WO2014157131A1

WO2014157131A1 - Curable resin composition, cured product, and optical article

Info

Publication number: WO2014157131A1
Application number: PCT/JP2014/058173
Authority: WO
Inventors: 林　健太郎; 次俊和佐野; 川辺　正直
Original assignee: 新日鉄住金化学株式会社
Priority date: 2013-03-25
Filing date: 2014-03-25
Publication date: 2014-10-02
Also published as: CN105073807A; JPWO2014157131A1; JP6525867B2; KR20150134398A

Abstract

Provided is a curable resin composition that exhibits superior optical properties, heat resistance, and accurate mold transferability, and is excellent as an optical lens or prism material. Also provided is a cured product of the same. The curable resin composition contains: 5.0-94wt% of a component (A), which is a polyfunctional copolymer having a plurality of reactive unsaturated groups, a Mw of 2,000-100,000, and solubility in a solvent such as toluene; 5.0-94wt% of a component (B), which is a (meth)acrylate including a bisphenolfluorene skeleton and at least one (meth)acryloyl group in a molecule; and 0.1-10wt% of a component (C), which is an initiator.

Description

Curable resin composition, cured product and optical article

The present invention relates to a curable resin composition, a cured product, and an optical article having excellent optical characteristics, heat resistance, and processability.

Conventionally, in the optical field such as camera lenses, relatively inexpensive thermoplastic resins such as polycarbonate resin, methacrylic resin, and alicyclic olefin polymer have been used. However, these thermoplastic resins have low heat resistance temperature and surface hardness, and have hardly been used in the advanced technical fields of optical and electronic materials that require high heat resistance, surface hardness and fine workability.

As a method for solving the disadvantages of such a thermoplastic polymer, Patent Document 1 is obtained by copolymerizing a monovinyl aromatic compound and a divinyl aromatic compound, and a reactive vinyl group derived from a divinyl aromatic compound is added to the side chain. A soluble polyfunctional copolymer having a structural unit is disclosed. However, although the soluble polyfunctional copolymer obtained by the technology disclosed therein has excellent heat resistance against heat history at high temperature, it has high workability required for the advanced field. It was difficult to achieve both refractive indexes.

On the other hand, bisphenol fluorene derivatives have a high refractive index and high heat resistance because they have a large number of aromatic rings, and also have features of low birefringence and low cure shrinkage because they form surfaces with different ring structures. have. Although these features are very excellent for use as an optical molding material, they are not sufficient in terms of the accuracy and strength of the optical surface shape in optical lens applications. Therefore, it has excellent optical properties, has a good balance of properties such as low water absorption, moldability, heat resistance, and surface hardness. In addition, it adheres to optical properties and inorganic materials under severe actual use conditions such as wet heat conditions. So far, there has been no soluble polyfunctional copolymer with improved moldability and precise transfer of mold shape, and a curable resin composition using the copolymer.

JP 2008-247978 A Japanese Patent No. 4558643 JP 2009-109579 A

The present invention has excellent optical properties such as high refractive index and high light transmittance, heat resistance, and processability, in addition, optical properties under severe actual use conditions such as wet heat conditions, and low water absorption. Good releasability during molding, scratch resistance, toughness, surface hardness, and soluble polyfunctional copolymer (A) with improved mold transferability and reactivity with bisphenolfluorene skeleton (meta) It aims at providing the curable resin composition, cured | curing material, and optical article which comprise an acrylate (B).

The present invention comprises the component (A): a plurality of reactive unsaturated groups, a weight average molecular weight of 2,000 to 100,000, and further soluble in toluene, xylene, tetrahydrofuran, dichloroethane, or chloroform. A polyfunctional copolymer obtained by copolymerizing a monomer having two saturated groups and a monomer having one;
(B) component: a (meth) acrylate having a fluorene skeleton represented by the general formula (1), and (C) component: a curable resin composition containing an initiator, wherein (A) to (C) The content of component (A) is 5.0 to 94 wt%, the content of component (B) is 5.0 to 94 wt%, and the content of component (C) is 0.1 to 10 wt% with respect to the total of components It is a curable resin composition.

(In the formula, R ₁ and R ₂ independently represent H or CH ₃ —, and R ₃ and R ₄ independently represent —CH ₂ O—, —CH ₂ CH ₂ O—, —CH ₂ CH (CH ₃ ) O—, —CH ₂ CH ₂ CH ₂ O—, —CH ₂ CH (OH) CH ₂ O—, or CH ₂ CH (OR ₅ ) CH ₂ O—, wherein R ₅ is a meta (acryloyl) group. , K and l are each independently 0 or a number of 1 or more, k + l is a number of 1 or more, and m and n independently represent a number of 0 to 4.)

In the present invention, the polyfunctional copolymer of the component (A) is a monofunctional (meth) acrylic acid ester (a) having an aromatic ring or alicyclic structure, and one or more types of bifunctional (meth) acrylic acid. A copolymer obtained by copolymerizing a component containing an ester (b), 2,4-diphenyl-4-methyl-1-pentene (c) and a thiol compound (d), and having bifunctional ( A structural unit derived from 2,4-diphenyl-4-methyl-1-pentene (c) and a thiol compound (d) having a reactive (meth) acrylic group derived from (meth) acrylic acid ester (b) It is a polyfunctional copolymer having the above-mentioned curable resin composition.

In the present invention, the polyfunctional copolymer of the component (A) is obtained by copolymerizing the monovinyl aromatic compound (e), the divinyl aromatic compound (f) and the aromatic ether compound, and has a side chain. A structural unit derived from an aromatic ether compound represented by the following formula (2) having a reactive vinyl group derived from a divinyl aromatic compound (f) and having an average of 1 or more per molecule at its end. It is a polyfunctional copolymer having the above-mentioned curable resin composition.

(In the formula, R ₆ represents H or CH ₃ , and R ₇ represents a hydrocarbon group having 1 to 18 carbon atoms which may contain an oxygen atom or a sulfur atom.)

Furthermore, the present invention provides a (meth) acrylate having 1 to 8 (meth) acryloyl groups in the molecule as the component (D) in addition to the components (A), (B) and (C) (provided that And (A) and (B) except for the above case), and the content of component (A) with respect to the total of components (A) to (D) is 5.0 to 84 wt%, and component (B) The content of the component (C) is 0.1 to 10 wt%, the content of the component (D) is 10 to 70 wt%, and the components (A) to (D) The curable resin composition described above, wherein the total amount of the component (A) and the component (B) is 30 to 90 wt% with respect to 100 parts by weight in total.

Further, the present invention is a cured resin obtained by curing the curable resin composition, and an optical article formed from the cured resin. Such optical articles include optical lenses, microlens arrays, and imaging devices.

The curable resin composition of the present invention or a cured resin obtained by curing this has excellent optical properties such as high refractive index, low birefringence, and high transparency, heat resistance, and processability, In addition, optical properties under severe actual use conditions such as reflow conditions, low water absorption and good mold release during molding, scratch resistance, toughness, surface hardness, and precise mold transfer are improved. . The cured resin of the present invention is excellent as an optical lens / prism material.

Hereinafter, the curable resin composition of the present invention will be described. First, the components (A) to (C) blended as essential components will be described.

The component (A) of the present invention has a plurality of reactive unsaturated bonds, has a weight average molecular weight of 2,000 to 100,000, and is further soluble in toluene, xylene, tetrahydrofuran, dichloroethane or chloroform. Is used. Hereinafter, the polyfunctional copolymer as the component (A) may be abbreviated as a copolymer.

The component (A) is a soluble polyfunctional copolymer, but the term “soluble” means soluble in toluene, xylene, tetrahydrofuran, dichloroethane or chloroform. Preferably it is soluble in all of the above solvents. The solubility test is performed under the conditions shown in the examples.

The copolymer (A) is composed of a monomer having one polymerizable reactive unsaturated group such as a monovinyl compound (monofunctional component) and a monomer having two polymerizable reactive unsaturated groups such as a divinyl compound (2 It is advantageously obtained by copolymerizing a monomer component mainly composed of a functional component). The bifunctional component provides a branched structure or a crosslinked structure, but the abundance of such a crosslinked structure is limited to the extent that it is soluble. The terminal of the branched structure contains an unreacted unsaturated group derived from a bifunctional component such as a divinyl compound. Therefore, it is a copolymer having an unreacted (meth) acryl group derived from a bifunctional component or an unsaturated group such as a vinyl group in the side chain. This unreacted unsaturated group is also referred to as a pendant (meth) acryl group or a pendant vinyl group, and since it exhibits polymerizability, it can be polymerized by further polymerization treatment to give a solvent-insoluble resin cured product. The average number of unreacted unsaturated groups needs to be 2 or more per molecule, but is preferably 3 or more. In order to increase the ratio of the unreacted unsaturated group, it is possible to increase the amount of the bifunctional component used for polymerization using a chain transfer agent.

Preferred copolymers include monofunctional (meth) acrylic acid ester (a) having an aromatic ring or alicyclic structure as a monomer having one unsaturated group, and one kind of monomer having two unsaturated groups. The above bifunctional (meth) acrylic acid ester (b) is used, and 2,4-diphenyl-4-methyl-1-pentene (c) and thiol compound (d) are used as subcomponents and polymerized. There is a copolymer (A-1) obtained as above.

Monofunctional monomer (meth) acrylic acid ester (a-1) having an aromatic ring structure constituting copolymer (A-1) includes benzyl acrylate, phenyl acrylate, phenoxyethyl acrylate, 2-naphthyl acrylate, thiophenol Examples thereof include one or more monofunctional (meth) acrylic acid esters selected from the group consisting of acrylates such as acrylate and benzyl mercaptan acrylate, and methacrylates thereof. Moreover, as monofunctional monomer (meth) acrylic acid ester (a-2) having an alicyclic structure, from acrylates such as cyclohexyl acrylate, dicyclopentanyl acrylate, dicyclopentenyl acrylate, isobornyl acrylate, and these methacrylates One or more monofunctional (meth) acrylic acid esters selected from the group consisting of can be mentioned, but the invention is not limited thereto.

Examples of the bifunctional (meth) acrylic acid ester (b) constituting the copolymer (A-1) include ethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, 1,4-butanediol di (meth) ) Acrylate, 1,6-hexanediol di (meth) acrylate, diethylene glycol di (meth) acrylate cyclohexane dimethanol di (meth) acrylate, dimethylol tricyclodecane di (meth) acrylate, EO modified bisphenol A diacrylate, Use bifunctional (meth) acrylic esters such as PO-modified bisphenol A diacrylate, 2,4-di (meth) acryloyloxynaphthalene, 9,9-bis [4-2 (-acryloyloxyethoxy) phenyl] fluorene However, it is not limited to these. Here, EO and PO mean ethylene oxide and propylene oxide.

When it is desired to impart functions such as toughness, releasability and reactivity to the copolymer (A-1), it can be arbitrarily adjusted depending on the (meth) acrylate used. Specific examples of (meth) acrylic acid esters include dicyclopentanyl (meth) acrylate, isobornyl (meth) acrylate having an alicyclic structure in terms of cost, ease of polymerization control and heat resistance of the obtained polymer, Cyclohexane dimethanol di (meth) acrylate and dimethylol tricyclodecane di (meth) acrylate are preferably used. In addition, n-butyl acrylate, n-hexyl acrylate, ethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, which do not have an alicyclic structure, in terms of moldability such as toughness and releasability of the cured product 1,4-butanediol di (meth) acrylate, hexanediol di (meth) acrylate, and diethylene glycol di (meth) acrylate are preferably used.

2,4-diphenyl-4-methyl-1-pentene (c) and thiol compound (d) function as a chain transfer agent and 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 100,000 as the weight average molecular weight Mw (where Mw is the weight average molecular weight in terms of standard polystyrene measured using gel permeation chromatography), preferably Is in the range of 2,500-60,000, more preferably 3,000-50,000. By using a copolymer having this molecular weight range, the moldability and mold release property of the cured resin can be further improved.

The thiol compound (d) may be any thiol compound known to act as a chain transfer agent, preferably t-dodecyl mercaptan, n-dodecyl mercaptan, t-octyl mercaptan, n-octyl mercaptan, Trimethylolpropane tris-3-mercaptopropionate, pentaerythritol tetrakis-3-mercaptopropionate, dipentaerythritol hex-3-mercaptopropionate and (tris-[(3-mercaptopropionyloxy) -ethyl ] -Isocyanurate). Of these, t-dodecyl mercaptan, n-dodecyl mercaptan, t-octyl mercaptan, n-octyl mercaptan, etc. are particularly preferably used from the viewpoint of ease of polymerization control and toughness of the produced copolymer. Is a monoalkyl mercaptan having 5 to 30 carbon atoms.

As another preferred copolymer, a monovinyl aromatic compound (e) is used as a monomer having one unsaturated group, a divinyl aromatic compound (f) is used as a monomer having two unsaturated groups, and There is a copolymer (A-2) obtained by using an aromatic ether compound as an accessory component.

The copolymer (A-2) includes the structural unit derived from the monovinyl aromatic compound (e) and the structural unit derived from the divinyl aromatic compound (f), as well as the above formula (2) derived from the aromatic ether compound. ) (Hereinafter also referred to as structural unit (g)). And the terminal group represented by the said Formula (2) is called terminal group (g). In general, it is desirable that the polymer chain (main chain and side chain) of the copolymer is generated from a divinyl aromatic compound and a monovinyl aromatic compound, and a part of the terminal is generated from an aromatic ether compound.

Preferred examples of the aromatic ether compound that gives the structural unit (g) or the terminal group (g) include 2-phenoxyethyl (meth) acrylate and alkoxylated 2-phenoxyethyl (meth) acrylate. However, it is not limited to these. In view of reactivity, heat resistance of the cured product, and availability, 2-phenoxyethyl (meth) acrylate is more preferable. Since 2-phenoxyethyl (meth) acrylate has a polymerizable group, it can be copolymerized with other monomers, but in order to become a terminal group (g), the polymerizable group has low reactivity, Most of them remain unreacted, and the benzene ring preferably has a structure in which the vinyl group of the divinyl aromatic compound (f) is reacted.

In the above formula (2), R ₆ represents H or CH _3, which depends on the aromatic ether compound used. R ₇ represents a hydrocarbon group having 1 to 18 carbon atoms which may contain an oxygen atom or a sulfur atom between carbon chains, preferably a hydrocarbon group having 1 to 6 carbon atoms, more preferably —CnH _2n An alkylene group represented by-. Here, n is more preferably in the range of 1 to 4.

As the monovinyl aromatic compound (e), one or more vinyl aromatic compounds selected from the group consisting of styrene, ethyl vinyl benzene, vinyl biphenyl and vinyl naphthalene are 50 mol% or more, preferably 70 mol% or more, more preferably A monovinyl aromatic compound containing 85 mol% or more is preferably used.

In addition, the monovinyl aromatic compound (e) may contain a monovinyl aromatic compound other than those described above, and may preferably contain a small amount of less than 50 mol%. Examples of these monovinyl aromatic compounds include nuclear alkyl substituted monovinyl aromatic compounds, α-alkyl substituted monovinyl aromatic compounds, β-alkyl substituted styrenes, alkoxy substituted styrenes and the like. Styrene, ethyl vinyl benzene (both isomers of m- and p-), ethyl vinyl biphenyl (including each isomer) to prevent copolymer gelation and improve solubility in solvents and processability ) Is suitable from the viewpoint of cost and availability.

Examples of divinyl aromatic compounds (f) include divinylbenzene (m- and p-isomers), divinylnaphthalene (including isomers), divinylbiphenyl (including isomers), etc. Although it can, it is not limited to these. Moreover, these can be used individually or in combination of 2 or more types. In particular, divinylbenzene (both isomers of m- and p-) is required from the viewpoint of cost and availability. When higher heat resistance is required, divinylnaphthalene (including each isomer), divinylbiphenyl (Including each isomer) is preferably used.

The Mw of the copolymer used in the present invention is in the range of 2,000 to 100,000, preferably 2,500 to 60,000, more preferably 3,000 to 50,000. If the Mw is less than 2,000, the copolymer is too low in viscosity, so that the processability is lowered. On the other hand, if the Mw exceeds 100,000, gel is easily formed and compatibility cannot be expected. The value of the molecular weight distribution (Mw / Mn) is 50.0 or less, preferably 20.0 or less, more preferably 1.5 to 3.0. When Mw / Mn exceeds 50.0, problems such as deterioration of the processing properties of the copolymer and generation of gel occur.

Since the copolymer used in the present invention has a (meth) acrylate group at the side chain or terminal, copolymerization with the (meth) acrylate compound can proceed well, and the (meth) acrylate compound and Very compatible with resin. Therefore, when it is copolymerized with a (meth) acrylate compound and cured, it is excellent in uniform curability and transparency.

The copolymer of component (A) used in the present invention is in accordance with the methods described in Patent Document 1, Japanese Patent Application Laid-Open No. 2004-123873, Japanese Patent Application Laid-Open No. 2005-213443, Japanese Patent Application Laid-Open No. 2010-229263, and the like. Obtainable.

Next, (meth) acrylate used as the component (B) of the curable resin composition of the present invention will be described.

The component (B) is a (meth) acrylate represented by the general formula (1) and having a fluorene skeleton. In general formula (1),
R ₁ and R ₂ are independently H or CH ₃ ,
R ₃ and R ₄ are independently CH ₂ O, CH ₂ CH ₂ O, CH ₂ CH (CH ₃ ) O, CH ₂ CH ₂ CH ₂ O, CH ₂ CH (OH) CH ₂ O, or CH ₂ CH (OR ₅ ) CH ₂ O.
R ₅ is a meta (acryloyl) group, and k and l are each independently 0 or a number of 1 or more, but both cannot be 0. Preferably, k + 1 is 0-4.
m and n independently represent a number from 0 to 4.
R ₃ and R ₄ are CH ₂ CH ₂ O, CH ₂ CH (OH) CH ₂ O, or CH ₂ CH (OR _{5 in} order to balance the properties such as high refractive index, compatibility, and reactivity in a balanced manner. ) CH ₂ O is preferred, and m and n are preferably 1 to 2. Further, the number of (meth) acryloyl groups possessed by this (meth) acrylate is preferably 1 to 4, more preferably 2 to 4.

Examples of the (meth) acrylate of the component B include, as a specific compound, a diacryl monomer having a bisphenolfluorene skeleton, a dimethacryl monomer, or a monomer having an acrylic group and a methacryl group. Specifically, 9,9-bis (4- (meth) acryloyloxyphenyl) fluorene, 9,9-bis (4- (meth) acryloyloxymethoxyphenyl) fluorene, 9,9-bis (4- (2 -(Meth) acryloyloxyethoxy) phenyl) fluorene, 9,9-bis (4- (2- (meth) acryloyloxypropoxy) phenyl) fluorene, 9,9-bis (4- (3- (meth) acryloyloxy) (Propoxy) phenyl) fluorene, 9,9-bis (4- (meth) acryloyloxydimethoxyphenyl) fluorene, 9,9-bis (4- (meth) acryloyloxydiethoxyphenyl) fluorene, 9,9-bis (4 -(Meth) acryloyloxydipropoxyphenyl) fluorene, 9,9-bis (4- (meth) acryloyloxytrimethoxyphenyl) fluorene, 9,9-bis (4- (meth) acryloyloxytriethoxyphenyl) fluorene, 9,9-bis (4- (meth) acryloylio Xytripropoxyphenyl) fluorene, 9,9-bis (4- (meth) acryloyloxy-3-methylphenyl) fluorene, 9,9-bis (4- (meth) acryloyloxymethoxy-3-methylphenyl) fluorene, 9,9-bis (4- (2- (meth) acryloyloxyethoxy) -3-methylphenyl) fluorene, 9,9-bis (4- (2- (meth) acryloyloxypropoxy) -3-methylphenyl) Fluorene, 9,9-bis (4- (3- (meth) acryloyloxypropoxy) -3-methylphenyl) fluorene, 9,9-bis (4- (meth) acryloyloxydimethoxy-3-methylphenyl) fluorene, 9,9-bis (4- (meth) acryloyloxydiethoxy-3-methylphenyl) fluorene, 9,9-bis (4- (meth) acryloyloxydipropoxy-3-methylphenyl) fluorene, 9,9- Bis (4- (meth) acryloyloxytrimethoxy-3-methylphenyl) full 9,9-bis (4- (meth) acryloyloxytriethoxy-3-methylphenyl) fluorene, 9,9-bis (4- (meth) acryloyloxytripropoxy-3-methylphenyl) fluorene, 9, 9-bis (4- (meth) acryloyloxy-3-ethylphenyl) fluorene, 9,9-bis (4- (meth) acryloyloxymethoxy-3-ethylphenyl) fluorene, 9,9-bis (4- ( 2- (meth) acryloyloxyethoxy) -3-ethylphenyl) fluorene, 9,9-bis (4- (2- (meth) acryloyloxypropoxy) -3-ethylphenyl) fluorene, 9,9-bis (4 -(3- (meth) acryloyloxypropoxy) -3-ethylphenyl) fluorene, 9,9-bis (4- (meth) acryloyloxydimethoxy-3-ethylphenyl) fluorene, 9,9-bis (4- ( (Meth) acryloyloxydiethoxy-3-ethylphenyl) fluorene, 9,9-bis (4- (meth) acrylo Ruoxydipropoxy-3-ethylphenyl) fluorene, 9,9-bis (4- (meth) acryloyloxytrimethoxy-3-ethylphenyl) fluorene, 9,9-bis (4- (meth) acryloyloxytriethoxy -3-ethylphenyl) fluorene, 9,9-bis (4- (meth) acryloyloxytripropoxy-3-ethylphenyl) fluorene, 9,9-bis (4- (meth) acryloyloxy-3-propylphenyl) Fluorene, 9,9-bis (4- (meth) acryloyloxymethoxy-3-propylphenyl) fluorene, 9,9-bis (4- (2- (meth) acryloyloxyethoxy) -3-propylphenyl) fluorene, 9,9-bis (4- (2- (meth) acryloyloxypropoxy) -3-propylphenyl) fluorene, 9,9-bis (4- (3- (meth) acryloyloxypropoxy) -3-propylphenyl) Fluorene, 9,9-bis (4- (meth) acryloyloxydimethoxy Cy-3-propylphenyl) fluorene, 9,9-bis (4- (meth) acryloyloxydiethoxy-3-propylphenyl) fluorene, 9,9-bis (4- (meth) acryloyloxydipropoxy-3- Propylphenyl) fluorene, 9,9-bis (4- (meth) acryloyloxytrimethoxy-3-propylphenyl) fluorene, 9,9-bis (4- (meth) acryloyloxytriethoxy-3-propylphenyl) fluorene 9,9-bis (4- (meth) acryloyloxytripropoxy-3-propylphenyl) fluorene, 9,9-bis (4- (meth) acryloyloxy- (2-hydroxy) propoxyphenyl) fluorene, 9-bis (4- (meth) acryloyloxy- (2-hydroxy) propoxy-3-methylphenyl) fluorene, 9,9-bis (4- (meth) acryloyloxy- (2-hydroxy) propoxyethoxyphenyl) fluorene , Bisphenol Acrylic acid adduct of glycidyl ether of orange hydroxy acrylate, ie 9,9-bis (4-hydroxyphenyl) fluorene (manufactured by Nippon Steel Chemical Co., Ltd.), bisphenol full orange methacrylate (manufactured by Nippon Steel Chemical Co., Ltd.), bisphenoxyethanol full orange Acrylate (Osaka Gas Co., Ltd., BPEF-A), bisphenoxyethanol full orange methacrylate (Osaka Gas Co., Ltd., BPEF-MA), bisphenoxyethanol full orange epoxy acrylate (Osaka Gas Co., Ltd., BPEF-GA) ), Bisphenol full orange epoxy acrylate (manufactured by Osaka Gas Co., Ltd., BPF-GA), biscresol full orange epoxy acrylate (manufactured by Osaka Gas Co., Ltd., BCF-GA), and the like.

(C) Component initiator includes photopolymerization initiator or thermal polymerization initiator. Here, as the photopolymerization initiator, compounds such as acetophenone-based, benzoin-based, benzophenone-based, thioxanthone-based, and acylphosphine oxide-based compounds can be suitably used. Specifically, trichloroacetophenone, diethoxyacetophenone, 1-phenyl-2-hydroxy-2-methylpropan-1-one, 1-hydroxycyclohexyl phenyl ketone, 2-methyl-1- (4-methylthiophenyl) -2 -Morpholinopropan-1-one, benzoin methyl ether, benzyldimethyl ketal, benzophenone, thioxanthone, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, methylphenylglyoxylate, camphorquinone, benzyl, anthraquinone, Michler's ketone, etc. can do. Moreover, the photoinitiator adjuvant and the sharpening agent which show an effect in combination with a photoinitiator can also be used together. These photopolymerization initiators may be used alone or in combination of two or more.

In addition, as the thermal polymerization initiator, various organic peroxides such as ketone peroxide, peroxyketal, hydroperoxide, dialkyl peroxide, diacyl peroxide, peroxydicarbonate, peroxyester, etc. A thing can be used conveniently. Specifically, cyclohexanone peroxide, 1,1-bis (t-hexaperoxy) cyclohexanone, cumene hydroperoxide, dicumyl peroxide, benzoyl peroxide, diisopropyl peroxide, t-butylperoxy 2-ethyl Although hexanoate etc. can be illustrated, it is not restrict | limited at all to this. These thermal polymerization initiators may be used alone or in combination of two or more.

In addition to the above components (A) to (C), if necessary, as a component (D), a (meth) acrylate having 1 to 8 (meth) acryloyl groups in the molecule (provided that the above (A), (B ) Except for cases corresponding to ingredients. In this case, the content of the curable resin composition is such that the content of the component (A) is 5.0 to 84 wt% with respect to the total of the components (A) to (D), the content of the component (B) is 5.0 to 84 wt%, And (C) component 0.1 to 10 wt%, (D) component content 10 to 70 wt%, and (A) component to (A) component (A) to 100 parts by weight of component (A) And (B) the total blending amount is preferably 30 to 90 wt%.

As the component (D), 1 to 8 functional (meth) acrylate is used. Among these, those having two or more (meth) acryloyl groups in the molecule are called polyfunctional (meth) acrylates, and preferably one or more of polyfunctional (meth) acrylates are used. Advantageously, the component (D) should have an average of 2 to 5 (meth) acryloyl groups per molecule. Here, the average number of (meth) acryloyl groups per molecule is calculated by the total number of (meth) acryloyl groups / total number of molecules, and the total number of molecules of (meth) acrylate having one or more (meth) acrylate groups. Although calculated as a sum, the components (A) and (B) and the (meth) acryloyl groups contained in them are excluded from the calculation.
These polyfunctional acrylates used as the component (D) are synergistically combined with the component (A) and the component (B), such as low color dispersion and high light transmittance, in addition to heat resistance and surface hardness. The optical properties are improved at the same time.

The polyfunctional (meth) acrylate is preferably copolymerizable with the component (A) and the component (B), such as 1,4-butanediol di (meth) acrylate, 1,6-hexanediol diester. (Meth) acrylate, 1,9-nonanediol di (meth) acrylate, bisphenol A polyethoxydi (meth) acrylate, bisphenol A polypropoxydi (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 Sa (meth) acrylate, polyethylene glycol di (meth) acrylate, tris (acryloxyethyl) isocyanurate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, tripentaerythritol hexa (meth) acrylate, tri Pentaerythritol penta (meth) acrylate, neopentyl glycol di (meth) acrylate hydroxybivalate, di (meth) acrylate of ε-caprolactone adduct of neopentyl hydroxybivalate (eg, Nippon Kayaku Co., Ltd.) , KAYARADHX-220, HX-620, etc.), trimethylolpropane tri (meth) acrylate, trimethylolpropane polyethoxytri (meth) acrylate, ditrimethylolpropane tetra (meth) Mention may be made of monomers such as acrylate, cyclohexanedimethanol di (meth) acrylate and dimethyloltricyclodecane di (meth) acrylate. From the viewpoint of surface hardness, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol hexa (meth) acrylate, tripentaerythritol hexa (meth) acrylate, tripentaerythritol penta (meth) ) Acrylate, trimethylolpropane polyethytri (meth) acrylate, and ditrimethylolpropane tetra (meth) acrylate.
On the other hand, from the viewpoint of the shape accuracy of the optical surface, preferred are cyclohexanedimethanol di (meth) acrylate and dimethyloltricyclodecanedi (meth) acrylate.

In addition, as the component (D), one or more monofunctional (meth) acrylates having one (meth) acryloyl group in the molecule can be used, but these monofunctional (meth) acrylates are ( By using together with A) component, (B) component and polyfunctional (meth) acrylate, the optical properties such as high color dispersion, low color dispersion, and high light transmittance are improved synergistically, and fluidity is improved. By raising, moldability can be improved. As the monofunctional (meth) acrylate, monofunctional (meth) acrylic acid ester (a) having an alicyclic structure used for producing the copolymer as component (A) is preferably used. In addition, 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 polyethoxy (meth) acrylate, p-cumylphenoxyethyl (meth) acrylate, isobornyl (meth) acrylate, tribromophenyloxyethyl (meth) acrylate, dicyclopentanyl (meth) acrylate, dicyclopentenyl (meth) ) Acrylate, dicyclopentenyloxyethyl (meth) acrylate, and the like.

The preferred blending composition of the curable resin composition of the present invention is as follows. The blending amount of component (A) is 5.0 to 80 wt%, preferably 5.0 to 60 wt%, the blending amount of component (B) is 5.0 to 80 wt%, preferably 10 to 60 wt%, and the blending amount of component (C) is 0.1 ~ 10wt%, preferably 0.1-5wt%. When the component (D) is blended, the amount of the component (D) is 10 to 70 wt%, preferably 20 to 60 wt%, based on the blending amount of the components (A) to (C). The content of component (A) + component (B) is 30 to 90 wt%, preferably 40 to 80 wt%.

When the blending amount of the component (A) is lower than 5.0 wt%, it is not preferable because the accuracy of the optical surface shape of the molded product is lowered, and when the blending amount of the component (A) is too large, the viscosity increases. In association with this, the moldability and handling properties are remarkably lowered, which is not preferable. On the other hand, if the blending amount of the component (B) is lower than 5.0 wt%, the refractive index of the cured product is lowered, which is not preferable. If it is too large, the cured product has low elasticity and the heat resistance of the molded product is lowered. It is not preferable. In addition, when an organic solvent and a filler are included in the curable resin composition, the blending amount is calculated by excluding this.

In addition, the curable resin composition of the present invention includes a polymerization inhibitor, an antioxidant, a release agent, a photosensitizer, an organic solvent, a silane coupling agent, a leveling agent, an antifoaming agent, and an antistatic agent as necessary. Furthermore, ultraviolet absorbers, light stabilizers, various inorganic and organic fillers, fungicides, antibacterial agents, and the like can be added to the curable resin composition of the present invention to impart desired functionality, respectively. is there.

The curable resin composition of the present invention can be obtained by mixing the component (A), the component (B), the component (C), and the component (D), if necessary, and other components in any order. . The curable resin composition of the present invention is stable over time.

The curable resin composition of the present invention can be cured by heating or light irradiation. When molding by heating, the molding temperature can be selected from a wide range from room temperature to around 200 ° C., depending on the selection of the thermal polymerization initiator.
In the case of molding by light irradiation, a cured product can be obtained by irradiating 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. When the curable resin composition of the present invention is cured by ultraviolet irradiation, the ultraviolet irradiation amount necessary for curing may be about 300 to 20,000 mJ / cm ² . In addition, a resin composition can be hardened more efficiently by hardening in inert gas atmosphere, such as nitrogen gas.

The curable resin composition of the present invention can be used for castings such as plastic lenses. As a method for producing a plastic lens using the resin composition of the present invention, a mold made of a gasket made of polyvinyl chloride, an ethylene vinyl acetate copolymer or the like and two glass molds having a desired shape is prepared. There is a method in which after the resin composition of the present invention is injected, the resin composition is cured by irradiating active energy rays such as ultraviolet rays, and the cured product is peeled off from the mold.

In addition, as a method for applying the curable resin composition of the present invention to a film-like substrate as a resin composition for a prism lens sheet, various methods known in the industry can be used. As a specific method, for example, a resin composition is coated on a mold having a prism lens shape on the surface, a resin composition layer is provided, and a colorless and transparent film-like substrate is formed on the resin composition layer. A material (for example, polyvinyl chloride, polystyrene, polycarbonate, poly (meth) acrylate, polyester, polyethylene terephthalate, etc.) is pressure-bonded so that bubbles do not enter, and then in that state, ultraviolet light is used from the film-like substrate side using a high-pressure mercury lamp. The film-like base material on which the prism lens-like resin layer is formed can be peeled off from the mold after curing the resin composition layer.

The cured resin obtained by molding and curing the curable resin composition of the present invention is excellent as an optical material or an optical article. In particular, it is useful as a material for optical plastic lenses such as Fresnel lenses, lenticular lenses, spectacle lenses, and aspheric lenses. And such a lens is used advantageously for an imaging device. In addition, the curable resin composition or the cured resin 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.

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 unless otherwise specified. Moreover, the measurement of the softening temperature etc. in an Example performed sample preparation and measurement with the method shown below.

(Measurement of physical properties of copolymer and its cured product)
1) Polymer molecular weight and molecular weight distribution GPC (Tosoh, HLC-8120GPC) is used for measuring the molecular weight and molecular weight distribution of the soluble polyfunctional copolymer, solvent: tetrahydrofuran (THF), flow rate: 1.0 ml / min, column temperature. : Performed at 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 ¹³ C-NMR and ¹ H-NMR analysis using a JNM-LA600 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) Measurement of solvent resistance and measurement of solvent solubility The solvent resistance was measured by immersing a sample plate prepared by vacuum press-molding the copolymer at 200 ° C for 1 hour in toluene at room temperature for 10 minutes. The change of the sample was visually confirmed, and the solvent resistance was evaluated by classifying it as ○: no change, Δ: swelling, ×: deformation, and swelling.
The solvent solubility was measured by adding 5 g of the copolymer to 100 ml of solvent and observing the dissolution state after stirring for 10 minutes at 25 ° C. When it was dissolved uniformly and the presence of undissolved matter and gel was not recognized, it was determined to be soluble.

(Measurement of physical properties of composition and its cured product)
(1) Refractive index measurement In order to measure the refractive index of the resin composition, a gap of 1.0mm thickness is opened between two glass plates 50mm wide, 50mm long and 1.0mm thick, and the outer periphery is fixed with polyimide tape. Inject the composition into the glass mold, 1) irradiate the glass mold with ultraviolet light for several seconds from the one side of the glass mold, or 2) use a SUS metal plate instead of the glass mold. A similar test piece mold was prepared and placed 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 or mold and used as a sample. The refractive index and Abbe number of the sample were measured with an Abbe refractometer (manufactured by Atago Co., Ltd.).

(2) Hue A flat plate having a thickness of 1.0 mm, a width of 40 mm, and a length of 40 mm was measured with a color difference meter (trade name “MODELTC — 8600”, manufactured by Tokyo Denshoku Co., Ltd.), and the YI value was shown.

(3) Haze (turbidity) and total light transmittance A test piece cured on a flat plate having a thickness of 1.0 mm, a width of 40 mm, and a length of 40 mm was prepared, and the Haze (turbidity) and total light transmittance were Measurement was performed using an integrating sphere light transmittance measuring device (Nippon Denshoku Co., Ltd., SZ-Σ90).

(4) Releasability Evaluation was made based on the degree of difficulty when the resin cured on a flat plate having a thickness of 1.0 mm, a width of 40 mm, and a length of 40 mm was released from the mold.
○ ... Good releasability from the mold.
△ ・・・ Slightly difficult to release,
× ・・・ Different mold release or mold stiffness

(5) Mold reproducibility The evaluation was performed by the surface shape of the resin layer cured into a spherical lens shape having a thickness of 0.6 mm and a diameter of 3.0 mm and the leakage of the resin into the mold clearance.
○ ・・・ Reproducibility is good × ・・・ Reproducibility is poor

(6) Burr, Molecule When the resin hardened into a spherical lens shape with a thickness of 0.6 mm and a diameter of 3.0 mm is released from the mold, the size of the burr generated outside the product area and the resin to the mold clearance Evaluation was based on the degree of leakage.
○ ... Burr generation amount is less than 0.05mm, resin leakage to mold clearance is less than 1.0mm. Δ ... Burr formation amount is 0.05mm or more and less than 0.2mm. Resin leakage into the mold clearance is 1.0 mm or more, less than 3.0 mm x ... Burr generation amount is 0.2 mm or more, and resin leakage into the mold clearance is 3.0 mm or more.

(7) Bubbles When the resin cured into a spherical lens shape having a thickness of 0.6 mm and a diameter of 3.0 mm was released from the mold, the evaluation was made based on the presence and size of bubbles generated in the molded product portion.
○ ... Bubble formation is not observed △ ... Bubble formation is observed and the size of the bubble is less than 2% of the volume of the molded product × ... Bubble formation is observed and the bubble size is large 2% or more of the volume of the molded product

(8) Cracking When the resin cured into a spherical lens shape with a thickness of 0.6 mm and a diameter of 3.0 mm was released from the mold, the evaluation was based on the presence and size of cracks generated in the product part of the molded product.
... Formation of cracks is not observed. Δ... Formation of cracks is observed, but is observed only at the corner portion of the outer peripheral portion of the molded product.
X: Formation of cracks is observed, and it is also observed other than the corner portion of the outer peripheral portion of the molded product.

(9) Reflow heat resistance Using a flat plate having a thickness of 1.0 mm, a width of 40 mm, and a length of 40 mm as a test piece, a 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-curing at 200 ° C. for 60 minutes and after the heat resistance test at 250 ° C. for 7 minutes in an air oven. The results of changes in spectral transmittance obtained by these measurements are shown in Table 3 below.

(10) Water absorption rate The weight of a 1.0mm thick, 40mm wide, 40mm long flat test piece vacuum-dried at 60 ° C for 24 hours was weighed and weighed with a balance capable of measuring ± 0.1mg. Humidification was performed for 1 week in a constant temperature and humidity chamber at a temperature of 85 ° C. and a relative humidity of 85%. After humidification, water attached to the test sample was wiped off, and the sample was weighed with a balance capable of measuring up to ± 0.1 mg. The water supply rate was calculated by the following formula (3). Three identical test samples were prepared and tested in the same manner.
Wo / W × 100 = water absorption rate (%) (3)

(11) Pencil Hardness According to JISK5400, the pencil hardness of a test piece cured on a flat plate having a thickness of 1.0 mm, a width of 40 mm, and a length of 40 mm was measured using a pencil scratch tester. A pencil was applied at a 45 degree angle and a 1 kg load was applied from the top, and scratched about 5 mm to confirm the degree of scratches. The measurement was performed 5 times, and the pencil hardness of one rank below where 2 or more outbreaks were observed in 5 times was described as the pencil hardness test result.

Synthesis example 1
1.6 mol (463.2 mL) of dimethylol tricyclodecane diacrylate,
1.2 mol (254.2 mL) of dicyclopentanyl methacrylate, 1.2 mol (226.3 mL) of 1,4-butanediol diacrylate, 0.4 mol (95.5 mL) of 2,4-diphenyl-4-methyl-1-pentene, t- Charge 2.4 mol (564.8 mL) of dodecyl mercaptan and 600 mL of toluene into a 3.0 L reactor, add 40 mmol (11.5 g) of t-butyl peroxy-2-ethylhexanoate at 90 ° C, and react for 2 hours 45 minutes I let you. After stopping the polymerization reaction by cooling, the reaction mixture was poured into a large amount of hexane at room temperature to precipitate a copolymer. The obtained copolymer was washed with hexane, filtered, dried and weighed to obtain 691.0 g of copolymer A.

Mw of the obtained copolymer A was 34,200, Mn was 5,620, and Mw / Mn was 6.1. Copolymer A has a total structural unit (1) derived from dimethylol tricyclodecane diacrylate of 39.6 mol% and a structural unit derived from dicyclopentanyl methacrylate (2 31.1 mol% in total, and 29.3 mol% of structural units (3) derived from 1,4-butanediol diacrylate. The terminal group (4) of the structure derived from 2,4-diphenyl-4-methyl-1-pentene (αMSD) includes the structural units (1), (2) and (3), the terminal group (4) and The total amount of terminal groups (5) derived from t-dodecyl mercaptan (TDM) (hereinafter referred to as the total amount of all structural units) was 1.8 mol%.
On the other hand, the end group (5) was present in an amount of 7.2 mol% based on the total amount of all the structural units.
Further, when copolymer A was subjected to a solvent solubility test in toluene, xylene, THF, dichloroethane, dichloromethane, or chloroform, no insoluble matter or gel was observed in any of the solvents.

Synthesis example 2
Dimethylol tricyclodecane diacrylate 2.64 mol (764.3 mL), dicyclopentanyl acrylate 0.24 mol (47.2 mL), 1,4-butanediol diacrylate 0.96 mol (181.0 mL), 2-hydroxypropyl acrylate 0.96 mol (118.5 mL), 0.48 mol (114.6 mL) of 2,4-diphenyl-4-methyl-1-pentene, 3.12 mol (734.3 mL) of t-dodecyl mercaptan, and 720 mL of toluene in a 3.0 L reactor at 90 ° C. 62 mmol (13.9 g) of t-butyl peroxy-2-ethylhexanoate was added and reacted for 2 hours 30 minutes. 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 782.2 g of copolymer B.
Table 1 shows the results of testing copolymer B in the same manner as copolymer A.

Synthesis example 3
Dimethylol tricyclodecane diacrylate 0.8 mol (231.5 mL), dicyclopentanyl methacrylate 2.0 mol (393.4 ml), 1,4-butanediol diacrylate 1.2 mol (226.3 mL), 2,4-diphenyl-4-methyl 1-pentene 0.4 mol (95.5 mL), t-dodecyl mercaptan 1.6 mol (376.45 mL) and toluene 600 mL were charged into a 3.0 L reactor and 40 mmol (11.5 g) t-butyl peroxy-2 at 90 ° C. -Ethylhexanoate was added and allowed to react for 2 hours 45 minutes. After stopping the polymerization reaction by cooling, the reaction mixture was poured into a large amount of hexane at room temperature to precipitate a copolymer. The obtained copolymer was washed with hexane, filtered, dried and weighed to obtain 536.4 g of copolymer C (yield: 73.2 wt%).
The results of testing the copolymer C in the same manner as the copolymer A are shown in Table 1.

Synthesis example 4
Reactor of 0.66 mol (94.0 mL) divinylbenzene, 0.0275 mol (3.9 mL) ethyl vinylbenzene, 1.56 mol (281.1 g) 4-vinylbiphenyl, 0.88 mol (167.1 mL) 2-phenoxyethyl methacrylate, 610 mL toluene Then, 50 mmol of boron trifluoride diethyl ether complex was added at 50 ° C. and reacted for 4 hours 30 minutes. After the polymerization solution was stopped with an aqueous sodium hydrogen carbonate solution, the oil layer was washed 5 times with pure water, and the reaction mixture was poured into a large amount of methanol at room temperature to precipitate a polymer. After the obtained polymer was dissolved in toluene and then reprecipitated with methanol three times, the powdered solid polymer was washed with methanol, filtered, dried, weighed, Combined D258.3g was obtained.
Table 1 shows the results of testing the copolymer D in the same manner as the copolymer A.

Synthesis example 5
A 3.0L reactor containing 0.44 mol (62.7 mL) of divinylbenzene, 0.0183 mol (2.6 mL) of ethylvinylbenzene, 1.76 mol (317.2 g) of 4-vinylbiphenyl, 0.66 mol (125.3 mL) of 2-phenoxyethyl methacrylate, and 610 mL of toluene Then, 50 mmol of boron trifluoride diethyl ether complex was added at 50 ° C. and reacted for 4 hours 30 minutes. After the polymerization solution was stopped with an aqueous sodium hydrogen carbonate solution, the oil layer was washed 5 times with pure water, and the reaction mixture was poured into a large amount of methanol at room temperature to precipitate a polymer. After the obtained polymer was dissolved in toluene and then reprecipitated with methanol three times, the powdered solid polymer was washed with methanol, filtered, dried, weighed, Combined E250.6g was obtained.
The results of testing the copolymer E in the same manner as the copolymer A are shown in Table 1.

Synthesis Example 6
Divinylbenzene 0.27 mol (38.5 mL), ethyl vinylbenzene 0.063 mol (9.0 mL), 2-vinylnaphthalene 0.567 mol (87.4 g), 2-phenoxyethyl methacrylate 0.36 mol (68.4 mL), toluene 250 mL 1.0 L reactor Then, 18 mmol of boron trifluoride diethyl ether complex was added at 50 ° C. and reacted for 4 hours and 00 minutes. After the polymerization solution was stopped with an aqueous sodium hydrogen carbonate solution, the oil layer was washed 5 times with pure water, and the reaction mixture was poured into a large amount of methanol at room temperature to precipitate a polymer. After the obtained polymer was dissolved in toluene and reprecipitated with methanol three times, the powdered solid polymer was washed with methanol, filtered, dried, weighed, Combined F85.3g was obtained.
The results of testing the copolymer F in the same manner as the copolymer A are shown in Table 1.

Examples 1 to 7 and Comparative Examples 1 to 4
Each component was mix | blended in the ratio shown in Table 2 (a number is a weight part), Adeka stub AO-60 0.1 weight part made from Adeka Co., Ltd. was added as a stabilizer, and the curable resin composition was obtained. Next, this curable resin composition was cured by the various test methods described above, and performance evaluation was performed. Table 3 shows the performance evaluation results.

Abbreviations used in the table are shown below.
BZ: benzyl methacrylate (monofunctional)
BPEF: 9,9-bis [4-2 (-acryloyloxyethoxy) phenyl] fluorene (bifunctional)
BPFEA: 9,9-bis [4-3 (-acryloyloxypropoxy, 2-hydroxy) phenyl] fluorene (bifunctional)
BPA: BPA-2EO-dimethacrylate
19NDA: 1,9-nonanediol diacrylate (bifunctional)
TMP: Trimethylolpropane trimethacrylate (trifunctional)
DPHA: Dipentaerythritol hexaacrylate (hexafunctional)
Perbutyl O: t-butyl peroxy-2-ethyl hexanate (Nippon Yushi Co., Ltd.)
Irgacure 184: 1-hydroxy-cyclohexyl-phenyl-ketone (BASF)

Claims

Component (A): It has a plurality of reactive unsaturated groups, has a weight average molecular weight of 2,000 to 100,000, is further soluble in toluene, xylene, tetrahydrofuran, dichloroethane or chloroform, and has two reactive unsaturated groups. A polyfunctional copolymer obtained by copolymerizing one monomer and one monomer,
(B) component: (meth) acrylate having a fluorene skeleton represented by general formula (1),

(In the formula, R 1 and R 2 independently represent H or CH 3 —, and R 3 and R 4 independently represent —CH 2 O—, —CH 2 CH 2 O—, —CH 2 CH (CH 3 ) O—, —CH 2 CH 2 CH 2 O—, —CH 2 CH (OH) CH 2 O—, or CH 2 CH (OR 5 ) CH 2 O—, wherein R 5 is a meta (acryloyl) group. , K and l are each independently 0 or a number of 1 or more, k + l is a number of 1 or more, and m and n independently represent a number of 0 to 4), and (C) Component: A curable resin composition containing an initiator, wherein the content of component (A) is 5.0 to 94 wt% relative to the total of components (A) to (C), and the content of component (B) is 5.0 to A curable resin composition comprising 94 wt% and a content of component (C) of 0.1 to 10 wt%.
The (A) component polyfunctional copolymer is a monofunctional (meth) acrylic acid ester (a) having an aromatic ring or alicyclic structure, one or more bifunctional (meth) acrylic acid esters (b), 2 , 4-Diphenyl-4-methyl-1-pentene (c) and a copolymer obtained by copolymerizing a component containing a thiol compound (d), and a bifunctional (meth) acrylic acid ester ( b) a polyfunctional copolymer having a reactive (meth) acrylic group derived from and having a structural unit derived from 2,4-diphenyl-4-methyl-1-pentene (c) and a thiol compound (d) at the terminal The curable resin composition according to claim 1, which is a coalescence.
The polyfunctional copolymer of component (A) is obtained by copolymerizing a monovinyl aromatic compound (e), a divinyl aromatic compound (f) and an aromatic ether compound, and the side chain has a divinyl aromatic compound (f ) -Derived polyfunctional copolymer having a reactive vinyl group and an average of at least one structural unit derived from an aromatic ether compound represented by the following formula (2) per molecule. The curable resin composition according to claim 1, wherein

(Wherein R 6 represents H or CH 3 , and R 7 represents a hydrocarbon group having 1 to 18 carbon atoms which may contain an oxygen atom or a sulfur atom.)
In addition to the components (A), (B) and (C), as the component (D), a (meth) acrylate having 1 to 8 (meth) acryloyl groups in the molecule (provided that the (A), (Excluding cases corresponding to the component (B)), the content of the component (A) is 5.0 to 84 wt% with respect to the total of the components (A) to (D), and the content of the component (B) is 5.0 to 84 wt%, and the content of component (C) is 0.1 to 10 wt%, the content of component (D) is 10 to 70 wt%, and the total amount of components (A) to (D) is 100 parts by weight ( 4. The curable resin composition according to claim 1, wherein the total amount of component A) and component (B) is 30 to 90 wt%.
A cured resin obtained by curing the curable resin composition according to any one of claims 1 to 4.
An optical article in which the cured resin product according to claim 5 is formed.
The optical article according to claim 6, wherein the optical article is an optical lens.