TWI688581B - (Meth)acrylate resin manufacturing method, optical member manufacturing method, curable composition manufacturing method, cured product manufacturing method - Google Patents

Abstract

The present invention provides a (meth)acrylate resin excellent in heat resistance, moisture absorption resistance, and yellowing resistance of a cured product, a photocurable composition containing the same, and a cured product thereof, and a product obtained by using the above photocurable composition Optical components. The present invention is a (meth)acrylic acid characterized by a reactant in which an aromatic diglycidyl ether compound (A), (meth)acrylic acid (B), and methacrylic anhydride (C) are essential reaction components An ester resin, a photocurable composition containing it and its cured product, and an optical member using the photocurable composition.

Description

(Meth)acrylate resin manufacturing method, optical member manufacturing method, curable composition manufacturing method, cured product manufacturing method

The present invention relates to a (meth)acrylate resin excellent in heat resistance, moisture absorption resistance, and yellowing resistance of a cured product, a photocurable composition containing the same, a cured product thereof, and an optical member.

The on-chip lens mounted on an image sensor such as CCD or CMOS is widely manufactured by a melting method that applies a dot pattern to a thermoplastic resin and shapes the spherical lens by heat flow, but the spherical lens Due to the large chromatic aberration, there is a limit to high definition and high sensitivity. In addition, it is difficult to use this fusion method to achieve narrow gap lens shaping. As a technique for forming lenses with reduced chromatic aberrations and narrow gaps, there has been proposed a shape transfer method in which a photocurable resin is shaped by a mold with an aspheric lens shape. The photocurable resin is composed of a resin or monomer having a photopolymerizable group such as (meth)acryloyl group, etc. It can achieve a low viscosity by containing a large amount of low molecular weight components, so it can achieve fine shape shaping Of material. However, when used for crystal-mounted lens applications, heat resistance or moisture resistance is not sufficient, and yellowing or deformation is likely to occur.

As a photocurable resin excellent in moisture resistance and the like, for example, a photocurable resin obtained by reacting a bisphenol A type epoxy resin with methacrylic anhydride is known (see Patent Document 1). Although such a resin having a high aromatic ring content shows relatively high heat resistance, when used for crystal-mounted lens applications, both heat resistance and moisture resistance are insufficient, and yellowing or deformation is likely to occur.

[Prior Technical Literature] [Patent Literature]

[Patent Document 1] Japanese Patent Laid-Open No. 2008-038029

Therefore, the problem to be solved by the present invention is to provide a (meth)acrylate resin excellent in heat resistance, moisture absorption resistance, and yellowing resistance of a cured product, a photocurable composition containing the cured product, a cured product thereof, and an optical member .

The inventors of the present invention conducted intensive studies to solve the above-mentioned problems, and found that the cured product of the methacrylate resin obtained by reacting the aromatic diglycidyl ether compound with (meth)acrylic acid and methacrylic anhydride The present invention has been completed by being excellent in heat resistance, moisture absorption resistance, and yellowing resistance.

That is, the present invention relates to a (meth)acrylate resin characterized in that it is an aromatic diglycidyl ether compound (A), (meth)acrylic acid (B), and methacrylic anhydride (C ) As reactants of necessary reaction components.

[式中，R¹為氫原子或甲基，X為下述通式(2-1)~(2-8)之任一者所表示之結構部位，

The present invention further relates to a (meth)acrylate resin characterized by having a molecular structure represented by the following general formula (1),

[In the formula, R ¹ is a hydrogen atom or a methyl group, X is a structural part represented by any one of the following general formulas (2-1) to (2-8),

(In the formula, R ^{2 is} independently any one of a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, or a phenyl group, and R ^{3 is} independently a number of carbon atoms. (Any of 1-4 alkyl, alkoxy of 1 to 4 carbon atoms, phenyl, n is an integer of 1 to 4)

Y is a hydrogen atom or a methacryloyl group], and at least one of Y present in the resin is a methacryloyl group.

The present invention further relates to a photocurable composition containing the above (meth)acrylate resin and a photopolymerization initiator.

The present invention further relates to a cured product of the above curable composition.

The present invention further relates to an optical member formed using a curable composition.

According to the present invention, it is possible to provide a (meth)acrylate resin excellent in heat resistance, moisture absorption resistance, and yellowing resistance of a cured product, a photocurable composition containing the cured product, a cured product thereof, and an optical member.

FIG. 1 is a GPC chart of the (meth)acrylate resin (1) obtained in Example 1. FIG.

Hereinafter, the present invention will be described in detail.

The (meth)acrylate resin of the present invention is characterized in that it is an aromatic diglycidyl ether compound (A), (meth)acrylic acid (B), and methacrylic anhydride (C) as necessary reactions The reactants of the ingredients. That is, the present invention uses (meth)acrylic acid (B) and methacrylic anhydride (C) together as a (meth)acrylic esterifying agent for aromatic diglycidyl ether compound (A), and The so-called epoxy acrylate resin has successfully achieved a photocurable resin material excellent in heat resistance, moisture absorption resistance, and yellowing resistance of the cured product.

Examples of the aromatic diglycidyl ether compound (A) used in the present invention include bisphenol epoxy resin, biphenyl epoxy resin, phenyl ether epoxy resin, naphthalene ether epoxy resin, and phenol Alkyl epoxy resin, naphthol aralkyl epoxy resin, dicyclopentadiene-phenol addition The reaction type epoxy resin, etc., More specifically, the compound etc. which are represented by any one of following structural formula (3-1)-(3-8) are mentioned.

In the formula, R ^{2 is} independently any one of a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, and a phenyl group, and R ^{3 is} each independently having 1 carbon atom Either alkyl group of ~4, alkoxy group of 1 to 4 carbon atoms, phenyl group, G represents epoxypropyl group, and n is an integer of 1 to 4)

These can be used individually or in combination of two or more. Among them, in terms of obtaining a methacrylate resin excellent in heat resistance, moisture absorption resistance, and yellowing resistance of the cured product, the compound represented by the above structural formula (3-1) is preferable.

The (meth)acrylic acid (B) may be either acrylic acid or methacrylic acid, or both. Among them, methacrylic acid is preferred from the viewpoint of the (meth)acrylate resin having excellent heat resistance as a cured product. In addition, acrylic acid is preferred in that it hardly generates gas when the cured product is heated.

In the production of the (meth)acrylate resin of the present invention, regarding the reaction ratio of the aromatic diglycidyl ether compound (A), (meth)acrylic acid (B), and methacrylic anhydride (C), It is preferable to use (meth)acrylic acid (B) and methacrylic anhydride relative to 1 mole of epoxy group in the aromatic diglycidyl ether compound (A) in a range of 0.9 to 1.1 mole in total (C).

Moreover, in terms of a methacrylate resin that is excellent in heat resistance, moisture absorption resistance, and yellowing resistance, which is a cured product, it is preferable that (meth)acrylic acid (B) and methacrylic anhydride (C) The ear ratio [(B)/(C)] is in the range of 1/9~6/4.

In the present invention, the production method of the (meth)acrylate resin is not particularly limited, and for example, the following method may be mentioned: an organic solvent is used in the presence of an esterification catalyst, an antioxidant, and a polymerization inhibitor as needed, The aromatic diglycidyl ether compound (A), (meth)acrylic acid (B), and methacrylic anhydride (C) are reacted in a temperature range of 100 to 150°C for about 5 to 12 hours.

The (meth)acrylate resin of the present invention produced by this method may, for example, have a molecular structure represented by the following general formula (1),

[In the formula, R ¹ is a hydrogen atom or a methyl group, X is a structural part represented by any one of the following general formulas (2-1) to (2-8),

(In the formula, R ^{2 is} independently any one of a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, or a phenyl group, and R ^{3 is} independently a number of carbon atoms. (Any of 1-4 alkyl, alkoxy of 1 to 4 carbon atoms, phenyl, n is an integer of 1 to 4)

Y is a hydrogen atom or a methacryloyl group], and at least one of Y present in the resin is a methacryloyl group.

Specific examples of the resin component having the molecular structure represented by the general formula (1) include the compounds represented by any of the following general formulas (1-1) to (1-3).

[In the formula, R ¹ is a hydrogen atom or a methyl group, X is a structural part represented by any one of the following general formulas (2-1) to (2-8),

(In the formula, R ^{2 is} independently any one of a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, or a phenyl group, and R ^{3 is} independently a number of carbon atoms. (1~4 alkyl group, 1-4 carbon atoms alkoxy group, phenyl group, n is an integer of 1-4)]

In terms of excellent heat resistance, moisture absorption resistance, and yellowing resistance of the cured product, the (meth)acryloyl equivalent of the methacrylate resin of the present invention calculated according to the amount of raw materials added is preferably 160 to 230 g /Equivalent range.

The photocurable composition of the present invention contains the above methacrylate resin and a photopolymerization initiator.

、2,4-二甲基9-氧硫

、2,4-二乙基9-氧硫

、2,4-二氯9-氧硫

之9-氧硫

系；如米其勒酮、4,4'-二乙基胺基二苯甲酮之胺基二苯甲酮系；及10-丁基-2-氯吖啶酮、2-乙基蒽醌、9,10-菲醌、樟腦醌等分子內奪氫型光聚合起始劑。該等既可分別單獨使用，亦可併用2 種以上。 Examples of the photopolymerization initiator used here include: diethoxyacetophenone, 2-hydroxy-2-methyl-1-phenylpropane-1-one, benzoyl dimethyl ketal, 1-(4-isopropylphenyl)-2-hydroxy-2-methylpropane-1-one, 4-(2-hydroxyethoxy)phenyl-(2-hydroxy-2-propyl)one , 1-hydroxycyclohexylphenyl ketone, 2-methyl-2-morpholinyl (4-thiomethylphenyl) propane-1-one, 2-benzyl-2-dimethylamino-1 -Acetophenone of (4-morpholinylphenyl) butanone; such as benzoin of benzoin, benzoin methyl ether, benzoin isopropyl ether; such as 2,4,6-trimethyl benzoin diphenylphosphine oxide Acyl phosphine oxide series; Intramolecular bond cleavage type photopolymerization initiators such as benzoyl acetoyl and methyl benzoate; or such as benzophenone, methyl o-benzoyl benzoate-4-phenyldi Benzophenone, 4,4'-dichlorobenzophenone, hydroxybenzophenone, 4-benzoyl-4'-methyl-diphenyl sulfide, propenated benzophenone, 3, 3',4,4'-tetrakis (third butylcarbonyl peroxide) benzophenone, 3,3'-dimethyl-4-methoxybenzophenone benzophenone series; such as 2 -Isopropyl 9-oxysulfur

, 2,4-Dimethyl 9-oxysulfur

, 2,4-Diethyl 9-oxysulfur

, 2,4-Dichloro 9-oxysulfur

9-Oxine

Series; such as Michelerone, 4,4'-diethylaminobenzophenone amine benzophenone series; and 10-butyl-2-chloroacridone, 2-ethylanthraquinone , 9,10-phenanthrenequinone, camphorquinone and other intramolecular hydrogen abstraction photopolymerization initiators. These can be used individually or in combination of two or more.

Examples of commercially available products of these photopolymerization initiators include: "Irgacure-184", "Irgacure-149", "Irgacure-261", "Irgacure-369", "Irgacure-500", "Irgacure-651" , "Irgacure-754", "Irgacure-784", "Irgacure-819", "Irgacure-907", "Irgacure-1116", "Irgacure-1664", "Irgacure-1700", "Irgacure-1800", "" Irgacure-1850'', ``Irgacure-2959'', ``Irgacure-4043'', ``Darocure-1173'' (manufactured by Ciba Specialty Chemicals), ``Lucirin TPO'' (manufactured by BASF), ``Kayacure-DETX'', ``Kayacure-MBP '', ``Kayacure-DMBI'', ``Kayacure-EPA'', ``Kayacure-OA'' (manufactured by Nippon Kayaku Co., Ltd.), ``Vicure-10'', ``Vicure-55'' (manufactured by Stauffer Chemical), ``Trigonal P1 '' (manufactured by Akzo), ``Sandray 1000'' (manufactured by SANDOZ), ``DEAP'' (manufactured by Upjohn), ``Quantacure-PDO'', ``Quantacure-ITX'', ``Quantacure-EPD'' (manufactured by Ward Blenkinsop), etc. .

The added amount of the photopolymerization initiator is, for example, used within a range of 1 to 20 parts by mass relative to 100 parts by mass of the photocurable composition.

The photocurable composition of the present invention may further contain other (meth)acrylate compounds other than the above methacrylate resins or photosensitizers, curing accelerators, organic solvents, non-reactive resins, fillers, inorganic fillers, Organic fillers, coupling agents, adhesion-imparting agents, defoamers, leveling agents, adhesion aids, mold release agents, lubricants, ultraviolet absorbers, antioxidants, heat stabilizers, plasticizers, flame retardants, pigments , Dyes and other additive components.

Examples of the other (meth)acrylate compounds include n-butyl (meth)acrylate, isobutyl (meth)acrylate, tert-butyl (meth)acrylate, n-pentyl (meth)acrylate, N-hexyl (meth)acrylate, n-octyl (meth)acrylate, isooctyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, glycidyl (meth)acrylate, mofu Chloroline (meth)acrylate, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, 2-methoxy (meth)acrylate Ethyl ester, 2-butoxyethyl (meth)acrylate, 2-ethoxyethyl (meth)acrylate, 2-(2-ethoxyethoxy)ethyl (meth)acrylate, 4-nonylphenoxyethylene glycol (meth)acrylate, tetrahydrofurfuryl (meth)acrylate, caprolactone modified tetrahydrofurfuryl (meth)acrylate, cyclohexyl (meth)acrylate , Cyclohexyl methyl (meth) acrylate, Cyclohexyl ethyl (meth) acrylate, Isoborn (meth) acrylate, Dicyclopentyl (meth) acrylate, Dicyclopentyl ethoxy (meth) acrylate Ester, dicyclopentenyl (meth)acrylate, dicyclopentenyloxyethyl (meth)acrylate, phenyl (meth)acrylate, benzyl (meth)acrylate, phenoxy (meth)acrylate Ethyl ethyl, phenoxy 2-methyl ethyl (meth) acrylate, phenoxy ethoxy ethyl (meth) acrylate, p-cumyl phenoxy ethyl (meth) acrylate, ( Phenoxybenzyl methacrylate, 2-hydroxy-3-phenoxypropyl (meth)acrylate, phenylbenzyl (meth)acrylate, phenylphenoxyethyl acrylate, hexahydro-o-phenyl Mono(meth)acrylate compounds such as 2-propenyloxyethyl dicarboxylate, mono-(meth)acrylate compounds containing a scaffold represented by the following general formula (4) or (5);

[In the formula, X is a hydrogen atom or a hydroxyl group, R ¹ and R ⁴ are independently a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, R ² is a hydrogen atom or a methyl group, and R ³ is a direct bond or sub Methyl, m is 0 or 1]

[In the formula, two Xs are each independently a hydrogen atom or a hydroxyl group, two R ₁ are each independently a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, R ₂ is a hydrogen atom or a methyl group, m and n Independently 0 or 1]

Ethylene glycol di(meth)acrylate, propylene glycol di(meth)acrylate, butylene glycol di(meth)acrylate, 1,4-butanediol di(meth)acrylate, 1,6- Hexanediol di(meth)acrylate, 1,9-nonanediol di(meth)acrylate, neopentyl glycol di(meth)acrylate, bisphenol A di(meth)acrylate, bis Phenol F di(meth)acrylate, dicyclopentyl di(meth)acrylate, glycerol di(meth)acrylate, neopentyl glycol hydroxypivalate di(meth)acrylate, caprolactone Quality hydroxypivalate neopentyl glycol di(meth)acrylate, tetrabromobisphenol A di(meth)acrylate, hydroxypivalaldehyde modified trimethylolpropane di(meth)acrylate, 1 ,4-Cyclohexanedimethanol di(meth)acrylate, bis[(meth)acryloylmethyl]biphenyl, bis-containing skeleton represented by the following general formula (6) or (7) Di(meth)acrylate compounds such as (meth)acrylate compounds;

[In the formula, X is independently a hydrogen atom or a hydroxyl group, R ^{1 is} independently a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, R ^{2 is} independently a hydrogen atom or a methyl group, and R ^{3 is} independently Ground is a direct bond or methylene, m and n are independently 0 or 1]

[In the formula, 2 Xs are each independently a hydrogen atom or a hydroxyl group, 2 R ₁ are each independently a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, and 2 R ₂ are each independently a hydrogen atom or a methyl group Basis, m and n are independently 0 or 1]

Trimethylolpropane tri(meth)acrylate, neopentaerythritol tri(meth)acrylate, glyceryl tri(meth)acrylate, di-trimethylolpropane tetra(meth)acrylate, di Neopentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate and other (meth) acrylate compounds with more than 3 functions; make butane-1,4-diisocyanate, hexamethylene Methyl diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, 2,4,4-trimethylhexamethylene diisocyanate, xylylene diisocyanate, m-tetramethylbenzene diisocyanate Methyl diisocyanate, cyclohexane-1,4-diisocyanate, isophorone diisocyanate, amine diisocyanate, dicyclohexylmethane-4,4'-diisocyanate, 1,3-bis(isocyanate group (Methyl) cyclohexane, methylcyclohexane diisocyanate, 1,5-naphthalene diisocyanate, 4,4'-diphenylmethane diisocyanate, 2,2'-bis (p-phenylisocyanate) propane, 4, 4'-dibenzyl diisocyanate, dialkyldiphenylmethane diisocyanate, tetraalkyldiphenylmethane diisocyanate, 1,3-benzenediisocyanate, 1,4-benzenediisocyanate, toluene diisocyanate and other diisocyanate compounds Or the modified urate and 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, 4-hydroxybutyl acrylate, glycerol diacrylate, trimethylolpropane diacrylate, neopentyl alcohol (Meth)propane obtained from the reaction of hydroxyl-containing (meth)acrylate compounds such as triacrylate and dipentaerythritol pentaacrylate Amino acid esters, etc. These other (meth)acrylate compounds may be used alone or in combination of two or more.

The photo-curable composition of the present invention exhibits particularly high heat resistance, moisture resistance, and yellowing resistance, and thus can be used for various applications such as electronic parts, molded products, and coating applications. In particular, it can effectively utilize the characteristics of excellent yellowing resistance and is preferably used for optical member applications. Examples of optical members include plastic lenses such as eyeglass lenses, crystal sensors for CCD or CMOS image sensors, Fresnel lenses, and prism lenses; and optical protective agents, hard coating agents, anti-reflection films, and optical fibers , Optical waveguides, holograms, lenticular lenses, LED sealing materials, coating materials for solar cells, etc.

The above-mentioned crystal lens or prism lens is manufactured by, for example, a shape transfer method using a forming mold such as a mold in which a lens pattern is formed or a resin mold. Specifically, a method may be mentioned in which a photocurable composition is applied to a shaping die, a transparent substrate is superposed on the surface of the composition, and active energy rays are irradiated from the transparent substrate side to be cured. Examples of the transparent substrate used herein include a plastic substrate made of acrylic resin, polycarbonate resin, polyester resin, polystyrene resin, fluororesin, and polyimide resin, or glass.

The lens sheet manufactured by this method can be directly attached to a transparent substrate and used directly, or it can be used as a lens alone after peeling off the transparent substrate. In the case of attaching to a transparent substrate and using it directly, in order to improve the adhesion between the lens and the transparent substrate, it is preferable to perform an adhesion improvement treatment such as primer coating on the surface of the transparent substrate in advance. On the other hand, in the case where the transparent substrate is peeled off and used, it is preferable to pretreat the surface of the transparent substrate with a polysiloxane or a fluorine-based peeling agent so that the transparent substrate can be easily peeled off.

When the photocurable composition of the present invention is used for such a shaped lens It is preferable to use the methacrylate resin of the present invention together with the other (meth)acrylate compounds described above, and adjust the viscosity (25°C) of the photocurable composition to the range of 100 mPa‧s to 800 mPa‧s . The other (meth)acrylate compound used is appropriately selected according to the required performance, for example, it is more preferable to adjust the refractive index of the hardened product to 1.5560 or more.

[Example]

Hereinafter, the present invention will be described in more detail using examples and comparative examples.

Example 1 Production of (meth)acrylate resin (1)

Into a flask equipped with a thermometer, stirrer, and reflux cooler, 374 parts by mass of bisphenol A epoxy resin (Epiclon 850-S manufactured by DIC Co., Ltd. epoxy equivalent 187g/equivalent) was added as an 0.6 parts by mass of dibutylhydroxytoluene as an oxidizing agent, 0.2 parts by mass of p-methoxyphenol as a thermal polymerization inhibitor, 86 parts by mass of methacrylic acid, 154 parts by mass of methacrylic anhydride, and 1.8 parts by mass of triphenylphosphine are added, While blowing air, the esterification reaction was carried out at 110° C. for 10 hours to obtain a (meth)acrylate resin (1). The (meth)acryloyl equivalent calculated based on the amount of raw material added to the (meth)acrylate resin (1) is 205 g/equivalent. Furthermore, the molar ratio [(B)/(C)] of methacrylic acid (B) and methacrylic anhydride (C) is 5/5.

Example 2 Production of (meth)acrylate resin (2)

Into a flask equipped with a thermometer, stirrer, and reflux cooler, 374 parts by mass of bisphenol A epoxy resin (Epiclon 850-S manufactured by DIC Co., Ltd. epoxy equivalent 187g/equivalent) was added as an After 0.6 parts by mass of dibutylhydroxytoluene as an oxidizing agent and 0.2 parts by mass of p-methoxyphenol as a thermal polymerization inhibitor, 52 parts by mass of methacrylic acid, 216 parts by mass of methacrylic anhydride, and 1.8 parts by mass of triphenylphosphine are added, While blowing air, the esterification reaction was performed at 110° C. for 10 hours to obtain a (meth)acrylate resin (2). According to (meth)acrylate tree The (meth)acryloyl equivalent calculated from the amount of the raw material added to the fat (2) was 188 g/equivalent. Furthermore, the molar ratio [(B)/(C)] of methacrylic acid (B) and methacrylic anhydride (C) is 3/7.

Example 3 Production of (meth)acrylate resin (3)

Into a flask equipped with a thermometer, stirrer, and reflux cooler, 374 parts by mass of bisphenol A epoxy resin (Epiclon 850-S manufactured by DIC Co., Ltd. epoxy equivalent 187g/equivalent) was added as an After 0.7 parts by mass of dibutylhydroxytoluene as an oxidizing agent and 0.2 parts by mass of p-methoxyphenol as a thermal polymerization inhibitor, 17 parts by mass of methacrylic acid, 278 parts by mass of methacrylic anhydride, and 2.0 parts by mass of triphenylphosphine are added, While blowing air, the esterification reaction was carried out at 110° C. for 10 hours to obtain a (meth)acrylate resin (3). The equivalent of (meth)acryloyl group calculated based on the added amount of the raw material of (meth)acrylate resin (3) was 176 g/equivalent. Furthermore, the molar ratio [(B)/(C)] of methacrylic acid (B) and methacrylic anhydride (C) is 1/9.

Example 4 Production of (meth)acrylate resin (4)

Into a flask equipped with a thermometer, stirrer, and reflux cooler, 374 parts by mass of bisphenol A epoxy resin (Epiclon 850-S manufactured by DIC Co., Ltd. epoxy equivalent 187g/equivalent) was added as an 0.6 parts by mass of dibutylhydroxytoluene as an oxidizing agent, 0.2 parts by mass of p-methoxyphenol as a thermal polymerization inhibitor, 72 parts by mass of acrylic acid, 154 parts by mass of methacrylic anhydride, and 1.8 parts by mass of triphenylphosphine were added while blowing The air was allowed to undergo esterification reaction at 110°C for 10 hours to obtain a (meth)acrylate resin (4). The (meth)acryloyl equivalent calculated based on the amount of raw materials added to the (meth)acrylate resin (4) is 200 g/equivalent. Furthermore, the molar ratio [(B)/(C)] of acrylic acid (B) and methacrylic anhydride (C) is 5/5.

Example 5 Production of (meth)acrylate resin (5)

Add bisphenol A epoxy tree to flask equipped with thermometer, stirrer, and reflux cooler 374 parts by mass of epoxy resin (Epiclon 850-S made by DIC Co., Ltd. 187g/equivalent), and 0.6 parts by mass of dibutylhydroxytoluene as an antioxidant and p-methoxyphenol as a thermal polymerization inhibitor After 0.2 parts by mass, 43 parts by mass of acrylic acid, 216 parts by mass of methacrylic anhydride, and 1.8 parts by mass of triphenylphosphine were added, and the esterification reaction was carried out at 110°C for 10 hours while blowing air to obtain (meth)acrylic acid Ester resin (5). The equivalent of (meth)acryloyl group calculated based on the added amount of the raw material of (meth)acrylate resin (5) was 186 g/equivalent. Furthermore, the molar ratio [(B)/(C)] of acrylic acid (B) and methacrylic anhydride (C) is 3/7.

Example 6 Production of (meth)acrylate resin (6)

Into a flask equipped with a thermometer, stirrer, and reflux cooler, 374 parts by mass of bisphenol A epoxy resin (Epiclon 850-S manufactured by DIC Co., Ltd. epoxy equivalent 187g/equivalent) was added as an 0.7 parts by mass of dibutylhydroxytoluene as an oxidizing agent, 0.2 parts by mass of p-methoxyphenol as a thermal polymerization inhibitor, 14 parts by mass of acrylic acid, 278 parts by mass of methacrylic anhydride, and 2.0 parts by mass of triphenylphosphine were added while blowing The air was allowed to undergo an esterification reaction at 110°C for 10 hours to obtain a (meth)acrylate resin (6). The (meth)acryloyl equivalent calculated based on the addition amount of the raw material of (meth)acrylate resin (6) is 175 g/equivalent. Furthermore, the molar ratio [(B)/(C)] of acrylic acid (B) and methacrylic anhydride (C) is 1/9.

Comparative Manufacturing Example 1 Manufacturing of (meth)acrylate resin (1')

Into a flask equipped with a thermometer, stirrer, and reflux cooler, 374 parts by mass of bisphenol A epoxy resin (Epiclon 850-S manufactured by DIC Co., Ltd. epoxy equivalent 187g/equivalent) was added as an 0.5 parts by mass of oxidizing agent dibutylhydroxytoluene, 0.2 parts by mass of p-methoxyphenol as a thermal polymerization inhibitor, 172 parts by mass of methacrylic acid and 1.6 parts by mass of triphenylphosphine were added, while blowing air at 110°C It waits for 10 hours for the esterification reaction to obtain (A Base) acrylate resin (1'). The (meth)acryloyl equivalent calculated based on the amount of the (meth)acrylate resin (1') added is 273 g/equivalent.

Comparative Manufacturing Example 2 Manufacturing of (meth)acrylate resin (2')

Into a flask equipped with a thermometer, stirrer, and reflux cooler, 374 parts by mass of bisphenol A epoxy resin (Epiclon 850-S manufactured by DIC Co., Ltd. epoxy equivalent 187g/equivalent) was added as an 0.5 parts by mass of oxidizing agent dibutylhydroxytoluene and 0.2 parts by mass of p-methoxyphenol as a thermal polymerization inhibitor, 144 parts by mass of acrylic acid and 1.6 parts by mass of triphenylphosphine were added, while blowing air at 110°C, etc. The esterification reaction was carried out for 10 hours to obtain (meth)acrylate resin (2'). The (meth)acryloyl equivalent calculated based on the amount of the (meth)acrylate resin (2') added is 259 g/equivalent.

Examples 7-12, Comparative Examples 1, 2

Using the (meth)acrylate resins obtained in Examples 1 to 6 and Comparative Manufacturing Examples 1 and 2, a curable composition and a cured product were prepared according to the following procedures, and various evaluation tests were performed. The results are shown in Table 1.

Preparation of hardening composition

1 g of a photopolymerization initiator ("Irgacure 184D" manufactured by BASF) was added to 100 g of (meth)acrylate resin to prepare a curable composition.

Determination of glass transition temperature

The curable composition obtained previously was applied on an acrylic plate so that the film thickness became 100 μm, and ultraviolet light of 2000 mJ/cm ^{2 was} irradiated with a high-pressure mercury lamp to obtain a cured product.

A 6 mm×25 mm test piece was cut out of the obtained hardened material, and a viscoelasticity measuring device (DMA: solid viscoelasticity measuring device “RSA-G2” manufactured by Rheometrics Corporation) was used. The stretching method: At a frequency of 1 Hz and a temperature increase rate of 3°C/min), the temperature at which the elastic modulus changes to the maximum (tan δ change rate is maximum) is evaluated as the glass transition temperature.

Determination of water absorption

A 6 mm×25 mm test piece was cut out from the same hardened material as the user of the glass transition temperature measurement and immersed in water at 23° C. for 24 hours. The weight change rate before and after immersion was evaluated as the water absorption rate.

Evaluation of yellowing resistance

The curable composition obtained previously was applied to a glass plate so that the film thickness became 100 μm, and ultraviolet light of 2000 mJ/cm ^{2 was} irradiated with a high-pressure mercury lamp to obtain a laminated film.

The obtained laminated film was heated in an oven at 265°C for 3 minutes. The transmittance (%) of light at 420 nm was measured for the test pieces before and after heating, and the evaluation was based on the difference between the two values.

Evaluation of gas generation

The curable composition previously obtained was coated on a glass plate so that the film thickness became 100 μm, and ultraviolet light of 1000 mJ/cm ² or 2000 mJ/cm ^{2 was} irradiated with a high-pressure mercury lamp to obtain a laminated film.

The obtained laminated film was heated on a hot plate at 265°C for 3 minutes. Observe visually whether gas is generated at this time and evaluate. No gas generation: ○, gas generation and foaming: ×

Claims (6)

A method for producing (meth)acrylate resin, which uses aromatic diglycidyl ether compound (A), (meth)acrylic acid (B), and methacrylic anhydride (C) as essential reaction components The reaction proceeds, and the molar ratio [(B)/(C)] of the (meth)acrylic acid (B) and the methacrylic anhydride (C) is 1/9~5/5. For example, the method of manufacturing a (meth)acrylate resin according to item 1 of the patent application, wherein the (meth)acrylate resin has a molecular structure represented by the following general formula (1),

[In the formula, R ¹ is a hydrogen atom or a methyl group, X is a structural part represented by any one of the following general formulas (2-1) to (2-8),

(In the formula, R ^{2 is} independently any one of a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, or a phenyl group, and R ^{3 is} independently a number of carbon atoms. 1~4 alkyl group, any one of 1-4 carbon atoms alkoxy group, phenyl group, n is an integer of 1~4) Y is a hydrogen atom or methacryloyl], and is present in the resin At least one of Y is methacryloyl. For example, the method of manufacturing a (meth)acrylate resin in item 1 or 2 of the patent application scope, wherein the (meth)acrylic acid equivalent of the (meth)acrylate resin is in the range of 160 to 230 g/equivalent. A method for manufacturing a hardenable composition, which incorporates a (meth)acrylate resin produced by the method for manufacturing a (meth)acrylate resin according to any one of claims 2 to 3, and photopolymerization Starter. A method for manufacturing a hardened product which hardens a hardenable composition prepared by the method for manufacturing a hardenable composition according to item 4 of the patent application. A method for manufacturing an optical member using the curable composition produced by the method for producing a curable composition as claimed in item 4 of the patent scope.

Images