) Reactivity The introduction amount of the (meth) acrylate group (c1) is 0.05 to 0.5 in terms of the molar fraction M _c1 represented by the following formula (2); M _c1 = (c1) / [(a) + ( b) + (c)] (2) and having a weight average molecular weight of from 2,000 to 20,000, further soluble in toluene, xylene, tetrahydrofuran, dichloroethane or chloroform. A soluble polyfunctional (meth) acrylate copolymer according to claim 1, wherein the aforementioned monofunctional structure having an alicyclic structure Acrylate (a) is isodecyl (meth)acrylate, isodecyl acrylate, cyclohexyl methacrylate, cyclohexyl acrylate, dicyclopentenyl acrylate, dicyclopentenyl oxyacrylate One or more selected from the group consisting of ester, dicyclopentanyl acrylate, dicyclopentenyloxyethyl methacrylate, dicyclopentenyloxyethyl methacrylate, and dicyclopentanyl methacrylate Functional (meth) acrylate. The soluble polyfunctional (meth) acrylate copolymer according to claim 1, wherein the monofunctional (meth) acrylate having an alcoholic hydroxyl group (b) is 2-hydroxypropyl methacrylate, A One or more (meth) acrylates having an alcoholic hydroxyl group selected from the group consisting of 2-hydroxyethyl acrylate and partially ethoxylated 2-hydroxy methacrylate. The soluble polyfunctional (meth) acrylate copolymer according to claim 1, wherein the aforementioned bifunctional (meth) acrylate (c) is composed of cyclohexane dimethanol diacrylate and dimethylol One or more bifunctional (meth) acrylates selected from the group consisting of cyclodecane diacrylate. A method for producing a soluble polyfunctional (meth) acrylate copolymer, which is a method for producing a soluble polyfunctional (meth) acrylate copolymer according to claim 1, which is characterized in that 2,4- Diphenyl-4-methyl-1-pentene (d) is present in an amount of 10 to 500 parts by weight relative to 100 parts by weight of the bifunctional (meth) acrylate (c), relative to a monofunctional having an alicyclic structure (meth) acrylate (a), monofunctional (meth) acrylate (b) having an alcoholic hydroxyl group, and bifunctional (meth) acrylate (c) in a total of 100 moles, and will contain an alicyclic ring Monofunctional (Meth) acrylate (a) 10 to 40 mol%, monofunctional (meth) acrylate having an alcoholic hydroxyl group (b) 10 to 40 mol%, and bifunctional (meth) acrylate (c) The monomer component of 20 to 50 mol% is polymerized at a temperature of 50 to 200 ° C in the presence of a radical polymerization initiator. A curable resin composition characterized by comprising (A) a component: a soluble polyfunctional (meth) acrylate copolymer according to claim 1 of the patent application, and (B) a component: a functional group having an unsaturated double bond One or more monomers having a molecular weight of 1000 or less and (C) components: a composite composition of vermiculite particles having an average particle diameter of 1 to 100 nm, and (A) component (A) component and (B) component The total blending amount is 2 to 83% by weight, the blending amount of the component (B) is 83 to 2% by weight, and the blending amount of the component (C) is 15 to 90% by weight. The curable resin composition of claim 6, wherein the component B is one or more selected from the group consisting of monofunctional (meth) acrylates and bifunctional (meth) acrylates having an alicyclic structure ( Methyl) acrylate. The curable resin composition of claim 6, wherein the photopolymerization initiator is further contained as the component (D). A cured product obtained by hardening a curable resin composition according to any one of claims 6 to 8.