JPH03244615A - Resin composition and cured product thereof - Google Patents

Abstract

PURPOSE:To provide a resin composition having a refractive index above a specified value and excelling castability and being colorless and excellent in transparency by mixing a high refractive index urethane (meth)acrylate with a specified (meth)acrylic ester and a photopolymerization initiator. CONSTITUTION:At least either a urethane (meth)acrylate with a refractive index of 1.5 or higher or a di(meth)acrylic ester of a bisphenol or biphenol type epoxy resin is mixed with a (meth)acrylic ester of formula I (wherein R is H or CH3), e.g. formula II, and a photopolymerization initiator (e.g. benzil dimethyl ketal) to produce a resin composition having a refractive index of 1.55 or higher. This resin composition is liquid at room temperature, so that it can be cast without being dissolved in a solvent or heated, and the cured product can be desirably used for lenses, prisms, etc.

Description

Detailed Description of the Invention (Field of Industrial Application) The present invention relates to a colorless, highly transparent, ultraviolet curable resin composition having a high refractive index used in optical materials such as lenses and prisms, and its curing. relating to things.

(Prior art) As a material to replace inorganic optical lenses, resin for high refractive index lenses made of transparent synthetic resin has been applied as a plastic material due to its light weight, impact resistance, and good moldability. is expanding. Polymethyl methacrylate, polydiethylene glycol bisallyl carbonate resin, and the like conventionally used as plastic lens materials have excellent transparency and light weight, but have the disadvantage that their refractive index is lower than that of glass. In addition, naphthyl methacrylate and bisphenol A dimethacrylate are useful as raw materials for resins with high refractive index, but since these monomers are solid at room temperature, they cannot be mixed with other liquid monomers during cast polymerization. There were restrictions such as the need to dissolve it in water or heat it to operate at a temperature above its melting point. On the other hand, vinylnaphthalene and vinylcarbazole can also be used as raw materials for resins having a high refractive index, but the resulting resins are not satisfactory as resins for plastic lenses because they are markedly colored.

(Problems to be Solved by the Invention) An object of the present invention is to provide a resin composition that does not require complicated operations during production, is colorless, has excellent transparency, and has a high refractive index, and a cured product thereof. It is in.

(Means for Solving the Problems) As a result of intensive studies in view of the current situation, the present inventors have found that diurethane (meth)acrylate and bisphenol-type or biphenol-type epoxy resins with a wind refraction index of 1.50 or more have been developed. It has been discovered that a resin composition obtained by using as essential components one or more members of the group consisting of (meth)acrylic esters and a (meth)acrylic ester with a specific structure, and a cured product thereof, solve the above problems, This has led to the completion of the present invention.

That is, the present invention provides at least one type (4) of the group consisting of urethane (meth)acrylate having a refractive index of 1.50 or more and di(meth)acrylic acid ester of bisphenol type or biphenol type epoxy resin, and the general formula [I] (However, R represents H or CH.) (
The present invention relates to a high refractive index resin composition having a refractive index of 1.55 or more, which contains meth)acrylic acid ester (Bl) and a photopolymerization initiator (0), and a cured product thereof.

Note that the refractive index in the present invention is measured at 25°C.

The urethane (meth)acrylate (4) having a refractive index of 1.50 or more used in the present invention is a polyester polyol (e.g., ethylene glycol, diethylene glycol,
．． Alcohol components such as 3-7" ethylene glycol, cyclohexane dimetatool, 3-methyl-1゜5-bentanediol, tricyclodecane dimethylol, propylene glycol and heptalic acid, tetrahydrophthalic acid, hexahydrophthalic acid, tetra Polyester diols obtained from acid components such as chlorophthalic acid, tetrabromophthalic acid, endomethylenetetrahydrophthalic acid, terephthalic acid, dibasic acids having a benzene nucleus or their anhydrides) and organic polyisocyanates (for example, tolylene diols) organic diisocyanates such as 4,4-dicyclohexylmethane diisocyanate, 4,4-dicyclohexylmethane diisocyanate, hexamethylene diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, etc.) and hydroxyl group-containing (meth)acrylic esters (e.g., β-hydroxyethyl (meth)acrylate, β-hydroxyprobyl (meth)acrylate, ε-caprolactone-β-hydroxyethyl (meth)acrylate,
1.4-butanediol mono(meth)acrylate, etc.)
It can be obtained by reacting. The ratio of these used in the urethanization reaction between polyester polyol and organic polyinsyanate is
NC of organic polyisocyanate per chemical equivalent of group
1.1 to 2.0 chemical equivalents of O groups are preferred, particularly preferably 1.5 to 2.0 chemical equivalents. This urethanization reaction can be carried out in procedures known to those skilled in the art. The reaction temperature of this urethanization reaction is room temperature to 100°C,
Preferably it is 50-80°C. The reaction is carried out until the concentration of isocyanate groups in the reaction solution reaches a predetermined concentration, and the reaction time is usually 5 to 20 hours. Then, in the (meth)acrylation reaction, a hydroxyl group-containing (meth)acrylic ester is added to the OH The group is preferably 0.9 to 1
．． 5 chemical equivalents, particularly preferably 1.0 to 1.1 chemical equivalents. The reaction temperature of this (meth)acrylation reaction is room temperature to 100°C, preferably 50 to 80°C. The reaction is carried out until the amount of isocyanate groups in the reaction solution becomes 0.5% or less, and the reaction time is usually 5 to 20 hours.

The di(meth)acrylic acid ester (4) of bisphenol type or biphenol type epoxy resin used in the present invention is:
Bisphenol type or biphenol type epoxy resin [e.g., bisphenol A type epoxy resin (e.g., Epicoat 828, 1001.100 manufactured by Yuka Shell Chemical ■)
4, etc.), bisphenol F-type epoxy resins (e.g., Yuka Shell Chemical Co., Ltd., Epicor 807, etc.), biphenol-type epoxy resins (e.g., Yuka Shell Chemical Co., Ltd., YX),
-4000, YL-6056, etc.) etc.]
and (meth)acrylic acid. The reaction between the epoxy resin and (meth)acrylic acid is carried out using about 0.8 to 1.1 chemical equivalents of (meth)acrylic acid, particularly preferably about 0.8 to 1.1 chemical equivalents of (meth)acrylic acid per chemical equivalent of the epoxy group of the epoxy resin. The reaction is carried out at a ratio of 9 to 1.05 chemical equivalents, and as a diluent during the reaction, for example, phenoxy ether (meth)acrylate, phenyl glycidyl ether (meth)acrylate, 2,2-bis-(
It is preferable to use (meth)acrylates such as 4-(meth)acryloyloxypolyethoxyphenyl)propane, bromophenyl (meth)acrylate, and tribromophenyloxyethyl (meth)acrylate, and in order to further accelerate the reaction. It is preferable to use a catalyst (for example, triethylamine, benzyldimethylamine, methyltriethylammonium chloride, triphenylstipine, etc.), and the amount of the catalyst used is preferably 0.1 to 10% by weight based on the reaction mixture. , particularly preferably 0.3 to 5% by weight. Polymerization inhibitors (e.g. methoquinone, hydroquinone,
phenothiazine etc.), the amount used is preferably from 0.01 to 1% by weight, particularly preferably from 0.05 to 0.5% by weight, based on the reaction mixture.

The reaction temperature is preferably 60-150°C, particularly preferably 80-120°C. The reaction is carried out by increasing the acid value of the reaction solution (m
The reaction time is usually 5 to 30 hours.

In the present invention, (meth)acrylic ester (81) represented by general formula [I] is used. (meth)acrylic ester (D is a compound represented by general formula [■]) and (meth)acrylic ester It can be obtained by reacting with an acid.Preferably about 0.8 to 1.1 chemical equivalents of (meth)acrylic acid per 1 chemical equivalent of the epoxy group of the compound represented by the general formula [■] , particularly preferably 0.9
The reaction is carried out at a ratio of ~1.05 chemical equivalents. In order to further promote the reaction, it is preferable to use a catalyst (for example, triethylamine, benzyldimethylamine, methyltriethylammonium chloride, triphenylstibine, etc.), and the amount of the catalyst used is preferably 0.5% based on the reaction mixture. 1 to 10% by weight, particularly preferably 0.3
~5% by weight.

In order to prevent polymerization during the reaction, it is preferable to use a polymerization inhibitor (for example, methoquinone, hydroquinone, phenothiazine, etc.), the amount of which is preferably from 0.01 to 1% by weight, especially from 0.01 to 1% by weight, based on the reaction mixture. Preferably 0.0
It is 5 to 0.5% by weight. The reaction temperature is preferably 60
-150°C, particularly preferably 80-120°C. The reaction is carried out until the acid value (mgKOH/g) of the reaction solution becomes 5 or less, and the reaction time is usually 5 to 30 hours.

Specific examples of preferred (meth)acrylic esters (Bl) include H Ut'i and the like.

Any known photopolymerization initiator can be used as the photopolymerization initiator (C1) used in the present invention, but
It is desirable to have good storage stability after blending. Specific examples of such photopolymerization initiators include, for example, 1-hydroxycyclohexylphenyl ketone, benzyl dimethyl ketal, 2-hydroxy-2-methylpropiophenone,
Benzophenone, 4-isopropyl-2-hydroxy-
Examples include 2-methylpropiophenone. These photopolymerization initiators can be used alone or in combination of two or more in any proportion. Preferred photopolymerization initiators include l-hydroxycyclohexylphenyl ketone,
Examples include 2-hydroxy-2-methylpropiophenone. In the resin composition having a high refractive index of the present invention, urethane (meth)acrylate and/or di(meth)acrylic acid ester (4) of a bisphenol type or biphenol type epoxy resin having a refractive index of 1.50 or more is added to
When it is 0 parts by weight, it is expressed by the general formula [■] (meta)
Acrylic acid ester (I3) is preferably 50 to 100
0 parts by weight, more preferably 1 part from 100 to 5 oOiJ. In addition, when the total amount of (Al component + (Bl component) is 100 parts by weight, photopolymerization initiator (0 is preferably 0)
．． It is preferable to use it in a proportion of 1 to 10 parts by weight, more preferably 0.3 to 5 parts by weight.

The resin composition having a high refractive index of the present invention can further contain reactive monomers other than components (4) and (a) as required, and the reactive monomers include, for example, phenyl (
meth)acrylate, benzyl(meth)acrylate,
Phenyloxyethyl (meth)acrylate, phenyloxypolyethoxy (meth)acrylate, tribromophenyloxyethyl (meth)acrylate, 2.2-
Bis-(4-(meth)acryloyloxypolyethoxyphenyl)propane, 2.2bis-(4-(meth)acryloyloxypolyethoxyphenyl)propane, 2.
Examples include 2-bis-(4-(meth)acryloyloxypolyethoxy-dibromophenyl)propane and (meth)acrylate of phenylglycidyl ether. These reactive monomers are preferably used in the range of 0 to 40 parts by weight based on the total amount of 100 parts by weight of the component (4), the f111 component, and the component (0).Also, known additives,
For example, ultraviolet absorbers, antioxidants, light stabilizers, mold release agents, antistatic agents, etc. can also be used. The resin composition of the present invention can be obtained by uniformly mixing each component.

The cured product of the resin composition having a high refractive index of the present invention is made of materials such as glass, resin, metal, etc., and is molded into a mold having a shape designed according to the purpose, such as a plate shape, a lens shape, a cylinder shape, or a spherical shape. ,
It can be obtained by injecting the composition, applying temperature and pressure if necessary, and irradiating it with ultraviolet rays in a conventional manner to cure it.

〔Example〕

Hereinafter, the present invention will be explained in more detail with reference to Examples, but the present invention is not limited to these. In the following, parts are parts by weight.

(Synthesis Examples 1 to 4 of urethane (meth)acrylate with a refractive index of 1.50 or more, di(meth)acrylic acid ester of bisphenol-type epoxy resin, and di(meth)acrylic acid ester of biphenol-type epoxy resin), Synthesis example 2448 parts of polyester diol (OH value 110, molecular weight 1020) of 1°terephthalic acid and 1,4-butanediol and 83.5 parts of tolylene diisocyanate were mixed at 80°C for 10 minutes.
The reaction mixture was reacted for 10 hours, and then 57.3 parts of 2-hydroxyethyl acrylate was reacted at 80° C. for 10 hours to obtain urethane acrylate (A-1), which is the active component of the composition of the present invention.

The refractive index (25°C) of the obtained urethane acrylate is 1
．． It was 5379.

Synthesis Example 2 Polyester diol of phthalic acid and diethylene glycol (OH value 117.0, molecular weight 958.9) 249,3
1 part and 90.5 parts of tolylene diisocyanate at 80°C.
0 hours, and then 62.1 parts of 2-hydroxyethyl acrylate was reacted at 80°C for 10 hours to form urethane acrylate (A-
2) was obtained.

The refractive index (25°C) of the obtained urethane acrylate is 1
．． It was 5589.

Synthesis Example 3 180 parts of bisphenol A type epoxy resin (manufactured by Yuka Shell Chemical ■, Epicoat 828, epoxy equivalent 180),
68.4 parts of acrylic acid, 0.2 parts of methoquinone, and 2.0 g of triphenylstipine were charged, and the mixture was reacted at 95°C for about 40 hours until the acid value (mg KOtl/g) of the reaction solution became 1.0 or less. A diacrylic acid ester (A-3) of a bisphenol type epoxy resin, which is component (1) of the composition of the present invention, was obtained. The refractive index (256C
) was 1.5627.

(manufactured by Yuka Shell Chemical ■, YX-4000, epoxy equivalent 185) 185 parts, acrylic acid 68.4 parts, phenoxyethyl acrylate (refractive index (25'C) 1.519
0) 50 parts, 0.2 parts of methoquinone, and 2.0 parts of triphenylstibine, and heated at 959C until the acid value (mg KOH/g) of the reaction solution reached 1.0 or less.
After 0 hours of reaction, diacrylic acid ester of biphenol type epoxy resin (A-4
) was obtained. The refractive index (25°C) of the diacrylic ester of the obtained biphenol type epoxy resin is 1.5532.
Met.

(Synthesis Examples 5 to 6 of (meth)acrylic acid ester (D) represented by general formula [I]) Synthesis Example 5゜Structural formula (manufactured by Sanko Kagaku ■, 0PP-G Epoxy equivalent: 226.
3) Prepare 226.3 parts of acrylic acid, 68.4 parts of acrylic acid, 02 parts of methoquinone, and 2.0 parts of triphenylstipine,
At 95°C, the acid value (mgKo)L/g) of the reaction solution was 1.
The reaction was carried out for about 40 hours until the temperature became 0 or less, and an acrylic acid ester (B-1), which is the Bl component of the composition of the present invention, was obtained.

Synthesis Example 6゜Structural formula 226.3 parts, acrylic acid 68.4 parts, methoquinone 02
1 part and 2.0 parts of triphenylstibine, and heated to 95°C.
The reaction solution was reacted for about 40 hours until the acid value (mgKOH/g) of the reaction solution became 1.0 or less, to obtain acrylic acid ester (B-2), which is the Bl component of the composition of the present invention.

Examples 1 to 5 Each component was mixed according to the formulation shown in Table 1 to prepare a high refractive index resin composition, and the refractive index was measured as described below. Furthermore, this composition was injected into a mold assembled with two glass plates and a gasket made of ethylene-ethyl acrylate copolymer, and a 2KW ultra-high pressure mercury lamp was used.
A cured product was obtained by irradiating with ultraviolet rays. The obtained cured product was tested for refractive index, transparency, initial coloration, and total light transmittance as described below. The results are shown in Table 1.

[Refractive index]

The refractive index of the resin composition and its cured product was determined by measuring the refractive index at 25° C. using an Atsube refractometer.

〔Transparency〕

The transparency of the cured product was visually determined.

○... Good transparency.

×・・・・・・ Bad.

[Initial coloring]

The yellowness (yellow index Y, I) of the cured product with a thickness of 2 mm was measured using a color difference meter (model: SZ-Σ80) (manufactured by Nihon Denki Kogyo ■).

[Total light transmittance]

( Integrating sphere haze meter (manufactured by Nippon Precision Optics) (Model I SEP-H-20) Measured using

Note) *■KAYARAD R-564: Made by Nippon Kayaku ■, phenyloxypolyethoxyacrylate ■KA
YARAD R-551: Nippon Kayaku ■, 2, 2-
Bis(4-acryloyloxyethoxyethoxyphenyl)propane*■ Irgacure 184: manufactured by Ciba Geigy, photopolymerization initiator.

(Effects of the Invention) The high refractive index resin composition of the present invention has a high refractive index, is colorless and has excellent transparency, and is a colorless and transparent liquid at room temperature, so it can be easily poured into a mold and irradiated with ultraviolet rays. A cured product can be obtained by doing this.

The resin composition of the present invention is particularly useful as an optical material. For example, the resin composition of the present invention is useful as an overcoat agent for optical discs, a coating agent for optical fibers, a sealant for optical elements, etc. The cured product of the resin composition of the present invention can also be used as lenses, films, and the like.

Claims (1)

[Scope of Claims] 1. One or more members (A) of the group consisting of urethane (meth)acrylate having a refractive index of 1.50 or more and di(meth)acrylic acid ester of bisphenol type or biphenol type epoxy resin and the general formula [ I 〕 ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼〔 I 〕 (However, R represents H or CH_3.)
meth)acrylic acid ester (B) and photopolymerization initiator (C)
A high refractive index resin composition having a refractive index of 1.55 or more. 2. A cured product of the high refractive index resin composition according to claim 1.