JPH05215902A - Plastic lens material - Google Patents

Abstract

PURPOSE:To obtain a lens having a high refractive index, and also, being excellent in low specific gravity, heat resistance, surface hardness and chemical resistance by allowing a resin composite consisting of a specific component to be subjected to radical polymerization hardening, and setting its refractive index to a specific value or above. CONSTITUTION:With respect to an epoxy compound shown by a formula I, and organic acid shown by a formula II, an equivalent ratio of an epoxy group of the former and a carboxyl group of the latter is allowed to react within a range of 1/0.8-1.2. Subsequently, 20-80 weight parts of an obtained methacrylate acid ester derivative, 20-80 weight parts of a compound having polymeric unsaturated double bond in a molecule, and 0.005-5 weight parts of a radical polymerization initiator to their total 100 weight parts are subjected to radical polymerization hardening. Also, the refractive index is set to >=1.58. In the formula I, X<1>-X<4> denote hydrogen, a methyl, bromine, and chlorine or iodine, respectively and (l), (m), (n) and (o) denote integer of 1-4, respectively. In the formula II, X<5> denotes hydrogen, a methyl, bromine, chlorine or iodine, (p) and (q) denote integers of 1-4, respectively, and R<1> and R<2> denote hydrogen or a methyl, respectively.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a plastic lens material having excellent heat resistance, surface hardness, chemical resistance and transparency, a high refractive index and a low specific gravity.

[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, since transparent plastics used as spectacle lenses are required to have heat resistance and chemical resistance, thermosetting of polydiethylene glycol bisallyl carbonate (CR-39) or the like rather than thermoplastics such as polymethylmethacrylate or polystyrene. Plastic was used.

However, since CR-39 has a low refractive index in recent years, many attempts have been made to develop a new transparent plastic having a high refractive index. In order to obtain a high refractive index plastic, it is common to introduce a halogen atom other than fluorine and an aromatic ring into the molecular structure. In particular, in order to obtain a high refractive index lens material having a refractive index of 1.58 or more, it is general to use a resin having an aromatic ring substituted with a halogen group other than fluorine.

[0004]

However, when a resin having an aromatic ring substituted with a halogen group is used, the specific gravity of the resin cured product becomes high, so that the lens cured product has a high refractive index and the lens thickness is reduced. Even if it became possible, there was a drawback that the effect of weight reduction would be offset. The present invention has been made against the background described above, and an object thereof is a plastic having a high refractive index of 1.58 or more and having a low specific gravity, heat resistance, surface hardness, and chemical resistance. It is to provide a material from which a lens can be obtained.

[0005]

Means for Solving the Problems As a result of intensive studies for solving the above problems, the present inventors have found that a copolymer of a radically polymerizable composition containing a specific compound as a main component can be used as a plastic lens. When applied, low specific gravity, heat resistance,
Refractive index 1.58 with excellent surface hardness, chemical resistance and transparency
The inventors have found that the above high-refraction plastic lens can be obtained, and completed the present invention.

That is, the plastic lens material of the present invention is obtained by radical polymerization curing a resin composition for plastic lenses comprising the following components (A), (B) and (C) and having a refractive index of 1. It is characterized by being 58 or more. (A) An epoxy compound represented by the following general formula (1) is added with an organic acid represented by the following general formula (2) in an equivalent amount of the former epoxy group (X) and the latter carboxyl group (Y). (Meth) acrylic acid ester derivative 20 to be obtained by reacting the ratio (X / Y) in the range of 1 / 0.8 to 1 / 1.2
80 parts by weight

[Chemical 3] (In the formula, X ¹ , X ² , X ³ and X ⁴ are each independently hydrogen,
Represents a methyl group, bromine, chlorine or iodine, l, m,
n and o each independently represent an integer of 1 to 4)

[Chemical 4] (In the formula, X ⁵ represents hydrogen, a methyl group, bromine, chlorine, or iodine, p and q each independently represent an integer of 1 to 4, and R ¹ and R ² each independently. Represents a hydrogen atom or a methyl group) (B) Compound 2 having a polymerizable unsaturated double bond in the molecule
0 to 80 parts by weight (C) at least one radical polymerization initiator 0.005
To 5 parts by weight (however, the total amount of the component (A) and the component (B) is 100 parts by weight, and the amount of the component (C) is 0.005 to 5 parts by weight based on 100 parts by weight of the total amount).

[0007]

The present invention will be described in detail below. The component (A) is an epoxy compound represented by the general formula (1), for example, 9,9-bis (4-hydroxyphenyl) fluorange glycidyl ether, and an organic acid represented by the general formula (2), for example, 2-methacryloyl. It is synthesized from oxyethylphthalic acid using a tertiary amine, a quaternary ammonium salt, and an imidazole compound as a catalyst. The component (A) is a basic component of the lens material of the present invention and is a component that imparts a high refractive index, heat resistance, surface hardness and chemical resistance to the lens.

As the component (B), any compound having at least a polymerizable unsaturated double bond in the molecule can be used. Examples of the type of polymerizable unsaturated double bond include a (meth) acryloyl group, a (meth) allyl group, and a vinyl group. From the viewpoint of solubility and dilutability, those having a low viscosity are desirable, and those having an aromatic ring in the molecule are desirable from the viewpoint of refractive index. In particular, styrene derivatives such as styrene, chlorostyrene, dichlorostyrene, bromostyrene, dibromostyrene, divinylstyrene, phenyl (meth) acrylate, benzyl (meth) acrylate,
(Meth) acrylic acid esters such as biphenyl (meth) acrylate, allyl compounds such as diallyl phthalate, dimethallyl phthalate and diallyl biphenylate are preferable. As the component (B), one type may be used alone, or several types may be used in combination.

The mixing ratio of the components (A) and (B) is
When the total amount of the component (A) and the component (B) is 100 parts by weight, the amount of the component (B) is 80 to 20 parts by weight with respect to 20 to 80 parts by weight of the component (A). When the amount of the component (A) is 80 parts by weight or more, the viscosity of the blend becomes too high and the workability deteriorates. If it is 20 parts by weight or less, the object of the invention cannot be achieved. Desirably, the total amount of component (A) and component (B) is 10
When the amount is 0 parts by weight, it is preferable to use 70 to 30 parts by weight of the component (B) with respect to 30 to 70 parts by weight of the component (A).

The radical polymerization initiator as the component (C) is not particularly limited. Heat, visible light, infrared,
Any substance capable of generating active radicals by active energy rays such as ultraviolet rays may be used. Examples of initiators (thermal polymerization initiators) that generate active radicals by heat are diisopropyl peroxydicarbonate (IPP), t-butylperoxy oxyisobutyrate, and 1,1,3,3-tetramethylperoxy-2. -Organic peroxide such as ethylhexanoate,
2,2-azobis (2,4-dimethylbarrelnitrile), azobisisobutyronitrile, etc. can be used. As an example of an initiator (photopolymerization initiator) that generates an active radical by an active energy ray, 2-hydroxy-2-
Methyl-1-phenylpropan-1-one, hydroxycyclohexylphenylketone, methylphenylglyoxylate, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, benzyldimethylketane
Can be used. The radical polymerization initiator as the component (C) may be used alone or in combination of several kinds. The amount of the component (C) used is 0.005 to 5 parts by weight based on 100 parts by weight when the total amount of the components (A) and (B) is 100 parts by weight.

The material of the present invention contains pentaethylene glycol di (meth) acrylate and nonaethylene glycol di (meth) in order to improve the impact resistance and dyeability of the plastic lens within the range not impeding the object of the present invention.
It is preferable to add an appropriate amount of an aliphatic monomer such as acrylate, nonabutylene glycol di (meth) acrylate, or diethylene glycol bisallyl carbonate. The plastic lens of the present invention may contain additives such as an antioxidant, an anti-yellowing agent, a UV inhibitor, a bluing agent, and a pigment. The curing method is to use two glass molds of the desired shape
A mold may be formed through a gasket made of polyvinyl chloride, ethylene-vinyl acetate copolymer or the like, and the composition may be injected into the mold, followed by heating, irradiation with active energy rays, or a combination thereof. ..

[0012]

EXAMPLES The present invention will be described in more detail below with reference to Examples and Comparative Examples.

Synthesis Example 1 A 2-liter 4-necked flask equipped with a stirrer and a condenser for reflux was placed in a diglycidyl ether of 9,9-bis (4-hydroxyphenyl) -fluorene (molecular weight: 462.5, epoxy equivalent: 246 g / eq, Nippon Steel Chemical Co., Ltd., trade name cardo epoxy resin ESF-300) 246 g, 2-
Methacryloyloxyethyl phthalic acid (molecular weight 278,
Kyoeisha Yushi Kagaku Kogyo Co., Ltd., trade name Light Ester H
O-MP) 278 g, benzyltrimethylammonium chloride 5.24 g, hydroquinone monomethyl ether 0.26 g, and toluene 500 g were added and stirred uniformly.

Thereafter, the reaction was carried out by heating while continuing stirring. First, 70 ℃ for 4 hours, 85 ℃ for 6 hours, 100 ℃
The reaction was carried out for 6 hours at 110 ° C. for 4 hours under reflux conditions. The progress of the reaction was carried out by measuring the acid value of the reaction solution, and the reaction was terminated when the acid value became 5 mgKOH / g or less. After completion of the reaction, toluene was removed by heating the reaction solution under reduced pressure to obtain a target methacrylic acid ester derivative.

Example 1 Methacrylic acid ester derivative 70 obtained in Synthesis Example 1
g, 30 g of styrene, and 1,1,3,3-tetramethylperoxy-2-ethylhexanoate as a catalyst.
1 g, t-butylperoxyisobutyrate 0.05 g
Was mixed to form a uniform mixture, and the mixture was depressurized to 50 mmHg and deaerated for 10 minutes.

Then, two pieces of tempered glass having a length of 100 mm, a width of 100 mm, and a thickness of 5 mm are made to face each other with a space of 2 mm, and the periphery is surrounded by a polyvinyl chloride tubular gasket into a mold. The above-mentioned compound was injected, and heated from 40 ° C. to 100 ° C. for 20 hours to be heated and cured. The cured product was demolded from the mold and heat-treated at 120 ° C. for 1 hour to remove the internal strain of the cured product to obtain a transparent flat plate. This flat plate had a visible light transmittance of 90% and a high refractive index (D-line of 589.3 mm) of 1.62. Furthermore, Tg by TMA is 160 ° C,
The chemical resistance of acetone, toluene, etc. was also excellent. The Rockwell hardness was HRM120 and the specific gravity was 1.23.

Example 2 Methacrylic acid ester derivative 50 obtained in Synthesis Example 1
g, biphenyl methacrylate 20 g, styrene 30
g, as a catalyst, 0.1 g of 1,1,3,3-tetramethylpa-oxy-2-ethylhexanoate and 0.05 g of t-butylpa-oxyisobutyrate were mixed and stirred at room temperature to form a uniform mixture. Then, reduce the pressure to 50 mmHg and
Degas for 0 minutes. Then, the mixture was poured into the same mold as that used in Example 1 and heated from 40 ° C. to 100 ° C. for 20 hours to be heated and cured. The cured product was demolded from the mold and heat-treated at 120 ° C. for 1 hour to remove the internal strain of the cured product to obtain a transparent flat plate. This flat plate had a visible light transmittance of 90% and a refractive index (D-line of 589.3 mm) of 1.
It was 60. The Tg by TMA was 140 ° C, and the chemical resistance of acetone, toluene and the like was also excellent. further,
The cured product had a Rockwell hardness of HRM110 and a specific gravity of 1.24.

Example 3 Methacrylic acid ester derivative 30 obtained in Synthesis Example 1
g, biphenyl methacrylate 30 g, styrene 40
g, as a catalyst, 0.1 g of 1,1,3,3-tetramethylpa-oxy-2-ethylhexanoate and 0.05 g of t-butylpa-oxyisobutyrate were mixed and stirred at room temperature to form a uniform mixture. Then, reduce the pressure to 50 mmHg and
Degas for 0 minutes. Then, the mixture was poured into the same mold as that used in Example 1 and heated from 40 ° C. to 100 ° C. for 20 hours to be heated and cured. The cured product was demolded from the mold and heat-treated at 120 ° C. for 1 hour to remove the internal strain of the cured product to obtain a transparent flat plate. This flat plate had a visible light transmittance of 89% and a refractive index (589.3 mm D-line) of 1.
It was 61. Rockwell hardness is HRM100, TM
The Tg according to A was 115 ° C., and the chemical resistance of acetone, toluene and the like was excellent. Furthermore, the specific gravity of the cured product was 1.22.

Comparative Example 1 Diethylene glycol bisallyl carbonate 100
g, diisopropyl peroxydica carbonate 2.5 g
After stirring well at room temperature to make a uniform mixture, 50 mmH
The pressure was reduced to g and the mixture was degassed for 10 minutes. Then, it was poured into the mold used in Example 1 and held at 40 ° C. for 10 hours, 60 ° C. for 5 hours, and 90 ° C. for 5 hours to be cured. After demolding, 10
It heat-processed at 0 degreeC for 1 hour. This flat plate had a visible light transmittance of 92% and a refractive index (589.3 mm D line) of 1.499. Furthermore, Tg by TMA is 80
It was ℃. The Rockwell hardness was HRM95 and the specific gravity was 1.32.

Synthesis Example 2 Tetrabrom bisphenol A diglycidyl ether was placed in a 1 liter 4-necked flask equipped with a stirrer and a reflux condenser.
Tell (epoxy equivalent 340 g / eq, manufactured by Tohto Kasei Co., Ltd., trade name YDB-340) 340 g, methacrylic acid (molecular weight 86.1 g, manufactured by Mitsubishi Rayon Co., Ltd.) 86.
1 g, benzyltrimethylammonium chloride 4.
26 g and hydroquinone monomethyl ether 0.21 g were put and stirred to obtain a uniform solution. Then, while continuing stirring, the reaction was carried out at 70 ° C. for 4 hours, 85 ° C. for 4 hours, 100 ° C. for 2 hours, and about 110 ° C. for 4 hours to obtain the desired epoxy methacrylate. The progress of the reaction was carried out by measuring the acid value of the reaction solution, and when the acid value was 1 mgKOH / g or less, it was regarded as the end point of the reaction.

Comparative Example 2 60 g of the epoxy methacrylate obtained in Synthesis Example 2, 40 g of styrene, 0.1 g of 1,1,3,3-tetramethylperoxy-2-ethylhexanoate as a catalyst,
After mixing 0.05 g of t-butylperoxyisobutyrate to form a uniform mixture, the pressure was reduced to 50 mmHg and the pressure was adjusted to 10
Deaerated for a minute.

Then, the mixture was poured into the same mold used in Example 1 and heated from 40 ° C. to 100 ° C. for 20 hours to be heated and cured. The cured product is demolded from the mold and heat-treated at 120 ° C. for 1 hour to remove the internal strain of the cured product,
A transparent plate was obtained. This flat plate has a visible light transmittance of 89.
%, And the refractive index (589.3 mm D line) is 1.59.
It was 9. Furthermore, Tg by TMA was 130 ° C. Rockwell hardness is HRM110 and specific gravity is 1.
It was as high as 40.

[0023]

As demonstrated in the above examples, the plastic lens material of the present invention can provide a low specific gravity plastic lens having a high refractive index of 1.58 or more. Further, it has excellent heat resistance, surface hardness and chemical resistance.

Claims (1)

[Claims] 1. A refractive index of 1.58 or more, which is obtained by radical polymerization curing of a resin composition for plastics lens comprising the following components (A), (B) and (C). Plastsch cleanse material. (A) An epoxy compound represented by the following general formula (1) is added with an organic acid represented by the following general formula (2) in an equivalent amount of the former epoxy group (X) and the latter carboxyl group (Y). (Meth) acrylic acid ester derivative 20 to be obtained by reacting the ratio (X / Y) in the range of 1 / 0.8 to 1 / 1.2
80 parts by weight (In the formula, X ¹ , X ² , X ³ and X ⁴ are each independently hydrogen,
Represents a methyl group, bromine, chlorine or iodine, l, m,
n and o each independently represent an integer of 1 to 4) (In the formula, X ⁵ represents hydrogen, a methyl group, bromine, chlorine, or iodine, p and q each independently represent an integer of 1 to 4, and R ¹ and R ² each independently. Represents a hydrogen atom or a methyl group) (B) Compound 2 having a polymerizable unsaturated double bond in the molecule
0 to 80 parts by weight (C) at least one radical polymerization initiator 0.005
To 5 parts by weight (however, the total amount of the component (A) and the component (B) is 100 parts by weight, and the amount of the component (C) is 0.005 to 5 parts by weight based on 100 parts by weight of the total amount).