JPH03157601A - High-refractive index optical resin - Google Patents

Abstract

PURPOSE:To obtain the plastic lens for spectacles having excellent transparency and high refractive index by polymerizing or copolymerizing raw material monomers contg. the org. sulfur compd. expressed by prescribed formulas. CONSTITUTION:The raw material monomers contg. the org. sulfur compd. expressed by the formula I are polymerized or copolymerized. In the formula, R is any in formula II. In the formula II, Y and Z denote a sulfur atom or oxygen atom and n and m denote 1 to 6 integer. In the formulas, X is a halogen atom or hydrogen atom and l is 1 to 4 integer. The high-refractive index optical resin is formed by polymerizing or copolymerizing the raw material monomers contg. such org. sulfur compd. The optical resin which has the high refractive index, small optical strains, excellent optical transparency, heat resistance, solvent resistance, and impact resistance and a small sp. gr. and allows easy control at the time of cursing polymn. is obtd. in this way. The optical resin useful for lenses for spectacles and cameras and other optical materials is thus obtd.

Description

DETAILED DESCRIPTION OF THE INVENTION <Industrial Application Field> The present invention relates to a high refractive index optical resin useful for plastic lenses for eyeglasses, etc., which has excellent transparency and a high refractive index.

<Prior Art> In recent years, synthetic resin materials that are lightweight, easy to mold, have excellent impact resistance, dyeability, etc. have been used as plastic lens materials in place of inorganic glass. As the synthetic resin material, for example, polymethyl methacrylate, polydiethylene glycol bisallyl carbonate, polystyrene, and polycarbonate are known. However, although polymethyl methacrylate and polydiethylene glycol bisallyl carbonate are lightweight and have excellent impact resistance, they have a low refractive index of about 1.49, so when used as lenses, they require thicker lenses than inorganic glasses. The drawback is that it is not suitable for high magnification and weight reduction.

In the case of polystyrene and polycarbonate, the refractive index is 1.58 to J. Although it is as high as 59, since the resin is thermoplastic, there is a problem that optical distortion due to birefringence is likely to occur during injection molding, and there are other drawbacks such as a lack of solvent resistance and scratch resistance.

Therefore, in recent years, several techniques have been developed to improve these conventional drawbacks with a high refractive index. For example, in Japanese Patent Application Laid-Open No. 53-7787,
A copolymer of non-glycol biscarbonate and diallyl isophthalate is disclosed in JP-A-59-81318, and a copolymer of diallylphta-1 note and unsaturated fatty acid alcohol benzoate is disclosed in JP-A-59-1917.
No. 08 discloses di(meth) containing bisphenol A.
A copolymer of acrylate, diallylisophthale-1-, diethylene glycol bisallyl carbonate-1-, etc. is disclosed.

However, each of the above polymers has a refractive index of 1.52 to
1.56, and there is a problem that unreacted allyl monomer tends to remain.
No. 5 discloses a copolymer of a styrenic vinyl monomer and an unsaturated carboxylic acid heavy salt, as disclosed in JP-A No. 60-55007.
The publication mentions a copolymer of halogen-substituted diallyl phthalate and halogen-substituted allyl benzoate, but although these have a high refractive index of about 1.58 to 1.60, they do not contain metal salts or Since the allylic monomer having the halogen pentasubstituted aromatic ring is used, the specific gravity of the polymer is large, making the lens heavy and reducing weight reduction.

Furthermore, JP-A No. 59-133211 discloses a copolymer of halogen-substituted styrene, di(meth)acrylate containing bisphenol A, benzyl methacrylate monomer, and phenol methacrylate monomer. The publication proposes a polymer of a hydroxyl (meth)acrylate or diisocyanate compound having an aromatic ring and a styrene yarn, but in these cases, the refractive index is around 1.60. Although it is expensive, the polymerization reaction is difficult to control, the specific gravity is large, and there are problems with weather resistance.

<Problems to be Solved by the Invention> An object of the present invention is to provide a resin that has desirable optical transparency, high refractive index, and excellent weather resistance, solvent resistance, and impact resistance as a resin for plastic lenses or other optical applications. The object of the present invention is to provide a resin for optical use with a high refractive index and a low specific gravity.

According to the present invention, the following general formula (I) [wherein R is -5(CL)nS-, -5(CHa
)sY (CHZ)nS-5n and m are integers of 1 to 6). Further, there is provided a high refractive index optical resin obtained by monopolymerizing or copolymerizing a raw material monomer containing an organic sulfur compound represented by The present invention will be explained in more detail below.

The high refractive index optical resin of the present invention is characterized by containing a specific organic sulfur compound as an essential raw material, and preferably has a refractive index of 1.60 or more, particularly preferably 1.65.
It is a resin that exhibits a high refractive index as described above and also has excellent physical properties.

In the present invention, the organic sulfur compound used as an essential raw material monomer can be represented by the following general formula (I).

[In the formula, R is -5(C)1. ), S-, -5(CH,)
,Y(CH,)nS-.

(However, Y and Z are sulfur atoms or oxygen atoms.

(However, Y and Z represent a sulfur atom or an oxygen atom.

n and m each represent an integer of 1 to 6), X represents a halogen atom or a hydrogen atom, and Q represents an integer of 1 to 4. When n and/or m are 7 or more, manufacturing is difficult. Examples of the organic sulfur compound represented by the general formula (I) include 1, for example, 1.

2-bis(p-vinylbenzylthio)ethane, 1°2-
Bis(m-vinylbenzylthio)ethane, ■.

3-bis(p-vinylbenzylthio)propane, bis(
p-vinylbenzylthioethyl) sulfite, 2,5-
Bis(p-vinylbenzylthio)-1,3,4-thiadiazole, 2,5-bis(m-vinylbenzylthio)-
Preferred examples include 1,3,4-thiadiazole and 1,4-bis(p-vinylbenzylthio)benzene. The organic sulfur compound can be easily prepared by, for example, coupling an aliphatic or aromatic dithiol compound with chloromethylstyrene in an appropriate solvent. Further, the blending ratio of the organic sulfur compound to the entire raw material is not particularly limited, but preferably 1 to 98% by weight,
Particularly preferred is a range of 20 to 90% by weight. Furthermore, when an organic sulfur compound is blended in a range of 1 to 20% by weight, it can also be used as a high-performance crosslinking agent with a high refractive index.

In the present invention, as a raw material monomer other than the organic sulfur compound that can be used as a raw material component,
For example, styrene, p-methylstyrene, p-chlorostyrene, 0-chlorostyrene.

p-bromustyrene, 0-bromustyrene, vinyl acetate, vinyl propionate, butyl methacrylate, methyl (meth)acrylate, ethyl acrylate, phenyl (meth)acrylate, benzyl (meth)acrylate, bromphenyl methacrylate, (meth)acrylonitrile, 2,2-bis(4-methacryloyloxyethoxyphenyl)propane, 2,2-bis(4-acryloyloxyethoxyphenyl)propane, diethylene glycol bisallyl carbonate, diallyl tetrachlorophthalate, diallyl phthalate, P-divinylbenzene, m - Divinylbenzene, divinylbiphenyl, diethylene glycol bis(meth)acrylate, ethylene glycol bis(meth)acrylate, dipropylene glycol bismethacrylate, triethylene glycol bisacrylate, tetraethylene glycol bisacrylate, bisphenol A bismethacrylate, diallyl tetrachlorophthalate , diallyl isophthalate,
Preferred examples include allyl methacrylate, propylene glycol bisacrylate, hexaethylene glycol bisacrylate, octaethylene glycol bisacrylate, and decaneethylene glycol bisacrylate.

To prepare the high refractive index optical resin of the present invention.

For example, it can be obtained by heating or copolymerizing the organic sulfur compound or a mixture of the organic sulfur compound and the vinyl comonomer in the presence of a radical polymerization initiator. As the radical polymerization initiator, an organic peroxide or an azo compound having a 10-hour half-life temperature of 160°C or less can be used, and specifically, for example, diisopropyloxydicarbonate, tert-butylperoxy-2-ethyl Hexanoate, tert-butyl peroxybivalate, tert-butyl peroxydiisobutyrate, lauroyl peroxide, t-butyl peroxyacetate, tert-peroxyoctoate, tert-butyl peroxybenzoate, azobisisobutyronitrile and these Examples include polymerization initiators selected from the group consisting of mixtures and the like. The amount of the radical polymerization initiator used is preferably 10 parts by weight or less, particularly preferably 1 part by weight or less, based on 100 parts by weight of the total monomers charged.

To carry out the thermal polymerization or copolymerization, for example, each of the monomers and, if necessary, a radical polymerization initiator are directly charged into a desired mold, preferably at 0 to 200°C, 1 to 48°C.
Polymerization or copolymerization can be carried out by heating for a period of time. At this time, it is desirable that the polymerization system be exposed to or under an atmosphere of an inert gas such as nitrogen, carbon dioxide, or helium.

Furthermore, before the polymerization or copolymerization, the raw material monomers can be prepolymerized, for example, at 0 to 200°C for 0.5 to 48 hours, and then placed in a desired mold for post-polymerization.

<Effects of the Invention> The high refractive index optical resin of the present invention has a high refractive index, low optical distortion, and excellent optical transparency, heat resistance, solvent resistance, and LII impact resistance. Moreover, it has a small specific gravity and can be made lightweight, and it is easy to control during curing and polymerization, so it is useful as a resin material for plastic lenses such as eyeglass lenses, camera lenses, and optical materials, or for other optical resin materials. It is.

<Examples> The present invention will be explained in more detail with reference to Examples below, but the present invention is not limited thereto.

Pointed shoulder ↓ 1. Mix 0.05 g of tert-butyl peroxybenzoate to a raw material mixture consisting of 6 g of 2-bis(p-vinylbenzylthio)ethane and 6 g of ste1one,
A 100% composition was obtained. Then, the 1,000 ml composition was poured into two glass molds.

Placed in a constant temperature bath at 80℃, heated at a curing temperature of 80℃ for 6 hours, then raised to 100℃ in another 3 hours, and finally heated to 10℃.
Cured resin was obtained by annealing at 0°C for 2 hours 9
The obtained cured resin was taken out from the mold, and its refractive index, Abe's number, transparency, and heat resistance were measured according to the following methods. The results are shown in Table 1.

・Refractive index and Atsbe number: Atsbe refractometer (manufactured by Atago Co., Ltd.) ・Transparency: those that are transparent when inspected with the naked eye
Those that were slightly cloudy were rated △.

・Heat resistance...Curing resin is placed in a dry base at 130℃.

After leaving it for 2 hours, the cured resin will be deformed and The changes in coloration were investigated. The change is recognized What you can't do is 0. what is recognized I set it as X.

A cured resin was prepared in the same manner as in Example 1 except that the raw materials shown in Table 1 were used, and each measurement was performed.

The results are shown in Table 1.

le fi, 1. - Example 1 except that the vinyl monomer shown in Table 1 was used.
A cured resin was obtained in the same manner as above, and various measurements were performed.

The results are shown in Table 1.

(Margin below) A

Claims (1)

[Claims] The following general formula (I) ▲There are mathematical formulas, chemical formulas, tables, etc.▼(I) [In the formula, R is -S(CH_2)_nS-, -S(CH_
2) _mY(CH_2)_nS-, ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼, ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ or ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (However, Y and Z represent a sulfur atom or an oxygen atom, and n and m represent integers of 1 to 6). In addition, X represents a halogen atom or a hydrogen atom, and l represents an integer of 1 to 4]
A high refractive index optical resin obtained by polymerizing or copolymerizing a raw material monomer containing an organic sulfur compound represented by: