JPH01213331A - Plastic spectacle frame - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

Detailed Description of the Invention [Industrial Field of Application] The present invention relates to plastic eyeglass frames, and more specifically, the present invention relates to plastic eyeglass frames obtained by mixing selected base ingredients, curing agents, flexibility imparting agents, and curing accelerators. The present invention relates to an epoxy resin composition as a material for plastic eyeglass frames, and an epoxy resin composition as a material for plastic eyeglass frames obtained by further adding and mixing an ultraviolet absorber and an antioxidant.

[Background of the invention]

Materials for eyeglass frames include metal and organic polymer compounds.

Organic polymer compounds are often used because they are lighter than metals and can have various colors.

[Conventional technology and its issues]

As organic polymer compounds, natural polymer compounds such as celluloid and acetate have been widely used.

These plastic eyeglass frames made of thermoplastic resins such as celluloid and cellulose derivatives such as acetate have problems in strength and have low heat deformation temperatures, so metal core rods are used in the temple parts.

Furthermore, since it is a thermoplastic resin, it uses a plasticizer, which evaporates over time, causing surface cracks and a decrease in strength.

These problems are caused because the cellulose derivative is a linear thermoplastic resin.

These problems are solved by using thermosetting resins, but this is due to the crosslinking reaction of the resins.

Among organic polymer compounds, thermosetting resins have excellent strength, so they do not require a metal core and are suitable for weight reduction.Since they do not use plasticizers, they do not change over time.
Furthermore, by using a substantially colorless and transparent cured product,
It is possible to have a rich variety of colors.

Although glass eyeglass frames using epoxy resin, which is a thermosetting resin, have largely solved the above-mentioned problems, they are still insufficient and may cause deformation (Japanese Patent Publication No. 49-24687).

This is considered to be mainly due to the fact that the heat distortion temperature is less than 80°C.

Even if an epoxy resin is used, if an amine compound is used as a hardener detergent, the amine has high reactivity with the epoxy.
The amount of self-heating of the epoxy resin composition increases, causing a phenomenon when the cured product is baked, and the plastic eyeglass frames, which are essentially the cured product, turn pale yellow.

Further, this coloration is also caused by the color of the amine compound itself.

When amine compounds are used as hardeners, color control is difficult because the cured product is not colorless and transparent, and there are also problems with weather resistance, which causes yellowing over time during daily use. .

Particularly when dyes are used for coloring, color fading occurs frequently. Furthermore, since amine compounds are highly irritating to the skin, they may cause skin damage at the contact area between the eyeglass frame and the skin.

This also applies to the production process, which can cause skin and respiratory problems for workers.

There is no other example of a plastic eyeglass frame made of an epoxy resin, which is a thermosetting plastic, using a compound other than an amine compound as a curing agent other than the patent application filed by the present applicant (Japanese Patent Application No. 61-281286). The reason is that
When a curing agent other than an amine-based compound is used, the reactivity with the epoxy resin, which is the main ingredient, is lowered, resulting in a decrease in productivity.

Furthermore, if tertiary amines, which are commonly used to increase the reactivity, are used as a curing accelerator, the cured product will be colored pale yellow, making it impossible to obtain a colorless and transparent cured product.

Furthermore, in order to use the compound represented by the general formula H1 in claim 1 as a curing agent, a flexibility imparting agent is required to improve flexibility.

However, when an unsuitable flexibility imparting agent is used in combination with this curing agent, there is a problem in that mechanical strength and heat distortion temperature are significantly lowered.

[Purpose of the invention]

As a result of intensive studies to improve the drawbacks of the above conventional methods, the present inventors have developed a structure that is non-toxic and capable of exhibiting high mechanical strength, using an epoxy resin selected as the main resin and a curing agent other than an amine compound. A compound and its blending amount are selected as the flexibility imparting agent, and a compound and its blending amount that can improve flexibility and maintain a high heat distortion temperature are selected as the flexibility imparting agent. By casting an epoxy resin composition obtained by using a specific amount of a curing accelerator and an epoxy resin composition obtained by adding and mixing an ultraviolet absorber and an antioxidant, and curing by heating. It is colorless, transparent, has excellent weather resistance, and has excellent weather resistance to colored dyes, does not cause skin damage, and has a well-balanced mechanical strength, flexibility, and heat distortion temperature, and does not lose its shape. The purpose is to provide plastic eyeglass frames.

[Means of invention]

That is, the plastic eyeglass frame of the present invention has the general formula (
A so-called epoxy resin selected from diepoxides derived from bisphenols represented by (a) and (b), either alone or in combination of two or more, is used as the main resin to form a compound represented by the general formula (c). Using one type or a combination of two or more types of curing agents selected from among, polyethers represented by the following general formulas A flexibility-imparting agent selected from polyols and polyether polyglycidyl ethers, or a combination of two or more thereof, is used, and furthermore, a flexibility-imparting agent selected from the general formulas (wo), (wa), and (4) 1 from class phosphonium salts, quaternary ammonium salts, or salts of 1,8-diazabicyclo(5,4,0)unzecene-7
An epoxy resin composition obtained by mixing a curing accelerator selected from seeds or a combination of two or more thereof, and an epoxy resin obtained by further mixing an ultraviolet absorber and an antioxidant. It is obtained by casting a composition and curing it by heating.It is colorless, transparent, and has excellent weather resistance.It also has excellent weather resistance for colored dyes, does not cause skin damage, and has excellent mechanical strength. , Flexibility-1: It is characterized by having a well-balanced heat distortion temperature and not causing deformation.

In the present invention, the jepoxide represented by the general formulas a) and (b) used as the main agent refers to a so-called epoxy resin obtained by reacting bisphenols represented by bisphenol A with epihalohydrin, and specifically refers to Representative examples include diglycidyl ethers of bisphenol A type, hydrogenated bisphenol A type, bisphenol F type, and bisphenol AD type.

The molecular weight of these bisphenol type diglycidyl ethers is from 300 to 2000. A degree of polymerization n=Q to 5 is used, and preferably a molecular weight of 300 to 1000.
Particularly preferred is an epoxy resin that has a molecular weight of 300 to 1000 and is liquid at room temperature.

Among these epoxy resins, one type or a combination of two or more types can be used as the main resin.

A preferred method is to use a bisphenol A type diglycidyl ether or a hydrogenated bisphenol A type diglycidyl ether blended with one type or other bisphenol type diglycidyl ether.

Preferably, bisphenol A diglycidyl ether and hydrogenated bisphenol A diglycidyl ether are used as a blend.

When hydrogenated bisphenol A type diglycidyl ether is blended and mixed with other bisphenol type diglycidyl ether, the blending ratio of other bisphenol type diglycidyl ether to hydrogenated bisphenol A type diglycidyl ether is from 105 to The amount is 190 parts by weight, preferably 130 to 180 parts by weight.

By using these epoxy resins as the main ingredient,
During molding, it becomes easier to shorten the defoaming time and prevent the generation of bubbles, thereby improving productivity.

The general formula is as follows: General formula (a) (wherein, R8 is a straight chain or branched alkylene group having 8 or less carbon atoms, from -0-1-5-1-SO, -1 or 10- The selected bonding group, n, is 0 or an integer of 5 or less.) In the present invention, the compound represented by the general formula l/-9 used as a curing agent for the epoxy resin as the main ingredient is phthalic anhydride.・Representative compounds, specifically trimellitic anhydride, Δ1-tetrahydrophthalic anhydride, 3-methyl-Δ1-tetrahydrophthalic anhydride,
4-Methyl-Δ4-tetrahydrophthalic anhydride, hexahydrophthalic anhydride, 3-methylhexahydrophthalic anhydride, 4-methylhexahydrophthalic anhydride, nadic anhydride, methylnadic anhydride, dimethylbutenyltetrahydrophthalic anhydride , conollic anhydride, dodecenylsuccinic anhydride, and the like.

One or a combination of two or more of these compounds can be used as a curing agent.

As a cured product, it is substantially colorless and transparent, and has weather resistance.
In order to maintain a balance between mechanical strength, flexibility, and heat distortion temperature, cycloaliphatic acid anhydrides are preferred as the curing agent.

Specifically, Δ4-tetrahydrophthalic anhydride, 3-methyl-Δ4-tetrahydrophthalic anhydride, 4-methyl-
Δ4-Tetrahydrophthalic anhydride, hexahydrophthalic anhydride, 3-methylhexahydrophthalic anhydride, 4-methylhexahydrophthalic anhydride, nadic anhydride, methylnadic anhydride, dimethylbutenyltetrahydrophthalic anhydride, succinic anhydride , dodecenyl succinic anhydride, and the like.

More preferably, the 3rd or 4th position, or 3 and 4
A cyclic aliphatic acid anhydride that has an alkyl group in the position and is liquid at room temperature.

Further, at this time, since it has a liquid state at room temperature, it may be a mixture of cyclic aliphatic acid anhydrides having alkyl groups at the 3- and 4-positions.

Specifically, 3-methyl-Δ4-tetrahydrophthalic anhydride, 4-methyl-Δ4-tetrahydrophthalic anhydride,
Representative examples include 3-methylhexahydrophthalic anhydride, 4-methylhexahydrophthalic anhydride, methylnadic anhydride, and dimethylbutenyltetrahydrophthalic anhydride.

Particularly preferred are 3-methylhexahydrophthalic anhydride and 4-methylhexahydrophthalic anhydride.

By using these compounds as a curing agent, it is virtually colorless and transparent, has excellent weather resistance and resistance to colored dyes, has high mechanical strength, and is non-toxic and does not cause skin damage. A hardened product can be obtained.

As a general formula, the general formula is O / \ / \ (wherein, R2 is an aromatic hydrocarbon group or a cycloaliphatic hydrocarbon group, and R5 is a straight chain or branched alkyl group or carboxyl group having 10 or less carbon atoms. group or hydrogen, X is a bonding group selected from -0-l-S-1 or -N-, and R4 is a straight chain or branched alkyl group having 7 or less carbon atoms.) In the present invention, Polyether polyols represented by the general formulas ), (f), h, nishiki) used as flexibility imparting agents include polyethylene glycol, polypropylene glycol, polytetramethylene glycol, polyneopentyl glycol, and polyhexamethylene glycol. Typical examples include poly(ethylene glycol/propylene glycotyl) obtained by copolymerizing ethylene oxide and propylene oxide, and polyether triol obtained by copolymerizing glycerin and propylene oxide. .

Examples of polyether polyglycidyl ethers represented by general formulas (e), (g), (s) and (4) include polyethylene glycol, polypropylene glycol, polytetramethylene glycol, polyneopentyl glycol, polyhexamethylene glycol, and ethylene oxide. Poly(
Representative examples include compounds in which the terminal hydroxyl group is converted to glycidyl ether, such as polyether triol obtained by polymerizing glycerin and propylene oxide (ethylene glycol/propylene glycol) and propylene oxide.

One type or a combination of two or more types of these polyether polyols and polyether polyglycidyl ethers are used as the flexibility imparting agent.

The molecular weight of these polyether polyols and polyether polyglycidyl ethers is from 60 to 5,000, preferably from 500 to 4,000, and more preferably from 1,000 to 3,000.

These polyether polyols and polyether polyglycidyl ethers can be used by blending two or more polymers with different functional numbers and molecular weights, but in order to keep the physical properties of the cured product constant, only one type of K is used. It is preferable to use

The blending amount of these flexibility imparting agents to the epoxy resin base resin is 5 to 60 parts by weight, preferably 10 to 40 parts by weight.
Parts by weight, more preferably 20 to 30 parts by weight.

By using these flexibility-imparting agents, it is possible to suppress a significant decrease in mechanical strength and heat distortion temperature, and improve flexibility.

The general formula is: General formula % formula %) General formula CH2CHCHt O+ Rs Osu1\ 1 General formula HO(-CH, -CH2-O+□ General formula General formula General formula General formula R, (-0CI-12-CH2 →-R, (-OCH3-CH, ← General formula (wherein, R3 is a straight chain or branched alkylene group having 8 or less carbon atoms, and R6 is a straight chain or branched alkyl group having 4 or less carbon atoms) , R,, R, and Ro are straight chain or branched alkylene groups having 5 or less carbon atoms, m and q are 0 or an integer of 10 or less, and ! and m+
n is 1 or more, p is an integer of 5 or less, and 0
isn't it. ) In the present invention, the quaternary phosphonium salts represented by the general formula (sword) used as a curing accelerator include methyltrioctylphosphonium dimethylphosphate, methyltributylphosphonium dimethylphosphate, tetrabutylphosphonium acetate, benzyltriphenylphosphonium chloride, Representative examples include benzyltriphenylphosphonium bromide, tetrabutylphosphonium chloride, triphenylethylphosphonium iodide, and triphenyl(methoxymethyl)phosphonium chloride.

As the quaternary ammonium salt represented by the general formula (wa),
Representative examples include benzyltrimethylammonium chloride, tetraethylammonium bromide, tetrabutylammonium acetate, benzyltriphenylammonium chloride, benzyltriphenylammonium bromide, triphenylethylammonium iodide, triphenyl (methoxymethyl) ammonium bromide, etc. can.

Furthermore, the general formula (1,8-diazabicyclo(5
, 4*O) Salts of undecene-7 [hereinafter abbreviated as DBU] include DBU/phenol salt, DBU-2-ethylhexanoate, DBU/formate, DBU-p-1 Rue/sulfonate, DBU - Typical examples include oleate, DBU-propionate, and DBU-benzoate.

One or a combination of two or more of these quaternary phosphonium salts, quaternary ammonium salts, and 1,8-diazabicyclo(5,4°0) undecene-7 salts are used as a curing accelerator.

These curing accelerators have excellent latent properties, have almost no catalytic activity at temperatures below 50°C, and only exhibit catalytic activity at temperatures above 80°C, making them more difficult to mold than other curing accelerators. It is possible to easily set conditions and improve moldability.

Furthermore, these curing accelerators have lower catalytic activity than other curing accelerators (specifically, tertiary amines represented by tris(dimethylaminomethyl)phenol), so
It is an excellent product that can reduce the amount of self-heating of the epoxy resin composition and produce a substantially colorless and transparent cured product.

・The general formula is: General formula (force R1゜R11P Rt3・X, [mR32 General formula (wa)) General formula (force (in the formula, s Rho s R11・Rt2% R,3 is・
Alkyl group - A group selected from alkenyl group, allyl group or benzyl group, R14s R15, Rt. ,R
, is a group selected from a hydrogen atom, an alkyl group, an alkenyl group, an alkoxy group, an allyl group, or a benzyl group, X,, X is a counter anion consisting of an inorganic acid or an organic acid, and X4 is It is a counter anion consisting of an organic acid. ) In the present invention, the blending amount of the system consisting of a curing agent and a flexibility imparting agent with respect to the main ingredient is 0.000 expressed as the ratio of the active group equivalent of the system consisting of a curing agent and a flexibility imparting agent to the epoxy equivalent of the main ingredient. 7 to 1.5, preferably 0.8 to 1.1.

The reason for this is that if this equivalent ratio is less than 1.0, the cured product will be colored pale yellow.

Antioxidants used in the present invention include:

Although the type thereof is not particularly limited, hindered phenolic antioxidants are preferred.

As a hindered phenol antioxidant, 2,6-G ter is used as a monocyclic hindered phenol.
t-butyl-4-methylphenol, 2-tc
r tert-butyl-4-methoxyphenol, 2,6-tert-butyl-2,4-methylphenol, 2,
6-tert-butylphenol, 2-tert-
Butyl-4-ethylphenol, 2,6-tert
-butyl-4-ethylphenol, n-octadecyl-
5-(4′-hydroxy-3,5-di-tert-butylphenyl)propionate, dioctadecyl-4-hydroxy-3,5-di-tert-butylbenzylphosphonate, and 6-(4-oxy-3°5- G-te
rt-butylanilino)-2,4-bis-(n-octylthio)-1,3,5-triazine, as a bicyclic hindered phenol, 4,4'-thiobis(6-te
r t -3-methylphenol), 4,4'-butylidenebis(6-tert-butylphenol), 4.
4'-methylenebis(6-tert-butylphenol), 4,4'-bis(2,6-tert-butylphenol), 4,4'-thiobis(5-tert-butyl-〇-cresol), 4,4 '-methylenebis(5-
tert-butyl-O-cresol), 2,2'-methylenebis(4-methyl-6-tert-butylphenol), 2,2'-thiobis(6-tert-butyl-4
-methylphenol) and 1,6-bis(3,5-di-tert-butyl-4-hydroxy-2-methylphenyl)butane, as polycyclic (two or more rings) hindered phenols, 1,1° 3-tris (3,5-te)
rt-butyl-4-hydroxybenzyl)methylene, 1
, 3,5-tris(3,5-di-tert-butyl-4-hydroxybenzyl)in cyanurate, tetrakis[β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionyloxymethylcomethane, etc. A typical example can be shown.

Among these antioxidants, monocyclic hindered phenols are preferred, and n-octadecyl-5-(4'-hydroxy-3°5-di-tert-
butylphenyl) propionate.

Examples of the ultraviolet absorber used in the present invention include salicylate compounds, benzophenone compounds, benzotriazole compounds, and hindered amine compounds.

Among these ultraviolet absorbers, hindered amine compounds are preferred, and 4-benzoyloxy-2,2',
6,6'-tetramethylpiperidine N-(2-ethylphenol) -N'-(2-ethoxy-3-ter
t-Butylphenol/I/) oxalic acid diamine, N-(2-ethyl-phenol)-N-(2-4
Toki'/-3-tert-butylphenol)
Oxalic acid diamine, bis(2,2',6
, 6'-tetramethyl-4-piperidine) sebacate, and the like.

Particularly preferred is bis(2,2',6,6'-tetramethyl-4-piperidine) sebacate.

In the present invention, the antioxidant and the ultraviolet absorber impart antioxidant and ultraviolet absorber functions to the surface of the eyeglass frame made of the epoxy resin composition according to claim 1, which does not contain the antioxidant and the ultraviolet absorber. It does not need to be used when a surface protective layer is applied, but it is necessary to use it when not applied.

By using these antioxidants and ultraviolet absorbers, it is possible to obtain a cured product that is even more excellent in weather resistance and resistance to coloring dyes.

The amount of the system consisting of an antioxidant and an ultraviolet absorber based on the epoxy resin base is 0.05 to 10 parts by weight,
Preferably it is 0.1 to 5 parts by weight.

In the present invention, the weight ratio of the antioxidant to the ultraviolet absorber to be blended is from 1:0.1 to 1=10, preferably from 1:0.2 to 1:5.

In the present invention, the curing temperature is from 80°C to 150°C, preferably from 100°C to 130°C, and the curing time is
It is 0.5 to 8.0 hours, preferably 1.0 to 3.0 hours.

In the curing reaction, complete curing can be achieved under one type of curing condition, but preferably, a stepwise curing condition is adopted to obtain a cured product. Note that the curing temperature and curing time can be arbitrarily controlled by adjusting the amount of the curing accelerator.

The amount of curing accelerator is usually 0.05 to 5% based on the base resin.
．． 0 parts by weight, preferably 0.5 to 4.0 parts by weight, particularly preferably 1.0 to 3.0 parts by weight.

The reason for this is that increasing the amount of curing accelerator will shorten the curing time, but if the amount exceeds 3.0, the amount of self-heating of the epoxy resin composition will increase, and the cured product will turn pale yellow. This is because it is colored.

The cured product obtained under these reaction conditions has excellent transparency and weather resistance, as well as excellent weather resistance for colored dyes, does not cause skin damage, and has low mechanical strength, flexibility, and heat distortion temperature. A well-balanced plastic eyeglass frame that does not lose its shape when maintained at 80 to 95° C. is obtained.

〔Example〕

Next, the present invention will be explained in more detail with reference to examples.
The present invention is not limited to this.

In the examples, the weather resistance test was carried out using a red disperse dye (Di
anix ACE-Trio, which has the worst weather resistance among the three primary colors, was used as an index. ) was carried out on samples stained using the same method.

The test conditions were: temperature 63±2℃, relative humidity 50%, 100%
Time and weather resistance were evaluated using color difference ΔE ab.

(Example 1) Diglycidyl ether of bisphenol A type (molecular weight:
368-388, epoxy equivalent: 190) 100 parts by weight, 89 parts by weight of methylhexahydrophthalic anhydride (acid anhydride equivalent: 168) as a hardening agent, and 23 parts by weight of polypropylene glycol (molecular weight: 2000) as a flexibility imparting agent. and 1.5 parts by weight of 1,8-diazabicyclo(s+4to)undecene-7(DBU)-2-ethylhexanoate as a curing accelerator were mixed well and uniformly, and after defoaming by a conventional method, a resin mold was formed. The mixture was poured into a mold and cured by heating at 120° C. for 2 hours to obtain a plastic eyeglass frame.

(Example 2) Diglycidyl ether of hydrogenated bisphenol A type (molecular weight = 440-480, epoxy equivalent = 230 ± 10) 1
00 parts by weight, 73 parts by weight of methylhexahydrophthalic anhydride (acid anhydride equivalent = 168) as a curing agent, and polypropylene glycol (molecular weight: 950 as a flexibility imparting agent).
) and 1.5 parts by weight of tetrabutylphosphonium acetate as a curing accelerator are mixed well and uniformly,
A plastic eyeglass frame was obtained in the same manner as in Example 1.

(Example 3) Diglycidyl ether of hisphenol FW (molecular weight:
320-350. Epoxy equivalent = 160-175) 10
0 parts by weight, 85 parts by weight of methyltetrahydrophthalic anhydride (anhydride equivalent: 166) as a curing agent, and a polyether triol (molecular weight: 200
0) and 1.2 parts by weight of tetraethylammonium bromide as a curing accelerator were mixed uniformly and well, and a plastic eyeglass frame was obtained in the same manner as in Example 1.

(Example 4) 100 parts by weight of bisphenol AD type diglycidyl ether (molecular weight: 344, epoxy equivalent: 172), 98 parts by weight of methylhexahydrophthalic anhydride (acid anhydride equivalent: 168) as a hardening agent, and a flexible 24.5 parts by weight of polypropylene glycol (molecular weight: 2000) as a imparting agent and 1.3 parts of DBU/phenol salt as a curing accelerator.
The parts by weight were mixed well and uniformly, and a plastic eyeglass frame was obtained in the same manner as in Example 1.

(Example 5) 60 parts by weight of bisphenol A type diglycidyl ether used in Example 1, 40 parts by weight of hydrogenated bisphenol A type diglycidyl ether used in Example 2, and Example 1 and 83 parts by weight of methylhexahydrophthalic anhydride used in step 2, 18 parts by weight of polypropylene glycol (molecular weight: 1000) as a flexibility imparting agent, and 1.5 parts by weight of benzyltriphenylphosphonium bromide as a curing accelerator were uniformly added. After mixing well, a plastic eyeglass frame was obtained in the same manner as in Example 1.

(Example 6) Diglycidyl ether of bisphenol A type (molecular weight =
368-388, epoxy half amount: 190) 100 parts by weight, and methylhexahydrophthalic anhydride (as a hardening agent)
Acid anhydride equivalent: 168) 105 parts by weight and polypropylene glycol diglycidyl ether (
Molecular weight: 2000) 19 parts by weight, and 1.5 parts by weight of DBU 2-ethylhexanoate and DB as curing accelerators.
0.3 parts by weight of U@p-toluenesulfonate was mixed well and uniformly, defoamed by a conventional method, and then cast into a resin mold.
A plastic eyeglass frame was obtained by heat curing at 30° C. for 1.5 hours.

(Comparative Example 1) A commercially available eyeglass frame using an amine compound as a hardening agent.

(Comparative Example 2) The epoxy resin main ingredient and the amine compound curing agent described in Japanese Patent Publication No. 49-24687 were uniformly and well mixed by chemical equivalent blending, and a plastic eyeglass frame was obtained by the method described in the same publication.

(Comparative Example 3) 1.3 parts by weight of tris(dimethylaminomethyl)phenol, which is a tertiary amine, as a curing accelerator, and the main agent, curing agent, and flexibility imparting agent used in Example 1 were The ingredients were mixed well and uniformly in the same amounts as in Example 1, and plastic eyeglass frames were obtained in the same manner.

Physical properties were compared between the eyeglass frames obtained in Comparative Examples 1 to 3 and the eyeglass frames obtained in Examples 1 to 6.

The comparison results are shown in Table 1.

*1 Deflection rate: Bending test (JIS K7203
).

Book 2 When the color difference ΔE ab is 2.5 or less, the human eye cannot see the color difference.

As shown in Examples 1 and 6, the main agent according to claim 1, a curing agent other than an amine compound, and a flexibility imparting agent selected to minimize the decrease in mechanical strength and heat distortion temperature. , and the use of a curing accelerator that has excellent potential for catalytic activity and can yield a colorless and transparent cured product, resulting in an excellent cured product with a good balance between mechanical strength, flexibility, and heat distortion temperature. A glass eyeglass frame with physical properties can be obtained.

In addition, the heat distortion temperature is 75°C shown in Comparative Examples 1 and 2.
It can be seen that the temperature range is from 80°C to 95°C compared to 78°C, indicating that the glass glasses frame does not easily lose its shape.

In particular, weather resistance to colored dyes can be dramatically improved compared to conventional products. Furthermore, it can be determined from Comparative Example 3 that when commonly used tertiary amines are used as a curing accelerator, the weather resistance to colored dyes decreases.
The importance of specific curing accelerators according to the present invention can be seen.

(Example 7) 1.0 parts by weight of n-octadecyl-5-(4'-hydroxy-3,5-di-tert-butylphenyl)propionate as an antioxidant and bis(2,2', 6,6'-tetramethyl-4-piperidine) sebacate and the main ingredient, curing agent, flexibility imparting agent, and curing accelerator used in Example 1 were mixed in the same manner as in Example 1. The blended amounts were mixed well and uniformly, and plastic eyeglass frames were obtained in the same manner.

(Comparative Example 4) Plastic eyeglass frame obtained in Example I without using an antioxidant and an ultraviolet absorber.

(Comparative Example 5) The epoxy resin base agent and amine compound curing agent used in Comparative Example 2 were used in the same amounts, and the antioxidant and ultraviolet absorber used in Example 7 were used in the same amounts. The mixture was mixed well and uniformly, and a plastic eyeglass frame was obtained in the same manner as in Example 7.

(Comparative example 6) Comparative Example IK Plastic eyeglass frame shown.

The physical properties of the eyeglass frames obtained in Comparative Examples 4 to 6 and the plastic eyeglass frame obtained in Example 7 were compared.

The comparison results are shown in Table 2.

Table 2 *1 Deflection rate: Bending test (JIS K7203
).

*2 If the color difference ΔE ab is 2.5 or less, the human eye cannot see the color difference.

From a comparison between Example 7 and Comparative Example 4, it was found that by using an antioxidant and an ultraviolet absorber, the weather resistance against coloring dyes of the plastic eyeglass frame obtained from the epoxy resin composition according to claim 1 was further improved. It turns out that it can be improved.

It is also found that the antioxidant and UV absorber do not affect the mechanical strength, flexibility and heat distortion temperature.

〔Effect of the invention〕

As described above, the plastic eyeglass frames obtained by cast molding and heat curing using the epoxy resin composition of the present invention are substantially colorless, transparent,
Excellent weather resistance and resistance to coloring dyes.
It does not cause skin damage.

Furthermore, it maintains a balance between mechanical strength, flexibility, and heat distortion temperature, and in particular reduces heat distortion temperature from 80°C to 95°C.
These are excellent plastic eyeglass frames that do not lose their shape when set at ℃.

Claims (2)

[Claims] (1) General formula (a) ▲There are mathematical formulas, chemical formulas, tables, etc.▼(a) General formula (b) ▲There are mathematical formulas, chemical formulas, tables, etc.▼ ▲There are mathematical formulas, chemical formulas, tables, etc.▼(b) ( In the formula, R_1 is a straight chain or branched alkylene group having 8 or less carbon atoms, or a bonding group selected from -O-, -S-, -SO_2-, or -C-, and n is 0 or 5 or less. A base resin consisting of a so-called epoxy resin having a molecular weight of 300 to 2000 and selected from diepoxides derived from bisphenols represented by the formula (an integer); ) ▲There are mathematical formulas, chemical formulas, tables, etc.▼(c) (In the formula, R_2 is an aromatic hydrocarbon group or a cycloaliphatic hydrocarbon group, and R_3 is a straight-chain or branched alkyl group having 10 or less carbon atoms. group, carboxyl group, or hydrogen; X_1 is -O-, -S-, or a bonding group selected from ▲Numerical formula, chemical formula, table, etc.; R_4 is a straight chain or branched chain having 7 or less carbon atoms. It is an alkyl group.)
A curing agent selected from one type or a combination of two or more of the compounds represented by General formula (d) ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (d) General formula (e) ▲ Numerical formulas, chemical formulas , tables, etc. ▼ ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (E) General formulas (F) ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (F) General formulas ( G) ▲There are mathematical formulas, chemical formulas, tables, etc.▼ ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (G) General formula (4) ▲There are mathematical formulas, chemical formulas, tables, etc.▼ ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (H) ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ General formulas (Li) ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (Li) ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ General formula (nu) ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (nu) ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ General formulas (ru) ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ ▲ Mathematical formulas, chemical formulas, tables, etc. There are ▼ ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (ru) ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (In the formula, R_5 is a straight line with 8 or less carbon atoms. chain or branched alkylene group, R_6 is a straight chain or branched alkyl group having up to 4 carbon atoms, R_7, R_8, and R_9
is a straight chain or branched alkylene group having 5 or less carbon atoms, m and q are 0 or an integer of 10 or less, and l
and m+q is 1 or more, p is an integer of 5 or less, and is not 0. ) A flexibility-imparting agent having a molecular weight of 60 to 5,000 and selected from polyether polyols and polyether polyglycidyl ethers represented by one type or a combination of two or more, and general formula (w) ▲ Numerical formula, chemical formula , tables, etc. ▼ (wo) General formula (wa) ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (wa) General formula (f) ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (f) (In the formula, R_1_0 , R_1_2, R_1_3 are groups selected from an alkyl group, an alkenyl group, an allyl group, or a benzyl group, and R_1_4, R_1_5, R_1_
6, R_1_7 is a group selected from a hydrogen atom, an alkyl group, an alkenyl group, an alkoxy group, an allyl group, or a benzyl group; It is a counter anion consisting of an acid. ) A curing accelerator selected from one type or a combination of two or more types of quaternary phosphonium salts, quaternary ammonium salts, or salts of 1,8-diazabicyclo(5,4,0)undecene-7 represented by an epoxy resin composition obtained by mixing the epoxy resin composition, wherein the ratio of the active group equivalent of the system consisting of the curing agent and the flexibility imparting agent to the epoxy equivalent of the base resin is from 0.7 to 1.5. The epoxy resin composition wherein the amount of the flexibility imparting agent is 5 to 60 parts by weight relative to the base resin, and the amount of the curing accelerator is 0.05 to 5.0 parts by weight relative to the base material. A plastic eyeglass frame characterized by being obtained by cast molding and heat curing. (2) A plastic characterized by being obtained by casting an epoxy resin composition obtained by mixing the epoxy resin composition according to claim 1 with an antioxidant and an ultraviolet absorber and curing with heat. eyeglass frames.