JPH0753776B2 - Optical resin lens and manufacturing method thereof - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION <Field of Industrial Application> The present invention relates to an optical resin lens obtained by polymerizing or copolymerizing a specific mesaconic acid ester and a method for producing the same, more specifically, a high refractive index. , An optical resin lens excellent in transparency and the like and a method for producing the same.

<Conventional Technology and Problems> Conventionally, plastic materials have been known for their transparency, lightness,
It has been used as a substitute for inorganic glass by taking advantage of its excellent properties such as safety and workability. Typical examples thereof include polymethyl methacrylate, polydiethylene glycol bisallyl carbonate, polystyrene and polycarbonate.

Although these plastic materials are inferior in scratch resistance, refractive index, and heat resistance to inorganic glass, they are widely used in the optical field by taking advantage of the above-mentioned excellent characteristics. However, for example, polymethyl methacrylate and polydiethylene glycol bisallyl carbonate have a low refractive index of about n _D = 1.49 to 1.50, and therefore, when used in the field of utilizing a refractive index such as a lens, as compared with inorganic glass. A thick one is required, and there is a drawback that it is not suitable for the recent size and weight reduction of optical materials.

Further, polystyrene and polycarbonate have a high refractive index of about n _D = 1.59 to 1.60, but they have drawbacks in solvent resistance and birefringence.
Many of them are melt-molded such as injection molding, and there is a drawback that they are not suitable for the cast molding method useful for the production of various items.

<Purpose of the Invention> The present invention is an optical resin suitable for a cast molding method, which has desirable colorless transparency and high refractive index as an optical resin lens, has a small shrinkage rate during polymerization molding and is excellent in heat resistance. It is an object to provide a lens and a manufacturing method thereof.

<Means for Solving Problems> According to the present invention, the following general formula (In the formula, A ₁ and A ₂ are the same or different groups, Or at least one group selected from R represents a group having an aromatic ring, X represents a halogen atom, and m represents 0 or 1
Or more and 5 or less, and R represents an alkyl group having 1 to 12 carbon atoms, an alkenyl group, or a cycloalkyl group having 3 to 12 carbon atoms). There is provided an optical resin lens obtained by copolymerizing a monomer with a comonomer.

According to the present invention, the following general formula (In the formula, A ₁ and A ₂ are the same or different groups, Or at least one group selected from R represents a group having an aromatic ring, X represents a halogen atom, m represents an integer of 0 or 1 and 5 or less, and R represents an alkyl group having 1 to 12 carbon atoms. Group, an alkenyl group or a cycloalkyl group having 3 to 12 carbon atoms) or a mixture of the mesaconic acid ester and a comonomer is selected. Organic peroxide having a half-life temperature of 120 ° C or less for 10 hours. The present invention provides a method for producing an optical resin lens, which comprises placing the resin in a predetermined mold and heating and curing it in the presence of one or more polymerization initiators selected from compounds and azo compounds.

Hereinafter, the present invention will be described in detail.

In the present invention, the following general formula (In the formula, A ₁ and A ₂ are the same or different groups, Or at least one group selected from R represents a group having an aromatic ring, X represents a halogen atom, m represents an integer of 0 or 1 and 5 or less, and R represents an alkyl group having 1 to 12 carbon atoms. Group, an alkenyl group or a cycloalkyl group having a carbon number of 3 to 12). The phenyl group and benzyl group in the mesaconic acid ester may be substituted with a halogen atom (m = 1 or more and an integer of 5 or less), or may not be substituted with a halogen atom (m = 0). When the mesaconic acid ester group is an alkyl group, an alkenyl group, or a cycloalkyl group, it cannot be used when the number of carbon atoms is 13 or more because the physical properties such as polymerizability and heat resistance are deteriorated.

Specific examples of the mesaconic acid ester that can be used in the present invention include mesaconic acid diphenyl ester, mesaconic acid di (orthochlorophenyl) ester, mesaconic acid di (orthobromophenyl) ester, mesaconic acid di (parachlorophenyl) ester. Ester, mesaconic acid di (metabromophenyl) ester, mesaconic acid di (2 ', 4'-
Dichlorophenyl) ester, mesaconic acid pro-bromophenyl-orthobromophenyl diester, mesaconic acid benzyl-phenyl diester, mesaconic acid dibenzyl ester, mesaconic acid di (orthochlorobenzyl ester), mesaconic acid di (orthobromobenzyl) ester, Mesaconic acid di (metabromobenzyl) ester, mesaconic acid benzyl orthochlorobenzyl diester, mesaconic acid di (parachlorobenzyl) ester, mesaconic acid benzyl-orthobromobenzyl diester, mesaconic acid di (2 ', 4'-dichlorobenzyl) ) Ester, mesaconic acid methyl-phenyl diester, mesaconic acid isopropyl-phenyl diester, mesaconic acid cyclohexyl-phenyl diester, mesaconic acid ethyl-benzyl diester, mesaco Acid isopropyl - benzyl diester, mesaconic acid cyclohexyl - benzyl diester, mesaconic acid allyl - benzyl diester, mesaconic acid Mesariru - benzyl diesters. However, those having different A ₁ and A ₂ in the mesaconic acid diester represented by the general formula (1) of the above specific example are named in the order of A ₁ and A ₂ .

The optical resin lens of the present invention can be obtained by polymerizing one or more of the above mesaconic acid esters. Further, the above mesaconic acid ester and a comonomer may be copolymerized. As the comonomer, one kind or two or more kinds of radically polymerizable vinyl monomer, crosslinkable vinyl monomer or crosslinkable allyl monomer can be used.

Radical-polymerizable vinyl monomers, crosslinkable vinyl monomers or crosslinkable allyl monomers include styrene and p
-Methylstyrene, p-chlorostyrene, o-chlorostyrene, p-bromostyrene, o-bromostyrene, p
-Divinylbenzene, m-divinylbenzene, divinylbiphenyl, vinyl acetate, vinyl propionate, methyl methacrylate, butyl methacrylate, methyl acrylate, ethyl acrylate, phenyl methacrylate, phenyl acrylate, benzyl methacrylate,
Benzyl acrylate, bromphenyl methacrylate, acrylonitrile, methacrylonitrile, ethylene glycol dimethacrylate, diethylene glycol dimethacrylate, ethylene glycol diacrylate,
Diethylene glycol diacrylate, polyethylene glycol diacrylate propylene glycol dimethacrylate, bisphenol A dimethacrylate, 2,2-
Bis (4-methacryloyloxyethoxyphenyl) propane, 2,2-bis (4-acryloyloxyethoxyphenyl) propane, allyl methacrylate, allyl acrylate, diallyl phthalate, diallyl tetrachlorophthalate, diallyl isophthalate, diallyl terephthalate, trimellitate Acid triallyl, triallyl cyanurate, triallyl isocyanurate, diethylene glycol bisallyl carbonate, diallyl tetrachlorophthalate, etc. are listed, but at least one kind is used for the purpose of improving the solvent resistance and heat resistance of the obtained resin. It is preferable to select a crosslinkable polyfunctional vinyl monomer and an allyl monomer. Examples of such vinyl monomers include divinylbenzene, ethylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, diallyl phthalate, diallyl isophthalate, ethylene glycol bisallyl carbonate, triallyl trimellitate, triallyl isocyanurate, and triaryl isocyanurate. Allyl cyanurate and the like can be mentioned.

The copolymerization composition ratio of the comonomer to the mesaconic acid ester is 10,000 to 100 parts by weight of the mesaconic acid ester.
A range of 1 part by weight is preferable, and a range of 5000 to 10 parts by weight is more preferable. In this case, when the amount exceeds 1000 parts by weight, the refractive index of the obtained resin becomes remarkably low, and when the amount is less than 1 part by weight, the effect of copolymerization of the comonomer is not sufficient.

As the polymerization initiator used for polymerizing the polymer or copolymer according to the present invention, one or more organic peroxides and azo compounds having a selected 10-hour half-life temperature of 120 ° C. or less are used. It

Examples of such initiators are benzoyl peroxide, diisopropyl peroxydicarbonate, tert-butyl peroxy 2-ethylhexanoate, tert-butyl peroxypiparate, tert-butyl peroxydiisobutyrate, lauroyl peroxide, di- -N-propyl peroxy dicarbonate, di-2-ethylhexyl peroxy dicarbonate, t-butyl peroxy neodecanoate, decanoyl peroxide, azobisisobutyronitrile and the like can be mentioned. The amount of the polymerization initiator used is preferably 10 parts by weight or less, more preferably 5 parts by weight or less, relative to 100 parts by weight of the raw material monomer. In preparing the optical resin lens of the present invention, a method is used in which a polymerization initiator is added to the raw material monomer, the mixture is directly charged into a desired mold, and the system is heat-cured. in this case,
In a timely manner, the polymerization system is maintained under an inert gas such as nitrogen, carbon dioxide,
It is desirable to replace it with helium or the like or place it in an atmosphere. Also, after adding the polymerization initiator to the raw material monomer, it is slightly polymerized or copolymerized at a predetermined temperature (30 to 70 ° C) in advance, and then charged into a predetermined mold and cured by heating to complete the polymerization. It is also possible to take a method.

The temperature for heat curing varies depending on the polymerization initiator used, but is preferably in the range of 30 to 150 ° C., more preferably about 10 hours half-life temperature of the polymerization initiator used. It is also possible to raise the curing temperature in a timely manner for the purpose of shortening the curing time and treating the unreacted monomer and the polymerization initiator. In this case, the total time required for curing is about 10 to 48 hours.

Optical resin lens of the present invention <Effects of the Invention> is n _D has a high refractive index of more than 1.55, a colorless, transparent, Abbe number 30 or more, small molding during polymerization shrinkage and heat resistance We provide materials that improve the defects of conventional optical resin lenses, such as excellent
It can be applied to optical resin lenses such as eyeglass lenses and camera lenses.

<Examples> The present invention will be described in more detail with reference to Examples below, but the present invention is not limited thereto. Various physical properties were measured by the methods described below.

Refractive index, Abbe number-Abbe refractive index Specific gravity-The resin weight / resin volume was determined by the underwater substitution method.

It was determined according to the formula (1-ρP / ρM) from the polymerization shrinkage-specific gravity (ρM) of the raw material monomer composition and specific gravity (ρP) of the cured resin.

Heat resistance: After being left in a dryer at -130 ° C for 2 hours, no deformation or coloring of the resin was observed.

Example 1 Mesaconic acid diphenyl ester 7 g, divinylstyrene 3 g
The raw material mixture consisting of 0.3 g of benzoyl peroxide was mixed and heated to 60 ° C, and the monomer composition was charged into two glass plates (using a silicon gasket) and placed in a constant temperature bath at 70 ° C under a nitrogen stream. After curing for an hour and annealing at 100 ° C. for 2 hours, an optical resin lens was taken out of the mold and evaluated by the above physical property test.

Examples 2 to 6 and Comparative Examples 1 and 2 In the same manner as in Example 1, raw material monomers having various compositions were prepared with a predetermined radical initiator and curing conditions to prepare optical resin lenses. The results are shown in Table 1. In addition, as a comparative example, the same experiment was conducted for diethylene glycol bisallyl carbonate and styrene, and the results are also shown.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁶ Identification number Internal reference number FI Technical display location C08F 220/30 MMS G02B 1/04 7724-2K (72) Inventor Takao Mogami 3 Yamato, Suwa City, Nagano Prefecture 3-5, Seiko Epson Corporation

Claims (4)

[Claims] 1. A general formula (In the formula, A ₁ and A ₂ are the same or different groups, Or at least one group selected from R represents a group having an aromatic ring, X represents a halogen atom, m represents an integer of 0 or 1 and 5 or less, and R represents an alkyl group having 1 to 12 carbon atoms. Group, an alkenyl group or a cycloalkyl group having 3 to 12 carbon atoms), or an optical resin lens obtained by polymerizing a mesaconic acid ester or copolymerizing the mesaconic acid ester and a comonomer. 2. The optical resin lens according to claim 1, wherein the comonomer is a radically polymerizable vinyl monomer or a crosslinkable vinyl monomer. 3. General formula (In the formula, A ₁ and A ₂ are the same or different groups, Or at least one group selected from R represents a group having an aromatic ring, X represents a halogen atom, m represents an integer of 0 or 1 and 5 or less, and R represents an alkyl group having 1 to 12 carbon atoms. Group, an alkenyl group or a cycloalkyl group having 3 to 12 carbon atoms) or a mixture of the mesaconic acid ester and a comonomer is selected. Organic peroxide having a half-life temperature of 120 ° C or less for 10 hours. And a azo compound selected from the group consisting of compounds and azo compounds, and a method for producing an optical resin lens, which comprises placing the resin in a predetermined mold and curing by heating. 4. The method for producing an optical resin lens according to claim 3, wherein the comonomer is a radically polymerizable vinyl monomer or a crosslinkable vinyl monomer.