KR20120102009A - Soluble polyfunctional (meth)acrylic ester copolymer having alicyclic structure, curable resin composition and cured product - Google Patents

Abstract

PURPOSE: A developable polyfunctional (meth)acrylic acid ester copolymer is provided to have low color dispersibility, high transmittance, low absorption, excellent processability, and excellent termal resistance. CONSTITUTION: A developable polyfunctional (meth)acrylic acid ester copolymer is obtained by copolymerization of components comprising monofunctional (meth)acrylic acid ester having a cycloaliphatic structure, bifunctional (meth)acrylic acid ester, 2,4-diphenyl-4-methyl-1-penene and a thiol compound, has a reactive (meth)acrylate group orininated from the bifunctional (meth)acrylic acid ester, and has a unit structure originated from 2,4-dipenyl-4-methyl-1-pentene and a thiol compound. The copolymer has an average molecular weight of 2,000-60,000, and is soluble into toluene, xylene, tetrahydrofuran, dichloroethane or chloroform.

Description

SOLUBLE POLYFUNCTIONAL (METH) ACRYLIC ESTER COPOLYMER HAVING ALICYCLIC STRUCTURE, CURABLE RESIN COMPOSITION AND CURED PRODUCT}

The present invention has excellent optical properties such as low color dispersion and high light transmittance, heat resistance, and workability, and also has excellent optical properties, low water absorption, and good releasability under molding under strict practical use conditions such as wet heat conditions. Curable resin composition and cured product comprising a soluble polyfunctional (meth) acrylic acid ester copolymer having an alicyclic structure with improved properties and precise mold transferability, and a soluble polyfunctional (meth) acrylic acid ester copolymer And to an optical article.

Most of the monomers having an unsaturated bond with reactive activity can produce a multimer by selecting a catalyst and an appropriate reaction condition in which the unsaturated bond is cleaved to cause a chain reaction. Generally, since the kind of monomer which has an unsaturated bond is very diverse, the richness of the kind of resin obtained is also remarkable. However, there are relatively few kinds of monomers capable of obtaining a high molecular weight of 10,000 or more, generally referred to as a high molecular compound. For example, ethylene, substituted ethylene, propylene, substituted propylene, styrene, alkyl styrene, alkoxy styrene, norbornene, various acrylic acid esters, butadiene, cyclopentadiene, dicyclopentadiene, isoprene, maleic anhydride, maleimide, fumaric acid Ester, an allyl compound, etc. are mentioned as a typical monomer. Many kinds of resins are synthesized by these monomers alone or by copolymerizing them.

The use of these resins is mainly limited to the field of relatively inexpensive consumer equipment, and there are few applications in the high-tech field where high heat resistance, dimensional stability and fine workability are required in the field of optoelectronic materials. The reason is that the polymer synthesized from the above-mentioned monomers is usually thermoplastic and needs to be made into a high molecular weight material in order to satisfy the mechanical properties. Therefore, the characteristics required in the high-tech field such as heat resistance and fine workability are sacrificed. It can be said that.

As a method of solving the fault of such a vinyl thermoplastic polymer, Patent Documents 1-3 have disclosed the polymer which has 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 heteropolymerizable monomers such as 2-vinyloxyethyl acrylate (VEA) and a photopolymerization initiator. In addition, Patent Document 2 discloses a photosensitive composition composed of a (meth) acryloyl group pendant polymer, a compound having a photoreactive unsaturated carboxyl group, and a photopolymerization initiator. In addition, Patent Document 3 discloses homopolymerization of heteropolymerizable monomers such as 2-vinyloxyethyl acrylate (VEA) using a cationic polymerization catalyst in a carboxylic acid ester solvent compound having a photoreactive unsaturated group which is inert to its own cationic polymerization. Or a method for obtaining a polymer solution by copolymerizing is disclosed.

However, in the case of using a reactive polymer prepared according to the technique using the heteropolymerizable monomer disclosed in these patent documents, the low absorption, heat resistance, moldability, and high optical properties required in the field of advanced optical lens prism applications A polymer having both a balance of properties and an optical property under strict practical use conditions such as wet heat conditions, low water absorption and good mold release property during molding, and precise mold transferability, and a curable resin composition have not been obtained.

On the other hand, in patent document 4, it is obtained by copolymerizing a monovinyl aromatic compound and a bifunctional (meth) acrylic acid ester, and the solubility which has a structural unit containing the reactive (meth) acrylate group derived from bifunctional (meth) acrylic acid ester in a side chain. Polyfunctional vinyl aromatic copolymers are disclosed. However, the soluble polyfunctional vinyl aromatic copolymer obtained by the technique disclosed therein has excellent thermal decomposition resistance against thermal history at high temperatures, has a reactive (meth) acrylate group in the side chain, and is excellent in workability and solvent solubility. Although it had a combination, there was a practical use restriction | limiting that it cannot use for the optical lens of low chromatic dispersion use, and it was a material which did not achieve high hardness.

Further, Patent Document 5 contains 1 to 25% by weight of di (meth) acrylate of a linear aliphatic dihydric alcohol having 4 to 8 carbon atoms as a constituent in methyl methacrylate (MMA) syrup. A composition is disclosed. Herein, the preparation of the MMA syrup composition may be performed by heating or heating polymerizing MMA or MMA, a vinyl copolymer copolymerizable with the same, and a chain transfer agent in an inert gas (for example, N ₂ gas) atmosphere in the presence of a polymerization initiator. It is disclosed to perform. Specific examples of the chain transfer agent include only sulfur compounds such as lauryl mercaptan, thioglycolic acid octyl ester, thiocresol, thionaphthol and benzyl mercaptan, and 2,4-diphenyl-4-methyl-1- The pentene (c) is not specifically disclosed. Moreover, the monofunctional and / or bifunctional (meth) acrylic acid ester which exists simultaneously with the terminal group derived from a thiol compound, and the terminal group derived from 2, 4- diphenyl-4-methyl-1- pentene, and has an alicyclic structure Since the structural unit derived from (a) coexists, it has not been suggested that the heat transfer optical characteristic and the precise transfer property of a metal mold | die can be controlled synergistically. Moreover, the composition obtained by the technique disclosed in this did not improve the adhesiveness with an inorganic material under stringent practical use conditions, such as wet heat conditions.

In addition, Patent Document 6 discloses a polymerizable composition composed of a vinyl monomer and a di (meth) acrylate compound, and the use of 2,4-diphenyl-4-methyl-1-pentene (c) is also disclosed. However, the amount used is a comma about several% as a normal chain transfer agent, and the product also crosslinked-gelled and did not show solvent solubility.

In addition, Patent Literature 7 includes a magnetic unit comprising a structural unit consisting of 1) an epoxy group-containing (meth) acrylate, 2) a hydroxyl group-containing (meth) acrylate, 3) (meth) acrylic acid, and 4) aromatic group-containing (meth) acrylate. A thermosetting resin composition for color filters comprising a curable copolymer and an organic solvent is disclosed. And the self-curable copolymer obtained by the technique disclosed here is a mercaptopropionic acid, a mercaptopropionic acid ester, thioglycol, thioglycerine, and dodecyl mercaptan in the polymerization step, in order to achieve the range of a preferable molecular weight. It is said that well-known molecular weight modifiers, such as (alpha) -methylstyrene dimer, can be used. However, in the technique disclosed herein, since at least one bifunctional or higher vinyl compound having a plurality of vinyl groups is not added at the time of polymerization, only a terminal group derived from one or less molecular weight regulators can be introduced into the polymer chain, and thus a function derived from a terminal group. There was a flaw that it could not be given enough. In addition, the self-curable copolymer obtained by the technique disclosed herein forms a thermosetting resin composition in a resin composition with an epoxy resin, but since a curing reaction does not occur between the acrylate resin, There was also a drawback of causing a decrease in strength and heat resistance.

Therefore, it has excellent optical properties such as low color dispersion and high light transmittance, balances properties such as low absorption, moldability and heat resistance, and improves optical properties and precise transferability of mold shape under strict practical use conditions such as wet heat conditions. Soluble polyfunctional (meth) acrylic acid ester copolymer and the curable resin composition using this copolymer did not exist until now.

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

The present invention has excellent optical properties such as low color dispersion and high light transmittance, and has excellent balance of various properties required for optical lens and prism materials in the advanced technical fields such as low absorption, workability and heat resistance, and also strict practical use such as wet heat conditions. An object of the present invention is to provide a soluble polyfunctional (meth) acrylic acid ester copolymer having improved optical properties and adhesion between inorganic materials and a curable resin composition, a cured product, and an optical article including the same.

The present invention is a monofunctional (meth) acrylic acid ester (a) having a cycloaliphatic structure, a bifunctional (meth) acrylic acid ester (b), a 2,4-diphenyl-4-methyl-1-pentene (c) and a thiol compound As a copolymer obtained by copolymerizing the component containing (d), it has a reactive (meth) acrylate group derived from bifunctional (meth) acrylic acid ester (b) in a side chain, and has 2, 4- diphenyl-4- at the terminal. Copolymer having structural units derived from methyl-1-pentene (c) and thiol compound (d), and having a weight average molecular weight of 2000 to 60,000, and soluble in toluene, xylene, tetrahydrofuran, dichloroethane or chloroform. It is a polyfunctional (meth) acrylic acid ester copolymer.

Moreover, this invention uses monofunctional (meth) acrylic acid ester (a2) containing a hydroxyl group with the monofunctional (meth) acrylic acid ester (MFM) which has an alicyclic structure as a monofunctional (meth) acrylic acid ester (MFM). It relates to the above-mentioned soluble polyfunctional (meth) acrylic acid ester copolymer.

As monofunctional (meth) acrylic acid ester (a) which has the said alicyclic structure, isobornyl methacrylate, isobornyl acrylate, cyclohexyl methacrylate, cyclohexyl acrylate, dicyclopentenyl acrylate, dicyclo At least one group selected from the group consisting of pentenyloxyethyl acrylate, dicyclopentanyl acrylate, dicyclopentenyloxyethyl methacrylate, dicyclopentenyloxyethyl methacrylate, and dicyclopentanyl methacrylate A functional (meth) acrylic acid ester is mentioned.

As said bifunctional (meth) acrylic acid ester (b), the group which consists of cyclohexane dimethanol diacrylate, cyclohexane dimethanol dimethacrylate, dimethylol tricyclodecane diacrylate, and dimethylol tricyclodecane dimethacrylate One or more types of bifunctional (meth) acrylic acid ester chosen from is mentioned.

Moreover, this invention is monofunctional (meth) acrylic acid ester (a) which has an alicyclic structure, bifunctional (meth) acrylic acid ester (b), 2, 4- diphenyl- 4-methyl-1- pentene (c), and thiol It is a manufacturing method of said soluble polyfunctional (meth) acrylic acid ester copolymer characterized by copolymerizing the component containing a compound (d).

Moreover, this invention is a composition containing (A) component: the soluble polyfunctional (meth) acrylic acid ester copolymer of Claim 1, (B) component: polyfunctional (meth) acrylate, and (C) component: initiator, The compounding quantity of (B) component is 5-250 weight part with respect to 100 weight part of (A) component, and the compounding quantity of (C) component is 0.1- with respect to a total of 100 weight part of the compounding quantity of (B) component and (A) component. It is 10 weight part, curable resin composition characterized by the above-mentioned.

As another aspect, as monofunctional (meth) acrylic acid ester (MFM) as (A) component, the monofunctional (meth) acrylic acid ester containing a hydroxyl group with the monofunctional (meth) acrylic acid ester (a) which has an alicyclic structure is contained. It is a curable resin composition using the said soluble polyfunctional (meth) acrylic acid ester copolymer using (a2), and using polyfunctional (meth) acrylate more than 5 functional as (B) component.

Moreover, this invention is formed by hardening | curing said curable resin composition, The cured resin characterized by the above-mentioned, and this resin hardened | cured material formed, It is an optical material characterized by the above-mentioned. As an optical material, there is an optical plastic lens.

According to the present invention, it has excellent optical properties such as low color dispersion and high light transmittance, and has excellent balance of various properties required for optical lens and prism materials in the advanced technical fields such as low absorption, workability and heat resistance, and it is also a strict seal such as wet heat conditions. It can be set as the material which the adhesiveness of the optical characteristic and an inorganic material improved under use conditions. Such an optical material is suitably used in the field centering on the field of imaging, such as an imaging device which requires a high optical characteristic.

Hereinafter, the soluble polyfunctional (meth) acrylic acid ester copolymer of this invention is demonstrated in detail. This soluble polyfunctional (meth) acrylic acid ester copolymer has an alicyclic structure and structural units 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 may be abbreviated as a copolymer.

The copolymer of the present invention is a monomer containing a monofunctional (meth) acrylic acid ester (a) and a bifunctional (meth) acrylic acid ester (b) having an alicyclic structure, and 2,4-diphenyl-4-methyl-1 A copolymer obtained by copolymerizing a pentene (c) and a thiol compound (d), and having a reactive (meth) acrylate group derived from a bifunctional (meth) acrylic acid ester (b) in the side chain, and further having 2 at the terminal. It is a soluble polyfunctional (meth) acrylic acid ester copolymer which has a structural unit derived from, 4-diphenyl-4-methyl-1- pentene (c) and a thiol compound (d). Here, soluble means soluble in toluene, xylene, tetrahydrofuran, dichloroethane or chloroform. The test of solubility consists of the conditions shown in the Examples. Here, together with the monofunctional (meth) acrylic acid ester (a) which has an alicyclic structure, the monofunctional (meth) acrylic acid ester (a2) containing a hydroxyl group can be used as monofunctional (meth) acrylic acid ester (MFM).

Since the chain structure of a copolymer is mainly obtained by copolymerizing a monofunctional (meth) acrylic acid ester and a bifunctional (meth) acrylic acid ester, it has a branched structure or a crosslinked structure, but the amount of such a structure is limited to the extent which shows solubility. . Therefore, it becomes a copolymer which has a structural unit (b1) containing the unreacted (meth) acryl group derived from bifunctional (meth) acrylic acid ester (b) in a side chain. This unreacted (meth) acryl group is also called a pendant (meth) acryl group, and since this shows polymerizability, it can superpose | polymerize by further polymerization process and can provide the resin hardened | cured material of a solvent insoluble.

In addition, the copolymer has a structural unit derived from 2,4-diphenyl-4-methyl-1-pentene (c) and a thiol compound (d) at the terminal. By introducing this structural unit into the end of the copolymer, a molding processability such as mold release property is improved, a linear expansion ratio that is advantageous for adhesion with an inorganic material is low, and a cured product excellent in heat resistance such as heat discoloration and weight reduction is obtained. You lose.

The copolymer is 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), and 2,4-diphenyl-4-methyl It has a structural unit derived from the 1-pentene (c) and thiol compound (d). Here, 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 two (meth) acryl groups participate in superposition | polymerization, and a branched structure or a crosslinked structure And a structural unit (b1) containing an unreacted (meth) acryl group in which only one vinyl group is involved in the polymerization and other vinyl groups do not react. 2,4-diphenyl-4-methyl-1-pentene (c) and thiol compound (d) act as chain transfer agents to prevent an increase in molecular weight and are present at the ends of the copolymer. As monofunctional (meth) acrylic acid ester (MFM), when monofunctional (meth) acrylic acid ester (a2) containing a hydroxyl group is used, it has a structural unit derived from (a2).

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

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

Here, (a), (b), (c) and (d) are derived from the structural unit derived from the monofunctional (meth) acrylic acid ester (a) which has an alicyclic structure, and bifunctional (meth) acrylic acid ester (b) The mole number of the structural unit derived from the structural unit, 2, 4- diphenyl- 4-methyl- 1-pentene (c), and a thiol compound (d) to be shown is shown. By introducing a structural unit derived from 2,4-diphenyl-4-methyl-1-pentene (c) and a thiol compound (d) in the above range at the terminal of the copolymer, heat resistance, mold release property and low water absorption, etc. can be improved. . When monofunctional (meth) acrylic acid ester (MFM) is used together with monofunctional (meth) acrylic acid ester (a2) containing a hydroxyl group, Formula (1) becomes as follows.

M _cd = (c) + (d) / [(a) + (a2) + (b) + (c) + (d)] (1 ')

Here, (a2) shows the number-of-moles of the structural unit derived from the monofunctional (meth) acrylic acid ester (a2) containing a hydroxyl group.

In addition, the ratio of 2,4-diphenyl-4-methyl-1-pentene (c) and thiol compound (d) is 5 to 50% of 2,4-diphenyl-4-methyl-1-pentene (c). It is preferable to, and 10 to 30% is especially preferable. Here, the ratio is calculated by the following equation.

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

The bifunctional (meth) acrylic acid ester (b) branches or crosslinks the copolymer, creates a pendant vinyl group, imparts curability to the copolymer, and plays an important role as a crosslinking component for expressing heat resistance during curing. .

As bifunctional (meth) acrylic acid ester, cyclohexane dimethanol diacrylate, dimethylol tricyclodecane diacrylate, cyclohexane dimethanol dimethacrylate, dimethylol tricyclodecane dimethacrylate, ethylene glycol diacrylate, Propylene glycol diacrylate, 1,4-butanediol diacrylate, hexanediol diacrylate, diethylene glycol diacrylate, ethylene glycol diacrylate, propylene glycol diacrylate, 1,4-butanediol dimethacrylate, Although bifunctional (meth) acrylic acid ester, such as hexanediol dimethacrylate and diethylene glycol dimethacrylate, can be used, It is not limited to these.

Suitable specific examples of the bifunctional (meth) acrylic acid ester include cyclohexanedimethanol diacrylate, cyclohexanedimethanol dimethacrylate, and dimethyloltricyclodecane diacrylate in terms of cost, ease of polymerization control and heat resistance of the obtained polymer. Or dimethylol tricyclodecane dimethacrylate is used preferably.

The copolymer has a structural unit (b1) containing a reactive (meth) acrylate group derived from a bifunctional (meth) acrylic acid ester (b) in the side chain, and the mole fraction of the structural unit (b1) represented by the formula (2) It is good that M _b1 is 0.05 or more, Preferably it is 0.1-0.7, More preferably, it is 0.3-0.5.

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

Here, (a) and (b) in the formula are moles of the structural unit derived from the monofunctional (meth) acrylic acid ester (a) having an alicyclic structure and the difunctional (meth) acrylic acid ester (b). Indicates. (B1) in a formula shows the number-of-moles of the structural unit (b1) containing a (meth) acrylate group. By satisfy | filling the said mole fraction, the molded article which is rich in sclerosis | hardenability in light and heat, and excellent in the heat resistance and mechanical property after hardening can be obtained. When using together monofunctional (meth) acrylic acid ester (a2) containing a hydroxyl group as monofunctional (meth) acrylic acid ester (MFM), Formula (2) becomes as follows.

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

Monofunctional (meth) acrylic acid ester (a) having an alicyclic structure is important for improving solvent solubility, low water absorption, heat resistance, optical properties and processability of the copolymer. As monofunctional (meth) acrylic acid ester which has such an alicyclic structure, 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 Although a branch can mention monofunctional (meth) acrylic acid ester, It is not limited to these. By introducing the structural units derived from these components into the copolymer, not only can the gelation of the copolymer be prevented and the solubility in the solvent can be improved, but also optical properties such as low color dispersion of the copolymer, low absorption and heat resistance can be improved. Can be.

Suitable embodiments include isobornyl methacrylate, isobornyl acrylate, cyclohexyl methacrylate, cyclohexyl acrylate, dicyclopentenyl acrylate, dicyclophene in terms of cost, gelling prevention and molding processability of the obtained polymer. At least one alicyclic structure selected from the group consisting of tenyloxyethyl acrylate, dicyclopentanyl acrylate, dicyclopentenyloxyethyl methacrylate, dicyclopentenyloxyethyl methacrylate and dicyclopentanyl methacrylate The monofunctional (meth) acrylic acid ester which has is mentioned.

As monofunctional (meth) acrylic acid ester (a2) containing a hydroxyl group, 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, 1,9-nonanediol monomethacrylate, etc. are mentioned. Among them, 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, 2-hydroxypropyl methacrylate, and 2- are suitable as viewpoints of compatibility with polyfunctional (meth) acrylates having 5 or more functional groups. Hydroxyethyl methacrylate is mentioned.

2,4-diphenyl-4-methyl-1-pentene (c) and thiol compound (d) function as chain transfer agents and control the molecular weight of the copolymer. The molecular weight of the copolymer of this invention is the range of 2000-60000 as weight average molecular weight Mw, Preferably it is the range of 3000-50000. The use of a relatively low molecular weight copolymer enhances the moldability and mold release property of the cured resin.

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

Moreover, it is possible to add the monofunctional (meth) acrylic acid ester which does not have an alicyclic structure as (e) component in order to improve the solvent solubility and processability of a copolymer. As such (meth) acrylic acid ester, methyl methacrylate, ethyl methacrylate, methyl acrylate, ethyl acrylate, n-butyl acrylate, 2-methylhexyl acrylate, 2-ethylhexyl acrylate, octyl acrylate, 2 -Hydroxyethyl methacrylate, and the like, preferably methyl methacrylate and n-butyl acrylate. These (meth) acrylic acid ester monomers may be used alone or in combination of two or more, but at least one (meth) acrylic acid ester selected from the group consisting of methyl methacrylate, methyl acrylate and n-butyl acrylate Is most preferred.

Moreover, it is good to set the structural unit derived from these other monomer components (e) in less than 30 mol% with respect to the monomer component (a) or the structural unit total amount derived from (a) and (a2).

In another aspect, the soluble polyfunctional (meth) acrylic acid ester copolymer of the present invention is derived from a structural unit derived from a monofunctional (meth) acrylic acid ester (a) having an alicyclic structure and a bifunctional (meth) acrylic acid ester (b). When the sum total of the structural units of is set to 100 mol%, the structural unit derived from (a) is preferably 10 to 60 mol%, preferably 15 to 50 mol%. The structural unit derived from (b) is preferably 40 to 90 mol%, preferably 50 to 85 mol%, more preferably 50 to 80 mol%. When the structural unit derived from (b) does not reach 10 mol%, heat resistance of hardened | cured material will run short, and when it exceeds 60 mol%, molding workability will fall and the strength of a molded article will fall remarkably, and it is unpreferable.

Moreover, when using monofunctional (meth) acrylic acid ester (a2) containing a hydroxyl group with monofunctional (meth) acrylic acid ester (a) which has alicyclic structure, it is derived from bifunctional (meth) acrylic acid ester (b). The molar ratio of the structural unit 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)] = 0.05-0.95, preferably 0.2-0.77

Moreover, it is preferable to introduce alicyclic structure into the structure derived from bifunctional (meth) acrylic acid ester (b), and the structural unit which has alicyclic structure matched with the monofunctional (meth) acrylic acid ester (a) which has alicyclic structure. The molar ratio of is 0.35 to 0.95, preferably 0.6 to 0.9 with respect to the entirety of [(a) + (a2) + (b)].

The soluble polyfunctional aromatic (meth) acrylic acid ester copolymer of the present invention is a monofunctional (meth) acrylic acid ester (a) having an alicyclic structure or a monofunctional (meth) acrylic acid ester (a) having an alicyclic structure and a hydroxyl group. Containing monofunctional (meth) acrylic acid ester (a2), bifunctional (meth) acrylic acid ester (b) and 2,4-diphenyl-4-methyl-1-pentene (c) and thiol compound (d) It is obtained by superposing | polymerizing the monomer which consists of 2-120 mol of 2, 4- diphenyl- 4-methyl-1- pentene (c) and a thiol compound (d) with respect to 100 mol of monomers at the temperature of 50-200 degreeC. . Here, 2,4-diphenyl-4-methyl-1-pentene (c) and thiol compound (d) are also known compounds as chain transfer agents. In the present invention, the amount of the monomer is greater than that used as the chain transfer agent. Be part of The amount of 2,4-diphenyl-4-methyl-1-pentene (c) and thiol compound (d) used is 2,4-diphenyl contained in the soluble polyfunctional aromatic (meth) acrylic acid ester copolymer of the present invention. The mole fraction of the structural units derived from -4-methyl-1-pentene (c) and thiol compound (d) is adjusted to be in the range of 0.02 to 0.35, which may be left unreacted due to its low reactivity. Can be. Therefore, although it is used in the range of 2-120 mol with respect to 100 mol of the said monomers, Preferably it is 20-100 mol, More preferably, it is the range of 50-80 mol.

From the viewpoint that 2,4-diphenyl-4-methyl-1-pentene (c) and thiol compound (d) also function as chain transfer agents, this amount of use is limited in crosslinking reaction, formation of pendant (meth) acrylate groups, It is preferable to exist in the range of 10-500 weight part with respect to 100 weight part of bifunctional (meth) acrylic acid esters (b) from the point of control of molecular weight distribution, and it is more preferable to exist in the range of 30-150 weight part. It is most preferable to exist in the range of 90-110 weight part.

Mono (meth) acrylic acid ester (a) having an alicyclic structure or mono (meth) acrylic acid ester (a) having an alicyclic structure and a monofunctional (meth) acrylic acid ester (a2) containing a hydroxyl group are used in (a). It is preferable to set it as 10-60 mol% with respect to 100 mol of total of (a), (a2), and a bifunctional (meth) acrylic acid ester (b), Preferably it is 15-50 mol%. It is preferable that the usage-amount of bifunctional (meth) acrylic acid ester (b) shall be 40-90 mol%, Preferably it is 50-85 mol%, More preferably, it is 50-80 mol%.

When producing the copolymer of this invention, when the initiation reaction rate by a thermal initiation reaction is small, you may add a radical polymerization initiator. In this case, as the radical polymerization initiator used, organic peroxide-based polymerization such as ketone peroxides, peroxy ketals, hydroperoxides, dialkyl peroxides, diacyl peroxides, peroxycarbonates, and peroxyesters An initiator and an azo polymerization initiator are mentioned. Although the usage-amount of these radical polymerization initiators is not specifically limited, Usually, based on 100 weight part of total amounts of a monomer component, it is preferable that it is 0.01-25 weight part, and it is more preferable to exist in the range which is 0.05-20 weight part. It is most preferable to exist in the range of 0.1-15 weight part.

Moreover, although polymerization reaction can be basically performed by bulk polymerization which does not use a solvent, it can also be performed in 1 or more types of organic solvent which melt | dissolves the produced | generated soluble polyfunctional (meth) acrylic-acid aromatic copolymer. As an organic solvent, it is a compound which does not essentially inhibit radical polymerization, and it can be used without a restriction | limiting in particular, if it melt | dissolves the chain transfer agent, the initiator, the monomer, and the polyfunctional (meth) acrylic acid ester aromatic copolymer of this invention, and forms a uniform solution. .

Examples of the compound that can be used as the organic solvent include aromatic hydrocarbons, linear aliphatic hydrocarbons, branched aliphatic hydrocarbons, cyclic aliphatic hydrocarbons, and paraffin oil obtained by hydrogenation of petroleum fraction. Among them, toluene, xylene, methylcyclohexane, and ethylcyclohexane are preferable from the viewpoint of the balance of polymerizability, solubility and availability.

The compound as these organic solvents is used individually or in combination of 2 or more types. There is no restriction | limiting in particular in the usage-amount of a solvent.

At the time of preparation of the copolymer of this invention, superposition | polymerization is performed in the temperature range of 50-200 degreeC. Since the polymerization rate is lowered when the polymerization reaction is performed at less than 50 ° C, 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 it is difficult to control the reaction and the insoluble gel by crosslinking It is not preferable because production is likely to occur.

The method of recovering a copolymer after stopping a polymerization reaction is not specifically limited, For example, what is necessary is just to use the method used normally, such as the heating reduced pressure devolatilization method, the steam stripping method, and precipitation in a poor solvent. .

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 all of the above solvents. Here, soluble means that 1 g or more, preferably 10 g or more dissolves in 100 ml of solvent at room temperature (25 degreeC). And it is preferable that generation | occurrence | production of a gel is not recognized after melt | dissolution.

Next, the curable resin composition of this invention and each component mix | blended with this are demonstrated in detail. Curable resin composition of this invention contains (A)-(C) component, and the said soluble polyfunctional (meth) acrylic acid ester copolymer is used as (A) component.

Polyfunctional (meth) acrylate is used as (B) component. Polyfunctional (meth) acrylate has two or more (meth) acryloyl groups in a molecule | numerator, 1 type, or 2 or more types are used. By using together with (A) component, the polyfunctional acrylate used as these (B) component synergistically improves heat resistance and optical characteristics, such as low chromatic dispersion and high light transmittance, simultaneously.

As said polyfunctional (meth) acrylate, what is copolymerizable with (A) component is good, For example, 1, 4- butanediol di (meth) acrylate, 1, 6- hexanediol di (meth) acrylate, 1, 9 Nonandiol di (meth) acrylate, tricyclodecane dimethanol (meth) acrylate, bisphenol A polyethoxydi (meth) acrylate, bisphenol A polypropoxydi (meth) acrylate, bisphenol F polyethoxy Sidi (meth) acrylate, ethylene glycol di (meth) acrylate, trimethylolpropane trioxyethyl (meth) acrylate, tris (2-hydroxyethyl) isocyanurate tri (meth) acrylate, pentaerythritol tree (Meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol hexa (meth) acrylate, polyethylene glycol di (meth) acrylate, tris (acryloxyethyl) isocyanurate, penta Thritol tetra (meth) acrylate, dipentaerythritol hexa (meth) acrylate, dipentaerythritol penta (meth) acrylate, tripentaerythritol hexa (meth) acrylate, tripentaerythritol penta (meth) acrylate, hydroxide Loxypivaline neopentylglycol di (meth) acrylate, di (meth) acrylate of ε-caprolactone adduct of hydroxypivaline neophenglycol (for example, Nippon Kayaku Co., Ltd., KAYARAD HX- 220, HX-620 etc.), the monomers, such as a trimethylol propane tri (meth) acrylate, a trimethylol propane polyethoxy tri (meth) acrylate, and a ditrimethylol propane tetra (meth) acrylate, are mentioned. Especially preferably, 1, 6- hexanediol di (meth) acrylate, a trimethylol propane tri (meth) acrylate, a trimethylol propane trioxyethyl (meth) acrylate, and a pentaerythritol tri (meth) acrylate are mentioned. have.

As (B) component, polyfunctional (meth) acrylate more than 5 functional is preferable. It is especially preferable when (A) component has a structural unit derived from (a2). The 5-functional or higher polyfunctional acrylate used as these (B) components forms a high crosslinking by using together with (A) component, especially improving hardness, and synergistically provides optical properties such as heat resistance, low color dispersion, and high light transmittance. This improves at the same time. In addition, the polyfunctional acrylate corresponding to (A) component is not calculated as (B) component. 1 type (s) or 2 or more types are used for a polyfunctional (meth) acrylate.

As said 5-functional or more polyfunctional (meth) acrylate, what is copolymerizable with (A) component is good, For example, dipentaerythritol hexa (meth) acrylate, dipentaerythritol penta (meth) acrylate, and tripentaerythritol hexa ( Monomers, such as a meta) acrylate and a tripentaerythritol penta (meth) acrylate, are mentioned. Especially preferably, dipentaerythritol hexa (meth) acrylate is mentioned.

Moreover, in this invention, 1 or more types of monofunctional (meth) acrylate which has one (meth) acryloyl group in a molecule | numerator can also be used as another copolymerization component (D). These monofunctional (meth) acrylates can improve moldability by synergistically improving optical properties such as low color dispersion and high light transmittance simultaneously while increasing fluidity by using together with (A) component. As a usage-amount, it is 0-40 weight part with respect to 100 weight part of (A) component, Preferably it is 0-20 weight part. If the amount is large, it is not preferable because the fluidity becomes too high and molding defects such as curling and leakage easily occur.

As monofunctional functional (meth) acrylate which can be used as said copolymerization component (D), monofunctional (meth) acrylic acid ester (a) which has an alicyclic structure used in order to manufacture the copolymer which is (A) component is preferable. In addition, for example, acryloyl morpholine, 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) acrylic Rate, phenylpolyethoxy (meth) acrylate, 2-hydroxy-3-phenyloxypropyl (meth) acrylate, o-phenylphenol monoethoxy (meth) acrylate, o-phenylphenol polyethoxy (meth) ) Acrylate, p- Cumylphenoxyethyl (meth) acrylate, isobornyl (meth) acrylate, tribromophenyloxyethyl (meth) acrylate, dicyclopentanyl (meth) acrylate, dicyclopentenyl (meth) acrylate, dicy Clofentenyloxyethyl (meth) acrylate etc. are mentioned.

Next, (C) component is demonstrated.

As a photoinitiator of (C) component, For example, benzoin, such as benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin propyl ether, benzoin isobutyl ether; Acetophenone, 2,2-diethoxy-2-phenylacetophenone, 2,2-diethoxy-2-phenylacetophenone, 1,1-dichloroacetophenone, 2-hydroxy-2-methyl-phenylpropane-1 Acetophenones such as -one, diethoxyacetophenone, 1-hydroxycyclohexylphenyl ketone, and 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropane-1-one; Anthraquinones such as 2-ethyl anthraquinone, 2-tertarybutyl anthraquinone, 2-chloroanthraquinone and 2-amyl anthraquinone; Thioxanthones such as 2,4-diethyl thioxanthone, 2-isopropyl thioxanthone and 2-chlorothioxanthone; Ketal such as acetophenone dimethyl ketal and benzyl dimethyl ketal; Benzophenones such as benzophenone, 4-benzoyl-4'-methyldiphenylsulfide and 4,4'-bismethylaminobenzophenone; Phosphine oxides such as 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 thereof, and may also be used as tertiary amines such as triethanolamine and methyldiethanolamine, ethyl esters of N, N-dimethylaminobenzoic acid, and isoamyl ester of N, N-dimethylaminobenzoic acid. It can be used in combination with accelerators, such as a benzoic acid derivative.

Curable resin composition of this invention contains the said (A) component, (B) component, and (C) component, The content rate is as follows. The compounding quantity of (B) component is 5-250 weight part with respect to 100 weight part of (A) component, Preferably it is 20-100 weight part. The compounding quantity of (C) component is 0.1-10 weight part with respect to a total of 100 weight part of the compounding quantity of (B) component and (A) component, Preferably it is 1.0-5 weight part.

In another viewpoint, (C) component: 0.1 with respect to the sum total of (A) component: 30-89 wt%, (B) component: 10-70 wt%, and (A) component, and (B) component in curable resin composition, respectively. It is preferable to contain -10wt%. More preferably, it is (A) component: 35-80 wt%, and (B) component: 10-40 wt%. When the compounding ratio of (A) component, (B) component, and (C) component exists in the said range, the balance of the characteristics of moldability, heat resistance, and optical characteristic which are synergistically exhibited in releasability and curability are improved. In addition, when there is too little (C) component, hardening shortage will arise easily, and heat resistance and light resistance will fall, and too much, mechanical strength will fall or heat resistance will fall. Moreover, when including an organic solvent and a filler in curable resin composition, the said content is calculated except these.

Moreover, the curable resin composition of this invention contains a polymerization inhibitor, antioxidant, a mold release agent, a photosensitizer, an organic solvent, a silane coupling agent, a leveling agent, an antifoamer, an antistatic agent, a ultraviolet absorber, a light stabilizer, an inorganic, organic as needed. It is also possible to add various fillers, an antifungal agent, an antibacterial agent, etc. to the curable resin composition of this invention, and to provide the target functionality respectively.

Curable resin composition of this invention can be obtained by mixing the said (A) component, (B) component and (C) component, and other components in arbitrary order as needed. Curable resin composition of this invention is stable over time.

Curable resin composition of this invention can obtain hardened | cured material by irradiating active energy rays, such as an ultraviolet-ray. Here, as a specific example of the light source used when irradiating and hardening an active energy ray, xenon lamp, a carbon arc, a germicidal lamp, a fluorescent lamp for ultraviolet rays, a high pressure mercury lamp for radiation, a medium pressure mercury lamp, a high pressure mercury lamp, an ultra high pressure mercury lamp, no Electrode beams, metal halide lamps, or electron beams by scanning or curtain-type electron beam accelerators may be cited. Moreover, when hardening curable resin composition of this invention by ultraviolet irradiation, the ultraviolet irradiation amount required for hardening may be about 300-20000mJ / cm <^2> . Moreover, in order to fully harden a resin composition, it is preferable to irradiate active energy rays, such as an ultraviolet-ray, in inert gas atmospheres, such as nitrogen gas.

Curable resin composition of this invention can be used for casting objects, such as a plastic lens. As a manufacturing method of the plastic lens using the resin composition of this invention, the gasket which consists of polyvinyl chloride, an ethylene vinyl acetate copolymer, etc., and the frame made from two glass molds of a desired shape are made, and the resin composition of this invention is made into this After the injection, there are methods of irradiating active energy rays such as ultraviolet rays to cure the resin composition, and peeling the cured product from the mold.

Moreover, as a method of apply | coating curable resin composition of this invention to a film-form base material as a resin composition for prism lens sheets, various methods known in the industry can be used. As a specific method, a resin composition is apply | coated to the metal mold | die which has a shape of a prism lens on the surface, a layer of a resin composition is provided, for example, and a colorless transparent film-like base material (for example, polyvinyl chloride, Polystyrene, polycarbonate, poly (meth) acrylate, polyester, polyethylene terephthalate, and the like) are compressed to prevent bubbles from entering, and then irradiated with ultraviolet light using a high pressure mercury lamp from the film-like substrate side in that state to form a layer of the resin composition. After hardening, the method of peeling the film-form base material on which the resin layer on the prism lens form was formed from a metal mold | die is mentioned.

It is preferable that the refractive index of the hardened | cured material of the resin composition of this invention obtained by irradiating active energy rays, such as an ultraviolet-ray, is 1.50 or more at 25 degreeC, More preferably, it is 1.52 or more at 25 degreeC. In particular, when producing a prism lens sheet with the resin composition of this invention, when the refractive index of hardened | cured material is less than 1.50 at 25 degreeC, the problem that sufficient front brightness cannot be ensured may arise. Moreover, it is preferable that Abbe's number of hardened | cured material (numeric-specific value which defines the property which changes the refractive index with respect to the wavelength of light) is 40.0 or more, More preferably, it is 50.0 or more. When the Abbe number of hardened | cured material is less than 40.0, since chromatic aberration is large and color bleeding occurs, it is not preferable.

The resin cured material obtained by shape | molding and hardening curable resin composition of this invention is excellent as an optical material. It is especially useful as a material for optical plastic lenses, such as a prism lens sheet, a Fresnel lens, a lenticular lens, a spectacle lens, an aspherical lens. And such a lens is advantageously used for an imaging device. Moreover, curable resin composition or cured resin can be used also for optoelectronics target uses, such as an optical disk, an optical fiber, an optical waveguide, a printing ink, a coating material, a clear coating agent, gloss varnish, etc.

<Examples>

Next, although an Example demonstrates this invention, this invention is not restrict | limited by these. In addition, all the parts in each case are a weight part unless there is particular notice. In addition, the measurement of the softening temperature etc. in the Example performed sample preparation and the measurement by the method shown below.

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

1) Molecular weight and molecular weight distribution of polymer

The molecular weight and molecular weight distribution of the soluble polyfunctional (meth) acrylic acid ester copolymer were measured using GPC (TOSO, HLC-8120GPC), solvent: tetrahydrofuran (THF), flow rate: 1.0 ml / min, column temperature: 40 It was performed at ℃. The molecular weight of the copolymer was measured as a polystyrene equivalent molecular weight using a calibration curve by monodisperse polystyrene.

2) polymer structure

It was determined by 13C-NMR and 1H-NMR analysis using a Nippon Denshi JNM-LA600 type nuclear magnetic resonance spectrometer. Chloroform-d1 was used as a solvent, and the resonance line of tetramethylsilane was used as an internal standard.

3) Sample preparation and measurement of 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 that the thickness after drying was 20 μm, and then dried by heating at 90 ° C. for 30 minutes using a hot plate. The obtained resin film on the glass substrate was set together with the glass substrate in a TMA (thermomechanical analyzer) measuring apparatus, heated to 220 ° C. at a temperature increase rate of 10 ° C./min under nitrogen airflow, and further heated at 220 ° C. for 20 minutes. Was cured (this cured product is called a sample). After allowing the glass substrate to cool to room temperature, the sample for analysis in the TMA measuring device was brought into contact with the analytical probe, and the measurement was performed by scanning from 30 ° C to 360 ° C at a temperature increase rate of 10 ° C / min under nitrogen airflow, and tangentially. The softening temperature was calculated | required by the method. In the case where the probe did not penetrate the resin film and exhibited a probe penetration amount smaller than the film thickness due to the heat resistance of the sample, in addition to the softening temperature, the penetration amount with respect to the temperature at which the probe entered and the film thickness was expressed as a percentage.

4) Determination of heat weight loss and heat discoloration resistance

The measurement of the thermal decomposition temperature and the heat discoloration resistance of the soluble polyfunctional (meth) acrylic acid ester copolymer was set in a TGA (thermobalance) measuring device, and the temperature was increased from 30 ° C. to 320 ° C. at a temperature increase rate of 10 ° C./min under a nitrogen stream. Measurement is performed by scanning to determine the amount of weight reduction at 300 ° C, and visually confirming the amount of discoloration of the sample after measurement. ◎: no heat discoloration, ○: pale yellow, Δ: dark brown, ×: black Sex was evaluated.

5) Measurement of Absorption Rate

The weight of the vacuum dried sample at 60 ° C. for 24 hours was Wo, and it was weighed on a scale capable of measuring up to ± 0.1 mg, and humidification was performed for one week in a constant temperature and humidity bath having a temperature of 85 ° C. and a relative humidity of 85%. After the humidification, the moisture adhered to the test sample was wiped off, and the sample was weighed with a scale that can measure up to ± 0.1 mg to obtain W. Absorption rate was computed by following formula (3). Three identical test samples were prepared and the same test was performed.

Wo / W × 100 = absorption rate (3)

6) Determination of solvent resistance and solvent solubility

The measurement of the solvent resistance of the soluble polyfunctional (meth) acrylic acid ester copolymer was carried out by immersing the sample plate subjected to vacuum press molding at 200 ° C for 1 hour in toluene for 10 minutes at room temperature, and visually changing the sample after immersion. The solvent resistance was evaluated by classifying it as (circle): no change, (triangle | delta): swelling, and x: deformation | transformation and swelling confirmed.

The measurement of solvent solubility added 5 g of soluble polyfunctional (meth) acrylic acid ester copolymers to 100 ml of solvent, and observed the dissolution state after stirring at 25 degreeC for 10 minutes. It was judged that the case where it melt | dissolved uniformly and the presence of a lysate and a gel was not recognized was soluble.

7) measurement of refractive index

The synthesized soluble polyfunctional (meth) acrylic acid ester copolymer was dissolved in toluene, and 1.0 parts by weight of perbutyl O was added to 100 parts by weight of the soluble polyfunctional (meth) acrylic acid ester copolymer. The cast sheet was created from this polymer solution, the cast sheet was crushed and pelletized, filled into a press die, and cured with a press molding machine at 170 ° C for 1 hour. Using the obtained hardened parallel flat plate as a test piece, the refractive index of d-line (587.6 nm) was measured by KPR-200 (made by Shimadzu Corporation). The measurement timing was made into 1 week after injecting into the constant temperature and humidity chamber of 85 degreeC * 85RH wet heat conditions immediately after shaping | molding. Moreover, the Abbe number was measured with the Abbe refractometer (made by Atago Co., Ltd.) using the same test piece.

8) adhesion test

The varnish obtained by diluting the copolymer with a solvent (methyl ethyl ketone) was applied onto a glass substrate, dried at 80 ° C. for 5 minutes, and then cured at 200 ° C. for 1 hour in an inert oven under a stream of nitrogen. It was done. Next, according to JIS K 5400, the glass substrate on which the hardened coating film of the copolymer was put was put 11 cutting lines vertically and horizontally at the 1 mm space | interval on the surface of a coating film, and 100 checkerboard scales were created. After the cellophane tape was brought into close contact with the surface, the number of remaining scales was counted without peeling off when peeled off at once.

(Measurement of physical properties of the composition)

(1) measurement of refractive index

In order to measure various physical properties of the resin composition, a gap of 50 mm in width and 50 mm in length was formed between a glass plate having a width of 60 mm, a length of 60 mm, and a thickness of 1.0 mm by using a silicon tape having a thickness of 1.0 mm and a width of 10 mm. The composition was injected into the glass frame which was wound and fixed with polyimide tape. 1) Irradiating ultraviolet light for several seconds from the one side of this glass frame with the above-mentioned high pressure mercury lamp, or 2) hardening it by putting it in the inner gas oven under nitrogen gas stream, and heating at 180 degreeC for 1 hour. . The resin plate which hardened | cured from the glass frame was taken out and it was set as sample B. The refractive index and Abbe number of sample B were measured with the Abbe refractometer (the product made by Atago).

(2) color

A flat plate having a thickness of 1.0 mm was measured with a chromatic color difference meter (trade name "MODEL TC-8600", manufactured by Tokyo Denshoku Co., Ltd.) to show its YI value.

(3) Haze (turbidity) and total light transmittance

A 0.2-mm-thick test piece was produced and its Haze (turbidity) and total light transmittance were measured using an integrating sphere light transmittance measuring apparatus (SZ-∑90, manufactured by Nihon Denshoku Co., Ltd.).

(4) release

Sample B used for the measurement of refractive index was evaluated according to the difficulty at the time of releasing from a glass frame.

○: Good release property from the glass frame

△: mold release is slightly difficult

×: Mold release is difficult or there is residual mold

(5) frame reproducibility

The surface shape of the hardened resin layer and the surface shape of the glass frame were observed.

○: good reproducibility

×: reproducibility is poor

(6) flipped, fountain

When the cured resin was released from the glass frame, evaluation was made according to the size of the entanglement other than the product portion of the molded article and the degree of leakage of the resin to the clearance of the glass frame.

(Circle): The amount of generation | occurrence | production of flipping is less than 0.05 mm, and the infiltration of resin to glass frame clearance is less than 1.0 mm

(Triangle | delta): The amount of formation of a fold | fall is 0.05 mm or more and less than 0.2 mm. Leaking of resin to glass frame clearance is more than 1.0mm, less than 3.0mm

X: The amount of generation of deflection is 0.2 mm or more, and the penetration of resin to the glass frame clearance is 3.0 mm or more

(7) Bubble: When the cured resin was released from the glass frame, evaluation was made according to the presence or absence of bubbles in the product portion of the molded article and the degree of size.

○: no formation of bubbles is observed

(Triangle | delta): Production | generation of foam is observed and a bubble size is less than 2% with respect to the volume of a molded article.

X: The formation of bubbles is observed, and the size of bubbles is 2% or more relative to the volume of the molded article.

(8) Cracking: When the cured resin was released from the glass frame, evaluation was made according to the presence or absence of cracks in the product portion of the molded article and the degree of size.

○: no cracking observed

(Triangle | delta): Although generation | occurrence | production of a crack is observed, the generation location of a crack is observed only in the corner part of the outer peripheral part of a molded article.

X: The generation | occurrence | production of a crack is observed, but the occurrence location of a crack is observed besides the corner part of the outer peripheral part of a molded article.

(7) Reflow heat resistance: Using the sample B, the spectral transmittance of wavelength: 400 nm was measured with the spectrophotometer CM-3700d (made by Konica Minolta). The measurement timing was made before the heat test which performed postcure at 190 degreeC 60 minutes, and after the heat test for 8 minutes at 260 degreeC in an air oven. The results of the spectral transmittance change 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 Wo and weighed on a weighable scale up to ± 0.1 mg, in a constant temperature and humidity chamber with a temperature of 85 ° C. and a relative humidity of 85%. Humidification was performed for 1 week. After the humidification, the moisture adhered to the test sample was wiped off, and the sample was weighed with a scale that can measure up to ± 0.1 mg to obtain W. Absorption rate was computed by following formula (1). Three test samples were prepared and the same test was performed.

Wo / W × 100 = absorption rate (1)

&Lt; Example 1 >

1.6 mol (463.2 ml) of dimethyloltricyclodecanediacrylate (DMTCD), 1.2 mol (254.2 ml) of dicyclopentanyl methacrylate, 1.2 mol (226.3 ml) of 1,4-butanediol diacrylate (BDDA), 2 0.4 mol (95.5 ml) of, 4-diphenyl-4-methyl-1-pentene (αMSD), 2.4 mol (564.8 ml) of t-dodecyl mercaptan (TDM) and 600 ml of toluene were charged into a 3.0 L reactor, 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 off, dried and weighed to obtain 536.4 g of copolymer A (yield: 73.2 wt%).

Mw of the obtained copolymer A was 34200, Mn was 5620, and Mw / Mn was 6.1. By performing ¹³ C-NMR, ¹ H-NMR analysis and elemental analysis, Copolymer A is a total of 39.6 mol% of the structural units (1) derived from dimethyloltricyclodecane diacrylate and derived from dicyclopentanyl methacrylate. The total of 31.1 mol% of structural units (2) and 29.3 mol% of structural units (3) derived from 1, 4- butanediol diacrylate were contained. Here, the said calculation calculates the total of the structural unit derived from the monofunctional (meth) acrylic acid ester (a) which has an alicyclic structure, and the structural unit derived from the bifunctional (meth) acrylic acid ester (b) as 100 mol%. .

In addition, the terminal group (4) of the structure derived from 2, 4- diphenyl-4-methyl-1- pentene is a structural unit (1), (2) and (3), and the terminal group (4) and t-dodecyl It existed 1.8 mol% with respect to the total amount of the terminal group 5 of the structure derived from mercaptan (henceforth a total amount of all structural units). On the other hand, the terminal group 5 existed 7.2 mol% with respect to the total amount of all the structural units.

In addition, the ratio of the pendant acrylate calculated by said formula (2) was 39.9 mol%.

Copolymer A is soluble in toluene, xylene, THF, dichloroethane, dichloromethane and chloroform, and no gel formation was recognized. In addition, the cast film of copolymer A was an unclear and transparent film.

Copolymer A was used as the cured sheet under various measurement conditions. About the sample obtained by cutting out the hardened sheet, the optical characteristic, water absorption, the amount of thermogravimetry reduction, heat discoloration resistance, and solvent resistance were measured.

As a result, the coefficient of linear expansion was 67 ppm / ° C, the water absorption rate was 0.48%, and the solvent resistance was ○.

Moreover, the softening temperature was 300 degreeC or more as a result of TMA measurement. As a result of the TGA measurement, the weight loss at 300 ° C was 0.8 wt%, and the heat discoloration resistance was?.

Moreover, the refractive index measurement of copolymer A was performed, and the refractive index (589 nm) after hardening was 1.522, and the refractive index (589 nm) after wet heat test was 1.523.

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

<Example 2>

2.64 mol (764.3 ml) of dimethyloltricyclodecanediacrylate, 0.24 mol (47.2 ml) of dicyclopentanyl acrylate (DCPA), 0.96 mol (181.0 ml) of 1,4-butanediol diacrylate, 2-hydroxypropyl 0.96 mol (118.5 ml) of acrylate (HOP-A), 0.48 mol (114.6 ml) of 2,4-diphenyl-4-methyl-1-pentene, 3.12 mol (734.3 ml) of t-dodecyl mercaptan, 720 ml of toluene Was charged into a 3.0 L reactor, and 62 mmol (13.9 g) of t-butylperoxy-2-ethylhexanoate was added at 90 ° C to react 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 off, dried and weighed to obtain 517.2 g of a copolymer B (yield: 71.5 wt%).

Mw of the obtained copolymer B was 39500, Mn was 7240, and Mw / Mn was 5.5. By performing ¹³ C-NMR, ¹ H-NMR analysis and elemental analysis, copolymer B had a total of 55.2 mol% of structural units (1) derived from dimethyloltricyclodecane diacrylate and a structure derived from dicyclopentanyl acrylate. 5.1 mol% of total units (2), 20.3 mol% of structural units (3) derived from 1, 4- butanediol diacrylate, and 19.4 mol% of structural units (6) derived from 2-hydroxypropyl acrylate, there was. In addition, the terminal group 4 of the structure derived from 2, 4- diphenyl-4-methyl-1- pentene existed 1.2 mol% with respect to the total amount of all the structural units.

On the other hand, the terminal group 5 of the structure derived from t-dodecyl mercaptan existed 7.6 mol% with respect to the total amount of all the structural units.

Copolymer B is soluble in toluene, xylene, THF, dichloroethane, dichloromethane and chloroform, and no gel formation was recognized. In addition, the cast film of copolymer B was an unclear and transparent film.

Copolymer B was used as a cured sheet according to various measurement conditions. About the sample obtained by cutting out the hardened sheet, the optical characteristic, water absorption, the amount of thermogravimetry reduction, heat discoloration resistance, and solvent resistance were measured.

As a result, the coefficient of linear expansion was 71 ppm / 占 폚, the water absorption: 0.76%, and the solvent resistance was ○.

Moreover, the softening temperature was 300 degreeC or more as a result of TMA measurement. As a result of the TGA measurement, the amount of weight reduction at 300 ° C was 0.92 wt%, and the heat discoloration resistance was?.

In addition, when the refractive index of the copolymer B was measured, the refractive index (589 nm) after hardening: 1.507, and the refractive index (589 nm) after wet-heat test: 1.509.

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

<Examples 3-8 and Comparative Examples 1-4>

It superposed | polymerized similarly to Example 1 using the raw material composition shown in Table 1 using various monofunctional (meth) acrylates and bifunctional acrylates.

Table 1 shows the test results of the copolymer and the cured product of the amount of the raw materials used for the reaction. Unless otherwise mentioned, other reaction conditions and measurement conditions are the same as Example 1. In Table 1, the amount of raw materials used is represented by moles and weights (g), but the format of the base material is moles / g. In addition, mole fraction (MR) was computed by making the sum total of (a) component and (b) component 100.

<Examples 9-11 and Comparative Examples 5 and 6>

Each component was mix | blended in the ratio shown in Table 3 (number is a weight part), 0.1 weight part of Adeka Stave AO-60 made from Adeka Corporation was added as a stabilizer, and the curable resin composition was obtained. Next, this curable resin composition was hardened by the above various test methods, and performance evaluation was performed. Table 4 shows the results of the performance evaluation.

<Examples 12-20 and Comparative Examples 7-9>

Each component was mix | blended in the ratio shown in Table 5 (number is a weight part), 0.1 weight part of Adeka Stave AO-60 by Adeka Corporation was added as a stabilizer, and the curable resin composition was obtained. Next, this curable resin composition was hardened by the above various test methods, and performance evaluation was performed. Table 6 shows the results of the performance evaluation.

The symbol used by the table | surface is shown below.

DMTCD: Dimethyloltricyclodecane diacrylate (bifunctional)

BDDA: 1,4-butanediol diacrylate (bifunctional)

DCPM: Dicyclopentanyl methacrylate (monofunctional)

DCPA: dicyclopentanyl acrylate (monofunctional)

HOP-A: 2-hydroxypropyl acrylate (monofunctional)

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

TDM: t-dodecyl mercaptan (d) component

TMPTA: trimethylolpropane triacrylate (trifunctional)

TMP: trimethylolpropane trimethacrylate (trifunctional)

CD536: Dioxoladiacrylate (bifunctional)

HPNDA: hydroxypivaline neopentyl glycol diacrylate (bifunctional)

Perbutyl O: t-butyl peroxy-2-ethylhexanate, (made by Nippon Yushi Co., Ltd.)

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

DPHA: dipentaerythritol hexaacrylate (6-functional)

PETIA: pentaerythritol triacrylate (trifunctional)

Irgacure 184: 1-hydroxycyclohexyl-phenyl-ketone (manufactured by BASF Corporation)

MR: mole fraction

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

Claims (10)

Monofunctional (meth) acrylic acid ester (a), bifunctional (meth) acrylic acid ester (b), 2,4-diphenyl-4-methyl-1- pentene (c), and thiol compound (d) which have an alicyclic structure As a copolymer obtained by copolymerizing the component containing these, it has a reactive (meth) acrylate group derived from bifunctional (meth) acrylic acid ester (b) in a side chain, and is 2, 4- diphenyl- 4-methyl- 1 at the terminal. It is a copolymer which has a structural unit derived from a pentene (c) and a thiol compound (d), and has a weight average molecular weight of 2000-60000, and is soluble in toluene, xylene, tetrahydrofuran, dichloroethane or chloroform. Soluble polyfunctional (meth) acrylic acid ester copolymer. The method of claim 1,
Monofunctional (meth) acrylic acid ester (a) in which a copolymer has an alicyclic structure, monofunctional (meth) acrylic acid ester (a2) containing a hydroxyl group, bifunctional (meth) acrylic acid ester (b), 2,4-di It is a copolymer obtained by copolymerizing the component containing a phenyl-4-methyl-1- pentene (c) and a thiol compound (d), The soluble polyfunctional (meth) acrylic acid ester copolymer characterized by the above-mentioned. The method of claim 1,
Monofunctional (meth) acrylic acid ester (a) which has the said alicyclic structure is isobornyl methacrylate, isobornyl acrylate, cyclohexyl methacrylate, cyclohexyl acrylate, dicyclopentenyl acrylate, dicyclo At least one group selected from the group consisting of pentenyloxyethyl acrylate, dicyclopentanyl acrylate, dicyclopentenyloxyethyl methacrylate, dicyclopentenyloxyethyl methacrylate, and dicyclopentanyl methacrylate It is a functional (meth) acrylic acid ester, The soluble polyfunctional (meth) acrylic acid ester copolymer characterized by the above-mentioned. The method of claim 1,
The said bifunctional (meth) acrylic acid ester (b) consists of cyclohexane dimethanol diacrylate, cyclohexane dimethanol dimethacrylate, a dimethylol tricyclodecane diacrylate, and a dimethylol tricyclodecane dimethacrylate Soluble polyfunctional (meth) acrylic acid ester copolymer characterized by the 1 or more types of bifunctional (meth) acrylic acid ester chosen from. The method of claim 1,
Monofunctional (meth) acrylic acid ester (a), bifunctional (meth) acrylic acid ester (b), 2,4-diphenyl-4-methyl-1- pentene (c), and thiol compound (d) which have an alicyclic structure A method for producing a soluble polyfunctional (meth) acrylic acid ester copolymer, comprising copolymerizing a component comprising a. (A) component: The soluble polyfunctional (meth) acrylic acid ester copolymer of Claim 1,
(B) component: polyfunctional (meth) acrylate, and
(C) Component: Initiator
It is a composition containing, The compounding quantity of (B) component is 5-250 weight part with respect to 100 weight part of (A) component, and the compounding quantity of (C) component is 100 in total of the compounding quantity of (B) component and (A) component. It is 0.1-10 weight part with respect to a weight part, Curable resin composition characterized by the above-mentioned. The method of claim 6,
(A) component: The soluble polyfunctional (meth) acrylic acid ester copolymer of Claim 2,
(B) component: 5-functional or more polyfunctional (meth) acrylate, and
(C) Component: Initiator
Curable resin composition characterized by including the. It is obtained by hardening | curing curable resin composition of Claim 6, The cured resin characterized by the above-mentioned. It is formed from the cured resin of Claim 8, The optical material characterized by the above-mentioned. 10. The method of claim 9,
An optical material, wherein the optical material is an optical plastic lens.