KR101841595B1 - Soluble polyfunctional (meth)acrylic ester copolymer having alicyclic structure, curable resin composition and cured product - Google Patents

Abstract

It has excellent optical properties such as low chromatic dispersion and high light transmittance and is excellent in various characteristic balance required for optical lens and prism material and has excellent optical characteristics such as high refraction index (Meth) acrylic acid ester copolymer and a curable resin composition using the same.
(B), 2,4-diphenyl-4-methyl-1-pentene (c) and thiol compound (d) having an alicyclic structure and having two or more functional (meth) ) Having a reactive (meth) acrylate group derived from a bifunctional (meth) acrylic acid ester (b) in its side chain and a reactive (meth) acrylate group derived from a 2,4- A copolymer having a structural unit derived from 1-pentene (c) and a thiol compound (d), and a curable resin composition containing the copolymer.

Description

(SOLUBLE POLYFUNCTIONAL (METH) ACRYLIC ESTER COPOLYMER HAVING ALICYCLIC STRUCTURE, CURABLE RESIN COMPOSITION AND CURED PRODUCT) [0002] The present invention relates to a soluble polyfunctional (meth) acrylic acid ester copolymer having an alicyclic structure,

The present invention has excellent optical properties such as low chromatic dispersion and high light transmittance, heat resistance and processability, and also has excellent optical properties under stringent conditions of use such as heat and humidity, low absorptivity and good releasability at molding (Meth) acrylic ester copolymer having an alicyclic structure with improved mold transferability and a soluble polyfunctional (meth) acrylic acid ester copolymer, a cured resin composition comprising the cured product And an optical article.

Most of the monomers having an unsaturated bond having a reactive activity can generate multimers by selecting an appropriate reaction condition and a catalyst which cleaves an unsaturated bond to cause a chain reaction. Generally, since the kinds of monomers having unsaturated bonds vary widely, the variety of the obtained resin is also remarkable. However, the types of monomers capable of obtaining a high molecular weight polymer having a molecular weight of 10,000 or more, which is generally referred to as a polymer compound, are relatively small. For example, a copolymer of ethylene, substituted ethylene, propylene, substituted propylene, styrene, alkylstyrene, alkoxystyrene, norbornene, various acrylic esters, butadiene, cyclopentadiene, dicyclopentadiene, isoprene, maleic anhydride, maleimide, Esters, allyl compounds and the like can be given as representative monomers. A wide variety of resins are synthesized by solely or copolymerizing these monomers.

The use of these resins is mainly limited to relatively inexpensive consumer electronics fields, and there is hardly any application to high-tech fields requiring high heat resistance, dimensional stability and fine workability in the field of optoelectronic materials. The reason for this is that the polymer synthesized from the above-mentioned monomers is usually thermoplastic (thermoplastic), and since it is necessary to use a high molecular weight material in order to satisfy the mechanical properties, the properties required in high technology fields such as heat resistance and micro- .

As a method for solving the drawbacks of such a vinyl-based thermoplastic polymer, Patent Documents 1 to 3 disclose a polymer having a (meth) acryloyl group or a vinyl ether group in a pendant. For example, Patent Document 1 discloses a photosensitive composition comprising a (meth) acryloyl group pendant polymer obtained by cationic polymerization of a heteropolymerizable monomer such as 2-vinyloxyethyl (VEA) acrylate and a photopolymerization initiator. Patent Document 2 discloses a photosensitive composition comprising a (meth) acryloyl group pendant polymer, a compound having a photoreactive unsaturated carboxyl group, and a photopolymerization initiator. Patent Document 3 discloses a process for producing a polymer having a polymerizable monomer, such as 2-vinyloxyethyl (VEA) acrylate, in a homopolymerization process using a cationic polymerization catalyst in a carboxylic ester solvent compound having a photoreactive unsaturated group, Or copolymerizing a polymer solution to obtain a polymer solution.

However, in the case of using a reactive polymer produced according to the technique using the heteropolymerizable monomers disclosed in these patent documents, there is a problem that the optical properties such as low absorptivity, heat resistance, moldability and high optical properties required in the fields of advanced optical lenses and prisms A polymer having both good balance of properties and improved optical properties under stringent conditions of use such as wet heat conditions, low water absorption, good releasability during molding, and accurate mold transferability, and a curable resin composition have not been obtained.

On the other hand, Patent Document 4 discloses a method for producing a poly (meth) acrylate having a structural unit obtained by copolymerizing a monovinyl aromatic compound and a bifunctional (meth) acrylic acid ester and having a reactive (meth) acrylate group derived from a bifunctional (meth) Polyfunctional vinyl aromatic copolymers are disclosed. However, the soluble polyfunctional vinyl aromatic copolymer obtained by the technique disclosed in this publication has excellent heat-decomposability against thermal history at high temperature, has a reactive (meth) acrylate group in the side chain, has excellent processability, However, there is a limitation in actual use that it can not be used for an optical lens for low-dispersion color applications, but it was a material which did not achieve high hardness.

Patent Document 5 discloses that a methyl methacrylate (MMA) syrup contains 1 to 25% by weight of a di (meth) acrylate of a straight chain aliphatic divalent alcohol having 4 to 8 carbon atoms as a constituent component Compositions are disclosed. Here, the production of the MMA-based syrup composition can be carried out by heating and polymerizing MMA or MMA and a vinyl copolymer capable of copolymerization therewith and a chain transfer agent at room temperature or in an inert gas atmosphere (for example, N ₂ gas) Is disclosed. Specific examples of the chain transfer agent include sulfur compounds such as lauryl mercaptan, thioglycolic acid octyl ester, thiocresol, thionaphthol and benzylmercaptan, and 2,4-diphenyl-4-methyl-1- The pentene (c) has not been specifically disclosed. Furthermore, a monofunctional and / or bifunctional (meth) acrylate ester which is present simultaneously with an end group derived from a thiol compound and an end group derived from 2,4-diphenyl-4-methyl-1-pentene and having an alicyclic structure it has not even been suggested that thermostable optical properties or precise transferability of a mold shape can be controlled in an integrated manner due to the coexistence of the structural units derived from the structural unit (a). In addition, the composition obtained by the technique disclosed in this publication is not improved in adhesion to an inorganic material under stringent conditions of use such as a humid condition.

Patent Document 6 discloses a polymerizable composition comprising a vinyl monomer and a di (meth) acrylate compound, and the use of 2,4-diphenyl-4-methyl-1-pentene (c) However, the amount of use thereof is about several percent of comma as a chain transfer agent, and the resultant product also shows no solvent solubility due to crosslinking gelation.

Patent Document 7 also discloses a method of producing a magnetic recording medium comprising a magnetic recording layer comprising a constituent unit composed of 1) an epoxy group-containing (meth) acrylate, 2) a hydroxyl group-containing (meth) acrylate, 3) a (meth) acrylic acid, A thermosetting resin composition for a color filter, which comprises a curable copolymer and an organic solvent, is disclosed. The self-curing copolymer obtained by the technique disclosed in this publication is a copolymer obtained by copolymerizing at least one monomer selected from the group consisting of mercaptopropionic acid, mercaptopropionic acid ester, thioglycol, thioglycerin, dodecyl mercaptan ,? -methylstyrene dimer, and the like can be used. However, in the technique disclosed in this publication, since no bifunctional or more functional vinyl compound having a plurality of vinyl groups is added during polymerization, only one or more end groups derived from a molecular weight modifier can be introduced into the polymer chain, There is a drawback that it can not be sufficiently granted. The self-curing copolymer obtained by the technique disclosed in this publication forms a thermosetting resin composition in a resin composition with an epoxy resin, but since a curing reaction does not occur with the acrylate resin, And the strength and heat resistance are deteriorated.

Accordingly, it has been desired to provide a resin composition which has excellent optical properties such as low color dispersion and high light transmittance, has a characteristic balance of low absorptivity, moldability and heat resistance, and is excellent in optical properties under stringent conditions of use such as heat and humidity, Soluble polyfunctional (meth) acrylic acid ester copolymer, and a curable resin composition using the copolymer have not existed so far.

Japanese Patent Publication No. 49-13212 Japanese Patent Publication No. 51-34433 Japanese Patent Publication No. 54-27394 Japanese Patent Application Laid-Open No. 2008-247978 Japanese Patent Application Laid-Open No. 57-167340 Japanese Patent Application Laid-Open No. 2002-121228 Japanese Patent Application Laid-Open No. 2009-1770

The present invention has excellent optical properties such as low color dispersion and high light transmittance and is excellent in balance of various characteristics required for optical lens and prism material in the technical field of low absorptivity, workability and heat resistance, and also, (Meth) acrylic acid ester copolymer improved in optical properties under conditions and adhesion of an inorganic material, and a curable resin composition, a cured product and an optical article containing the same.

(B), 2,4-diphenyl-4-methyl-1-pentene (c) and a thiol compound (c) having an alicyclic structure, (meth) acrylate ester (b) having a reactive (meth) acrylate group derived from a bifunctional (meth) acrylic acid ester (b) Methyl-1-pentene (c) and a thiol compound (d) and having a weight average molecular weight of 2000 to 60000 and a solubility in toluene, xylene, tetrahydrofuran, dichloroethane or chloroform (Meth) acrylic acid ester copolymer.

The present invention also relates to a process for producing a polyfunctional (meth) acrylic acid ester (MFM), which comprises using a monofunctional (meth) acrylic acid ester (a2) containing a hydroxyl group together with a monofunctional (meth) acrylic acid ester Soluble (meth) acrylic acid ester copolymer.

Examples of the monofunctional (meth) acrylic acid ester (a) having an alicyclic structure include isobornyl methacrylate, isobornyl acrylate, cyclohexyl methacrylate, cyclohexyl acrylate, dicyclopentenyl acrylate, At least one member selected from the group consisting of dicyclopentanyl methacrylate, dicyclopentenyloxyethyl methacrylate, dicyclopentanyl methacrylate, and dicyclopentanyl methacrylate; And a functional (meth) acrylic acid ester.

Examples of the bifunctional (meth) acrylic acid ester (b) include a group consisting of cyclohexanedimethanol diacrylate, cyclohexanedimethanol dimethacrylate, dimethyloltricyclodecane diacrylate, and dimethyloltricyclodecane dimethacrylate (Meth) acrylic acid esters selected from the group consisting of bifunctional (meth) acrylic acid esters.

The present invention also relates to a process for producing a polyfunctional (meth) acrylic acid ester (a) having an alicyclic structure, a bifunctional (meth) acrylic acid ester (b), a 2,4- (Meth) acrylic acid ester copolymer obtained by copolymerizing the component containing the compound (d).

The present invention also relates to a composition comprising component (A): soluble polyfunctional (meth) acrylic acid ester copolymer according to claim 1, component (B): polyfunctional (meth) acrylate, and component (C) (B) is 5 to 250 parts by weight based on 100 parts by weight of the component (A), and the amount of the component (C) is 0.1 to 50 parts by weight based on 100 parts by weight of the total of the components (B) 10 parts by weight of a curable resin composition.

(Meth) acrylic acid ester (a) having an alicyclic structure and a monofunctional (meth) acrylic acid ester (a) containing a hydroxyl group as the monofunctional (meth) acrylic acid ester (meth) acrylate copolymer using the above-mentioned soluble polyfunctional (meth) acrylate copolymer (a2) and a polyfunctional (meth) acrylate having 5 or more functional groups as the component (B).

Further, the present invention is an optical material characterized by comprising a resin cured product obtained by curing the above-mentioned curable resin composition, and a cured product of the resin. As the optical material, there is an optical plastic lens.

According to the present invention, in the advanced technical fields of low absorbency, workability, and heat resistance, excellent optical characteristics such as low color dispersion and high light transmittance, excellent balance of various characteristics required for optical lens and prism material, A material having improved optical properties under the use conditions and adhesion of inorganic materials can be obtained. Such an optical material is suitably used in a field mainly focusing on the imaging field such as an imaging device requiring high optical characteristics.

Hereinafter, the soluble polyfunctional (meth) acrylic acid ester copolymer of the present invention will be described in detail. This soluble polyfunctional (meth) acrylic acid ester copolymer has an alicyclic structure and a structural unit derived from 2,4-diphenyl-4-methyl-1-pentene and a thiol compound at the terminal. Hereinafter, this soluble polyfunctional (meth) acrylic acid ester copolymer is abbreviated as a copolymer.

The copolymer of the present invention is obtained by copolymerizing a monomer containing a monofunctional (meth) acrylate ester (a) having an alicyclic structure and a bifunctional (meth) acrylic acid ester (b) (Meth) acrylate ester (b) having a reactive (meth) acrylate group derived from a bifunctional (meth) acrylic acid ester (b) in the side chain and having a reactive (Meth) acrylic acid ester copolymer having a structural unit derived from a polyfunctional (meth) acrylate, a 4-diphenyl-4-methyl-1-pentene (c) and a thiol compound (d). Here, the term "soluble" means soluble in toluene, xylene, tetrahydrofuran, dichloroethane or chloroform. The test for the availability is made under the conditions shown in the examples. Here, a monofunctional (meth) acrylic acid ester (a2) containing a hydroxyl group as the monofunctional (meth) acrylic acid ester (MFM) may be used together with the monofunctional (meth) acrylate ester (a) having an alicyclic structure.

Since the chain structure of the copolymer is obtained by copolymerizing mainly a monofunctional (meth) acrylic acid ester and a bifunctional (meth) acrylic acid ester, it has a branched structure or a crosslinked structure, and the abundance amount of such a structure is limited to the degree of exhibiting solubility . Therefore, it is a copolymer having in its side chain a structural unit (b1) containing an unreacted (meth) acrylic group derived from a bifunctional (meth) acrylic acid ester (b). The unreacted (meth) acrylic group is also referred to as a pendant (meth) acryl group. Since the unreacted (meth) acrylic group exhibits polymerizability, it can be polymerized by further polymerization to give a resin-insoluble resin cured product.

The copolymer also has a structural unit derived from 2,4-diphenyl-4-methyl-1-pentene (c) and thiol compound (d) at the terminal. By introducing the structural unit at the end of the copolymer, a molding processability such as releasability is improved, a cured product having a low coefficient of linear expansion favorable for adhesion with an inorganic material and excellent in heat resistance such as heat discoloration and weight reduction is obtained .

The copolymer includes a structural unit derived from a monofunctional (meth) acrylic acid ester (a) having an alicyclic structure, a structural unit derived from a bifunctional (meth) acrylic acid ester (b) -1-pentene (c) and thiol compound (d). In the structural unit derived from the bifunctional (meth) acrylic acid ester (b), both of the polymerizable double bonds (referred to as vinyl groups) contained in the two (meth) acrylic groups are involved in the polymerization to form a branched structure or a crosslinked structure And a structural unit (b1) containing an unreacted (meth) acrylic group in which only one vinyl group participates in polymerization and the other vinyl groups remain unreacted. 2,4-diphenyl-4-methyl-1-pentene (c) and thiol compound (d) act as a chain transfer agent to prevent an increase in molecular weight and exist at the end of the copolymer. When a monofunctional (meth) acrylic acid ester (a2) containing a hydroxyl group is used as the monofunctional (meth) acrylic acid ester (MFM), it has a structural unit derived from (a2).

The introduction amount of 2,4-diphenyl-4-methyl-1-pentene (c) and thiol compound (d) into the copolymer is 0.02 to 0.35 as the mole fraction M _cd expressed by the following formula (1) 0.03 to 0.30, and particularly preferably 0.08 to 0.27.

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

Here, (a), (b), (c) and (d) are structural units derived from a monofunctional (meth) acrylate ester (a) having an alicyclic structure, a structural unit derived from a bifunctional (meth) , The structural unit derived from 2,4-diphenyl-4-methyl-1-pentene (c), and the thiol compound (d). By introducing the structural unit derived from 2,4-diphenyl-4-methyl-1-pentene (c) and the thiol compound (d) into the end of the copolymer within the above range, heat resistance, releasability, . In the case of using a monofunctional (meth) acrylic acid ester (a2) containing a hydroxyl group as the monofunctional (meth) acrylic acid ester (MFM), the formula (1) is as follows.

M _cd = (c) + (d) / [(a) + a2 + b + c +

(A2) represents the number of moles of the structural unit derived from the monofunctional (meth) acrylic acid ester (a2) containing a hydroxyl group.

The ratio of 2,4-diphenyl-4-methyl-1-pentene (c) to thiol compound (d) is 5 to 50% , And particularly preferably from 10 to 30%. Here, the ratio is calculated by the following equation.

(c) / [(c) + (d)]

The bifunctional (meth) acrylic acid ester (b) plays an important role as a crosslinking component for branching or crosslinking the copolymer, generating a pendant vinyl group, giving the copolymer curability, and exhibiting heat resistance at the time of curing .

Examples of the bifunctional (meth) acrylic esters include cyclohexanedimethanol diacrylate, dimethyloltricyclodecane diacrylate, cyclohexanedimethanol dimethacrylate, dimethyloltricyclodecane dimethacrylate, ethylene glycol diacrylate, Propylene glycol diacrylate, 1,4-butanediol diacrylate, hexanediol diacrylate, diethylene glycol diacrylate, ethylene glycol diacrylate, propylene glycol diacrylate, 1,4-butanediol dimethacrylate, Bifunctional (meth) acrylic acid esters such as hexanediol dimethacrylate, diethylene glycol dimethacrylate and the like can be used, but not limited thereto.

As specific examples of the bifunctional (meth) acrylic acid ester, cyclohexanedimethanol diacrylate, cyclohexanedimethanol dimethacrylate, dimethylol tricyclodecane diacrylate, cyclohexanedimethanol dimethacrylate, Or dimethyloltricyclodecane dimethacrylate are preferably used.

The copolymer has a structural unit (b1) containing a reactive (meth) acrylate group derived from a bifunctional (meth) acrylate ester (b) in its side chain. The molar fraction of the structural unit (b1) represented by the formula (2) M _b1 is preferably 0.05 or more, preferably 0.1 to 0.7, and more preferably 0.3 to 0.5.

M _b1 = (b1) / [(a) + (b)] (2)

Here, (a) and (b) in the formulas represent the number of moles of the structural unit derived from the monofunctional (meth) acrylic acid ester (a) having an alicyclic structure and the structural unit derived from the bifunctional (meth) acrylic acid ester . (B1) represents the number of moles of the structural unit (b1) containing a (meth) acrylate group. By satisfying the above-mentioned mole fractions, a molded article having excellent curability in light and heat and having excellent heat resistance and mechanical properties after curing can be obtained. In the case of using a monofunctional (meth) acrylic acid ester (a2) containing a hydroxyl group as the monofunctional (meth) acrylic acid ester (MFM), the formula (2) is as follows.

M _b1 = (b1) / [(a) + (a2) + (b)] (2 '

The monofunctional (meth) acrylic acid ester (a) having an alicyclic structure is important for improving the solvent solubility, low absorptivity, heat resistance, optical characteristics and processability of the copolymer. Examples of the monofunctional (meth) acrylic acid ester having an alicyclic structure include isobornyl methacrylate, isobornyl acrylate, cyclohexyl methacrylate, cyclohexyl acrylate, dicyclopentenyl acrylate, dicyclopentenyloxy At least one alicyclic structure selected from the group consisting of ethyl acrylate, dicyclopentanyl acrylate, dicyclopentenyloxyethyl methacrylate, dicyclopentenyloxyethyl methacrylate, and dicyclopentanyl methacrylate, (Meth) acrylic acid esters, which are not limited thereto. By introducing the structural units derived from these components into the copolymer, gelation of the copolymer can be prevented, solubility in a solvent can be enhanced, and optical properties such as low color dispersibility of the copolymer, low water absorbability and heat resistance can be improved .

Suitable specific examples include isobornyl methacrylate, isobornyl acrylate, cyclohexyl methacrylate, cyclohexyl acrylate, dicyclopentenyl acrylate, dicyclopentyl acrylate, dicyclopentyl acrylate, and dicyclopentyl acrylate in terms of cost, prevention of gelation, At least one alicyclic structure selected from the group consisting of dicyclopentanyl acrylate, dicyclopentanyl acrylate, dicyclopentenyloxyethyl methacrylate, dicyclopentenyloxyethyl methacrylate and dicyclopentanyl methacrylate, (Meth) acrylic acid esters having a number average molecular weight

Examples of the monofunctional (meth) acrylate ester (a2) containing a hydroxyl group include 2-hydroxypropyl acrylate, 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, 2-hydroxypropyl methacrylate, 2- Hydroxyethyl methacrylate, polyethylene glycol acrylate, polyethylene glycol methacrylate, 1,4-butanediol monoacrylate, 1,6-hexanediol monoacrylate, 1,9-nonanediol monoacrylate, 1,4 -Butanediol monomethacrylate, 1,6-hexanediol monomethacrylate, and 1,9-nonanediol monomethacrylate. Among them, 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, 2-hydroxypropyl methacrylate and 2-hydroxypropyl methacrylate are preferable from the viewpoint of compatibility with a polyfunctional (meth) And hydroxyethyl methacrylate.

2,4-diphenyl-4-methyl-1-pentene (c) and the thiol compound (d) function as a chain transfer agent and control the molecular weight of the copolymer. The weight average molecular weight Mw of the copolymer of the present invention is in the range of 2000 to 60000, preferably in the range of 3000 to 50,000. The use of a copolymer having a relatively low molecular weight improves the moldability and releasability of the resin cured product.

As the thiol compound (d), any thiol compound known to act as a chain transfer agent can be used, and preferably t-dodecyl mercaptan, n-butyl mercaptan, isobutyl mercaptan, n-octyl mercaptan, Mercaptan and t-butyl mercaptan.

Further, as a component (e), a monofunctional (meth) acrylic acid ester having no alicyclic structure can be added for the purpose of improving the solvent solubility and processability of the copolymer. Examples of such (meth) acrylic esters include methyl methacrylate, ethyl methacrylate, methyl acrylate, ethyl acrylate, n-butyl acrylate, 2-methylhexyl acrylate, 2-ethylhexyl acrylate, octyl acrylate, -Hydroxyethyl methacrylate, and the like. Of these, methyl methacrylate and n-butyl acrylate are preferable. These (meth) acrylic acid ester-based monomers may be used alone or in combination of two or more, and at least one (meth) acrylic acid ester selected from the group consisting of methyl methacrylate, methyl acrylate and n- Is most preferable.

The structural units derived from these other monomer components (e) are preferably within a range of less than 30 mol% based on the total amount of the structural units derived from the monomer components (a) or (a) and (a2).

In another aspect, the soluble multifunctional (meth) acrylic acid ester copolymer of the present invention is obtained by copolymerizing a structural unit derived from a monofunctional (meth) acrylate ester (a) having an alicyclic structure and a bifunctional (meth) , The structural unit derived from (a) is preferably from 10 to 60 mol%, more preferably from 15 to 50 mol%, based on 100 mol% of the total structural units. (b) is preferably 40 to 90 mol%, more preferably 50 to 85 mol%, and still more preferably 50 to 80 mol%. If the structural unit derived from (b) does not reach 10 mol%, heat resistance of the cured product is insufficient, and if it exceeds 60 mol%, moldability is lowered and the strength of the molded article is remarkably decreased.

When a monofunctional (meth) acrylate ester (a2) containing a hydroxyl group together with a monofunctional (meth) acrylate ester (a) having an alicyclic structure is used, the monofunctional (meth) acrylic ester The molar ratio of the structural units is preferably in the following range.

(a) / [(a) + (a2) + (b)] = 0.02 to 0.55, preferably 0.04 to 0.5

(a2) / [(a) + (a2) + (b)] = 0.03 to 0.4, preferably 0.09 to 0.3, more preferably 0.13 to 0.18

(c) / [(a) + (a2) + (c)] = 0.05 to 0.95, preferably 0.2 to 0.87

In addition, it is preferable to introduce an alicyclic structure into the structure derived from the bifunctional (meth) acrylic acid ester (b), and a structural unit having an alicyclic structure aligned with the monofunctional (meth) acrylic ester (a) having an alicyclic structure Is preferably in the range of 0.35 to 0.95, preferably 0.6 to 0.9 with respect to the whole of [(a) + (a2) + (b)].

The soluble polyfunctional aromatic (meth) acrylic acid ester copolymer of the present invention is obtained by copolymerizing a monofunctional (meth) acrylate ester (a) having an alicyclic structure or a monofunctional (meth) acrylate ester (a) having an alicyclic structure with a hydroxyl group (B), 2,4-diphenyl-4-methyl-1-pentene (c) and thiol compound (d) which contain a monofunctional (meth) acrylic acid ester Is obtained by polymerizing a monomer containing 2 to 120 moles of 2,4-diphenyl-4-methyl-1-pentene (c) and thiol compound (d) at a temperature of 50 to 200 DEG C per 100 moles of the monomer . Here, the 2,4-diphenyl-4-methyl-1-pentene (c) and the thiol compound (d) are known compounds as chain transfer agents. In the present invention, however, the amount thereof used is larger than that used as a chain transfer agent. . The amount of 2,4-diphenyl-4-methyl-1-pentene (c) and thiol compound (d) to be used is preferably in the range of 2, 4-diphenyl (meth) -4-methyl-1-pentene (c) and the thiol compound (d) is adjusted to be in the range of 0.02 to 0.35, since the reactivity is low and may remain unreacted. . Therefore, it is used in the range of 2 to 120 moles, preferably 20 to 100 moles, and more preferably 50 to 80 moles per 100 moles of the monomer.

From the viewpoint that the 2,4-diphenyl-4-methyl-1-pentene (c) and the thiol compound (d) also function as a chain transfer agent, the amount used is limited by the crosslinking reaction, pendant (meth) (B) is preferably in the range of 10 to 500 parts by weight, more preferably in the range of 30 to 150 parts by weight, based on 100 parts by weight of the bifunctional (meth) acrylic acid ester (b). And most preferably in the range of 90 to 110 parts by weight.

The amount of the mono (meth) acrylic acid ester (a) having an alicyclic structure or the mono (meth) acrylic acid ester (a) having an alicyclic structure and the monofunctional (meth) acrylic acid ester (a2) is preferably from 10 to 60 mol%, more preferably from 15 to 50 mol%, based on 100 mol of the total of the (meth) acrylic ester (a2) and the bifunctional (meth) acrylic acid ester (b). The amount of the bifunctional (meth) acrylic acid ester (b) to be used is preferably 40 to 90 mol%, more preferably 50 to 85 mol%, and still more preferably 50 to 80 mol%.

A radical polymerization initiator may be added when the initiation reaction rate due to the thermal initiation reaction is small in the production of the copolymer of the present invention. In this case, examples of the radical polymerization initiator to be used include organic peroxide polymerization such as ketone peroxides, peroxyketals, hydroperoxides, dialkyl peroxides, diacyl peroxides, peroxycarbonates and peroxy esters Initiators and azo-based polymerization initiators. The amount of these radical polymerization initiators to be used is not particularly limited, but is preferably 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 monomer components. And most preferably in the range of 0.1 to 15 parts by weight.

In addition, the polymerization reaction can be basically carried out by bulk polymerization without using a solvent, and it can also be carried out in one or more organic solvents in which the resulting soluble polyfunctional (meth) acrylic acid ester aromatic copolymer is dissolved. The organic solvent is not particularly limited as long as it is a compound which does not substantially inhibit radical polymerization and forms a homogeneous solution by dissolving the chain transfer agent, the initiator, the monomer, and the polyfunctional (meth) acrylic acid ester aromatic copolymer of the present invention .

Examples of the compound usable as an organic solvent include aromatic hydrocarbons, straight chain aliphatic hydrocarbons, branched aliphatic hydrocarbons, cyclic aliphatic hydrocarbons, and paraffin oils obtained by hydrogenating and refining petroleum fractions. Of these, toluene, xylene, methylcyclohexane and ethylcyclohexane are preferable from the viewpoint of balance of polymerizability and solubility and easiness of obtaining water.

These organic solvents may be used alone or in combination of two or more. The amount of the solvent to be used is not particularly limited.

In the production of the copolymer of the present invention, the polymerization is carried out in a temperature range of 50 to 200 ° C. If the polymerization reaction is carried out at a temperature lower than 50 ° C, the polymerization rate is lowered. Therefore, it is not preferable from the viewpoint of industrial practice, and if it exceeds 200 ° C, the selectivity of the reaction is lowered so that the reaction is difficult to control. And generation is likely to occur.

A method for recovering the copolymer after the termination of the polymerization reaction is not particularly limited and a commonly used method such as a thermal decompression devolatilization method, a steam stripping method, and precipitation in a poor solvent can be used .

The soluble polyfunctional (meth) acrylic acid ester copolymer of the present invention is soluble in at least one solvent selected from toluene, xylene, THF, dichloroethane, dichloromethane and chloroform. It is preferably soluble in the entirety of the solvent. The term "soluble" as used herein means that 1 g or more, preferably 10 g or more is dissolved in 100 ml of a solvent at room temperature (25 ° C.). It is preferable that no gel is formed after dissolution.

Next, the curable resin composition of the present invention and the respective components to be mixed therewith will be described in detail. The curable resin composition of the present invention contains the components (A) to (C), and the soluble polyfunctional (meth) acrylic acid ester copolymer is used as the component (A).

(Meth) acrylate is used as the component (B). The polyfunctional (meth) acrylate is one having two or more (meth) acryloyl groups in the molecule, and one or more of them are used. When used in combination with the component (A), the multifunctional acrylate used as the component (B) synergistically improves the optical properties such as low color dispersion and high light transmittance in addition to heat resistance.

The polyfunctional (meth) acrylate is preferably copolymerizable with the component (A), and examples thereof include 1,4-butanediol di (meth) acrylate, 1,6-hexanediol di (meth) (Meth) acrylate, bisphenol A polypropoxydi (meth) acrylate, bisphenol A polyethoxydi (meth) acrylate, bisphenol A polypropoxydi (meth) acrylate, bisphenol F polyethoxylate (Meth) acrylate, trimethylolpropane trioxyethyl (meth) acrylate, tris (2-hydroxyethyl) isocyanurate tri (meth) acrylate, pentaerythritol tri (Meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol hexa (metha) acrylate, polyethylene glycol di (meth) acrylate, tris (acryloxyethyl) isocyanurate, (Meth) acrylate, dipentaerythritol hexa (meth) acrylate, dipentaerythritol penta (meth) acrylate, tripentaerythritol hexa (metha) acrylate, tripentaerythritol penta Di (meth) acrylate of ε-caprolactone adduct of hydroxypivalic acid neopentyl glycol (for example, KAYARAD HX- (meth) acrylate of Nippon Kayaku Co., Ltd.) 220 and HX-620), trimethylol propane tri (meth) acrylate, trimethylol propane polyethoxy tri (meth) acrylate, and ditrimethylol propane tetra (meth) acrylate. Particularly preferable examples include 1,6-hexanediol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, trimethylolpropane trioxyethyl (meth) acrylate and pentaerythritol tri (meth) have.

(Meth) acrylate having 5 or more functional groups is preferable as the component (B). It is particularly preferable that the component (A) has a structural unit derived from (a2). The pentafunctional or higher functional polyfunctional acrylate used as the component (B) may be used in combination with the component (A) to form a high degree of crosslinking to improve the hardness. In addition to these properties, the optical properties such as heat resistance, low- . The polyfunctional acrylate corresponding to the component (A) is not calculated as the component (B). One or more polyfunctional (meth) acrylates are used.

The above-mentioned polyfunctional (meth) acrylate having 5 or more functional groups is preferably copolymerizable with the component (A), and examples thereof include dipentaerythritol hexa (meth) acrylate, dipentaerythritol penta (meth) acrylate, tripentaerythritol hexa (Meth) acrylate, tripentaerythritol penta (meth) acrylate, and the like. Particularly preferred is dipentaerythritol hexa (meth) acrylate.

In the present invention, at least one monofunctional (meth) acrylate having one (meth) acryloyl group in the molecule may be used as the other copolymerizable component (D). By using these monofunctional (meth) acrylates in combination with the component (A), optical properties such as low color dispersion and high light transmittance can be synergistically improved at the same time, and moldability can be improved by increasing fluidity. The amount to be used is 0 to 40 parts by weight, preferably 0 to 20 parts by weight based on 100 parts by weight of the component (A). If the used amount is too large, the fluidity becomes too high and it is not preferable because molding defects such as tilting and founting are liable to occur.

The monofunctional (meth) acrylate which can be used as the copolymerization component (D) is preferably a monofunctional (meth) acrylic ester (a) having an alicyclic structure and used for producing a copolymer which is the component (A) (Meth) acrylate, 2-hydroxyethyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, polyethylene glycol (Meth) acrylates such as mono (meth) acrylate, polypropylene glycol mono (meth) acrylate, cyclohexane-1,4-dimethanol mono (meth) acrylate, tetrahydrofurfuryl (Meth) acrylate, o-phenylphenol monoethoxy (meth) acrylate, o-phenylphenol polyethoxy (meth) acrylate, ) Acrylate, p- (Meth) acrylate, dicyclopentenyl (meth) acrylate, dicyclopentenyl (meth) acrylate, dicyclopentenyl (meth) acrylate, dicyclopentanyl And chloropentenyloxyethyl (meth) acrylate.

Next, the component (C) will be described.

Examples of the photopolymerization initiator of the component (C) include benzoin such as benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin propyl ether and benzoin isobutyl ether; Acetophenone, 2,2-diethoxy-2-phenylacetophenone, 2,2-diethoxy-2-phenylacetophenone, 1,1-dichloroacetophenone, 2-hydroxy- Acetophenones such as diethoxyacetophenone, 1-hydroxycyclohexyl phenyl ketone and 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropane-1-one; Anthraquinones such as 2-ethyl anthraquinone, 2-tertiarybutylanthraquinone, 2-chloro anthraquinone, and 2-amylanthraquinone; Thioxanthones such as 2,4-diethylthioxanthone, 2-isopropylthioxanthone and 2-chlorothioxanthone; Ketal such as acetophenone dimethyl ketal and benzyl dimethyl ketal; Benzophenones such as benzophenone, 4-benzoyl-4'-methyldiphenyl sulfide and 4,4'-bismethylaminobenzophenone; 2,4,6-trimethylbenzoyldiphenylphosphine oxide, and bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide.

These may be used alone or as a mixture of two or more kinds. Further, tertiary amines such as triethanolamine and methyldiethanolamine, N, N-dimethylaminobenzoic acid ethyl ester and N, N-dimethylaminobenzoic acid, Benzoic acid derivatives, and the like.

The curable resin composition of the present invention comprises the above components (A), (B) and (C), and the content thereof is as follows. The blending amount of the component (B) is 5 to 250 parts by weight, preferably 20 to 100 parts by weight based on 100 parts by weight of the component (A). The amount of the component (C) is 0.1 to 10 parts by weight, preferably 1.0 to 5 parts by weight based on 100 parts by weight of the total of the components (B) and (A).

(C) component: 0.1 to 30% by weight of the total of the components (A) and (B) By weight to 10% by weight. More preferably, the component (A) is 35 to 80 wt%, and the component (B) is 10 to 40 wt%. When the compounding ratio of the component (A) and the component (B) and the component (C) is within the above range, the balance of moldability, heat resistance and optical characteristics exhibited synergistically in releasability and curability is improved. If the amount of the component (C) is too small, hardening is likely to occur and the heat resistance and light resistance are deteriorated. If too much, the mechanical strength is lowered and the heat resistance is lowered. When the organic resin and the filler are contained in the curable resin composition, the content is calculated by excluding the above.

The curable resin composition of the present invention may further contain additives such as a polymerization inhibitor, an antioxidant, a releasing agent, a photosensitizer, an organic solvent, a silane coupling agent, a leveling agent, a defoamer, an antistatic agent, an ultraviolet absorber, Various fillers, antifungal agents, antimicrobial agents, and the like may be added to the curable resin composition of the present invention to impart desired functionality.

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

The curable resin composition of the present invention can obtain a cured product by irradiating active energy rays such as ultraviolet rays. Specific examples of the light source used in the case of curing by irradiation with an active energy ray include fluorescent lamps for ultraviolet rays, high pressure mercury lamps for copying, medium pressure mercury lamps, high pressure mercury lamps, ultra high pressure mercury lamps, An electrode lamp, a metal halide lamp, or an electron beam by a scanning type curtain type electron beam accelerating furnace. When the curable resin composition of the present invention is cured by ultraviolet irradiation, the amount of ultraviolet radiation required for curing may be about 300 to 20000 mJ / cm ² . Further, in order to sufficiently cure the resin composition, it is preferable to irradiate active energy rays such as ultraviolet rays in an inert gas atmosphere such as nitrogen gas.

The curable resin composition of the present invention can be used in molds such as plastic lenses and the like. As a production method of a plastic lens using the resin composition of the present invention, a gasket made of polyvinyl chloride, ethylene-vinyl acetate copolymer or the like and a mold made of two glass molds of a desired shape are prepared, and the resin composition of the present invention A method of curing the resin composition by irradiating an active energy ray such as ultraviolet ray after injection and releasing the cured product from the mold.

As a method for applying the curable resin composition of the present invention to a film substrate as a resin composition for a prismatic lens sheet, various methods known in the art can be used. As a specific method, for example, a resin composition is applied on a surface of a gold plate having a prism lens shape to form a resin composition layer, and a colorless transparent film-like substrate (for example, polyvinyl chloride, Pressure mercury lamp is irradiated from the film-like substrate side in such a state that ultraviolet rays are irradiated to the layer of the resin composition to form a layer of the resin composition (hereinafter referred to as " layer of resin composition " And then the film-like base material on which the resin layer on the prism lens is formed is peeled from the mold.

The refractive index of the cured product of the resin composition of the present invention obtained by irradiating active energy rays such as ultraviolet rays is preferably 1.50 or more at 25 占 폚, and more preferably 1.52 or more at 25 占 폚. Particularly, when the prism lens sheet is manufactured using the resin composition of the present invention, when the refractive index of the cured product is less than 1.50 at 25 캜, there arises a problem that a sufficient front luminance can not be secured. Also, Abbe's number of the cured product (a value inherent to the material that defines the property of changing the refractive index according to the wavelength of light) is preferably 40.0 or more, and more preferably 50.0 or more. When the Abbe number of the cured product is less than 40.0, chromatic aberration is large and color bleeding occurs, which is not preferable.

The resin cured product obtained by molding and curing the curable resin composition of the present invention is excellent as an optical material. And is particularly useful as a material for an optical plastic lens such as a prism lens sheet, a Fresnel lens, a lenticular lens, a spectacle lens, or an aspheric surface lens. Such a lens is advantageously used in an image pickup apparatus. In addition, the curable resin composition or the resin cured product can be used in applications for optoelectronics such as optical disks, optical fibers, optical waveguides, printing inks, paints, clear coating agents, gloss varnishes and the like.

<Examples>

EXAMPLES The present invention will now be described by way of examples, but the present invention is not limited thereto. All parts in the examples are parts by weight unless otherwise specified. In addition, the measurement of the softening temperature and the like in the examples was carried out by preparing and measuring samples by the following methods.

(Measurement of physical properties of copolymer and its cured product)

1) Molecular weight and molecular weight distribution of polymer

The measurement of the molecular weight and the molecular weight distribution of the soluble polyfunctional (meth) acrylic acid ester copolymer was carried out by using a solvent: tetrahydrofuran (THF), a flow rate of 1.0 ml / min, a column temperature of 40 &Lt; / RTI &gt; The molecular weight of the copolymer was measured as polystyrene-reduced molecular weight using a calibration curve of monodispersed polystyrene.

2) Structure of polymer

NMR analysis and &lt; 1 &gt; H-NMR analysis using a JNM-LA600 type nuclear magnetic resonance spectrometer manufactured by Nihon Denshi Co., Chloroform-d1 was used as a solvent, and the resonance line of tetramethylsilane was used as an internal standard.

3) Preparation and measurement of samples for glass transition temperature (Tg) and softening temperature measurement

The soluble polyfunctional (meth) acrylic acid ester copolymer solution was uniformly applied to a glass substrate so as to have a thickness of 20 mu m after drying, and then dried by heating at 90 DEG C for 30 minutes using a hot plate. The obtained resin film on the glass substrate was placed in a TMA (thermomechanical analyzer) measuring apparatus together with the glass substrate, heated to 220 DEG C at a temperature raising rate of 10 DEG C / min under a nitrogen stream, and further subjected to heat treatment at 220 DEG C for 20 minutes, (This cured product is referred to as a sample). After cooling the glass substrate to room temperature (cooling), the sample in the TMA measurement apparatus was brought into contact with the probe for analysis, and the measurement was performed by scanning the sample at 30 DEG C to 360 DEG C at a heating rate of 10 DEG C / min under a nitrogen stream, The softening temperature was determined by the method. When the probe does not pass through the resin film but does not show a probe penetration amount smaller than the film thickness due to the heat resistance of the sample, the penetration amount with respect to the temperature and the film thickness at which the probe penetrates outside of the softening temperature is expressed as a percentage.

4) Measurement of thermal weight loss and thermal discoloration

To measure the thermal decomposition temperature and heat discoloration resistance of the soluble polyfunctional (meth) acrylic acid ester copolymer, the sample was set in a TGA (thermogram) measuring apparatus and heated at 30 DEG C to 320 DEG C at a heating rate of 10 DEG C / The measurement was carried out by scanning to determine the amount of decrease in weight at 300 占 폚 and the amount of discoloration of the sample after measurement was visually observed.?: No discoloration of heat,?: Pale yellow,?: Dark brown, .

5) Measurement of Absorption Rate

The weight of the sample vacuum-dried at 60 ° C for 24 hours was defined as Wo and weighed with a balance measurable up to ± 0.1 mg and humidified for one week in a thermo-hygrostat at a temperature of 85 ° C and a relative humidity of 85%. After the humidification, the moisture adhering to the test sample was wiped off, and the sample was weighed to a measurable scale up to ± 0.1 mg to make W. The absorption rate was calculated by the following formula (3). Three identical test samples were prepared and tested in the same manner.

Wo / W x 100 = absorption rate (3)

6) Measurement of solvent resistance and measurement of solvent solubility

The measurement of the solvent resistance of the soluble polyfunctional (meth) acrylic acid ester copolymer was carried out by immersing this copolymer in toluene at room temperature for 10 minutes by vacuum press molding the copolymer at 200 DEG C for 1 hour and changing the sample after immersion The results were evaluated as follows:?: No change;?: Swelling; and?: Deformation and swelling.

Solvent solubility was measured by adding 5 g of a soluble polyfunctional (meth) acrylic acid ester copolymer to 100 ml of a solvent and observing the dissolution state after stirring at 25 캜 for 10 minutes. A case in which the presence of the undissolved product and the gel was not recognized uniformly was determined to be usable.

7) Measurement of refractive index

The synthesized soluble polyfunctional (meth) acrylic acid ester copolymer was dissolved in toluene, and 1.0 part by weight of perbutyl O as an initiator was added to 100 parts by weight of the soluble polyfunctional (meth) acrylic acid ester copolymer. A cast sheet was prepared from this polymer solution, and the cast sheet was crushed and pelletized, filled in a press mold, and cured at 170 DEG C for 1 hour by a press molding machine. The obtained cured parallel plate was used as a test piece, and the refractive index of d line (587.6 nm) was measured with KPR-200 (Shimadzu Calusa). Immediately after molding, the measurement timing was set for one week in a thermostatic hygrostat under a humid condition of 85 ° C × 85 RH. The Abbe number was measured with an Abbe's refractive index meter (Atago Co.) using the same test piece.

8) Adhesion test

The varnish prepared by diluting the copolymer with a solvent (methyl ethyl ketone) was coated on a glass substrate, dried at 80 ° C for 5 minutes, cured at 200 ° C for 1 hour in a nitrogen oven in an inert oven . Next, a glass substrate on which a cured coating film of the copolymer was placed was cut in a vertical direction and a horizontal direction by 11 cutting lines on the surface of the coated film according to JIS K5400, thereby forming 100 grid squares. The cellophane tape was brought into close contact with the surface of the cellophane tape, and then peeled off at the same time, the number of remaining scales was counted without peeling off.

(Measurement of physical properties of composition)

(1) Measurement of refractive index

For measurement of various physical properties of the resin composition, voids having a width of 50 mm and a length of 50 mm were formed between two glass plates having a width of 60 mm, a length of 60 mm and a thickness of 1.0 mm using a silicon tape having a thickness of 1.0 mm and a width of 10 mm, Outer periphery) was wound with a polyimide tape and the composition was injected into a fixed glass frame. 1) irradiating ultraviolet rays from the one side of the glass frame with the above-described high-pressure mercury lamp for several seconds, or 2) placing the glass mold in an inert gas oven under a nitrogen gas stream and heating at 180 DEG C for 1 hour . The resin plate cured from the glass frame was taken out to be Sample B. The refractive index and the Abbe number of the sample B were measured with an Abbe refractometer (manufactured by Atago Co.).

(2) Color

A flat plate having a thickness of 1.0 mm was measured with a colorimeter (trade name "MODEL TC-8600 ", manufactured by Tokyo Denshoku Co., Ltd.) and the YI value thereof was shown.

(3) Haze (turbidity) and total light transmittance

A test piece having a thickness of 0.2 mm was prepared and its haze (turbidity) and total light transmittance were measured using an integrating sphere type light transmittance measuring device (SZ-Σ90, manufactured by Nippon Denshoku).

(4) Dissimilarity

The sample B used for the measurement of the refractive index was evaluated according to the degree of difficulty when it was released from the glass frame.

Good: Good releasability from the glass frame

DELTA: Release slightly difficult

X: Difficulty in releasing or remnants of the frame

(5) Frame reproducibility

The surface shape of the cured resin layer and the surface shape of the glass mold were observed.

○: Good reproducibility

×: poor reproducibility

(6) Leaving, Sam

When the cured resin was released from the glass mold, it was evaluated according to the size of the tilting outside the product portion of the molded product and the degree of leaking of the resin to the clearance of the glass mold.

?: Less than 0.05 mm of the amount of yielding, less than 1.0 mm of leaking of resin to glass frame clearance

DELTA: The amount of yielding is 0.05 mm or more and less than 0.2 mm. The leakage of resin to the glass frame clearance is 1.0 mm or more and less than 3.0 mm

X: The amount of yield of the backlash is 0.2 mm or more, the leakage of the resin to the glass frame clearance is 3.0 mm or more

(7) Bubbles: When the cured resin was released from the glass mold, it was evaluated according to the presence or absence of bubbles in the product portion of the molded article and the degree of size.

○: No bubble formation observed

?: The formation of bubbles was observed, and the bubble size was less than 2% of the volume of the molded article

X: The formation of bubbles was observed, and the size of the bubbles was 2% or more

(8) Cracking: When the cured resin was released from the glass mold, it was evaluated according to the degree of the presence or absence of cracks in the product portion of the molded product and the size thereof.

○: No generation of crack was observed

DELTA: Creation of cracking was observed, but occurrence of cracking was observed only at the corner portion of the outer periphery of the molded article

X: Creation of cracking was observed, but occurrence of cracking was observed in addition to the corner portion of the outer periphery of the molded article

(7) Reflow heat resistance: The sample B was used to measure the spectral transmittance at a wavelength of 400 nm with a spectroscopic colorimeter CM-3700d (manufactured by Konica Minolta). The measurement timings were made before the heat-resistant test at post-cure at 190 占 폚 for 60 minutes and after the heat-resistance test at 260 占 폚 for 8 minutes in an air oven. The results of the spectral transmittance changes obtained by these measurements are shown in Table 3 below.

(8) Absorption rate

Using Sample B, the weight of the test sample vacuum-dried at 60 ° C for 24 hours was defined as Wo and weighed with a measurable scale up to ± 0.1 mg. The sample was weighed in a thermostatic humidity chamber at 85 ° C. and 85% And humidification was performed for one week. After the humidification, the moisture adhering to the test sample was wiped off, and the sample was weighed to a measurable scale up to ± 0.1 mg to make W. The absorption rate was calculated by the following equation (1). Three of the same test samples were prepared and tested in the same manner.

Wo / W x 100 = absorption rate (1)

&Lt; Example 1 >

1.6 mol (463.2 mL) of dimethyloltricyclodecane diacrylate (DMTCD), 1.2 mol (254.2 mL) of dicyclopentyl methacrylate, 1.2 mol (226.3 mL) of 1,4-butanediol diacrylate , 0.4 mole (95.5 ml) of 4-diphenyl-4-methyl-1-pentene (? MSD), 2.4 moles (564.8 ml) of t- 40 mmol (11.5 g) of t-butylperoxy-2-ethylhexanoate was added at 90 deg. C and reacted for 2 hours and 45 minutes. 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 copolymer. The resulting copolymer was washed with hexane, filtered, dried and weighed to obtain 536.4 g of copolymer A (yield: 73.2 wt%).

The Mw of the obtained copolymer A was 34200, the Mn was 5620, and the Mw / Mn was 6.1. By conducting ¹³ C-NMR, ¹ H-NMR analysis and elemental analysis, copolymer A contained 39.6 mol% of the structural unit (1) derived from dimethylol tricyclodecane diacrylate in total, , The total of the structural unit (2) was 31.1 mol%, and the structural unit (3) derived from 1,4-butanediol diacrylate was 29.3 mol%. Here, the above calculation is calculated assuming that the total of the structural unit derived from the monofunctional (meth) acrylic acid ester (a) having an alicyclic structure and the structural unit derived from the bifunctional (meth) acrylic ester (b) is 100 mol% .

The terminal group (4) having a structure derived from 2,4-diphenyl-4-methyl-1-pentene has structural units (1), (2) and (3), terminal group Based on the total amount of the terminal groups (5) of the mercaptan-derived structure (hereinafter referred to as the total amount of all constituent units). On the other hand, the terminal group (5) was present in an amount of 7.2 mol% based on the total amount of all constituent units.

The ratio of the pendant acrylate calculated by the above formula (2) was 39.9 mol%.

Copolymer A was soluble in toluene, xylene, THF, dichloroethane, dichloromethane and chloroform, and no gel formation was observed. The cast film of copolymer A was also a non-hazy transparent film.

The copolymer A was made into a cured sheet under various measurement conditions. The cured sheet was cut out, and the obtained sample was subjected to measurement of optical characteristics, water absorption, reduction in heat weight, heat discoloration resistance and solvent resistance.

As a result, the coefficient of linear expansion was 67 ppm / 占 폚, the water absorption rate was 0.48%, and the solvent resistance was?.

As a result of TMA measurement, the softening temperature was 300 DEG C or more. As a result of the TGA measurement, the weight loss at 300 캜 was 0.8 wt% and the heat discoloration was ◎.

Further, the refractive index of the copolymer A was measured. The refractive index after curing (589 nm) was 1.522, and the refractive index after moist heat testing (589 nm) was 1.523.

In addition, it was confirmed that the number of remaining scales in the adhesion test remained on the substrate without missing 100 scales.

&Lt; Example 2 >

0.24 mole (47.2 ml) of dicyclopentanyl acrylate (DCPA), 0.96 mole (181.0 ml) of 1,4-butanediol diacrylate, 2-hydroxypropyl acrylate Acrylate (HOP-A), 0.48 mol of 2,4-diphenyl-4-methyl-1-pentene, 1142 ml of t-dodecyl mercaptan, 734.3 ml of t- Was charged into a 3.0 L reactor and 62 mmol (13.9 g) of t-butyl peroxy-2-ethylhexanoate was added at 90 deg. C for 2 hours and 30 minutes. 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. The obtained polymer was washed with hexane, filtered, dried and weighed to obtain 517.2 g of copolymer B (yield: 71.5 wt%).

The Mw of the obtained copolymer B was 39500, the Mn was 7240, and the Mw / Mn was 5.5. By conducting ¹³ C-NMR, ¹ H-NMR analysis and elemental analysis, copolymer B had a total of 55.2 mol% of the structural unit (1) derived from dimethylol tricyclodecane diacrylate, a structure derived from dicyclopentanyl acrylate , A total of 5.1 mol% of units (2), 20.3 mol% of the structural unit (3) derived from 1,4-butanediol diacrylate, 19.4 mol% of the structural unit (6) derived from 2-hydroxypropyl acrylate there was. The terminal group (4) having a structure derived from 2,4-diphenyl-4-methyl-1-pentene was present in an amount of 1.2 mol% based on the total amount of all the structural units.

On the other hand, the terminal group (5) of the structure derived from t-dodecyl mercaptan was present in an amount of 7.6 mol% based on the total amount of all the structural units.

Copolymer B was soluble in toluene, xylene, THF, dichloroethane, dichloromethane and chloroform, and no gel formation was observed. The cast film of Copolymer B was also a non-hazy transparent film.

The copolymer B was made into a cured sheet according to various measurement conditions. The cured sheet was cut out, and the obtained sample was subjected to measurement of optical characteristics, water absorption, reduction in heat weight, heat discoloration resistance and solvent resistance.

As a result, the coefficient of linear expansion was 71 ppm / 캜, the water absorption rate was 0.76%, and the solvent resistance was ◯.

As a result of TMA measurement, the softening temperature was 300 DEG C or more. As a result of TGA measurement, the weight loss at 300 占 폚 was 0.92 wt%, and the heat discoloration resistance was?.

Further, the refractive index of the copolymer B was measured. The refractive index after curing (589 nm) was 1.507 and the refractive index after moist heat testing (589 nm) was 1.509.

Also, it was confirmed that the number of scales remaining in the adhesion test remained on the substrate without missing 100 scales.

&Lt; Examples 3 to 8 and Comparative Examples 1 to 4 >

Various monofunctional (meth) acrylates and bifunctional acrylates were polymerized in the same manner as in Example 1 with the raw material compositions shown in Table 1.

The amounts of the raw materials used in the reaction are shown in Table 1, and the results of the tests of the copolymer and its cured product are shown in Table 2. Other reaction conditions and measurement conditions are the same as in Example 1 unless otherwise specified. In Table 1, the amount of the raw material to be used is expressed in terms of mol and weight (g), and the type of the substrate is mol / g. The mole fractions (MR) were calculated by taking the sum of the components (a) and (b) as 100.

&Lt; Examples 9 to 11 and Comparative Examples 5 and 6 >

Each component was blended in the proportions shown in Table 3 (number parts by weight), and 0.1 parts by weight of Adekastab AO-60 manufactured by Adeka Co., Ltd. as a stabilizer was added to obtain a curable resin composition. Next, the curable resin composition was cured by the various test methods described above and evaluated for performance. Table 4 shows the performance evaluation results.

&Lt; Examples 12 to 20 and Comparative Examples 7 to 9 >

Each component was blended in the proportions shown in Table 5 (number parts by weight), and 0.1 part by weight of Adekastab AO-60 manufactured by Adeka Co., Ltd. as a stabilizer was added to obtain a curable resin composition. Next, the curable resin composition was cured by the various test methods described above and evaluated for performance. Table 6 shows the performance evaluation results.

The abbreviations used in the table are shown below.

DMTCD: dimethyloltricyclodecane diacrylate (bifunctional)

BDDA: 1,4-butanediol diacrylate (bifunctional)

DCPM: dicyclopentanyl methacrylate (unifunctional)

DCPA: dicyclopentanyl acrylate (unifunctional)

HOP-A: 2-hydroxypropyl acrylate (unifunctional)

? MSD: 2,4-diphenyl-4-methyl-1-pentene (c)

TDM: t-dodecyl mercaptan (d) Component

TMPTA: trimethylolpropane triacrylate (trifunctional)

TMP: trimethylolpropane trimethacrylate (trifunctional)

CD536: dioxolanediacrylate (bifunctional)

HPNDA: hydroxypivalic acid neopentyl glycol diacrylate (bifunctional)

Perbutyl O: t-butylperoxy-2-ethyl hexanate (manufactured by Nippon Oil Co., Ltd.)

Perocta O: 1,1,3,3-tetramethylbutyl-peroxy-2-ethylhexanoate (manufactured by Nippon Oil Co., Ltd.)

DPHA: dipentaerythritol hexaacrylate (6-functional)

PETIA: pentaerythritol triacrylate (trifunctional)

Irgacure 184: 1-Hydroxy-cyclohexyl-phenyl-ketone (from BASF)

MR: mole fraction

(a ') Component: (a) component + (a2) Component

Claims (10)

(B), 2,4-diphenyl-4-methyl-1-pentene (c) and thiol compound (d) having an alicyclic structure, (Meth) acrylate ester (b) having a reactive (meth) acrylate group in its side chain and a reactive (meth) acrylate group derived from a 2,4-diphenyl- - a copolymer having a structural unit derived from a pentene (c) and a thiol compound (d) and having a weight average molecular weight of 2,000 to 60,000, and is soluble in toluene, xylene, tetrahydrofuran, dichloroethane or chloroform Soluble polyfunctional (meth) acrylic acid ester copolymer. The method according to claim 1,
(Meth) acrylic acid ester (a) having a cycloaliphatic structure, a monofunctional (meth) acrylic acid ester (a2) containing a hydroxyl group, a bifunctional (meth) acrylic acid ester (b) (Meth) acrylic acid ester copolymer, which is a copolymer obtained by copolymerizing a component containing (c) phenyl-4-methyl-1-pentene and a thiol compound (d). The method according to claim 1,
Wherein the monofunctional (meth) acrylic acid ester (a) having an alicyclic structure is selected from the group consisting of isobornyl methacrylate, isobornyl acrylate, cyclohexyl methacrylate, cyclohexyl acrylate, dicyclopentenyl acrylate, At least one member selected from the group consisting of dicyclopentanyl methacrylate, dicyclopentenyloxyethyl methacrylate, dicyclopentanyl methacrylate, and dicyclopentanyl methacrylate; Functional (meth) acrylic acid ester copolymer is characterized by being a functional (meth) acrylic acid ester. The method according to claim 1,
Wherein the bifunctional (meth) acrylic acid ester (b) is selected from the group consisting of cyclohexanedimethanol diacrylate, cyclohexanedimethanol dimethacrylate, dimethyloltricyclodecane diacrylate and dimethyloltricyclodecane dimethacrylate (Meth) acrylate ester selected from the group consisting of a polyfunctional (meth) acrylic acid ester and a polyfunctional (meth) acrylic acid ester. (B), 2,4-diphenyl-4-methyl-1-pentene (c) and thiol compound (d) having an alicyclic structure, (Meth) acrylic acid ester copolymer according to claim 1, wherein the component (B) is copolymerized with the component (A). (A): The soluble polyfunctional (meth) acrylic acid ester copolymer according to claim 1,
(B): polyfunctional (meth) acrylate, and
(C) Ingredient: initiator
Wherein the amount of the component (B) is 5 to 250 parts by weight based on 100 parts by weight of the component (A), and the amount of the component (C) to the total amount of the component (B) Is 0.1 to 10 parts by weight based on the weight of the curable resin composition. The method according to claim 6,
(A): the soluble polyfunctional (meth) acrylic acid ester copolymer according to claim 2,
(B): a polyfunctional (meth) acrylate having 5 or more functional groups, and
(C) Ingredient: initiator
And a curing agent. A cured resin product obtained by curing the curable resin composition according to claim 6. An optical material characterized by being formed of the resin cured product according to claim 8. 10. The method of claim 9,
Wherein the optical material is an optical plastic lens.