JPH04294301A - High-refractive index resin molded body - Google Patents

Abstract

PURPOSE:To obtain a plastic lens which produces neither bad odor nor anomalous odor during machining or polishing by incorporating a specified perfume into a specified highrefractive index resin. CONSTITUTION:A six-member ring ether compd. is incorporated as a perfume by 0.01-3.0wt.% into a copolymer of thiocarboxylic acid ester compd. expressed by the formula and monomers having two or more polymerizable groups which can make copolymers with atom or methyl group, R2 and R3 are same or different hydrogen atoms or alkyl groups, R4 is substd. or unsubstd. benzyl group, and m is >1 integer. When this resin compsn. is used for a plastic lens, it is preferable to add 20-500 pts.wt. of copolymerizable monomers to 100 pts.wt. of thiocarboxylic acid ester compd., e.g. benzyl thioethyl thiomethacrylate. It is especially preferable to use 1.8-cineole as the six-member ring ether compd. If the amt. of the perfume exceeds 3.0wt.%, the aroma becomes too severe, while if the amt. is <=0.01wt.%, bad odor or anomalous odor generates.

Description

[Detailed description of the invention]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a high refractive index resin molded body that is suitable for use in plastic lenses that prevents the generation of bad or unusual odors during cutting and polishing.

0002

BACKGROUND OF THE INVENTION In recent years, various studies have been conducted on synthetic resins with excellent optical properties to replace inorganic glass, and synthetic resins with excellent physical properties have been developed. In particular, plastic lenses for eyeglasses are being made to have a high refractive index by containing halogen atoms, sulfur atoms, and phosphorus atoms. Odors during polishing became a problem. In particular, the odor produced during cutting and polishing of resins containing sulfur atoms is a uniquely nauseating odor, and countermeasures are therefore needed. Specifically, it is possible to improve exhaust equipment and wear protective masks, but the former has the drawback of increasing costs and the latter of worsening workability.

0003

SUMMARY OF THE INVENTION An object of the present invention is to provide a high refractive index resin molded body that does not emit bad or unusual odors during cutting and polishing.

0004

[Means for Solving the Problems] As a result of various studies carried out by the present inventors in order to achieve the above object, by incorporating a specific fragrance into a specific high refractive index resin, it is possible to It was discovered that malodors and foreign odors can be completely masked, leading to the present invention.

That is, the present invention is based on the general formula [1] (where R1
is a hydrogen atom or a methyl group, R2 and R3 are the same or different hydrogen atoms or alkyl groups, respectively, and R
4 is a substituted or unsubstituted benzyl group, m is 1
is an integer greater than or equal to ) and a copolymer of a monomer having two or more polymerizable groups copolymerizable with the thiocarboxylic acid ester compound shown in ), containing 0.01 to 3.0% by weight of a 6-membered ring ether compound as a fragrance. It is a high refractive index resin molded body characterized by being made of

In the general formula [1], R2 and R3 may be the same or different hydrogen atoms or alkyl groups, respectively. As the alkyl group, an alkyl group having 1 to 4 carbon atoms such as a methyl group, an ethyl group, and a propyl group is suitable, but from the viewpoint of using the copolymer obtained by polymerization in plastic lenses, R2 and R3 is preferably a hydrogen atom or a methyl group.

In the general formula [1], R4 is a substituted or unsubstituted benzyl group. As the substituent for the benzyl group represented by R4 above, a halogen atom, particularly a chlorine atom and a bromine atom, is preferable. Furthermore, in the above general formula [1], m may be an integer of 1 or more. Generally, the larger the value of m, the higher the content of sulfur atoms per molecule, and therefore the refractive index of the resin obtained by polymerization increases and the impact resistance also improves. However, if m is made too large, a problem arises in that the heat resistance of the resin obtained by polymerization is impaired. Therefore, in consideration of the refractive index, impact resistance, and heat resistance of the resulting resin, m is preferably selected in the range of 1 to 5, particularly in the range of 1 to 3.

In the present invention, known monomers having two or more polymerizable groups copolymerizable with the thiocarboxylic acid ester compound represented by the general formula [1] can be used without any particular restriction. Typical examples are ethylene glycol diacrylate, diethylene glycol dimethacrylate, ethylene glycol bisglycidyl methacrylate, bisphenol A dimethacrylate, 2,2,6,6-tetrabromobisphenol A dimethacrylate, 2,2- Bis(4-methacryloyloxyethoxyphenyl)propane, 2,2-bis(3,5
Acrylic acid and methacrylic acid ester compounds such as -dibromo-4-methacryloyloxyethoxyphenyl)propane; diallyl phthalate, diallyl terephthalate, diallyl isophthalate, diallyl tartrate, diallyl epoxysuccinate, diallyl maleate, diallyl chlorendate, diallyl hexaphthalate , diallyl carbonate, allyl compounds such as allyl diglycol carbonate, urethane oligomers having two or more (meth)acrylate groups, divinylbenzene, and the like. These monomers can be used alone or in combination of two or more.

In the present invention, the mixing ratio of the thiocarboxylic acid ester compound represented by the general formula [1] and the above-mentioned monomer having two or more copolymerizable polymerizable groups varies depending on the use of the resulting resin, but When used as a lens, the amount of the copolymerizable monomer is preferably 20 to 500 parts by weight per 100 parts by weight of the thiocarboxylic acid ester.
The amount of the copolymerizable monomer per part by weight is more preferably 20 to 200 parts by weight.

Furthermore, in the present invention, unsaturated carboxylic acids such as acrylic acid, methacrylic acid, maleic anhydride, and fumaric acid; methyl acrylate, methyl methacrylate, benzyl methacrylate, phenyl methacrylate,
- Acrylic acid and methacrylic acid ester compounds such as hydroxyethyl methacrylate and trifluoromethyl methacrylate; monomethyl fumarate, diethyl fumarate,
Mixtures of fumaric acid ester compounds such as diphenyl fumarate; allyl compounds such as allyl cinnamate and allyl isocyanate; aromatic vinyl compounds such as styrene, chlorostyrene, methylstyrene, vinylnaphthalene, isopropenylnaphthalene, bromostyrene, dibromostyrene, etc. It can also be used as

In the present invention, the polymerization method for obtaining the polymer is not particularly limited, and any known radical polymerization method can be employed. Polymerization initiation means include the use of radical polymerization initiators such as various peroxides and azo compounds, or ultraviolet rays, alpha rays, beta rays,
This can be carried out by irradiation with gamma rays or the like, or by a combination of both. An example of a typical polymerization method is cast polymerization, in which a monomer mixture containing a radical polymerization initiator is injected between molds held by elastomer gaskets or spacers, cured in an air oven, and then taken out. Adopted.

[0012] The radical polymerization initiator is not particularly limited and any known one can be used, but representative examples include benzoyl peroxide, p-chlorobenzoyl peroxide, decanoyl peroxide, and lauroyl peroxide. , diacyl peroxides such as acetyl peroxide; peroxy esters such as t-butylperoxy-2-ethylhexanate, t-butylperoxyneodecanate, cumylperoxyneodecanate, t-butylperoxybenzoate; Percarbonates such as diisopropyl peroxydicarbonate, di-2-ethylhexyl peroxydicarbonate, and di-sec-butyl peroxydicarbonate; azo compounds such as azobisisobutyronitrile.

[0013] The amount of the radical polymerization initiator to be used varies depending on the polymerization conditions, the type of initiator, and the composition of the above-mentioned monomers, and cannot be absolutely limited, but it is generally in the range of 100 parts by weight of the total monomers. 0.01 to 10 parts by weight, preferably 0.0
It is suitable to use it in a range of 1 to 5 parts by weight.

Among polymerization conditions, temperature in particular affects the properties of the high refractive index resin obtained. This temperature condition is affected by the type and amount of initiator and the type of monomer, so it cannot be absolutely limited, but generally polymerization is started at a relatively low temperature and the temperature is slowly raised. It is preferable to carry out so-called tapered two-stage polymerization in which the polymer is cured at high temperature upon completion of polymerization. Like temperature, polymerization time also varies depending on various factors, so it is preferable to determine the optimal time according to these conditions in advance, but in general, conditions should be selected so that polymerization is completed in 2 to 40 hours. is preferred.

Of course, during the polymerization, various stabilizers and additives such as mold release agents, ultraviolet absorbers, antioxidants, color inhibitors, antistatic agents, fluorescent dyes, dyes, and pigments may be selected as necessary. It can be used as

The fragrance used in the present invention can be used without any particular restriction as long as it is a 6-membered ring ether compound. Typical examples include rose oxide, 3,3,6-trimethyl-6-vinyltetrahydropyran, dihydromethylpentenylpyran, 1,8-cineole, bicyclodihydrohomofarnesyl oxide, and galaxolide. These fragrances can be used alone or in a mixture of two or more.

In the present invention, 1,8-cineole is particularly preferred among the above six-membered ring ether compounds. The reason for this is that although it is not possible to identify the components of the bad odor and foreign odor generated during cutting and polishing, it is presumed from the odor that it is a compound with a mercapto group, which is incorporated into the ring structure of the 6-membered ring ether compound. This is thought to be masked by hydrogen bonding with oxygen atoms.

[0018] The content of the fragrance used in the present invention varies depending on the type of monomer and the type of fragrance, but generally the proportion in the total amount of the resin component and fragrance is 0.01 to 3.0.
It is preferably 0.05 to 1.0% by weight, more preferably 0.05 to 1.0% by weight. The above-mentioned resin component is the total amount of monomers forming the resin before polymerization, and is the resin itself after polymerization. If the content exceeds 3.0% by weight, the fragrance will be too strong and the worker will feel uncomfortable no matter how fragrant it is. Furthermore, the physical properties of the resulting polymer, such as surface hardness and heat resistance, for use as a plastic lens may also be reduced. On the other hand, if the content is less than 0.01% by weight, it is difficult to mask bad smells and foreign odors.

[0019] In the present invention, the method of incorporating the fragrance into the high refractive index resin is not particularly limited, and any known method can be employed. Specifically, methods include adding a fragrance to a monomer mixture and polymerizing it to uniformly disperse the fragrance in a resin, or dissolving or dispersing a fragrance in water or an organic solvent and creating a solution or dispersion of this solution. There is a method of immersing a high refractive index resin in the resin and allowing the fragrance to penetrate near the surface of the resin.

Generally, the former is preferable because it is easier to operate, but since the physical properties of the copolymer obtained as a plastic lens may be markedly deteriorated by adding a fragrance, the type of fragrance, The method of inclusion may be selected depending on the amount added, the type of monomer, etc.

[0021] The high refractive index resin molded product containing a fragrance can also be subjected to the following treatments depending on its use. In other words, dyeing using dyes such as disperse dyes, hard coating agents whose main components are silane coupling agents and sols of oxides such as silicon, zirconium, antimony, and aluminum, and hard coatings whose main components are organic polymers. Hard coating treatment with agent, SiO2, TiO2,
It is also possible to perform processing and secondary treatments such as antireflection treatment and antistatic treatment by vapor deposition of a thin film of a metal oxide such as ZrO2 or coating of a thin film of an organic polymer.

[0022]

[Effects] The high refractive index resin molded article containing the fragrance of the present invention has masked bad smells and foreign odors emitted during use or cutting and polishing. Therefore, even if exhaust equipment is not provided or protective masks are not worn, there will be no adverse effects such as discomfort on the workers.

[0023]

[Examples] In order to specifically explain the present invention, Examples and Comparative Examples will be shown below, but the present invention is not limited to these Examples. In addition, in the examples, various physical properties of the obtained high refractive index resin molded bodies were measured by the following test methods.

(1) Refractive index (n20D) Atago Co., Ltd.
The refractive index and Abbe number at 20° C. were measured using an Abbe refractometer (Model 3T) manufactured by Co., Ltd. Bromonaphthalin was used as the contact liquid.

(2) Odor during beading The beading machine manufactured by Tokyo Kogaku Kikai Co., Ltd. (TOPCON AL
E-60), the high refractive index resin molded body was polished. Those with a bad odor, strange odor, or irritating odor were rated as ×, those with a slightly foul odor, off-odor, or irritating odor were rated as △, and those with no odor or a faintly pleasant odor were evaluated as ○.

Example 1 40 parts by weight of 2-benzylthioethyl thiomethacrylate,
25 parts by weight of diethylene glycol dimethacrylate, 2
, 0.3 parts by weight of 1,8-cineole per 35 parts by weight of 2-bis(3,5-dibromo-4-methacryloyloxyethoxyphenyl)propane;
1 part by weight of t-butylperoxy-2-ethylhexanate was added and mixed well. This mixed solution was poured into a mold consisting of two glass plates and a gasket made of ethylene-vinyl acetate copolymer, and cast polymerization was performed. Polymerization was carried out using an air furnace, and the temperature was gradually raised from 30°C to 90°C over 18 hours, and the temperature was maintained at 90°C for 2 hours. After the polymerization was completed, the mold was taken out from the air oven, and after cooling, the polymer was removed from the glass mold. The refractive index of the obtained polymer was 1.593, and the odor during polishing was rated as ○.

Examples 2 to 5, Comparative Example 1, Example 1 except that the fragrance shown in Table 1 was used instead of 1,21,8-cineole.
It was carried out in exactly the same way. The results are also shown in Table 1. The refractive indexes of the obtained polymers were all 1.593, unchanged from Example 1. Further, as a comparative example, the same procedure as in Example 1 was carried out except that no perfume was used, and the results are also shown in Table 1.

[0028]

[Table 1]

Examples 6 to 10 Examples 6 to 10 were carried out in the same manner as in Example 1, except that the polymerizable composition of the thiocarboxylic acid ester and the copolymerizable monomer shown in Table 2 and the fragrance were used. The results are shown in Table 2.

[0030]

[Table 2]

Comparative Example 3 The same procedure as in Example 1 was carried out except that a mixture of 50 parts by weight of 2,2-bis(4-methacryloyloxyethoxyphenyl)propane and 50 parts by weight of dibromostyrene was used as the polymerizable composition. . The refractive index of the obtained polymer is 1
．． 605, but the odor at the time of rolling was △.

Comparative Example 4 2,2-bis(3,5-dibromo-
4-allyloxycarbonyloxyethoxyphenyl)
40 parts by weight of propane, 40 parts by weight of diallyl phthalate,
Example 1 was carried out in the same manner as in Example 1, except that 1.5 parts by weight of diisopropyl percarbonate was used as a radical polymerization initiator in a mixture consisting of 20 parts by weight of diethylene glycol bisallyl carbonate. The refractive index of the obtained polymer is 1
．． 565, but the odor at the time of rolling was △.

Claims (1)

[Claims] Claim 1: The following formula (where R1 is a hydrogen atom or a methyl group, and R2
and R3 are the same or different hydrogen atoms or alkyl groups, R4 is a substituted or unsubstituted benzyl group, and m is an integer of 1 or more. ) and a copolymer of a monomer having two or more polymerizable groups copolymerizable with the thiocarboxylic acid ester compound shown in (6) as a fragrance.
A high refractive index resin molded article containing 0.01 to 3.0% by weight of a membered ring ether compound.