JPH02120305A - Curable composition - Google Patents

Abstract

PURPOSE:To obtain a curable compsn. with excellent curability and providing a cured product with high refractive index, excellent heat resistance, low water- absorbing properties and optical uniformity by compounding 1,4- dimercaptophenyl dimethacrylate with another vinyl monomer. CONSTITUTION:A compsn. with excellent curability is obtd. by compounding 10-90 pts.wt. 1,4-dimercaptophenyl dimethacrylate of the formula with 90-10 pts.wt. other vinyl monomer copolymerizable with this monomer (e.g., methyl methacrylate). A cured product with excellent optical uniformity, high refractive index and physical features such as high heat resistance and low water-absorbing properties can be obtd. by performing radical polymn. of this curable compsn. using a radical polymn. catalyst [e.g., 2,2'-azobis(2,4-dimethylvaleronitrile)] and is useful in such industrial fields as optical materials as well as coatings, sealing agents, paints, adhesives, etc.

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Field of Application] The present invention relates to a curable composition, and more specifically, 4-
The present invention relates to a curable composition containing dimercaptophenyl dimethacrylate as one component.

The curable composition of the present invention not only has excellent curability, but also the cured product obtained by curing the curable composition has a high refractive index, heat resistance, low water absorption, and optical properties. Due to its excellent uniformity, it can be used as an optical material coach ink agent, sealant IL agent,
It is extremely useful in industrial fields such as paints and adhesives, especially in the field of optical materials.

(Conventional technology) Conventionally, polystyrene resins, polymethyl methacrylate resins, polycarbonate resins, diethylene glycol diallyl carbonate polymers, etc. have been used as organic optical materials, and these are lightweight and safe. Due to its excellent processability, dyeability, etc., demand for it has increased in recent years.

However, conventional organic optical materials, such as polymethyl methacrylate resin, have a high hygroscopic property and therefore change in shape and refractive index, making them unstable as optical materials. Furthermore, polystyrene resins and bosocarbonate resins have drawbacks such as optical birefringence, generation of scattered light, and decreased transparency due to changes over time. Furthermore, the diethylene glycol sialyl carbonate polymer has a low refractive index (refractive index = 1.499), which limits its range of application as an optical material.

Various resins for optical materials have been proposed to improve these drawbacks. Examples of these are:

For example, Japanese Unexamined Patent Publication No. 57-28115, No. 57-281
Publication No. 16, Publication No. 59-184210, Publication No. 60-7
No. 314, No. 60-179406, No. 60-
Publication No. 17906, Publication No. 6゜-185514, M
2O-166307 publication, 6゜1033 old publication,
No. 60-124607, No. 62232414, No. 62-2359 [No. 11, No. 62-2673]
Publication No. 16, Publication No. 63-15811 1st issue 53-46
Publications No. 213 and No. 63-72707 can be mentioned. However, the cured products obtained by these prior art techniques were not necessarily satisfactory as optical materials, as they were optically non-uniform, had significant weathering coloring, and lacked dimensional stability.

(Problems to be Solved by the Invention) An object of the present invention is to overcome the drawbacks of the conventional resins for optical materials, and to make the resins not only suitable as optical materials but also coating agents, sealants, paints, adhesives, etc. Our objective is to provide a curing system suitable for producing a well-balanced cured product that has various physical properties such as optical uniformity, low water absorption, and heat resistance, which can also be used as a material for .

(Means for Solving the Problems) The present invention provides a curable composition that can achieve the above objects.

That is, the present invention uses 10 to 90% by weight of the polymerizable monomer represented by formula (I) and Type I)
・1 Other vinyl monomers that can be copolymerized with the monomer 90-1
It relates to a curable composition consisting of 0 ball amount%.

The polymerizable monomer represented by the above formula (I) is represented by the following formula (I
T) The dithiol represented by T) can be dissolved in, for example, an alkaline aqueous solution and reacted with methacrylic acid chloride to give 1.

The polymerizable purse represented by the formula (I) can be easily mixed with other organic compounds, has extremely low affinity for water, and has a high refractive index (refractive index of a single cured product = 1. 65
5). Therefore, the composition can be cured by mixing this polymerizable monomer with other vinyl monomers that can be copolymerized in a blending ratio depending on the purpose of use. It is possible to improve the refractive index of the obtained cured product, reduce the water absorption, etc. The amount of the polymerizable monomer used to achieve the object of the present invention is 1
It ranges from 0 to 90% by weight, preferably from 15 to 85% by weight. If the amount of the Tamasha single-attached body used is less than 10% by weight, it is expected that the cured product obtained by curing will have a sufficient effect on any of the optical properties, water absorption, and heat resistance. Use of polymerizable monomers! If it exceeds 6 or 90 ton hl:%, it is not preferable because mechanical properties such as impact resistance deteriorate. The amount of the polymerizable purse string used can be freely varied within the range of 10 to 90% by weight depending on the purpose of use and the type of other vinyl monomers that can be copolymerized with the polymerizable purse. Ru.

Other copolymerizable vinyl monomers 71. used in the present invention. There are no particular limitations on the monomer as long as it is compatible with the polymerizable monomer represented by the formula (I). Two or more types of other vinyl monomers copolymerizable with the polymerizable monomer may be used in combination.

The amount of other vinyl monomer copolymerizable with the polymerizable monomer is 10 to 90% by weight, preferably 15 to 85% by weight.
It is. If the amount of other vinyl monomers used is less than 10% by weight, it is not preferable that the cured product obtained by curing becomes brittle or has insufficient mechanical properties. Also,
If the amount of other vinyl monomers used is more than 90% by weight, it is not preferable because it may cause problems in optical properties, water absorption, and heat resistance. Other vinyl monomers copolymerizable with the polymerizable monomer include, for example, unsaturated fatty acid esters, aromatic vinyl compounds, unsaturated fatty acids and their derivatives, unsaturated dibasic acids and their derivatives, (meth) ) Examples include vinyl cyanide compounds such as acrylonitrile. Examples of unsaturated fatty acid esters include methyl (meth)acrylate, ethyl (meth)acrylate, butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, octyl (meth)acrylate, dodecyl (meth)acrylate, and octadecyl (meth)acrylate. ,
Alkyl (meth)acrylates such as cyclohexyl (meth)acrylate, methylcyclohexyl (meth)acrylate, (iso)bornyl (meth)acrylate, adamantyl (meth)acrylate, phenyl (meth)acrylate, pencil (meth)acrylate, l-naphthyl (meth)acrylate, fluorophenyl (meth)acrylate, chlorophenyl (meth)acrylate, bromophenyl (meth)acrylate, tribromophenyl (meth)acrylate, methoxyphenyl (meth)acrylate, cyanophenyl (meth)acrylate, biphenyl ( meth)acrylate, bromobenzyl(
Aromatic acrylic esters such as meth)acrylate, haloalkyl(meth)acrylates such as fluoromethyl(meth)acrylate, chloromethyl(meth)acrylate, bromoethyl(meth)acrylate, trichloromethyl(meth)acrylate, 2-hydroxyethyl (
In addition to meth)acrylate, (meth)acrylic acid polyethylene glycol ester, etc., (meth)acrylic esters such as chrysyl(meth)acrylate and alkylamino(meth)acrylate can be mentioned.

Further examples include α-substituted acrylic ugly esters such as α-fluoroacrylic acid ester and α-cyanoacrylic acid ester.

Examples of aromatic vinyl compounds include styrene, α-substituted styrenes such as α-methylstyrene, α-ethylstyrene, and α-chlorostyrene, and nuclear shields such as fluorostyrene, chlorostyrene, bromostyrene, chloromethylstyrene, and methoxystyrene. I can give you styrene.

Examples of unsaturated fatty acids and derivatives thereof include (meth)acrylamide, N,N-dimethyl(meth)acrylamide,
(meth) such as N,N-diethyl(meth)acrylamide
Examples include acrylamides and (meth)acrylic acid.

Unsaturated dibasic acids and their derivatives include N-methylmaleimide, N-ethylmaleimide, N-methylmaleimide, N-cyclohexylmaleimide, N-phenylmaleimide, N-methylphenylmaleimide, N-chlorophenylmaleimide, N- Examples include N-substituted maleimides such as -carboxyphenylmaleimide, maleic acid, maleic anhydride, fumarugly, and the like.

In addition to the monofunctional vinyl monomer mentioned above, other vinyl monomers that can be copolymerized with the polymerizable monomer used in the present invention include crosslinked polyfunctional vinyl monomers. For example, ethylene glycol di(meth)acrylate, diethylene glycol di(meth)acrylate, triethylene glycol di(meth)acrylate, tetraethylene glycol di(meth)acrylate,
meth)acrylate, tripropylene glycol cyclo(meth)acrylate, l,3-phthylene glycol cyclo(meth)acrylate, 1,4-butanethiol cyclo(meth)acrylate
Acrylate, 1.5-pentashiol cy(meth)acrylate, 1.6-hexanethiol cy(meth)acrylate, neobentyl glycol cy(meth)acrylate, hydroxypivalic acid neobentyl glycol ester cy(meth)acrylate, Oligoester (meth)acrylate, polyphthalate (meth)acrylate
1.,2.2-bis(4-(meth)acryloyloxyphenyl)propane, 2.2-bis(4-(ω-(meth)acryloyloxypolyethoxy)phenyl)propane, 2.2-bis(4 -(ω-(meth)acryloyloxypolyethoxy)difuromophenyl)propane, 2.
2-bis(4-(ω-(meth)acryloyloxypolypropoxy)phenyl)propane, bis(4-(ω-(
Cy(meth)acrylates such as meth)acryloyloxypolyethoxy)phenyl)methane, diallyl phthalate, sialyl isophthalate, sialyl terephthalate-1
-, sialyl carbonate, thiethylene glycol diallyl carbonate, divinylbenzene, N, N' -m
- Bifunctional purse strings such as fluorine bismaleimite, trimethylolethane tri(meth)acrylate, trimethylolpropane tri(meth)acrylate, pentaerythritol tri(meth)acrylate, tri(meth)allylisocyanurate.

Examples include trifunctional crosslinkable In forms such as triallyl trimellitate and sialylchlorendate, and tetrafunctional crosslinkable monomers such as pentaerythritol tetra(meth)acrylate.

The curable composition of the present invention can be cured by radical polymerization. The radical polymerization initiator used in radical polymerization can be any radical polymerization initiator that can generate radicals by heat, microwaves, infrared rays, or ultraviolet rays. , can be selected as appropriate depending on the purpose.

Examples of radical polymerization initiators that can be used in polymerization using heat, microwaves, or infrared rays include 2.2°-azobisisovaleronitrile, 2゜2゛-azobisisovaleronitrile, 2.2'azobis(2, azo compounds such as 4-dimethylvaleronitrile), ketone peroxides such as methyl ethyl ketone peroxide, methyl isophthyl ketone peroxide, cyclohexanone peroxide, acetylacetone peroxide, isophthyryl peroxide, 2.4- Dichlorobenzoyl peroxide, 0-
Diasilver oxides such as methylbenzoyl peroxide, lauroyl peroxide, p-chlorobenzoyl peroxide, 2,4.4-trimethylpentyl-2-
Hydroperoxides such as hydroperoxide, diisopropylbenzene peroxide, cumene hydroperoxide, t-phthyl peroxide, dicumyl peroxide, t-butylcumyl peroxide, t-phthyl peroxide, tris(1- Dialkyl peroxides such as (phthyl baroxy) triazine, peroxy ketals such as 1,1-cy(t-phthyl baroxy)cyclohexane, 2,2-cy(t-phthyl baroxy) butane, t-butyl baroxypi Halate, t-notylbaroxy-2
-ethylhexanoate, 7-butylperoxyisophthylate, t-phthyl peroxy hexahydroterephthalate, t-phthyl peroxy azelate, t-
Alkyl peresters such as phthyl peroxy-3,5,5-trimethylhexanoate, t-phthyl peroxy acetate, t-phthyl peroxybenzoate, di-t-butylperoxytrimethyl acybate, cyisopropylper Examples include percarbonates such as oxycycarbonate, di-5ec-phthylperoxycycarbonate, and t-phthylbaroxyisobrobyl carbonate.

For example, acetophenone can be used as an intermediate initiator for radicals that can be used during polymerization by ultraviolet rays.

2.2-dimethoxy-2-phenylacetophenone, 2
．． 2-Jethoxyacetophenone, 4'isopropyl-
2-Hydroxy-2-methylpropiophenone, 2-hydroxy-2-methylpropiophenone, 4.4'-
Bis(diethylamino)benzophenone, pentuphenone, methyl(0-benzoyl)benzoate, l-phenyl 1,2-propanedione-2-(o-ethoxycarbonyl)oxime, l-phenyl-1,2-bropansion-2- (o-benzoyl)oxime, benzoin,
Benzoin methyl ether, benzin ethyl ether, pentwin isopropyl ether, pentwin isofthyl ether, pentwin octyl ether, hensyl, pentyl dimethyl ketal, benzyl diethyl ketal.

Diacetyl carbonyl compounds, methylanthraquinone, chloroanthraquinone, chlorothioxanthone, 2
- anthraquinone or thioxanthone derivatives such as methylthioxanthone and 2-isopropylthioxanthone;
Examples include yellow compounds such as diphenyl disulfide and dithiocarbamate.

The amount of the radical polymerization initiator to be used cannot be determined unconditionally because it varies depending on the type of radical polymerization initiator, the type of monomer charged, and the composition ratio, but it is usually determined by the amount of the polymerizable monomer and the polymerizable monomer. in the range of 0.0 to 20 mol%, preferably 0.01% to 20% by mole based on the total amount of other vinyl monomers copolymerizable with the vinyl monomer.
It is in the range of ~10 mol%. If the amount of radical polymerization initiator used is less than 0.0 mol%, polymerization will not substantially proceed.
Further, if the amount used exceeds 20 mol %, it is not only uneconomical but also undesirable because it may cause foaming during the polymerization or the molecular weight of the cured product obtained by one polymerization becomes extremely small.

When the curable composition of the present invention is not particularly required to be translucent, various fillers may be added thereto as required. Examples of fillers used here include glass fibers, alumina fibers, carbon fibers, aramid fibers, etc., as well as powder fillers such as silica, alumina, barium chloride, and titanium oxide. others,
It goes without saying that flame retardants, dyes, pigments, etc. can also be used in combination.

The polymerization temperature and polymerization time for curing the curable composition cannot be unconditionally defined because they vary depending on the type and amount of radical polymerization initiator used, and the polymerization temperature is usually in the range of 0 to 200°C. The polymerization time is preferably in the range of usually 0.5 to 50 hours.

〔Example〕

Hereinafter, the present invention will be explained in more detail by giving Examples and Comparative Examples.

In addition, various physical properties of the cured products obtained in the Examples and Comparative Examples were measured by the following methods.

(1) Using a refractive index Atsube refractometer (Shimaritsu Seisakusho, 3L type),
The refractive index at °C was measured.

(2) Light Transmittance Using a spectrophotometer (manufactured by Hitachi, Model 150-20), the transmittance of the lower plate having a thickness of 3111 was measured using light having a wavelength of 550 ns.

(3) Glass transition temperature (Tg) Tan
By reading the peak (inflection point) of δ, the sample (
The glass transition temperature was set at a thickness of 0.1*m).

(4) Using a test piece with water absorption JIS-7209, the percentage of weight increase when a sample dried under reduced pressure at 50°C for 5 days is immersed in water at 100°C for 2 hours, based on the dry weight. Ta.

Example 1 1.4-dimercaptophenyl dimethacrylate 35g
and 15 g of methyl methacrylate.
0.2 g of 2.2°-azobis(2,4-dimethylvaleronitrile) as a radical polymerization initiator was dissolved in 50 g of h, and a glass mold of 5 cax 5 CIIX O: l cm and 0.2 mm x 50 mm x 20 s was prepared.
+* injected into each glass cell and heated for 35 minutes under a nitrogen stream.
After heating for 10 hours at
The mold was removed by heating to 0'C, and then heated and cured at 100C for 1 hour.The resulting cured product was a uniform, colorless and transparent resin. The physical property values of the cured product are shown in Table 2.

Examples 2 to 10 and Comparative Examples 1 to 3 1,4-dimercaptophenyl dimethacrylate (A)
and 77% of each of the various vinyl monomers (B) shown in Table 1.
A cured product was obtained in the same manner as in Example 1, except that the mixture ratios shown in Table 2 were used. However, in Comparative Example 1, 2 g of isopropyl peroxycarbonate was used instead of 2,2'-azobis(2,4-dimethylvaleronitrile).

Table 2 shows the physical properties of the obtained cured product.

(Margin below) I set it.

It can be seen that the cured product obtained by curing the curable composition of the present invention has a higher refractive index and a lower water absorption 2 V than the cured product obtained by curing the curable composition of the present invention.

(Effect of the invention) The curable composition of the present invention not only has excellent curability, but also the cured product obtained by curing the curable composition of the present invention 011 has excellent optical uniformity. Excellent.

It has physical properties such as high refractive index, high heat resistance, and low water absorption, so it is especially useful in the optical material industry, as well as coach inks, month-fixing agents, paints, and adhesives. It is also useful in industrial fields such as

Claims (1)

[Claims] 10 to 90% by weight of a polymerizable monomer represented by formula (I) ▲There are mathematical formulas, chemical formulas, tables, etc.▼(I) and other copolymerizable monomers that can be copolymerized with the polymerizable monomer. A curable composition comprising 90 to 10% by weight of a vinyl monomer.