TW201302814A - Soluble polyfunctional (meth) acrylic ester copolymer having alicyclic structure, curable resin composition and cured product - Google Patents

Abstract

The present invention provides a novel polyfunctional (meth) acrylic ester copolymer and a curable resin composition using the same with excellent optical characteristics such as the low dispersion and the high light transmittance, with various balanced characteristics required by an optical lens/prism material, and without generation of the refractive index divergence even when used in a stringent actual condition such as a wet/hot environment, thereby maintaining high optical properties. The present invention provides a copolymer obtained by copolymerizing a mono-functional (meth)acrylic ester (a), a bi-functional (meth)acrylic ester (b), 2,4-diphenyl-4-methyl-1-pentene (c) and a thiol compound (d), which is a copolymer wherein the side chain of the copolymer comprises a reactive (meth) acrylic ester group from the bi-functional (meth)acrylic ester (b), and the terminal comprises structural units from 2,4-diphenyl-4-methyl-1-pentene (c) and the thiol compound (d). The curable resin composition containing the copolymer is also provided.

Description

Soluble polyfunctional (meth) acrylate copolymer having an alicyclic structure, a curable resin composition and a cured product

The present invention relates to excellent optical properties, heat resistance, and processability with low color dispersion, high light transmittance, and optical properties under low practical conditions such as moist heat conditions, low water absorption, and good release during molding. Moulding property, and a soluble polyfunctional (meth) acrylate copolymer having an alicyclic structure for improving precision mold transferability, and a curable resin composition containing the soluble polyfunctional (meth) acrylate copolymer , hardened materials and optical articles.

Most of the monomers having a reactive unsaturated bond can be formed by cracking the unsaturated bond, causing a catalyst for the chain reaction and appropriate reaction conditions to form a polymer. Generally, the types of monomers having unsaturated bonds are extremely different, so that the types of resins obtained are also significantly rich. However, a monomer having a polymer polymer having a molecular weight of 10,000 or more, which is generally referred to as a polymer compound, can be obtained in a small amount. E.g., ethylene, substituted ethylene, propylene, substituted propylene, styrene, alkyl styrene, alkoxy styrene, norbornene, various acrylates, butadiene, cyclopentadiene, bicyclo Pentadiene, isoprene, maleic anhydride, maleic imide, fumarate, acrylic acid, and the like are representative monomers. These monomers can be synthesized into a wide variety of resins by polymerization alone or by such copolymerization.

The use of these resins is mainly limited to the field of relatively cheap livelihood equipment, for light. High heat resistance and dimensional stability in the field of electronic materials The cutting-edge technology field of sexual or micro-machining is almost impossible to apply. The reason for this is that the polymer which is usually synthesized from the above-mentioned monomer is thermoplastic, and since it is required to be a polymer polymer satisfying mechanical properties, it is required to sacrifice heat resistance or fine workability.

As a method for solving the disadvantages of the ethylene-based thermoplastic polymer, Patent Documents 1 to 3 disclose a polymer having a (meth)acryl fluorenyl group or a vinyl ether group in a side chain. For example, Patent Document 1 discloses a (meth)acrylonitrile-based side chain type polymer obtained by cationically polymerizing a heterogeneous polymerizable monomer such as 2-vinyloxyethyl acrylate (VEA), and a photopolymerization initiator. A photosensitive composition composed of the composition. Further, Patent Document 2 discloses a photosensitive composition composed of a (meth)acrylonitrile-based side chain type polymer, a compound having a photoreactive unsaturated carboxyl group, and a photopolymerization initiator. Further, Patent Document 3 discloses a carboxylic acid ester solvent in which a heterogeneous polymerizable monomer such as 2-vinyloxyethyl acrylate (VEA) or the like has a photoreactive unsaturated group which is inert to its own cationic polymerization. Among the compounds, a method of producing a polymer solution is obtained by homopolymerization or copolymerization using a cationic polymerization catalyst.

However, when the reactive polymer produced by the technique using a heterogeneous polymerizable monomer is disclosed in the above patent documents, an advanced optical lens cannot be obtained. The characteristics of low water absorption, heat resistance, formability, and high optical characteristics required in the field of use, as well as optical properties under low practical conditions such as damp heat conditions, low water absorption, and good release during forming Modularity, as well as a polymer for improving precision mold transferability, and a curable resin composition.

On the other hand, Patent Document 4 discloses that a monovinyl aromatic compound is obtained. Copolymerization of a difunctional (meth) acrylate with a soluble polyfunctional ethylene aromatic having a structural unit derived from a reactive (meth) acrylate group derived from a difunctional (meth) acrylate Family copolymer. However, the soluble polyfunctional ethylene aromatic copolymer obtained by the techniques disclosed in the above, although having excellent thermal decomposition resistance to thermal history at high temperatures, and having a reactive (meth) acrylate group in the side chain, It is excellent in workability and solvent solubility, but it cannot be used in optical lenses for low-color dispersion applications. It is limited in practical use and is a material that cannot achieve high hardness.

Further, Patent Document 5 discloses a composition characterized in that it contains 1 to 25% by mass of a linear aliphatic diol having 4 to 8 carbon atoms in a methyl methacrylate (MMA)-based liquid. (Meth) acrylate is used as a constituent component. Here, it is disclosed that the MMA-based liquid composition is produced by using MMA, or MMA, and a vinyl copolymer or chain copolymerizable therewith in the presence of a polymerization initiator in an inert gas (for example, N ₂ gas) atmosphere. The transfer agent is subjected to normal temperature or heat polymerization. Further, specific examples of the chain transfer agent are disclosed as sulfur compounds such as lauryl mercaptan, octyl thioglycolate, thiocresol, thionaphthol, benzyl mercaptan, etc. regarding 2,4-diphenyl 4-methyl-1-pentene (c) is not specifically disclosed. Moreover, it has not been taught that by having both a terminal group derived from a thiol compound and a terminal group derived from 2,4-diphenyl-4-methyl-1-pentene, and derived from an alicyclic structure The structural unit of the monofunctional and/or difunctional (meth) acrylate (a) coexists, and the heat transfer optical property or the precision transfer property of the mold shape can be multiplied. Moreover, the composition obtained by the techniques disclosed in the above is such that the adhesion to the inorganic material cannot be improved under severe use conditions such as moist heat conditions.

Further, Patent Document 6 discloses a polymerizable composition composed of a vinyl monomer and a di(meth)acrylate compound, and also discloses the use of 2,4-diphenyl-4-methyl-1-pentene ( c), but the amount used was about a few tenths of a part of the general chain transfer agent, and neither the product nor the crosslinked gelled agent showed solvent solubility.

Further, Patent Document 7 discloses a thermosetting resin composition for a color filter, which comprises (1) an epoxy group-containing (meth) acrylate and 2) a hydroxyl group-containing (meth) acrylate. An ester, 3) (meth)acrylic acid, 4) an autocure copolymer containing a constituent unit composed of an aromatic (meth) acrylate, and an organic solvent. Further, in the polymerization stage, the self-hardening copolymer obtained by the techniques disclosed in the above may be used, in order to achieve a desired molecular weight range, mercaptopropionic acid, mercaptopropionate, thioglycol, thioglycerol may be used. A conventional molecular weight modifier such as dodecyl mercaptan or α-methylstyrene dimer. However, in the technique disclosed in the above, since a difunctional or higher ethylene compound having a plurality of vinyl groups is not added during the polymerization, only one of the following terminal groups derived from the molecular weight modifier can be introduced into the polymer chain. There is a disadvantage that the function derived from the terminal group cannot be sufficiently imparted. Further, the self-curable copolymer obtained by the technique disclosed in the above-mentioned resin forms a thermosetting resin composition in the resin composition with the epoxy resin, but does not cause a hardening reaction with the acrylate resin, so There is a disadvantage that the strength and heat resistance of the resin composition which causes the blending are lowered.

[Previous Technical Literature] [Patent Literature]

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

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

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

[Patent Document 4] JP-A-2008-247978

[Patent Document 5] JP-A-57-167340

[Patent Document 6] JP-A-2002-121228

[Patent Document 7] JP-A-2009-1770

According to this, it has excellent optical characteristics of low color dispersion and high light transmittance, and has characteristics of low water absorption, formability, heat resistance, and improvement of optical characteristics and mold under severe practical conditions such as damp heat conditions. A shape-precision transfer-soluble soluble polyfunctional (meth) acrylate copolymer, and a curable resin composition using the copolymer have not been present so far.

The object of the present invention is to provide an optical lens with excellent optical properties of low color dispersion and high light transmittance, and in the advanced technical field of low water absorption, processability and heat resistance. A soluble polyfunctional (meth) acrylate copolymer excellent in balance of various properties required for bismuth materials, and improved in optical properties under the severe use conditions such as moist heat conditions and adhesion to inorganic materials, and A curable resin composition, a cured product, and an optical article.

The present invention is a soluble polyfunctional (meth) acrylate copolymer which is obtained by containing a monofunctional (meth) acrylate (a) having a alicyclic structure, and a difunctional (meth) acrylate (b). , a copolymer obtained by copolymerization of a component of 2,4-diphenyl-4-methyl-1-pentene (c) and a thiol compound (d), having a difunctional origin derived from a side chain a (meth) acrylate group of (meth) acrylate (b), and having a terminal derived from 2,4-diphenyl-4-methyl-1-pentene (c) and a thiol compound ( d) a structural unit of a copolymer having a weight average molecular weight of from 2,000 to 60,000 and further soluble in toluene, xylene, tetrahydrofuran, dichloroethane or chloroform

Further, the present invention relates to the aforementioned soluble polyfunctional (meth) acrylate copolymer which uses a monofunctional (meth) acrylate (a) having an alicyclic structure, and a monofunctional group having a hydroxy group (A) The acrylate (a2) acts as a monofunctional (meth) acrylate (MFM).

The monofunctional (meth) acrylate (a) having the alicyclic structure is exemplified by isobornyl methacrylate, isobornyl acrylate, cyclohexyl methacrylate, cyclohexyl acrylate, dicyclopentene acrylate. Ester, dicyclopentenyloxyethyl acrylate, dicyclopentanyl acrylate, dicyclopentenyloxyethyl methacrylate, dicyclopentenyloxyethyl methacrylate and bicyclo methacrylate One or more monofunctional (meth) acrylates selected from the group consisting of amyl esters.

The above difunctional (meth) acrylate (b) is exemplified by cyclohexane dimethanol diacrylate, cyclohexane dimethanol dimethacrylate, dimethylol tricyclodecane diacrylate and dihydroxyl One or more difunctional (meth) acrylates selected from the group consisting of methyltricyclodecane dimethacrylate.

Further, the present invention is a process for producing the above-mentioned soluble polyfunctional (meth) acrylate copolymer, which comprises a monofunctional (meth) acrylate (a) having an alicyclic structure, and a difunctional (A) The components of the acrylate (b), 2,4-diphenyl-4-methyl-1-pentene (c) and the thiol compound (d) are copolymerized.

Further, the present invention is a curable resin composition characterized by: (A) component: a soluble polyfunctional (meth) acrylate copolymer as in the first application of the patent scope, (B) component: polyfunctional (meth) acrylate, and (C) component: a composition of a starter, 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 (C) The blending amount is 0.1 to 10 parts by weight based on 100 parts by weight of the total amount of the components (B) and (A).

The other aspect is a curable resin composition using a monofunctional (meth) acrylate (a) having an alicyclic structure and a monofunctional (meth) acrylate (a2) having a hydroxyl group as a monofunctional group. As the (A) component, the above-mentioned soluble polyfunctional (meth) acrylate copolymer of (meth) acrylate (MFM) is used, and a polyfunctional (meth) acrylate having five or more functional groups is used as the component (B).

Furthermore, the present invention is a cured resin obtained by curing the curable resin composition, and an optical material characterized by being formed of the cured resin. Here, the optical material has an optical plastic lens.

According to the present invention, it can be an optical technique having low color dispersion, excellent optical transmittance, and advanced technology in low water absorption, workability, and heat resistance. In the field of surgery, optical lenses. The various properties required for the bismuth material are excellently balanced, and materials which improve the adhesion between the optical properties and the inorganic materials under severe practical conditions such as damp heat conditions. The optical material can be preferably used in the field of image processing such as a photographic apparatus having high optical characteristics.

Hereinafter, the soluble polyfunctional (meth) acrylate copolymer of the present invention will be described in detail. The soluble polyfunctional (meth) acrylate copolymer has an alicyclic structure and a structural unit having a terminal derived from 2,4-diphenyl-4-methyl-1-pentene and a thiol compound. Hereinafter, the soluble polyfunctional (meth) acrylate copolymer is sometimes referred to simply as a copolymer.

The copolymer of the present invention is a monomer having a monofunctional (meth) acrylate (a) having an alicyclic structure and a difunctional (meth) acrylate (b), and 2,4-diphenyl- a copolymer obtained by copolymerization of 4-methyl-1-pentene (c) and a thiol compound (d), which is derived from a difunctional (meth) acrylate (b) in a side chain. a reactive (meth) acrylate group, and a soluble polyfunctional group derived from a structural unit derived from 2,4-diphenyl-4-methyl-1-pentene (c) and a thiol compound (d) (Meth) acrylate copolymer. Here, "soluble" means soluble in toluene, xylene, tetrahydrofuran, dichloroethane or chloroform. The solubility test was carried out under the conditions shown in the examples. Here, a monofunctional (meth) acrylate (a2) having a hydroxyl group can be used as a monofunctional (meth) acrylate (MFM) together with a monofunctional (meth) acrylate (a) having an alicyclic structure. ).

Since the chain structure of the copolymer is mainly obtained by copolymerization of a monofunctional (meth) acrylate and a difunctional (meth) acrylate, it has a branched structure or a crosslinked structure, but the amount of the structure is limited to exhibit solubility. The extent of it. Therefore, a copolymer having a structural unit (b1) containing an unreacted (meth)acrylic group derived from a difunctional (meth) acrylate (b) in the side chain is obtained. The unreacted (meth)acrylic group is also referred to as a side chain (meth)acrylic group, and since it exhibits polymerizability, it can be further polymerized by a polymerization treatment to obtain a solvent-insoluble resin cured product.

Further, the copolymer has a structural unit derived from 2,4-diphenyl-4-methyl-1-pentene (c) and a thiol compound (d) at the terminal. By introducing the structural unit to the end of the copolymer, it is possible to obtain a moldability which improves mold release property, a linear expansion ratio which is advantageous for adhesion to an inorganic material, and an excellent heat resistance against heat discoloration or weight reduction. Hardened matter.

The copolymer has a structural unit derived from a monofunctional (meth) acrylate (a) having an alicyclic structure, a structural unit derived from a difunctional (meth) acrylate (b), and derived from 2, 4-di The structural unit of phenyl-4-methyl-1-pentene (c) and the thiol compound (d). Here, the structural unit derived from the difunctional (meth) acrylate (b) is a polymerized double bond (referred to as a vinyl group) contained in two (meth)acrylic groups, but also contains a component. The structural unit (b2) of the branched structure or the crosslinked structure related to the polymerization and the unreacted (meth)acrylic acid structural unit (b1) in which only one vinyl group participates in polymerization and the other vinyl groups do not react. 2,4-Diphenyl-4-methyl-1-pentene (c) and a thiol compound (d) act as a chain transfer agent to prevent an increase in molecular weight and are present at the end of the copolymer. Use a monofunctional (meth) acrylate (a2) containing a hydroxyl group as a single official In the case of (meth) acrylate (MFM), it has a structural unit derived from (a2).

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

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

Here, (a), (b), (c), and (d) represent a structural unit derived from a monofunctional (meth) acrylate (a) having an alicyclic structure, derived from a difunctional (methyl) group. The structural unit of the acrylate (b), the molar number of the structural unit derived from the 2,4-diphenyl-4-methyl-1-pentene (c) and the thiol compound (d). The heat resistance can be improved by introducing a structural unit derived from 2,4-diphenyl-4-methyl-1-pentene (c) and a thiol compound (d) into the end of the copolymer within the above range. , mold release and low water absorption. When a monofunctional (meth) acrylate (a2) having a hydroxyl group is used as the monofunctional (meth) acrylate (MFM), the formula (1) is as follows.

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

Here, (a2) represents the number of moles derived from the structural unit of the hydroxyl group-containing monofunctional (meth) acrylate (a2).

Further, the ratio of 2,4-diphenyl-4-methyl-1-pentene (c) and the thiol compound (d) is preferably 2,4-diphenyl-4-methyl-1- The pentene (c) is 5 to 50%, preferably 10 to 30%. Here, the above ratio is calculated by the following formula.

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

The difunctional (meth) acrylate (b) plays an important role as a crosslinking component which exhibits heat resistance when the copolymer is branched or crosslinked, a side chain vinyl group is produced, and the copolymer is cured.

As the difunctional (meth) acrylate, cyclohexane dimethanol diacrylate, dimethylol trioxane diacrylate, cyclohexane dimethanol dimethacrylate, dimethylol tricyclodecane can be used. Dimethacrylate, ethylene glycol diacrylate, propylene glycol diacrylate, 1,4-butanediol diacrylate, hexanediol diacrylate, diethylene glycol diacrylate, ethylene glycol diacrylate a difunctional (meth) acrylate such as propylene glycol diacrylate, 1,4-butanediol dimethacrylate, hexanediol dimethacrylate or diethylene glycol dimethacrylate, but not Limited to these.

A preferred embodiment of the difunctional (meth) acrylate is preferably cyclohexane dimethanol diacrylate or cyclohexane dimethanol in terms of cost, ease of polymerization control, and heat resistance of the obtained polymer. Methacrylate, dimethylolcyclodecane diacrylate or dimethylol tricyclodecane dimethacrylate.

The copolymer has a structural unit (b1) having a reactive (meth) acrylate group derived from a difunctional (meth) acrylate (b), but a structural unit represented by (2) (b1) The molar fraction M _{b1 is} preferably 0.05 or more, preferably 0.1 to 0.7, more preferably 0.3 to 0.5.

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

Here, (a) and (b) in the formula represent a structural unit derived from a monofunctional (meth) acrylate (a) having an alicyclic structure and derived from a difunctional (meth) acrylate (b) The number of moles of the structural unit. (b1) in the formula represents the number of moles of the structural unit (b1) containing a (meth) acrylate group. By satisfying the above molar fraction, it is rich in curability under light or heat, and a molded article excellent in heat resistance and mechanical properties after curing can be obtained. When a monofunctional (meth) acrylate (a2) having a hydroxyl group is used as the monofunctional (meth) acrylate (MFM), the formula (2) is as follows.

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

The monofunctional (meth) acrylate (a) having an alicyclic structure is important for improving the solvent solubility, low water absorption, heat resistance, optical properties, and processability of the copolymer. The monofunctional (meth) acrylate having an alicyclic structure may be exemplified by isobornyl methacrylate, isobornyl acrylate, cyclohexyl methacrylate, cyclohexyl acrylate, dicyclopentenyl acrylate, Dicyclopentenyloxyethyl acrylate, dicyclopentanyl acrylate, dicyclopentenyloxyethyl methacrylate, dicyclopentenyloxyethyl methacrylate and dicyclopentanyl methacrylate One or more monofunctional (meth) acrylates having an alicyclic structure selected from the group consisting of, but not limited to, these. By introducing a structural unit derived from the components into the copolymer, it is possible to prevent gelation of the copolymer, improve solubility in a solvent, and improve optical properties such as low color dispersion of the copolymer, and low water absorption. Heat resistance.

As a preferable specific example, from the viewpoints of cost, gelation prevention, and moldability of the obtained polymer, there are exemplified by isobornyl methacrylate, isobornyl acrylate, and cyclohexyl methacrylate. Cyclohexyl acrylate, dicyclopentenyl acrylate, dicyclopentenyloxyethyl acrylate, dicyclopentanyl acrylate, dicyclopentenyloxyethyl methacrylate, dicyclopentenyl methacrylate One or more monofunctional (meth) acrylates having an alicyclic structure selected from the group consisting of oxyethyl ester and dicyclopentanyl methacrylate.

The monofunctional (meth) acrylate (a2) having a hydroxyl group may, for example, be 2-hydroxypropyl acrylate, 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, 2-hydroxypropyl methacrylate, methacrylic acid. 2-hydroxyethyl ester, polyethylene glycol acrylate, polyethylene glycol methacrylate, 1,4-butanediol monoacrylate, 1,6-diol diol monoacrylate, 1,9-fluorene Alcohol monoacrylate, 1,4-butanediol monomethacrylate, 1,6-hexanediol monomethacrylate, and 1,9-nonanediol monomethacrylate. Among these, from the viewpoint of compatibility with a pentafunctional or higher polyfunctional (meth) acrylate, preferred are 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, and methacrylic acid 2 -Hydroxypropyl ester and 2-hydroxyethyl methacrylate.

2,4-Diphenyl-4-methyl-1-pentene (c) and a thiol compound (d) function as a chain transfer agent and control the molecular weight of the copolymer. The molecular weight of the copolymer of the present invention is in the range of from 2,000 to 60,000, preferably from 3,000 to 50,000, in terms of the weight average molecular weight Mw. The formability and mold release property of the cured resin are improved by using a copolymer having a lower molecular weight.

As long as the thiol compound (d) is known to function as a chain transfer agent The thiol compound may be, but is preferably a tert-dodecyl mercaptan, n-butyl mercaptan, isobutyl mercaptan, n-octyl mercaptan, n-dodecyl mercaptan, and a third butyl group. Mercaptan and the like.

Further, a monofunctional (meth) acrylate having no alicyclic structure may be added as the component (e) for improving solvent solubility and processability of the copolymer. The (meth) acrylate is exemplified by methyl methacrylate, ethyl methacrylate, methyl acrylate, ethyl acrylate, n-butyl acrylate, 2-methylhexyl acrylate, 2-ethylhexyl acrylate. And octyl acrylate, 2-hydroxyethyl methacrylate, etc., preferably methyl methacrylate or n-butyl acrylate. These (meth) acrylate monomers may be used singly or in combination of two or more kinds, but it is preferably one or more selected from the group consisting of methyl methacrylate, methyl acrylate, and n-butyl acrylate ( Methyl) acrylate.

Further, the structural unit derived from the other monomer component (e) is preferably in a range of less than 30 mol% based on the total amount of the structural unit derived from the monomer component (a) or (a) and (a2). Inside.

Further, from another viewpoint, the soluble polyfunctional (meth) acrylate copolymer of the present invention is derived from a structural unit derived from a monofunctional (meth) acrylate (a) having an alicyclic structure and derived from two When the total of the structural units of the functional (meth) acrylate (b) is 100 mol%, the structural unit derived from (a) is preferably from 10 to 60 mol%, preferably from 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) is less than 10 mol%, the heat resistance of the cured product is insufficient, and when it exceeds 60 mol%, under the formability It is not good that the strength of the molded article is lowered significantly.

Further, when a monofunctional (meth) acrylate (a2) having a hydroxyl group is used together with a monofunctional (meth) acrylate (a) having an alicyclic structure, it is derived from a difunctional (meth) acrylate (b). The molar ratio of the structural unit is preferably as follows.

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

(a2)/[(a)+(a2)+(b)]=0.03~0.4, preferably 0.09~0.3

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

Further, the structural unit derived from the difunctional (meth) acrylate (b) is preferably introduced into an alicyclic structure, and the monofunctional (meth) acrylate (a) having an alicyclic structure and the alicyclic group having a complex structure The molar ratio of the structural unit of the structural fat is preferably in the range of 0.35 to 0.95, preferably 0.6 to 0.9, relative to the total of [(a) + (a2) + (b)].

The soluble polyfunctional aromatic (meth) acrylate copolymer of the present invention is obtained by using a monofunctional (meth) acrylate having an alicyclic structure (a) or a monofunctional having an alicyclic structure ( Methyl) acrylate (a) with a monofunctional (meth) acrylate (a2) containing a hydroxyl group, a difunctional (meth) acrylate (b) and 2,4-diphenyl-4-methyl-1 - pentene (c) and thiol compound (d) monomer 100 moles, containing 2 to 120 moles of 2,4-diphenyl-4-methyl-1-pentene (c) and thiol The monomer of the compound (d) is obtained by polymerization at a temperature of 50 to 200 °C. Here, 2,4-diphenyl-4-methyl-1-pentene (c) and a thiol compound (d) are conventionally known as chain transfer compounds, but in the present invention, the ratio is used as a chain. Since the amount of the transfer agent used is large, it is a part of the monomer component. 2,4-diphenyl-4-methyl-1-pentene (c) and thiol compound (d) The amount used in the soluble polyfunctional aromatic (meth) acrylate copolymer of the present invention derived from 2,4-diphenyl-4-methyl-1-pentene (c) and mercaptan The molar fraction of the structural unit of the compound (d) is adjusted so as to be in the range of 0.02 to 0.35. However, since it has a low reactivity and remains unreacted, it can be used in more than the theoretical amount. For this reason, it is used in the range of 2 to 120 moles, preferably 20 to 100 moles, more preferably 50 to 80 moles, relative to the monomer 100.

The function of 2,4-diphenyl-4-methyl-1-pentene (c) and the thiol compound (d) as a chain transfer agent is limited in the amount of cross-linking reaction, side chain ( The control of the formation of the methyl acrylate group and the control of the molecular weight distribution are preferably in the range of 10 to 500 parts by weight, more preferably 30 parts by weight based on 100 parts by weight of the difunctional (meth) acrylate (b). Within the range of ~150 parts by weight. It is preferably in the range of 90 to 100 parts by weight.

Mono(meth)acrylate (a) having an alicyclic structure, or mono(meth)acrylate (a) having an alicyclic structure and a monofunctional (meth)acrylate (a2) having a hydroxyl group The amount used is preferably 100 to 60 mol%, preferably 15 to 50 mol%, based on 100 mol of the total of (a), (a2) and the difunctional (meth)acrylate (b). The difunctional (meth) acrylate (b) is preferably used in an amount of from 40 to 90 mol%, preferably from 50 to 85 mol%, more preferably from 50 to 80 mol%.

When the copolymer of the present invention is produced, a radical polymerization initiator may be added when the initial reaction rate caused by the thermal initiation reaction is slow. In this case, the radical polymerization initiator used may be exemplified by a ketone peroxide, a peroxy ketal, a hydrogen peroxide, a dialkyl peroxide, or a dithiol peroxidation. An organic peroxide-based polymerization initiator such as a substance, a peroxycarboxylic acid ester or a peroxyester, or an azo polymerization initiator. The amount of the radical polymerization initiator to be used is not particularly limited, but is usually preferably from 0.01 to 25 parts by weight, more preferably from 0.05 to 20 parts by weight, based on 100 parts by total of the total of the monomer components. Inside. It is preferably in the range of 0.1 to 15 parts by weight.

Further, the polymerization reaction can be carried out substantially without bulk polymerization using a solvent, but it can also be carried out in one or more organic solvents in which a soluble polyfunctional (meth) acrylate aromatic copolymer formed by dissolution is dissolved. The organic solvent is a compound which does not interfere with radical polymerization in nature, as long as the chain transfer agent, the initiator, the monomer, and the polyfunctional (meth)acrylate aromatic copolymer of the present invention are dissolved to form a homogeneous solution. It can be used without any special restrictions.

Examples of the compound which can be used as the organic solvent include aromatic hydrocarbons, linear aliphatic hydrocarbons, branched aliphatic hydrocarbons, cyclic aliphatic hydrocarbons, and alkane oils obtained by hydrogenation of petroleum fractions. Among them, toluene, xylene, methylcyclohexane and ethylcyclohexane are preferred from the viewpoints of uniformity in polymerization and solubility and ease of availability.

These compounds as an organic solvent may be used singly 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 at a temperature ranging from 50 to 200 °C. When the polymerization reaction is carried out at less than 50 ° C, the polymerization rate is low, so it is less preferable from the viewpoint of industrial implementation, and when it exceeds 200 ° C, the selectivity of the reaction is lowered, so that the reaction is difficult to control, and it is easy to be insoluble due to crosslinking. Gel formation is less preferred.

After the termination of the polymerization reaction, the method of recovering the polymer is not particularly limited. It is only necessary to use a method which is usually used, for example, by heating, a reduced pressure devolatilization method, a vapor stripping method, or a weak solvent.

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

Next, the curable resin composition of the present invention and the components blended therein will be described in detail. The curable resin composition of the present invention contains the components (A) to (C), and the component (A) is the soluble polyfunctional (meth)acrylate copolymer.

As the component (B), a polyfunctional (meth) acrylate is used. The polyfunctional (meth) acrylate is one having two or more (meth) acrylonitrile groups in the molecule, and one type or two or more types may be used. The polyfunctional acrylate used as the component (B) is improved in heat resistance by being used in combination with the component (A), and at the same time, optical characteristics of low color dispersion and high light transmittance are also improved.

The above polyfunctional (meth) acrylate is preferably one which can be copolymerized with the component (A), and examples thereof include 1,4-butanediol di(meth)acrylate and 1,6-hexanediol di(a). Acrylate, 1,9-nonanediol di(meth)acrylate, tricyclodecane dimethanol (meth) acrylate, bisphenol A polyethoxy di(meth) acrylate, bisphenol A polypropoxy di(meth) acrylate, bisphenol F polyethoxy di(meth) acrylate, ethylene glycol di(meth) acrylate, trimethylolpropane trioxyethyl (a Acrylate, ginseng (2-hydroxyethyl) Isocyanurate tri(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol hexa(meth)acrylate, polyethylene glycol di(methyl) Acrylate, propylene (propylene oxyethyl) isocyanurate, pentaerythritol tetra (meth) acrylate, dipentaerythritol hexa (meth) acrylate, dipentaerythritol penta (meth) acrylate, tripentaerythritol (meth) acrylate, tripentaerythritol penta (meth) acrylate, hydroxypivalic acid neopentyl glycol di(meth) acrylate, hydroxypivalic acid neopentyl glycol ε-caprolactone adduct Di(meth)acrylate (for example, manufactured by Nippon Kayaku Co., Ltd., KAYARAD HX-220, HX-620, etc.), trimethylolpropane tri(meth)acrylate, trimethylolpropane polyethylene Monomers such as oxytri(meth)acrylate and di-trimethylolpropane tetra(meth)acrylate. The most preferred ones are 1,6-hexanediol di(meth)acrylate, trimethylolpropane tri(meth)acrylate, trimethylolpropane trioxyethyl (meth)acrylate. Pentaerythritol tri(meth)acrylate.

The component (B) is preferably a pentafunctional or higher polyfunctional (meth) acrylate. In particular, it is preferred that the component (A) has a structural unit derived from (a2). The penta-functional or higher polyfunctional acrylate used as the component (B) can be used in combination with the component (A) to form a high degree of crosslinking, in particular, to improve the hardness, and to simultaneously improve the heat resistance and the low color dispersion. , optical properties of high light transmittance. Further, the polyfunctional acrylate corresponding to the component (A) is not calculated as the component (B). One or two or more kinds of polyfunctional (meth) acrylates can be used.

The above-mentioned pentafunctional or higher polyfunctional (meth) acrylate is preferably one which can be copolymerized with the component (A), and is exemplified by, for example, dipentaerythritol hexa(meth)acrylic acid. Monomers such as ester, dipentaerythritol penta (meth) acrylate, tripentaerythritol hexa (meth) acrylate, and tripentaerythritol penta (meth) acrylate. Preferably, it is dipentaerythritol hexa(meth)acrylate.

Further, in the present invention, one or more monofunctional (meth) acrylate having one (meth) acrylonitrile group in the molecule may be used as the other copolymer component (D). These monofunctional (meth) acrylates can improve the optical properties of low color dispersion and high light transmittance by multiplying them in combination with the component (A), and the moldability can be improved by improving fluidity. The amount used is 0 to 40 parts by weight, preferably 0 to 20 parts by weight, per 100 parts by weight of the component (A). When the amount of use is large, fluidity cannot be improved, and it is prone to poor formability such as burrs and leaks.

It is preferable to use a monofunctional (meth) acrylate which can be used as the above-mentioned copolymerization component (D), and a monofunctional (meth) acrylate having an alicyclic structure which is preferably used for producing a copolymer of the component (A). (a), but other examples are acryloyl morpholine, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, poly Ethylene glycol mono(meth)acrylate, polypropylene glycol mono(meth)acrylate, cyclohexane-1,4-dimethanol mono(meth)acrylate, tetrahydrofurfuryl (meth)acrylate, Phenyloxyethyl (meth)acrylate, phenylpolyethoxy(meth)acrylate, 2-hydroxy-3-phenyloxypropyl (meth)acrylate, o-phenyl (meth)acrylate Phenol monoethoxylate, o-phenylphenol polyethoxylate (meth)acrylate, p-cumylphenoxyethyl (meth)acrylate, isobornyl (meth)acrylate, (methyl) ) Tribromophenyloxyethyl acrylate, dicyclopentanyl (meth)acrylate, dicyclopentenyl (meth)acrylate, dicyclopentanyl (meth)acrylate Alkenyloxyethyl ester and the like.

Next, the component (C) will be described.

The photopolymerization initiator of the component (C) is exemplified by benzoin such as benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin propyl ether, benzoin isobutyl ether or the like. Acetophenone, 2,2-diethoxy-2-phenylacetophenone, 2,2-diethoxy-2-phenylacetophenone, 1,1-dichloroacetophenone, 2 -hydroxy-2-methyl-phenylpropan-1-one, diethoxyacetophenone, 1-hydroxycyclohexyl phenyl ketone, 2-methyl-1-[4-(methylthio)phenyl Acetophenones such as 2-morpholinopropan-1-one; anthracene such as 2-ethylhydrazine, 2-tert-butylhydrazine, 2-chloroindole, 2-aminoindole 2,4-diethylthioxanthone, 2-isopropylthioxanthone, 2-chlorothioxanthone, etc.; acetophenone dimethyl ketal, benzyl dimethyl ketal, etc. a ketal; a benzophenone such as benzophenone, 4-benzylidene-4'-methyldiphenyl sulfide or 4,4'-bismethylaminobenzophenone; 2,4 a phosphine oxide such as 6-trimethylbenzimidylphenylphosphine oxide or bis(2,4,6-trimethylbenzylidene)-phenylphosphine oxide.

These may be used singly or in combination of two or more, and further may be a tertiary amine such as triethanolamine or methyldiethanolamine, ethyl N,N-dimethylaminobenzoate or N,N-dimethylamine. An accelerator or the like such as a benzoic acid derivative such as isoamyl benzoate is used in combination.

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

In other respects, the curable resin composition preferably contains (A) component: 30 to 89% by weight, (B) component: 10 to 70% by weight, and total of (A) component and (B) component. (C) Component: 0.1 to 10% by weight. More preferably (A) component: 35 to 80% by weight, and (B) component: 10 to 40% by weight. By setting the blending ratio of the component (A), the component (B) and the component (C) within the above range, the release property of the multiplication or the moldability as seen in the curability, and the heat resistance and optical properties are improved. Balanced features. Further, when the component (C) is too small, the hardening is likely to occur, and the heat resistance and the light resistance are lowered. When the amount is too large, the mechanical strength is lowered to lower the heat resistance. Further, when the curable resin composition contains an organic solvent and a filler, the above content is calculated by excluding such an amount.

Further, the curable resin composition of the present invention may optionally contain a polymerization inhibitor, an antioxidant, a release agent, a photosensitizer, an organic solvent, a decane coupling agent, a leveling agent, an antifoaming agent, an antistatic agent, and further ultraviolet rays. An absorbent, a light stabilizer, various inorganic, organic fillers, an antifungal agent, an antibacterial agent, and the like are added to the curable resin composition of the present invention to impart functionality for each purpose.

The curable resin composition of the present invention can be obtained by mixing the above-mentioned (A) component, (B) component, (C) component, and other components as needed 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 irradiation with an active energy ray such as ultraviolet rays. Here, specific examples of the light source used when the active energy ray is irradiated and hardened may be, for example, a xenon lamp, a carbon arc lamp, a germicidal lamp, an ultraviolet ray fluorescent lamp, a high pressure mercury lamp for copying, a medium pressure mercury lamp, a high pressure mercury lamp, and an ultrahigh pressure mercury lamp. , an electrodeless lamp, a metal halide lamp, or an electron beam formed by a scanning type, a curtain type electron beam acceleration path, or the like. When the curable resin composition of the present invention is cured by ultraviolet rays, the amount of ultraviolet rays required for curing is preferably about 300 to 20,000 mJ/cm ² . Further, in order to sufficiently cure the resin composition, it is preferred to irradiate an active energy ray such as ultraviolet rays in an inert gas atmosphere such as nitrogen.

The curable resin composition of the present invention can be used in an injection molded article such as a plastic lens. A plastic lens using the resin composition of the present invention has a method of producing a mold made of a polyvinyl chloride, an ethylene vinyl acetate copolymer or the like and a mold of a desired shape, which is made of a glass mold, into which a mold is injected. After the resin composition of the invention, the active energy ray such as ultraviolet rays is irradiated to cure the resin composition, and the cured product is peeled off from the mold.

In addition, various methods known in the art can be used as a method of applying the curable resin composition of the present invention as a resin composition for a bismuth lens sheet to a film-form substrate. The specific method is, for example, that a resin composition is applied onto a mold having a 稜鏡 lens shape on the surface, a resin composition layer is provided, and a colorless transparent film is pressed on the resin composition layer so as not to allow bubbles to enter. a substrate (for example, polyvinyl chloride, polystyrene, polycarbonate, poly(meth)acrylate, polyester, polyethylene terephthalate, etc.), followed by using a high pressure mercury lamp in this state. The film-form substrate side is irradiated with ultraviolet rays, and after the resin composition layer is cured, a film-form substrate having a resin layer of a lenticular lens shape is peeled off from the mold.

The refractive index of the cured product of the resin composition of the present invention obtained by irradiating an active energy ray such as ultraviolet rays is preferably 1.50 or more at 25 ° C, more preferably 25 ° C. The next is 1.52 or more. In particular, when a ruthenium lens sheet is prepared from the resin composition of the present invention, when the refractive index of the cured product is less than 1.50 at 25 ° C, there is a problem that sufficient front luminance cannot be ensured. Further, the Abbe number of the cured product (the material specific value which defines the property of changing the refractive index due to the wavelength of light) is preferably 40.0 or more, more preferably 50.0 or more. When the Abbe number of the hardened material is less than 40.0, the chromatic aberration is large and the color is unclear, which is not preferable.

The cured resin obtained by molding and curing the curable resin composition of the present invention is excellent as an optical material. In particular, it is useful as a material for optical plastics such as a bismuth lens sheet, a Fresnel lens, a lenticular lens, a spectacle lens, and an aspherical lens. Therefore, the lenses can be advantageously used in a photographic apparatus. Further, the curable resin composition or the cured resin may be used in photovoltaic applications such as optical disks, optical fibers, and optical waveguides, printing inks, paints, clear coating agents, gloss paints, and the like.

[Examples]

The invention is illustrated by the following examples, but the invention is not limited thereto. Moreover, the parts in each case are parts by weight unless otherwise specified. Further, the measurement of the softening temperature and the like in the examples was carried out by the following methods to prepare and measure the samples.

(Measurement of physical properties of copolymers and their cured products) 1) Molecular weight and molecular weight distribution of polymers

The molecular weight and molecular weight distribution of the soluble polyfunctional (meth) acrylate copolymer was determined by GPC (manufactured by TOSOH, HLC-8120GPC). The solvent was used: tetrahydrofuran (THF), a flow rate: 1.0 ml/min, and a column temperature: 40 °C. The molecular weight of the copolymer was measured using a polystyrene-converted molecular weight using a calibration line made of monodisperse polystyrene.

2) Structure of the polymer

The JNM-LA600 type nuclear magnetic resonance spectroscopic device manufactured by JEOL was determined by 13C-NMR and 1H-NMR analysis. Chloroform-d1 was used as a solvent, and a resonance line of tetramethylnonane was used as an internal standard.

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

After the soluble polyfunctional (meth) acrylate copolymer solution was uniformly dried by drying on a glass substrate to a thickness of 20 μm, it was heated at 90 ° C for 3 minutes using a hot plate and dried. The resin film on the obtained glass substrate was fixed to a TMA (thermomechanical analyzer) measuring apparatus together with the glass substrate, and the temperature was raised to 220 ° C at a temperature increase rate of 10 ° C /min under a nitrogen gas flow, followed by heat treatment at 220 ° C for 20 minutes. The resin is hardened (this hardened material is called a sample). After the glass substrate was allowed to cool to room temperature, the sample for analysis was brought into contact with the sample in the TMA measuring device, and the sample was scanned from 30 ° C to 360 ° C at a temperature increase rate of 10 ° C/min under a nitrogen gas flow, and the wire was obtained by a wiring method. Soften the temperature. Depending on the heat resistance of the sample, when the probe does not penetrate the resin film and does not exhibit a probe intrusion amount smaller than the film thickness, the temperature at which the probe invades and the amount of penetration into the film thickness are expressed in percentages in addition to the softening temperature.

4) Determination of thermal weight loss and heat discoloration

The thermal decomposition temperature and heat discoloration resistance of the soluble polyfunctional (meth) acrylate copolymer were measured by fixing the sample on a TGA (thermal balance) measuring device, and scanning from 30 ° C at a heating rate of 10 ° C / min under a nitrogen stream. To The measurement was carried out at 320 ° C, and the weight loss at 300 ° C was determined, and the amount of discoloration of the sample after the measurement was visually confirmed, and classified according to ◎: no thermal discoloration, ○: light yellow, Δ: brown, and ×: black. Evaluation of heat discoloration resistance.

5) Determination of water absorption rate

The weight of the sample dried under vacuum at 60 ° C for 24 hours was set to W ₀ , weighed to a scale of 0.1 mg, and humidified in a constant temperature and humidity chamber at a temperature of 85 ° C and a relative humidity of 85%. 1 week. After humidification, the water vapor was scraped off against the test sample, and the sample was weighed to a scale of ±0.1 mg, which was W. The water absorption rate was calculated by the following formula (3). Prepare the same test by preparing three identical samples.

W ₀ /W×100=water absorption rate (3)

6) Determination of solvent resistance and determination of solvent solubility

The solvent resistance of the soluble polyfunctional (meth) acrylate copolymer was measured by vacuum-forming the copolymer at 200 ° C for one hour, and the sample plate was immersed in toluene at room temperature for 10 minutes to visually confirm the immersion. The change of the sample, and according to ○: no change, △: swelling, ×: deformation. Expansion and classification were carried out to evaluate the solvent resistance.

The solvent solubility was measured by adding 5 g of a soluble polyfunctional (meth) acrylate copolymer to 100 ml of a solvent, and the dissolution state after stirring at 25 ° C for 10 minutes was observed. It was uniformly dissolved, and it was judged to be soluble when the presence of undissolved matter and gel was not confirmed.

7) Determination of refractive index

The synthesized soluble polyfunctional (meth) acrylate copolymer was dissolved in toluene, and then 1.0 part by weight of PERBUTYL O was added as a starter with respect to 100 parts by weight of the soluble polyfunctional (meth) acrylate copolymer. A cast sheet was prepared from the polymer solution, and the cast sheet was pulverized, granulated, filled in a press mold, and hardened at 170 ° C for 1 hour in a press molding machine. The obtained hardened parallel plate was used as a test piece, and the refractive index of the d line (587.6 nm) was measured by KPR-200 (manufactured by Shimadzu KALNEW Co., Ltd.). The measurement timing was one week after the high temperature and high humidity device which was placed in a moist heat condition of 85 ° C × 85 RH immediately after molding. Further, using the same test piece, the Abbe number was measured with an Abbe refractometer (manufactured by ATAGO Co., Ltd.).

8) Adhesion test

The paint obtained by diluting the copolymer with a solvent (methyl ethyl ketone) was coated on a glass substrate, dried at 80 ° C for 5 minutes, and then hardened at 200 ° C for one hour in an inert gas oven under a nitrogen gas stream. Next, the glass substrate on which the cured coating film of the copolymer was mounted was cut into a grid of 11 squares on the surface of the coating film at intervals of 1 mm in accordance with JIS K5400. After the cellophane tape was adhered to the surface thereof, the number of meshes remaining without peeling off at the time of peeling was calculated.

(Measurement of physical properties of the composition) (1) Determination of refractive index

Thickness is used between two glass plates having a width of 60 mm, a length of 60 mm, and a thickness of 1.0 mm for various physical properties of the resin composition. A xenon tape of 1.0 mm and a width of 10 mm was formed into a void having a width of 50 mm and a length of 50 mm, and a composition was injected into a glass mold obtained by winding and fixing the outer periphery of a polyimide film. By 1) from the single side of the glass mold, using the high-pressure mercury lamp described above, irradiating the ultraviolet light for a few seconds, or 2) placing the glass mold in an inert gas oven under a nitrogen gas stream, and heating it at 180 ° C for 1 hour to harden it. . The hardened resin sheet was released from the glass mold as Sample B. The refractive index and Abbe number of the sample B were measured by an Abbe refractometer (manufactured by ATAGO Co., Ltd.).

(2) Hue

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

(3) Haze (turbidity) and total light transmittance

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

(4) Demoulding

The degree of difficulty in demolding the sample B used in the measurement of the refractive index from the glass mold was evaluated.

○: Good release property from glass mold

△: demoulding is slightly difficult

×: Demolding is difficult or left in the mold

(5) mold reproducibility

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

○: good reproducibility

×: poor reproducibility

(6) Burr, leakage

When the hardened resin is released from the glass mold, the size of the burrs generated outside the product portion of the finished product and the degree of leakage of the resin toward the gap of the glass mold are evaluated.

○: The amount of burrs generated was less than 0.05 mm, and the leakage of the resin into the gap of the glass mold was less than 1.0 mm.

△: The amount of burrs generated was less than 0.05 mm above 0.05 mm, and the leakage of the resin into the gap of the glass mold was 1.0 mm or more and less than 3.0 mm.

×: The amount of burrs generated was 0.2 mm or more, and the leakage of the resin into the gap of the glass mold was 3.0 mm or more.

(7) Air bubbles: When the hardened resin is released from the glass mold, it is evaluated according to whether or not the product portion of the molded article is bubbled and the size is large.

○: No bubble formation was observed.

△: Bubble formation was observed, and the size of the bubble was less than 2% with respect to the volume of the molded article.

X: Bubble formation was observed, and the size of the bubble was 2% or more with respect to the volume of the molded article.

(8) Crack: When the hardened resin is released from the glass mold, it is evaluated according to the presence or absence of the crack generated by the product portion of the molded article.

○: No crack formation was observed

△: Although crack formation was observed, the crack formation site was observed only in the corner portion of the outer peripheral portion of the molded article.

X: Although crack formation was observed, the formation portion of the crack was observed in addition to the corner portion of the outer peripheral portion of the molded article.

(7) Reflow heat resistance: The sample B was measured by a spectrophotometer CM-3700d (manufactured by Konica Minolta Co., Ltd.) at a wavelength of 400 nm. The measurement timing was carried out before the heat resistance test at 190 ° C for 60 minutes, and after the heat resistance test at 260 ° C for 8 minutes in an air oven. The results of the change in the spectral transmittance obtained by these measurements are shown in Table 3 below. (8) Water absorption rate

Using sample B, the weight of the test piece which was vacuum dried at 60 ° C for 24 hours was set to W ₀ , and the scale was measured to a scale of ± 0.1 mg, and the temperature was 85 ° C, and the relative humidity was 85%. The inside was humidified for 1 week. After humidification, the water vapor was scraped off against the test sample, and the sample was weighed to a scale of ±0.1 mg, which was W. The water absorption rate was calculated by the following formula (1). Prepare the same test by preparing three identical samples.

W ₀ /W×100=water absorption rate (1)

Example 1

Dimethylol tricyclodecane diacrylate (DMTCD) 1.6 mol (463.2 ml), dicyclopentanyl methacrylate 1.2 mol (254.2 ml), 1,4-butanediol diacrylate (BDDA) 1.2 mol (226.3 ml), 2,4-diphenyl-4-methyl-1-pentene (αMSD) 0.4 mol (95.5 ml), tri-dodecyl mercaptan (TDM) 2.4 Moore (564.8 ml) and 600 ml of toluene were placed in a 3.0 L reactor, and 40 mmol (11.5 g) of tributylperoxy was added at 90 °C. Base-2-ethylhexanoate and reacted for 2 hours and 45 minutes. After the polymerization reaction was terminated by cooling, the reaction mixture was poured into a large amount of hexane at room temperature to precipitate a copolymer. The obtained copolymer was washed with hexane, filtered, dried, and weighed to obtain 536.4 g of a copolymer A (yield: 73.2% by weight).

The obtained copolymer A had Mw of 34,200, Mn of 5620, and Mw/Mn of 6.1. By performing ¹³ C-NMR, ¹ H-NMR analysis and elemental analysis, the copolymer A contained a total of 39.6 mol% of structural units derived from dimethylol tricyclodecane diacrylate (1), totaling 31.1 mo % of the ear is derived from the structural unit (2) of dicyclopentanyl methacrylate, 29.3 mol% of the structural unit derived from 1,4-butanediol diacrylate (3). Here, the above calculation is based on the total of the structural unit derived from the monofunctional (meth) acrylate (a) having an alicyclic structure and the structural unit derived from the difunctional (meth) acrylate (b). 100% of the calculator.

Further, the terminal group (4) derived from the structure of 2,4-diphenyl-4-methyl-1-pentene is relative to the structural units (1), (2) and (3), and the terminal group (4) And the total of the terminal groups (5) derived from the structure of the third-dodecylmercaptan (hereinafter referred to as the total amount of all structural units) is 1.8 mol%. On the other hand, the end group (5) has 7.2 mol% relative to the total amount of all structural units.

Further, the ratio of the side chain 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. Further, the cast film of the copolymer A was not cloudy and was a transparent film.

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

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

Further, as a result of TMA measurement, the softening temperature was 300 ° C or higher. As a result of TGA measurement, the weight loss at 300 ° C was 0.8 wt%, and the heat resistance to heat was ◎.

Further, after the refractive index measurement of the copolymer A, the refractive index after curing (589 nm): 1.522, and the refractive index after the wet heat test (589 nm): 1.523.

Further, the number of grids remaining in the adhesion test was counted, and it was confirmed that 100 grids remained on the substrate without any shortage.

Example 2

Dimethylol tricyclodecane diacrylate 2.64 mol (764.3 ml), dicyclopentanyl acrylate (DCPA) 0.24 mol (47.2 ml), 1,4-butanediol diacrylate 0.96 mol ( 181.0 ml), 2-hydroxypropyl acrylate (HOP-A) 0.96 mol (118.5 ml), 2,4-diphenyl-4-methyl-1-pentene 0.48 mol (114.6 ml), third - Dodecyl mercaptan 3.12 mol (734.3 ml), 720 ml of toluene were placed in a 3.0 L reactor, and 62 mmol (13.9 g) of t-butylperoxy-2-ethylhexanoate was added at 90 ° C. , the reaction was 2 hours and 30 minutes. After the polymerization was terminated by cooling, the reaction mixture was poured into a large amount of hexane at room temperature to precipitate a copolymer. The obtained copolymer was washed with hexane, filtered, dried, and weighed to obtain a copolymer B. 517.2 g (yield: 71.5 wt%).

The obtained copolymer B had a Mw of 39,500, an Mn of 7,240 and an Mw/Mn of 5.5. By performing ¹³ C-NMR, ¹ H-NMR analysis and elemental analysis, the copolymer B contained a total of 55.2 mol% of structural units derived from dimethylol tricyclodecane diacrylate (1), totaling 5.1 mol. % of the ear derived from the structural unit of dicyclopentanyl acrylate (2), 20.3 mol% of the structural unit derived from 1,4-butanediol diacrylate (3), 19.4 mol% derived from acrylic acid 2 Structural unit of -hydroxypropyl ester (6). Further, the terminal group (4) derived from the structure of 2,4-diphenyl-4-methyl-1-pentene has 1.2 mol% relative to the total amount of all structural units.

On the other hand, the terminal group (5) derived from the structure of the third-dodecyl mercaptan is present in an amount of 7.6 mol% with respect to the total amount of all structural units.

Copolymer B was soluble in toluene, xylene, THF, dichloroethane, dichloromethane, and chloroform, and no gel formation was observed. Further, the cast film of the copolymer B was a haze and was a transparent film.

The copolymer B was made into a cured sheet according to various measurement conditions. The optical properties, water absorption, thermal weight reduction, heat discoloration resistance, and solvent resistance of the sample obtained by cutting out the cured sheet were measured.

As a result, the coefficient of linear expansion was 71 ppm/° C., the water absorption ratio was 0.76%, and the solvent resistance was ○.

Further, as a result of TMA measurement, the softening temperature was 300 ° C or higher. As a result of TGA measurement, the weight loss at 300 ° C was 0.92 wt%, and the heat resistance to heat was ◎.

In addition, after the refractive index measurement of the copolymer B, the refraction after hardening Rate (589 nm): 1.507, refractive index after the moist heat test (589 nm): 1.509.

Further, the number of grids remaining in the adhesion test was counted, and it was confirmed that 100 grids remained on the substrate without any shortage.

Examples 3-8 and Comparative Examples 1~4

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

The amount of the raw materials used for the reaction is shown in Table 1, and the test results of the copolymer and the cured product thereof 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 raw materials used is expressed in terms of moles and weight (g), but the description is in the form of mol/g. Further, the molar fraction (MR) is calculated by taking the total of the components (a) and (b) as 100.

Examples 9 to 11 and Comparative Examples 5 and 6

The components (numbers are parts by weight) were blended in the proportions shown in Table 3, and 0.1 part by weight of ADEKASTAB AO-60 manufactured by ADEKA Co., Ltd. was added as a stabilizer to obtain a curable resin composition. Next, the curable resin composition was cured by the above various test methods and evaluated for performance. The results of the performance evaluation are shown in Table 4.

Examples 12 to 20 and Comparative Examples 7 to 9

The ingredients (numbers are parts by weight) were formulated in the proportions shown in Table 5, and ADEKASTAB AO-60 0.1 manufactured by ADEKA Co., Ltd. was added. The amount of the stabilizer was used as a stabilizer to obtain a curable resin composition. Next, the curable resin composition was cured by the above various test methods and evaluated for performance. The results of the performance evaluation are shown in Table 6.

The abbreviations used in the table are as follows.

DMTCD: Dimethylol tricyclodecane diacrylate (difunctional)

BDDA: 1,4-butanediol diacrylate (difunctional)

DCPM: Dicyclopentyl methacrylate (monofunctional)

DCPA: Dicyclopentyl acrylate (monofunctional)

HOP-A: 2-hydroxypropyl acrylate (monofunctional)

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

TDM: third-dodecyl mercaptan (d) component

TMPTA: Trimethylolpropane triacrylate (trifunctional)

TMP: Trimethylolpropane trimethacrylate (trifunctional)

CD536: Dioxolane diacrylate (difunctional)

HPNDA: Hydroxypivalic acid neopentyl glycol diacrylate (difunctional)

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

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

DPHA: dipentaerythritol hexaacrylate (hexafunctional)

PETIA: pentaerythritol triacrylate (trifunctional)

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

MR: Molar fraction

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

Claims (10)

A soluble polyfunctional (meth) acrylate copolymer which comprises a monofunctional (meth) acrylate (a) having an alicyclic structure, a difunctional (meth) acrylate (b), 2, a copolymer obtained by copolymerization of a component of 4-diphenyl-4-methyl-1-pentene (c) and a thiol compound (d) having a difunctional (meth)acrylic acid derived from a side chain a reactive (meth) acrylate group of ester (b) and having a structural unit derived from 2,4-diphenyl-4-methyl-1-pentene (c) and a thiol compound (d) at the end The copolymer has a weight average molecular weight of from 2,000 to 60,000 and is further soluble in toluene, xylene, tetrahydrofuran, dichloroethane or chloroform. A soluble polyfunctional (meth) acrylate copolymer according to claim 1, wherein the copolymer is a monofunctional (meth) acrylate (a) having a alicyclic structure, and a hydroxy group-containing Functional (meth) acrylate (a2), difunctional (meth) acrylate (b), 2,4-diphenyl-4-methyl-1-pentene (c) and thiol compound (d) The copolymer obtained by copolymerization of the obtained copolymer. A soluble polyfunctional (meth) acrylate copolymer according to claim 1, wherein the monofunctional (meth) acrylate having an alicyclic structure (a) is isobornyl methacrylate or acryl Borneol ester, cyclohexyl methacrylate, cyclohexyl acrylate, dicyclopentenyl acrylate, dicyclopentenyloxyethyl acrylate, dicyclopentanyl acrylate, dicyclopentenyloxy methacrylate One or more monofunctional (meth) acrylates selected from the group consisting of esters, dicyclopentenyloxyethyl methacrylate and dicyclopentanyl methacrylate. The soluble polyfunctional (meth) acrylate copolymer according to claim 1, wherein the aforementioned difunctional (meth) acrylate (b) is cyclohexane dimethanol diacrylate, cyclohexane dimethanol One or more difunctional (meth) acrylates selected from the group consisting of dimethacrylate, dimethylol tricyclodecane diacrylate, and dimethylol tricyclodecane dimethacrylate. A method for producing a soluble polyfunctional (meth) acrylate copolymer according to the first aspect of the patent application, characterized in that a monofunctional (meth) acrylate (a) having an alicyclic structure and a difunctional group are provided. The components of (meth) acrylate (b), 2,4-diphenyl-4-methyl-1-pentene (c), and thiol compound (d) are copolymerized. A curable resin composition characterized by: (A) component: a soluble polyfunctional (meth) acrylate copolymer according to claim 1 of the patent application, (B) component: polyfunctional (meth)acrylic acid And the component (C): the composition of the component (B) is 5 to 250 parts by weight based on 100 parts by weight of the component (A), and the compounding amount of the component (C) is relative to The total amount of the components (B) and (A) is 100 parts by weight in an amount of 0.1 to 10 parts by weight. A sclerosing resin composition according to claim 6 which contains: (A) component: a soluble polyfunctional (meth) acrylate copolymer as claimed in claim 2, (B) component: a pentafunctional or higher polyfunctional (meth) acrylate, and (C) component: an initiator. A cured resin obtained by curing a curable resin composition according to item 6 of the patent application. An optical material characterized by being formed of a cured resin of a resin according to item 8 of the patent application. An optical material according to claim 9 wherein the optical material is an optical plastic lens.