JP2000327754A - Synthetic resin-made lens - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a synthetic resin-made lens having a high refractivity and a low density, excellent in optical properties such as dyeability and shock resistance, and easy in handleability due to a one-pack type raw material by copolymerizing a composition consisting of a (bromine-substituted) bisphenol A-type epoxy resin, a bifunctional thiol and the like, and a monomer copolymerizable with these compounds. SOLUTION: This lens having a reflectivity of 1.60 or more is obtained by copolymerizing a composition consisting of (A) 5-60 wt.% of one or both 5 a bisphenol A-type epoxy resin of formula (X is Br or H; and (n) is 0, 1, 2...) and a bromine-substituted bisphenol A-type epoxy resin, (B) 5-60 wt.% of a bi- or more functional thiol (e.g. ethylene glycol bisthioglycolate), (C) 10-90 wt.% of a bi- or more functional compound having acrylic groups, methacrylic groups or vinyl groups (e.g. trivinylbenzene) and (D) 0-40 wt.% of a monomer copolymerizable with these compounds.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a synthetic resin lens, and more particularly, to a synthetic resin lens made of a copolymer having good optical and mechanical properties.

[0002]

2. Description of the Related Art Conventionally, various inorganic glasses and synthetic resins have been used as optical lens materials. Various physical properties are required for optical lens materials. For example, in the field of spectacle lenses, high refractive index, high Abbe number, and low specific gravity are extremely important. In other words, if the lens used has a high refractive index and a low specific gravity, the lens can be made thinner and lighter, and if the lens has a high Abbe number, light dispersion is small and a comfortable wearing feeling can be obtained. That's why.

[0003] Therefore, the refractive index of eyeglass lens materials tends to increase year by year, and the tendency is particularly remarkable in synthetic resin lenses which are extremely light in weight as compared with inorganic glass.

In the field of spectacle lenses, as a material of a synthetic resin lens, there is a material called "CR-39" made from diethylene glycol bisallyl carbonate as a typical example at the beginning. However,
Since this material has a refractive index of about 1.50, the entire lens becomes thick, and is not satisfactory as an eyeglass lens. On the other hand, as a synthetic resin lens material having a high refractive index, a urethane resin material obtained by thermally polymerizing a thiol and an isocyanate (JP-A-2-27085)
No. 9), a material obtained by preparing a prepolymerized product (prepolymer) of a thiol and a vinyl monomer (Japanese Unexamined Patent Publication No.
-57831) and the like. actually,
Some synthetic resin lenses obtained by polymerizing these materials have achieved a refractive index of 1.60 or more.

[0005]

However, the material obtained by urethane polymerization of thiol and isocyanate is a synthetic resin obtained by a urethane reaction, and has a high refractive index and a high refractive index.
Although a lens having a high Abbe number and excellent impact resistance can be obtained, there are problems such as inconvenience of handling with a two-pack type, generation of an odor during lens processing, and low dyeability. In addition, a material obtained by preparing a prepolymerized product (prepolymer) of a thiol and a vinyl monomer has a problem that a complicated prepolymerization step is required, so that the operation steps are complicated.

As described above, conventional synthetic resin lens materials which have achieved a high refractive index have a problem in properties such as dyeability, or have problems in simplicity of handling and working steps. It is.

Accordingly, an object of the present invention is to provide a synthetic composition which has a high refractive index and a low specific gravity, has good optical properties such as dyeability and impact resistance, and is easy to handle with a one-pack raw material. An object of the present invention is to provide a resin lens.

[0008]

According to the present invention, the structural formula (1)
An epoxy reaction product of one or both of a bisphenol A type epoxy resin and a brominated bisphenol A type epoxy resin, and a thiol having two or more functional groups represented by
By copolymerizing with a radically polymerizable composition comprising a monomer copolymerizable with this reaction product, a synthetic resin lens that solves the above problem can be obtained. That is, one or both of a bisphenol A type epoxy resin and a brominated bisphenol A type epoxy resin represented by the following structural formula (1) is 5 to 60% by weight, and a bifunctional or higher thiol is 5 to 60% by weight, It is obtained by copolymerizing a composition comprising 10 to 90% by weight of a compound having a functional or higher acrylic group, methacryl group, or vinyl group, and 0 to 40% by weight of a monomer copolymerizable therewith. Which has a refractive index of 1.60 or more. In addition, the material has good dyeing properties and impact resistance, and has the effect of being a one-pack material that is easy to handle.

[0009]

Embedded image

[0010]

DETAILED DESCRIPTION OF THE INVENTION The present invention comprises a bisphenol A type epoxy resin and / or a brominated bisphenol A type epoxy resin represented by the structural formula (1) as an essential component, It is characterized by containing a reaction product obtained by an epoxy ring-opening reaction as a main component.

In the present invention, the bisphenol A type epoxy resin and / or the brominated bisphenol A type epoxy resin may be contained in an amount of 5 to 60% by weight, preferably 10 to 50% by weight.
Must be included. If the bisphenol A type epoxy resin and / or the bromine substituted bisphenol A type epoxy resin is less than 5% by weight, it becomes difficult to achieve the high refractive index characteristic of the present invention,
This is because, when the value exceeds 1, it becomes difficult to have sufficient mechanical strength as an optical lens.

The content of the thiol having two or more functional groups is
It is determined by the content of the bisphenol A epoxy resin and / or the brominated bisphenol A epoxy resin. That is, when the number of SH groups in the bifunctional or higher thiol is smaller than the number of epoxy groups in the bisphenol A type epoxy resin and / or the brominated bisphenol A type epoxy resin, radical polymerization becomes impossible. Needs to be adjusted so as to be more than epoxy groups. Therefore, bifunctional or higher thiol is 5
Epoxide group of bisphenol A type epoxy resin and / or bromine-substituted bisphenol A type epoxy resin: SH group of thiol having two or more functional groups = 10: 90 to 5% by weight.
0:50, preferably 20:80 to 40:60.
This is because when the content of the bifunctional or higher thiol is less than 5% by weight or the epoxy group / SH group is less than 10/90, the content of the bisphenol A type epoxy resin and / or the bromine substituted bisphenol A type epoxy resin is relatively high. This is because it is difficult to achieve the high refractive index, which is a feature of the present invention, because the amount is low, and the thiol having two or more functional groups exceeds 60% by weight, or the epoxy group / SH group = 50.
If it exceeds / 50, it is difficult to have sufficient mechanical strength as an optical lens.

At this time, examples of the bifunctional or higher functional thiol to be reacted with the bisphenol A type epoxy resin and / or the brominated bisphenol A type epoxy resin include:
Ethylene glycol bisthioglycolate (EGT
G), bifunctional sulfur compounds such as thiodietanthiol (DMDS), trifunctional sulfur compounds such as trimethylolpropane tristhioglycolate (TMTG) and trimethylolpropane tristhiopropionate (TMTP), and pentaerythritol tetrakisthio Examples include, but are not limited to, tetrafunctional sulfur compounds such as glyconate (PETG) and pentaerythritol tetrakisthiopropionate (PETP).

For the epoxy ring-opening reaction at this time, a known epoxy ring-opening reaction technique can be applied. That is, it is preferable to carry out the reaction at room temperature or in a heated state after adding a catalyst such as a tertiary amine or a secondary amine.

In the present invention, in order to form the above reaction product into a radically polymerizable form, a compound having a bifunctional or higher functional acryl group, methacryl group, or vinyl group is added in an amount of 10 to 90% by weight, preferably Is 20-80% by weight
Must be included. When the amount of the compound having a bifunctional or higher functional acryl group, methacryl group, or vinyl group is less than 10% by weight, it is difficult to have sufficient mechanical strength as an optical lens. This is because it becomes difficult to achieve a high refractive index, which is a feature of the present invention.

A bifunctional or higher functional acryl group, methacryl group,
Examples of the compound having a vinyl group include polyfunctional acrylates such as neopentyl glycol diacrylate (NPG), polyethylene glycol diacrylate (A-400), and tetramethylol methane triacrylate (TMM-3); , 3-Dimethacrylate (701), 2,2-bis (4-methacryloxypolyethoxyphenyl) propane (BPE-500),
Trimethylolpropane trimethacrylate (TMP
T) and other polyfunctional methacrylates, divinylnaphthalene (DVN), divinylbenzene (DVB), trivinylbenzene (TVB) and other polyfunctional vinyl monomers, and the like, but are not limited thereto.

In the present invention, in addition to the above-mentioned components, a monomer copolymerizable with those components can be added if necessary. However, if the amount exceeds 40% by weight, it becomes difficult to obtain sufficient heat resistance as an optical lens. Therefore, the range of 0 to 40% by weight is preferable.

The monomer at this time may be any as long as it can be copolymerized with the above components. However, in order not to impair the high refractive index characteristic of the present invention, the monomer may be used. It is desirable that the material itself has a high refractive index. Examples include styrene (St), α-methylstyrene dimer (MS
D), benzyl methacrylate (BzMA), 2-phenylphenol polyethoxy acrylate (OPP-
1) and the like, but are not limited thereto.

The thiol, unsaturated ester, and unsaturated vinyl compound introduced at this time need not necessarily be one kind each. That is, several types of thiols, unsaturated esters, and unsaturated vinyl compounds can be introduced in order to impart various properties to the obtained copolymer.

The synthetic resin lens of the present invention can be obtained by subjecting the composition obtained as described above to radical polymerization, and by appropriately combining the ratios of the above components, the viscosity of the composition can be sufficiently increased. By lowering it, it is possible to make the fluidity sufficiently high. Therefore, for example, it can be executed collectively in a casting container, and can be manufactured easily and at low cost.

As a casting polymerization method or a casting reaction method using a casting container, a well-known technique can be used. As the casting container, a plate-shaped, lens-shaped, cylindrical-shaped, etc. A mold or a mold frame designed according to the above can be used, and any material such as inorganic glass, plastic, and metal can be used.

For radical polymerization, a known radical polymerization technique can be applied. That is, peroxide-based,
It is preferable to add a radical polymerization initiator such as an azo compound, and perform radical polymerization at room temperature or in a heated state.

The mixture of the components may contain a coloring agent, an ultraviolet absorber, a heat stabilizer, and other auxiliary materials, if necessary. Further, a hard coat agent, a non-reflective coat, and other surface coats can be applied to the surface of the obtained copolymer.

The synthetic resin lens of the present invention is characterized in that it is a copolymer as described above. Therefore, in addition to the casting polymerization method, the lens made of a plate material or other copolymer is first cut off. It can also be manufactured by the method of dispensing.

[0025]

EXAMPLES The present invention will be described in more detail with reference to the following Examples, but it should not be construed that the invention is limited thereto. In addition,
The evaluation methods of the obtained physical properties are as follows.

A test piece having a refractive index of 10 mm × 20 mm × 3 mm was prepared, and the refractive index at room temperature (20 ° C.) was measured using “Abe Refractometer 1T” manufactured by Atago, using α-bromonaphthalene as a contact liquid. It was measured.

Abbe Number The Abbe number was measured by the same measuring device and measuring method as used in the above-mentioned refractive index measurement.

A test piece having a specific gravity of 10 mm × 20 mm × 3 mm was prepared, and the specific gravity at room temperature (20 ° C.) was measured using “SGM-6” manufactured by METTLER TOLEDO.

Stainability A dye solution is prepared by mixing 1 g each of Seiko Plux Brown manufactured by Hattori Seiko Co., Ltd. and 1000 g of pure water, and the obtained lens is immersed in the dye solution at 92 ° C. for 10 minutes. The dye was stained by the method, and the total light transmittance was measured using an ultraviolet-visible spectrophotometer “UV-2200” manufactured by Shimadzu Corporation. .

Impact Resistance Ten test samples having a diameter of 78 mm, a radius of curvature of 0.1 m, and a center thickness of 2 mm were prepared, and steel balls weighing 16.2 g (diameter 10/16 inch) were weighed 1.27 m. In accordance with the FDA falling ball impact strength standard, the sample was determined to be good if none of the ten samples were broken, and was judged to be defective if one of the samples was broken.

Example 1 Bromine-substituted bisphenol A type epoxy resin (EPO) 4
0 g, divinylbenzene (DVB) 32 g, ethylene glycol bisthioglycolate (EGTG) 28 g
Measure into a 00 ml Erlenmeyer flask and add triethylamine 1
g and a stirrer were added and the mixture was stoppered, followed by stirring at 60 ° C. for 3 hours to carry out an epoxy ring-opening reaction. After cooling to room temperature, 0.1 g of a radical polymerization initiator 2,2-azobis (2,4-dimethylvaleronitrile) was added, and the mixture was poured into a casting mold composed of two glass plates and a gasket to conduct polymerization. Was done. Polymerization is performed in a hot air circulating furnace for 4 hours.
The temperature was gradually raised from 5 ° C to 100 ° C over 10 hours,
After maintaining at 00 ° C for 2 hours, it was gradually cooled to 65 ° C. Thereafter, the copolymer was taken out of the casting mold to obtain a finished product.

As a result, a good copolymer having the following physical properties could be obtained.

Composition Physical properties EPO: 40 Refractive index: 1.612 DVB: 32 Abbe number: 32.2 EGTG: 28 Specific gravity: 1.410 Dyeing property: Good Epoxy group: SH group = 28: 72 Impact resistance: Good

Example 2 Bromine-substituted bisphenol A type epoxy resin (EPO) 3
0 g, divinylbenzene (DVB) 50 g, ethylene glycol bisthioglycolate (EGTG) 20 g
Measure into a 00 ml Erlenmeyer flask and add triethylamine 1
g and a stirrer were added and the mixture was stoppered, followed by stirring at 60 ° C. for 3 hours to carry out an epoxy ring-opening reaction. After cooling to room temperature, 0.1 g of a radical polymerization initiator 2,2-azobis (2,4-dimethylvaleronitrile) was added, and the mixture was poured into a casting mold composed of two glass plates and a gasket to conduct polymerization. Was done. Polymerization is performed in a hot air circulating furnace for 4 hours.
The temperature was gradually raised from 5 ° C to 100 ° C over 10 hours,
After maintaining at 00 ° C for 2 hours, it was gradually cooled to 65 ° C. Thereafter, the copolymer was taken out of the casting mold to obtain a finished product.

As a result, a good copolymer having the following physical properties could be obtained.

Composition Physical properties EPO: 30 Refractive index: 1.618 DVB: 50 Abbe number: 31.4 EGTG: 20 Specific gravity: 1.340 Dyeing property: Good Epoxy group: SH group = 28: 72 Impact resistance: Good

Example 3 Bromine-substituted bisphenol A type epoxy resin (EPO) 2
2 g, 43 g of divinylbenzene (DVB), 15 g of ethylene glycol bisthioglycolate (EGTG) and 20 g of styrene (St) were measured in a 200 ml Erlenmeyer flask, and 1 g of triethylamine and a stirrer were added. The epoxy ring-opening reaction was performed by stirring for 3 hours. After cooling to room temperature, 0.1 g of a radical polymerization initiator 2,2-azobis (2,4-dimethylvaleronitrile) was added, and the mixture was poured into a casting mold composed of two glass plates and a gasket to conduct polymerization. Was done. In the polymerization, the temperature was gradually raised from 45 ° C. to 100 ° C. over 10 hours in a hot air circulating furnace, and the temperature was maintained at 100 ° C. for 2 hours.
Cooled slowly to 5 ° C. Thereafter, the copolymer was taken out of the casting mold to obtain a finished product.

As a result, a good copolymer having the following physical properties could be obtained.

Composition Physical properties EPO: 22 Refractive index: 1.602 DVB: 43 Abbe number: 29.2 EGTG: 15 Specific gravity: 1.292 St: 20 Dyeing property: Good Impact resistance: Good Epoxy group: SH group = 28 : 72

Example 4 Bromine-substituted bisphenol A type epoxy resin (EPO) 1
5 g, divinylbenzene (DVB) 50 g, trimethylolpropane tristhioglycolate (TMTG) 10
g, 25 g of 2,2-bis (4-methacryloxypolyethoxyphenyl) propane (BPE-500) for 200 m
The mixture was weighed and placed in an Erlenmeyer flask, 1 g of triethylamine and a stirrer were added and the mixture was stoppered, followed by stirring at 60 ° C. for 3 hours to carry out an epoxy ring-opening reaction. Thereafter, the mixture was cooled to room temperature, and 0.1 g of 2,2-azobis (2,4-dimethylvaleronitrile) as a radical polymerization initiator was added.
The polymerization was carried out by pouring into a casting mold composed of two glass plates and a gasket. Polymerization is performed at 45 ° C in a hot air circulation furnace.
From 100 to 100 ° C over 10 hours.
After holding at 2 ° C. for 2 hours, the mixture was gradually cooled to 65 ° C. Thereafter, the copolymer was taken out of the casting mold to obtain a finished product.

As a result, a good copolymer having the following physical properties could be obtained.

Composition Physical properties EPO: 15 Refractive index: 1.602 DVB: 50 Abbe number: 28.8 TMTG: 10 Specific gravity: 1.236 BPE-500: 25 Dyeing property: Good Impact resistance: Good Epoxy group: SH group = 29: 71

Example 5 Bisphenol A type epoxy resin (EPO2) 25 g,
200 g of 50 g of divinylbenzene (DVB) and 25 g of ethylene glycol bisthioglycolate (EGTG)
The mixture was weighed and placed in an Erlenmeyer flask, 1 g of triethylamine and a stirrer were added and the mixture was stoppered, followed by stirring at 60 ° C. for 3 hours to carry out an epoxy ring-opening reaction. Thereafter, the mixture was cooled to room temperature, and 0.1 g of 2,2-azobis (2,4-dimethylvaleronitrile) as a radical polymerization initiator was added.
The polymerization was carried out by pouring into a casting mold composed of two glass plates and a gasket. Polymerization is performed at 45 ° C in a hot air circulation furnace.
From 100 to 100 ° C over 10 hours.
After holding at 2 ° C. for 2 hours, the mixture was gradually cooled to 65 ° C. Thereafter, the copolymer was taken out of the casting mold to obtain a finished product.

As a result, a good copolymer having the following physical properties could be obtained.

Composition Physical properties EPO2: 25 Refractive index: 1.603 DVB: 50 Abbe number: 34.2 EGTG: 25 Specific gravity: 1.208 Dyeing property: Good Epoxy group: SH group = 36: 64 Impact resistance: Good

Comparative Example 1 As a comparative example, copolymerization was carried out under the conditions that the content of the bromine-substituted bisphenol A type epoxy resin and the bifunctional or higher functional sulfur compound was less than 5% by weight.

4 g of a brominated bisphenol A type epoxy resin (EPO), 46 g of divinylbenzene (DVB),
Ethylene glycol bisthioglycolate (EGTG)
4 g and 46 g of 2,2-bis (4-methacryloxypolyethoxyphenyl) propane (BPE-500)
The mixture was weighed and placed in a ml Erlenmeyer flask, 1 g of triethylamine and a stirrer were added and the mixture was stoppered, followed by stirring at 60 ° C. for 3 hours to carry out an epoxy ring-opening reaction. Thereafter, the mixture was cooled to room temperature, and 0.1 g of 2,2-azobis (2,4-dimethylvaleronitrile) as a radical polymerization initiator was added.
The polymerization was carried out by pouring into a casting mold composed of two glass plates and a gasket. Polymerization is performed at 45 ° C in a hot air circulation furnace.
From 100 to 100 ° C over 10 hours.
After holding at 2 ° C. for 2 hours, the mixture was gradually cooled to 65 ° C. Thereafter, the copolymer was taken out of the casting mold to obtain a finished product.

As a result, a copolymer having the following physical properties was obtained, but not only the refractive index was less than 1.60, but also two out of ten pieces were found to be damaged in the falling ball impact test. As a result, problems were found in the refractive index and impact resistance.

Composition Physical properties EPO: 4 Refractive index: 1.588 DVB: 46 Abbe number: 36.8 EGTG: 4 Specific gravity: 1.198 BPE-500: 46 Dyeing property: Good Impact resistance: Poor Epoxy group: SH group = 21: 79

Comparative Example 2 As a comparative example, copolymerization was carried out under the condition that the bromine-substituted bisphenol A type epoxy resin was used in an amount exceeding 60% by weight.

62 g of brominated bisphenol A type epoxy resin (EPO), 22 of divinylbenzene (DVB)
g, thiodietanthiol (DMDS) 16 g to 200
The mixture was weighed and placed in a ml Erlenmeyer flask, 1 g of triethylamine and a stirrer were added and the mixture was stoppered, followed by stirring at 60 ° C. for 3 hours to carry out an epoxy ring-opening reaction. Thereafter, the mixture was cooled to room temperature, and 0.1 g of 2,2-azobis (2,4-dimethylvaleronitrile) as a radical polymerization initiator was added.
The polymerization was carried out by pouring into a casting mold composed of two glass plates and a gasket. Polymerization is performed at 45 ° C in a hot air circulation furnace.
From 100 to 100 ° C over 10 hours.
After holding at 2 ° C. for 2 hours, the mixture was gradually cooled to 65 ° C. Thereafter, the copolymer was taken out of the casting mold to obtain a finished product.

As a result, the obtained copolymer was insufficient in mechanical strength as it was soft even at room temperature, and the refractive index and other physical properties could not be measured.

Composition Physical properties EPO: 62 (not measurable) DVB: 22 DMDS: 16 Epoxy group: SH group = 43: 57

Comparative Example 3 As a comparative example, copolymerization was carried out under the condition that styrene, which is a radically polymerizable monofunctional vinyl compound, was used in an amount exceeding 40% by weight instead of divinylbenzene, which is a bifunctional vinyl compound. .

30 g of bromine-substituted bisphenol A type epoxy resin (EPO), 20 g of ethylene glycol bisthioglycolate (EGTG) and 50 g of styrene (St) were measured in a 200 ml Erlenmeyer flask, and 1 g of triethylamine and a stirrer were added thereto, and stoppered. Then, stirring was performed at 60 ° C. for 3 hours to carry out an epoxy ring-opening reaction. After cooling to room temperature, 0.1 g of a radical polymerization initiator 2,2-azobis (2,4-dimethylvaleronitrile) was added, and the mixture was poured into a casting mold composed of two glass plates and a gasket to conduct polymerization. Was done. Polymerization is performed in a hot air circulating furnace for 4 hours.
The temperature was gradually raised from 5 ° C to 100 ° C over 10 hours,
After maintaining at 00 ° C for 2 hours, it was gradually cooled to 65 ° C. Thereafter, the copolymer was taken out of the casting mold to obtain a finished product.

As a result, the obtained copolymer was insufficient in mechanical strength as it was soft even at room temperature, and the refractive index and other physical properties could not be measured.

Composition Physical properties EPO: 30 (not measurable) EGTG: 20 St: 50 Epoxy group: SH group = 29: 71

(List of Substances Used in Examples and Comparative Examples) EPO: bromine-substituted bisphenol A epoxy resin (described in structural formula 1, n = 0, X = Br is used in this example) EPO2: bisphenol A DVB: divinylbenzene BPE-500: 2,2-bis (4-methacryloxypolyethoxyphenyl) propane EGTG: ethylene Glycol bisthioglycolate TMTG: trimethylolpropane tristhioglycolate DMDS: thiodietanthiol St: styrene

[0059]

As described above, the synthetic resin lens of the present invention has 1.60.
In addition to enabling the above high refractive index, it has also become possible to solve the problem of inconvenient work steps and handling. Therefore, it is possible to easily obtain a synthetic resin lens having a high refractive index.

 ────────────────────────────────────────────────── ─── Continued on the front page (72) Inventor Kenji Uno 2- 40-2 Hongo, Bunkyo-ku, Tokyo F-term in the seed company (reference) 4J036 AA05 AD05 AD08 CA30 CC01 CD01 CD03 JA15

Claims (2)

[Claims] 1. A bisphenol A type epoxy resin and a brominated bisphenol A type epoxy resin represented by the following structural formula (1):
5 to 60% by weight of a bifunctional or higher functional thiol, 10 to 90% by weight of a compound having a bifunctional or higher functional acryl group, methacryl group or vinyl group, and a monomer 0 to 40 copolymerizable therewith. It is a copolymer obtained by copolymerizing a composition consisting of 1% by weight, and has a refractive index of 1.
A synthetic resin lens having a size of 60 or more. Embedded image 2. The ratio of one or both of the epoxy group of the bisphenol A type epoxy resin and the bromine-substituted bisphenol A type epoxy resin to the SH group of the bifunctional or higher thiol is from 10:90 to 50:50. Claim 1
The synthetic resin lens according to the above.