JPH1053632A - Resin composition, composition for casting and its cured product - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a lightweight resin composition, excellent in impact resistance and transparency, having >=1.55 refractive index and useful as a plastic lens, etc., by using an epoxy (meth)acrylate having a specific structure. SOLUTION: This resin composition comprises (A) an epoxy (meth)acrylate prepared by reacting (i) an epoxy compound, obtained by reacting (a) a diol compound represented by the formula (a) and (b) are each 1-10; the average value of [(a)+(b)] is 2-20; R1 is H, CH3 or C2 H5 } with (b) epichlorohyrin with (ii) (meth)acrylic acid, (B) an unsaturated group-containing compound other than the component A (e.g. styrene) and (C) a photopolymerization initiator (e.g. methyl phenylglyoxylate) as an optional component. Furthermore, the mixing ratio is preferably 30-80 pts.wt. component B based on 20-70 pts.wt. component A when the total amount of the component A and B is 100 pts.wt. and 0.001-3 pts.wt. component C based on 100 pts.wt. total amount of the component A and B.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention
The present invention relates to a resin composition suitable for a high refractive index plastic lens material and a cured product thereof.

[0002]

2. Description of the Related Art Plastic lenses are widely used in optical products because of their features such as easy molding and light weight. Above all, transparent plus chalk used as eyeglass lenses requires heat resistance and chemical resistance,
Thermosetting plastics such as polydiethylene glycol bisallyl carbonate (hereinafter referred to as CR-39) have been used instead of thermoplastics such as polymethyl methacrylate and polystyrene. However, CR-
No. 39 has a drawback that the refractive index is as low as about 1.50.

[0003] A plastic lens material having a high refractive index has an advantage that when it is made into a lens, the thickness can be reduced and a product can be made compact. Many attempts have been made to develop plastics.

In order to obtain a transparent plastic having a high refractive index, as disclosed in JP-B-58-14449, a halogen atom other than fluorine is introduced into a molecular structure of a resin composition for a plastic lens, and an aromatic ring is removed. The general formula is to introduce. However, the plastic lens resin having the halogen-substituted aromatic ring in the molecular structure has a disadvantage that it is apt to be brittle. In order to obtain a tough plastic lens resin, a method of introducing a urethane bond having excellent impact resistance into the molecular structure of the plastic lens resin is an effective method. In order to obtain a tough plastic lens resin having a high refractive index, a resin having an aromatic ring substituted by a urethane bond and a halogen group other than fluorine in the molecular structure of the plastic lens resin is exemplified. Specifically, JP-A-60-51706, JP-A-63-193914, and JP-B-4-11
No. 570, for example.

However, in the technique of improving the refractive index by including a halogen group in the molecular structure of the plastic lens resin, the specific gravity of the plastic lens resin increases at the same time according to the halogen group content. Even if the thickness of the plastic lens can be reduced by increasing the refractive index of the cured resin for the lens, the effect of reducing the weight of the plastic lens is offset. To solve this drawback, Japanese Patent Laid-Open Publication No.
The technology proposed in US Pat. No. 2612 is effective. This is a copolymer obtained from a diol compound having a hydroxyl group in the molecule and a sulfur atom in the molecule and a polyisocyanate, and the formed urethane bond exhibits impact resistance and the sulfur atom is introduced. Therefore, it has a relatively high refractive index without increasing the specific gravity.

[0006]

However, when a sulfur atom is introduced into the copolymer, it is not satisfactory because it has poor light resistance and is easily colored, and is easily colored by heat.

The present invention has been made in view of the above background, and has as its object to cast a plastic lens or the like which is lightweight, has excellent impact resistance, and has a high refractive index of 1.55 or more. An object of the present invention is to provide a resin composition useful for the composition and a cured product thereof.

[0008]

Means for Solving the Problems The present inventors have proposed:
As a result of intensive studies to solve the above problems, the use of an epoxy (meth) acrylate having a specific structure has resulted in a plastic that is lightweight, has excellent impact resistance, has a refractive index of 1.55 or more, and has excellent transparency. A resin composition suitable for a casting composition such as a lens and a cured product thereof have been found.

That is, the present invention provides a diol compound (a) represented by the general formula (1):

[0010]

Embedded image

(In the formula (1), a and b are numbers from 1 to 10, and the average value of a + b is 2 to 15, preferably 2 to 10. R ₁ is a hydrogen atom, CH ₃ or C ₂ H ₅
It is. ) With epichlorohydrin and an epoxy (meth) acrylate (A) obtained by reacting (meth) acrylic acid with an epoxidized compound obtained by reacting the compound with an unsaturated group-containing compound (B) other than the component (A). A resin composition comprising a photopolymerization initiator (C) as a component,
The present invention relates to a casting composition and a cured product thereof.

Hereinafter, the present invention will be described in detail. (A)
The component is obtained by adding an epoxide obtained by reacting the diol compound (a) represented by the general formula (1) with epichlorohydrin and (meth) acrylic acid. Specific examples of the diol compound (a) represented by the general formula (1) include, for example,

[0013]

Embedded image

[0014]

Embedded image

[0015]

Embedded image

[0016]

Embedded image

[0017]

Embedded image

And the like. The reaction between the diol compound (a) represented by the general formula (1) and epichlorohydrin can be performed by a known method. For example,
In the presence of dimethyl sulfoxide, it is obtained by using at least one equivalent of epichlorohydrin with respect to one equivalent of the hydroxyl group of the diol compound (a) represented by the formula (1) and reacting. In carrying out the reaction, usually an alkali metal hydroxide is used. As the alkali metal hydroxide, caustic soda, caustic potash, lithium hydroxide, calcium hydroxide and the like can be used, but caustic soda is preferable. The amount of the alkali metal hydroxide used may be approximately one equivalent to one equivalent of the alcoholic hydroxyl group of the diol compound (a) represented by the formula (1). The alkali metal hydroxide may be used in the form of a solid or an aqueous solution. When used in the form of an aqueous solution, the reaction can be carried out while distilling water out of the reaction system under normal pressure or reduced pressure during the reaction. The reaction temperature is preferably from 30 to 100C. After completion of the reaction, excess epichlorohydrin and dimethyl sulfoxide are distilled off under reduced pressure, and then the resulting resin is dissolved in an organic solvent, and a dehydrohalogenation reaction can be performed with an alkali metal hydroxide. On the other hand, after completion of the reaction, water separation was carried out to separate by-product salts and dimethyl sulfoxide, and excess epichlorohydrin was distilled off from the oil layer under reduced pressure. A hydrogen reaction may be performed. As the organic solvent, methyl isobutyl ketone, benzene, toluene, xylene and the like can be used,
The use of methyl isobutyl ketone is preferred. These organic solvents can be used alone or in a mixture.

In the reaction between the epoxidized product and the (meth) acrylic acid, the ratio of (meth) acrylic acid used is 0.5 to 2.0 equivalents per equivalent of the epoxidized product. The reaction temperature is preferably from 70 to 130C, particularly preferably from 80 to 100C. The reaction can be promoted using a catalyst. Such catalysts are known catalysts such as triphenylstibine, triethylamine, benzyldimethylamine, methyltriethylammonium chloride and triphenylphosphine.
It is preferably from 0.5 to 20%, particularly preferably from 0.1 to 5%.
%used.

In the present invention, an unsaturated group-containing compound (B) other than the component (A) is used. The component (B) preferably has a low viscosity from the viewpoint of solubility and dilutability, and preferably has an aromatic ring in the molecule from the viewpoint of refractive index. Especially,
Styrene derivatives such as styrene, chlorostyrene, dichlorostyrene, bromostyrene, dibromostyrene, divinylstyrene, phenyl (meth) acrylate, benzyl (meth) acrylate, o-biphenyl (meth) acrylate, o-biphenyloxyethyl (meth) Preferred are (meth) acrylates such as acrylate, o-biphenyloxyethyloxyethyl (meth) acrylate, and bisphenol A polyethoxydi (meth) acrylate, and allyl compounds such as diallyl phthalate, dimethallyl phthalate and diallyl biphenylate.

As the component (B), one type may be used alone, or several types may be used in combination.

The mixing ratio of the component (A) and the component (B)
When the total amount of the components (A) and (B) is 100 parts by weight, the amount of the component (B) is preferably 20 to 90 parts by weight, and particularly preferably 10 to 80 parts by weight of the component (A). Refers to 20 to 70 parts by weight of component (A) and component (B) 30
８０80 weight.

The polymerization initiator of the component (C) is not particularly limited as long as it generates active radicals by active energy rays such as visible light, infrared light, ultraviolet light or heat.

Specific examples of the polymerization initiator (thermal polymerization initiator) that generates an active radical by heat include diisopropyl peroxydicarbonate, t-butyl peroxyisobutyrate, 1,1,3,3-tetramethyl Peroxy-
Organic peroxides such as 2-ethylhexanoate;
Examples include azo compounds such as azobis (2,4-dimethylvalernitrile) and azobisisobutyronitrile.

Specific examples of radical polymerization initiators (photopolymerization initiators) that generate active radicals by active energy rays include 2-hydroxy-2-methyl-1-phenylpropan-1-one, hydroxycyclohexylphenyl ketone, Methylphenylglyoxylate, 2,4,6
-Trimethylbenzoyldiphenylphosphine oxide, bis (2,6-dimethoxybenzoyl) -2,
4,4-trimethylpentylphosphine oxide, benzyldimethyl ketal, and the like can be used.

The polymerization initiator of the component (C) may be used alone or in combination of several kinds.

The amount of component (C) used is (A) component +
When the total amount of the component (B) is 100 parts by weight, the amount is preferably 0.005 to 5 parts by weight, particularly preferably 0.001 to 3 parts by weight, based on 100 parts by weight of the total amount.

The composition of the present invention contains pentaethylene glycol di (meth) acrylate and nonaethylene glycol di (meth) acrylate in order to improve the properties such as impact resistance and dyeability within a range not to impair the object of the present invention. Meth) acrylate, nonabutylene glycol di (meth) acrylate,
An appropriate amount of an aliphatic monomer such as diethylene glycol bisallyl carbonate may be added.

The composition of the present invention may contain an antifoaming agent, an antioxidant, an anti-yellowing agent, an ultraviolet absorber, a light stabilizer, a bluing agent, a pigment and the like within a range not to impair the object of the present invention. It may contain additives.

The resin composition, the casting composition and the cured product of the present invention are suitable for plastic lens materials and ophthalmic lenses, but also include protective coating agents for optical disks, adhesives, waterproof paints, and the like. Useful for a wide range of applications such as printing inks.

The composition of the present invention can be prepared by mixing, heating, dissolving and dispersing the components (A) to (C).

The cured product of the composition of the present invention can be cured by heating in a conventional manner, irradiation with active energy rays, or a combination thereof. The curing of the casting composition of the present invention is performed, for example, by combining two glass molds having a desired shape via a gasket made of, for example, polyvinyl chloride or an ethylene-vinyl acetate copolymer. , Heat after injecting the composition into this,
Curing can be performed by irradiating with an active energy ray or a combination thereof.

[0033]

EXAMPLES The present invention will be specifically described below with reference to Synthesis Examples and Examples, but the present invention is not limited thereto. The various physical properties obtained in the examples were measured by the following test methods using a cured product of a casting composition molded to a thickness of 2 mm for testing.

Visible light transmittance (%): ASTM D100
Measured according to 3-61. Refractive index: The Abbe refractometer measured the refractive index at 25 ° C. at a D line of 589.3 nm. Yellowness Index: Gardiner Colerimet
Measured by er Model XL835, the larger the value, the greater the yellowness. Rockwell hardness: measured according to JIS K 7202. Impact resistance: A steel ball drop test was conducted in which a steel ball weighing 16.3 g was dropped from a height of 127 cm to a test cured product according to the US FDA standard. If no damage was observed, it was rated "good (O)".

(Synthesis Example of Epoxidized Product of Diol Compound (a) Represented by General Formula (1)) Synthesis Example 1 205.3 g of diol compound (a-1) of the following formula, 925 g of epichlorohydrin, and dimethyl sulfoxide 46
After dissolving 2.5 parts, 98.5% at 70 ° C. under stirring.
52.8 g of NaOH were added over 100 minutes.

[0036]

Embedded image

After the addition, the reaction was further performed at 70 ° C. for 3 hours. Next, most of the excess unreacted epichlorohydrin and dimethyl sulfoxide are distilled off under reduced pressure, and the reaction product containing by-product salt and dimethyl sulfoxide is dissolved in 750 g of methyl isobutyl ketone.
0 g was added and reacted at 70 ° C. for 1 hour. After the completion of the reaction, the resultant was washed twice with 200 g of water. After oil-water separation, methyl isobutyl ketone is distilled and recovered from the oil layer, and the epoxy equivalent is 2
74 solid epoxidized products were obtained. The structural formula of the obtained epoxidized product is as follows.

[0038]

Embedded image

(Synthesis Example of Epoxy (meth) acrylate (A)) Synthesis Example 2 2740 g (10 equivalents) of the epoxy compound obtained in Synthesis Example 1, 720 g (10 equivalents) of acrylic acid, 2.6 g of p-methoxyphenol, o 1736.5 g of -phenylphenyloxyethyl acrylate was charged, and heated and dissolved at 90 ° C. Next, the reaction solution was cooled to 60 ° C., 15.6 g of triphenylphosphine was charged, heated to 100 ° C., and reacted for about 32 hours to obtain a reaction product having an acid value of 1.0 mgKOH / g. The viscosity (25 ° C.) of the reaction product was 1,300 poise, and the refractive index (25 ° C.) was 1.5917.

Synthesis Example 3 2880 g (10 equivalents) of an epoxy compound of the following structural formula obtained in the same manner as in Synthesis Example 1.

[0041]

Embedded image

720 g (10 equivalents) of acrylic acid, 2.6 g of p-methoxyphenol, and 1806 g of o-phenylphenyloxyacrylate were charged and dissolved at 90 ° C. by heating. Next, the reaction solution was cooled to 60 ° C., 15.6 g of triphenylphosphine was charged, heated to 100 ° C., and reacted for about 32 hours to obtain a reaction product having an acid value of 1.0 mgKOH / g. The viscosity of the reaction product (25 ° C.) is 1400 poise,
The refractive index (25 ° C.) was 1.5891.

Synthesis Example 4 3410 g (10 equivalents) of an epoxy compound of the following structural formula obtained in the same manner as in Synthesis Example 1.

[0044]

Embedded image

720 g (10 equivalents) of acrylic acid and 2.6 g of p-methoxyphenol were charged, and heated and dissolved at 90 ° C. Next, the reaction solution was cooled to 60 ° C., 18.6 g of triphenylphosphine was charged, heated to 100 ° C., and reacted for about 32 hours to obtain a reaction product having an acid value of 1.0 mgKOH / g. The viscosity (60 ° C.) of the reaction product was 100 poise and the refractive index (25 ° C.) was 1.56.

Examples 1 to 3 and Comparative Examples 1 and 2 Casting compositions were prepared according to the composition table in Table 1.
Next, a glass 2 having a length of 10 cm, a width of 10 cm, and a thickness of 5 mm
The above-mentioned composition was poured into a mold constituted by surrounding the surroundings with a tubular gasket made of polyvinyl chloride, with the sheets facing each other so as to have an interval of 2 mm. Then, ultraviolet rays were irradiated for 5 minutes from a 120 w / cm high-pressure mercury lamp at a distance of 20 cm from both sides of the mold to polymerize and cure.
Thereafter, the cured product was released from the mold and heat-treated at 120 ° C. for 2 hours to obtain a transparent flat plate. This plate was evaluated for visible light with respect to transmittance, refractive index, yellowness index, Rockwell hardness, and impact resistance. The evaluation results are shown in Table 1.

[0047]

Table 1-1 Example * 1 * 1 123 (A) component Epoxy acrylate obtained in Synthesis Example 2 60 Epoxy acrylate obtained in Synthesis Example 3 50 Epoxy acrylate obtained in Synthesis Example 4 Benzyl methacrylate 15 10 Styrene 20 10 o-Phenylphenyloxy methacrylate 15 20 2,2-bis (4-acryloxyethoxyethoxy-phenyl) propane 20 20 20 2,2-bis (4-methacryloxyethoxy-3,5 -Dibromophenyl) propane diethylene glycol bisallyl carbonate (C) component methylphenylglyoxylate 0.05 0.05 1-hydroxycyclohexylphenylketone 0.05 0.05 1,1,3,3-tetramethylperoxy-2-ethyl hexanoate 0.2 0.2 0.2 t -Butyl peroxyisobutyrate 0.1 diisopropylpa Oxydicarbonate Visible light transmittance (%) 91 92 91 Refractive index (25 ° C) 1.597 1.595 1.597 Yellowness index 1.1 1.1 1.0 Rockwell hardness 95 98 92 Impact resistance ○ ○ ○ Table 1-2 Comparative example * 1 * 1 1 2 (A) component Epoxy acrylate obtained in Synthesis Example 2 Epoxy acrylate obtained in Synthesis Example 3 Epoxy acrylate obtained in Synthesis Example 4 (B) Component Benzyl methacrylate styrene 50 o-phenylphenyloxy methacrylate 2,2-bis ( 4-acryloxyethoxy ethoxy-senyl) propane 2,2-bis (4-methacryloxyethoxy-3,5-dibromophenyl) propane 50 diethylene glycol bisallyl carbonate 100 (C) component methylphenylglyoxylate 1-hydroxy Cyclohexyl phenyl ketone 1,1,3,3-tetramethyl Luperoxy-2-ethyl hexanoate 0.2 t-butylperoxyisobutyrate 0.1 diisopropylperoxydicarbonate 2.5 Visible light transmittance (%) 92 89 Refractive index (25 ° C) 1.499 1.592 Yellowness index 1.0 1.1 Rockwell hardness 92 110 Resistance Impact properties ○ × Note) * 1: The curing conditions of Example 3 and Comparative Examples 1 and 2 were cured by heating from 40 ° C. to 100 ° C. over 20 hours.

From the evaluation results in Table 1, it is clear that the resin composition of the present invention has a high refractive index, is transparent and has excellent impact resistance.

[0049]

The resin composition of the present invention and the cured product thereof are:
It has a high refractive index, is transparent and has excellent impact resistance, and is useful for casting compositions such as plastic lenses.

Claims (3)

[Claims] 1. A diol compound (a) represented by the general formula (1): (Where a and b are numbers from 1 to 10, the average value of a + b is from 2 to 20, and R ₁ is a hydrogen atom, CH ₃ or C ₂ H ₅ ) and epichlorohydrin. Epoxy (meth) acrylate (A) obtained by reacting the epoxidized product obtained by the reaction with (meth) acrylic acid and an unsaturated group-containing compound (B) other than the component (A), and photopolymerization initiation as an optional component A resin composition containing an agent (C). 2. An epoxy (meth) acrylate (A) according to claim 1, an unsaturated group-containing compound (B) other than the component (A), and a photopolymerization initiator (C) as an optional component. Casting composition. 3. A cured product of the composition according to claim 1 or 2.