JPS647092B2 - - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a thermosetting resin composition having excellent abrasion resistance, flexibility, and dyeability. Plastic molded products are used in large quantities because of their advantages such as light weight, easy workability, and impact resistance.
However, on the other hand, it has disadvantages such as insufficient hardness and easy scratching, easy attack by solvents, and insufficient heat resistance, making it unsatisfactory in practical applications for use in eyeglass lenses, window glass sheets, etc. It was hot. Many proposals have been made to overcome these drawbacks, such as coating with high-hardness materials or developing high-hardness plastics, but the reality is that none of them has been fully satisfactory. Particularly when trying to improve the surface characteristics of plastic lenses and other products by coating them with paint, appearance defects may occur on the surface due to the atmosphere during painting or foreign matter or gel-like substances in the paint. There is a big problem that high quality products cannot be obtained. A method that has been considered to solve these problems has been a method of curing cut and polished glass in a mold. The coating composition used in this method must not contain substances such as solvents that have a low boiling point and are substantially non-reactive, and coating compositions that have been conventionally used in such methods as,
Examples include polyfunctional acrylic monomers and diethylene glycol bisallyl carbonate. Such a coating composition is polymerized in a glass mold in the presence of a radical polymerization catalyst to provide the desired product. However, the materials obtained by these methods have serious problems such as low hardness or inability to be dyed with disperse dyes. As an alternative to the above-mentioned method, commonly used methods include, for example, vacuum deposition, sputtering, or ion plating to improve the surface properties of plastic lenses, especially their surface hardness. Although various studies have been conducted, such as the formation of a film,
There are problems with productivity, dyeability, heat resistance, etc., and a satisfactory product has not been obtained. Also, JP-A-53-147796 and JP-A-53
JP-147798 discloses a composition in which an aluminum compound or a titanium compound is used as a catalyst in a compound having an epoxy group. However, the composition in such technology is
It did not have sufficient scratch resistance. Further, JP-A-53-111336 describes a coating composition mainly consisting of a compound having an epoxy group, a silanol and/or a siloxane group, and an aluminum chelate compound. However, this technique has a problem in that when heated and polymerized in a closed mold, curing does not progress sufficiently and a molded product with sufficient wear resistance cannot be obtained. An object of the present invention is to provide a thermosetting resin composition that has excellent abrasion resistance and can be made into a molded article having sufficient abrasion resistance, particularly by heating polymerization in a closed mold. The inventors of the present invention have conducted intensive studies to achieve the above object, and as a result, have arrived at the present invention described below. That is, the present invention provides the following component A: a silane compound having at least one epoxy group and a hydroxyl group bonded to a silicon atom in the molecule. B Aluminum chelate compound represented by the general formula Al・X ¹ _o・Y ¹ _3-o . Here, X ¹ is a C ₁ to C ₈ alkoxy group, and Y ¹ is
A ligand derived from a compound selected from the group consisting of M ¹ COCH ₂ COM ² and M ³ COCH ₂ COOM ⁴ , where M ¹ , M ² , M ³ and M ⁴ are lower alkyl groups, and n is 0, 1 Or 2. C A titanium compound represented by the general formula Ti.X ² _n.Y ² _4-n or a condensate thereof. Here, X ² is a hydroxyl group or C ₁ to C ₈ , HOR ^a
A ligand derived from a compound selected from the group consisting of COOH and N(R ^b OH) ₃ , M ⁵ ,
M ⁶ , M ⁷ and M ⁸ are lower alkyl groups, R ^a and R ^b are C ₁ to _{C 8} hydrocarbon groups, and m is 2, 3 or 4. A thermosetting resin composition comprising: The main features of the thermosetting resin composition of the present invention are that it has excellent scratch resistance, flexibility, and dyeability. Useful in coating agents, laminating resins, and molded articles, particularly in molded articles obtained by thermal polymerization in closed molds, providing a product with excellent abrasion resistance. etc. Next, each component forming the thermosetting resin composition of the present invention will be explained. A silane compound having at least one epoxy group and a hydroxyl group bonded to a silicon atom in the molecule of component A is defined by the general formula or (However, R ¹ is C ₁ to C ₆ alkyl, alkoxyalkyl, acyl, R ² is C ₁ to C ₆ alkyl,
Halogenated alkyl, aryl or halogenated aryl, R ³ is hydrogen or methyl group, n is 2 or 3, a is 1 to 6, b is 0 to 2, R ⁴ is C ₁ to C ₆
Alkyl, alkoxyalkyl, acyl, R ⁵
is _C1 - _C6 alkyl, halogenated alkyl, aryl or halogenated aryl, m is 2 or 3). It is a hydrolyzate of a compound represented by Specific representative examples of such compounds include γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane, γ-(β-glycidoxyethoxy)propyltrimethoxysilane, and γ-glycidoxypropyltrimethoxysilane. Xypropylmethyldimethoxysilane, γ-glycidoxypropylmethyldiethoxysilane, γ-glycidoxypropylphenyldimethoxysilane, β-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, β-
Examples include (3,4-epoxycyclohexyl)ethyltriethoxysilane. The aluminum chelate compound represented by the general formula Al・X ¹ _o・Y ¹ _{3-o, which} is component B of the present invention, includes:
Various compounds can be mentioned, but the solubility in the composition,
Particularly preferred from the viewpoint of effectiveness as a curing catalyst are aluminum acetylacetonate, aluminum bisethylacetoacetate monoacetylacetonate, and aluminum di-n.
-butoxide-monoethyl acetoacetate, aluminum-di-iso-propoxide-monomethylacetoacetate, etc. It is also possible to use a mixture of two or more of these. General formula Ti・X ² _n・Y ² _4-n which is component C of the present invention
Various types of titanium compounds and condensates thereof can be mentioned, and specific representative examples of such compounds include tetraethoxytitanium, tetra-i-propoxytitanium, and tetra-i-propoxytitanium.
n-butoxytitanium, tetrakis(2-ethylhexoxy)titanium, tetra-i-propoxytitanium oligomer, tetra-i-propoxytitanium polymer, tetra-n-butoxytitanium oligomer, tetra-n-butoxytitanium polymer, di-
i-propoxy bis(acetylacetonate)
Titanium, di-n-butoxy bis(triethanolaminate) titanium, dihydroxy-bis(lactate) titanium, trihydroxy mono(lactate) titanium, dihydroxy bis(tartrate) titanium, dihydroxy bis(citrate) titanium, etc. can be mentioned. In addition to the above-mentioned components, various compounds can be added to the composition of the present invention depending on its purpose or use, specific examples of which include organosilicon compounds other than component A, epoxy resins, organic polymers, etc. . As organosilicon compounds, methyl silicate,
Ethyl silicate, i-propyl silicate, n
-Propyl silicate, n-butyl silicate,
Tetraalkoxysilanes such as sec-butyl silicate and t-butyl silicate, methyltrimethoxysilane, methyltriethoxysilane,
Methyltrimethoxyethoxysilane, ethyltrimethoxysilane, methyltriacetoxysilane,
Ethyltriethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, vinyltrimethoxyethoxysilane, vinyltriacetoxysilane, phenyltrimethoxysilane, γ-chloropropyltrimethoxysilane, 3,3,3-trifluoropropyltri Methoxysilane, γ-methacryloxypropyltrimethoxysilane, γ-
Trialkoxy or triacyloxysilanes such as mercaptopropyltrimethoxysilane, β-cyanoethyltriethoxysilane, and dimethyldimethoxysilane, phenylmethyldimethoxysilane, dimethyldiethoxysilane, γ-chloropropylmethyldimethoxysilane, dimethyldiacetoxysilane, γ - There are dialkoxysilanes or diacyloxysilanes such as methacryloxypropylmethyldimethoxysilane, γ-mercaptopropylmethyldimethoxysilane, and methylvinyldimethoxysilane. Component A of the present invention and the hydrolyzate of the above silane compound are produced by adding pure water or an acidic aqueous solution such as hydrochloric acid or sulfuric acid and stirring. During hydrolysis, alcohol, alkoxy alcohol, organic carboxylic acids such as acetic acid, etc. are produced, so hydrolysis can be carried out without a solvent. Furthermore, the silane compound can be mixed with a suitable solvent and then hydrolyzed. Depending on the purpose, it is also possible to use the product after hydrolyzing it without a solvent and removing an appropriate amount of the resulting alcohol, alkoxy alcohol, or organic carboxylic acid such as acetic acid, and water under heating and/or reduced pressure. It is also possible to substantially replace the solvent by subsequently adding a suitable solvent. Various solvents such as alcohols, esters, ethers, ketones, halogenated hydrocarbons, and aromatic solvents such as toluene can be used depending on the purpose, and mixed solvents can also be used if necessary. Examples of epoxy resins are those that are widely used in paints, casting, etc., such as polyolefin epoxy resins synthesized by peroxidation method, cyclopentadiene oxide, cytoclohexene oxide, hexahydrophthalic acid or water. Alicyclic epoxy resin such as polyglycidyl ester or polyglycidyl ether obtained from added bisphenol A and epichlorohydrin, bisphenol A, bisphenol F and catechol,
Polyglycidyl ethers obtained from polyhydric phenols such as resorcinol or polyhydric alcohols such as (poly)ethylene golicol, (poly)propylene glycol, neopentyl glycol, glycerin, trimethylolpropane, pentaerythritol, diglycerol, and sorbitol, and epichlorohydrin. , epoxidized vegetable oils, epoxy novolacs obtained from novolac-type phenolic resin and epichlorohydrin, epoxy resins obtained from phenolphthalein and epichlorohydrin, and co-existence with acrylic monomers such as glycidyl methacrylate and methyl methacrylate, or styrene, etc. Examples include polymers. Examples of organic polymers include polyvinyl alcohol, hydroxyl group-containing polymers such as cellulose acetate butyrate, polyhydroxyethyl methacrylate, and bidroxyethyl cellulose, polyvinyl acetate, and copolymers of acrylic esters and/or methacrylic esters (among them (including copolymers with other vinyl monomers), polyamides,
Polyester, various amino resins (melamine resin,
(including urea resins, etc.). The curing reaction of the thermosetting resin composition containing the above components is achieved at room temperature or by heating. When the composition of the present invention is used for molding or laminating, it is preferable to substantially completely remove the solvent including water in order to eliminate defects caused by foaming. Various methods can be used to make the composition of the present invention substantially solvent-free, such as removal by heating under normal pressure or reduced pressure, or removal using various adsorbents. When using the composition of the present invention as a coating agent, a surfactant may be used to improve fluidity during application, improve the smoothness of the coating film, and reduce the coefficient of friction on the coating surface. In particular, block or graft copolymers of dimethylsiloxane and alkylene oxide are effective. Furthermore, it is also possible to add an ultraviolet absorber for the purpose of improving weather resistance, and an antioxidant to improve thermal deterioration. The objects to be coated with the composition of the present invention include polymethyl methacrylate and copolymers thereof, acrylonitrile-styrene copolymers, polycarbonates, cellulose acetate,
polyvinyl chloride, polyethylene terephthalate,
Epoxy resin, unsaturated polyester resin, CR―
Examples include plastic molded products such as 39 (diethylene glycol bisallyl carbonate polymer), films, inorganic glass, wood, and metal articles. As the application means, commonly used coating methods such as brush coating, dip coating, roll coating, spray coating, and flow coating can be easily used. Furthermore, the composition of the present invention can be made substantially solvent-free, and in particular can be heated and polymerized in a closed mold, making it possible to transfer a template. The molded product obtained by this method can have particularly excellent surface appearance. The amount of component B added in the present invention is 0.1 to 100 parts by weight, particularly preferably 0.5 parts by weight, per 100 parts by weight of component A.
~50 parts by weight is appropriate, and if it is less than 0.1 parts by weight, curing will be insufficient, and if a molded product is obtained by heating polymerization in a closed curing mold, sufficient wear resistance will not be provided. I can't. On the other hand, if it exceeds 100 parts by weight, defects such as decreased transparency of the coating film or resin will occur. The amount of component C added is per 100 parts by weight of component A.
0.01 to 10 parts by weight, particularly preferably 0.1 to 5 parts by weight, is appropriate; if it is less than 0.01 parts by weight, curing will be insufficient, and when a molded product is obtained by heating and polymerizing in a closed curing mold. , cannot impart sufficient wear resistance. On the other hand, if it exceeds 10 parts by weight, gelation tends to occur. Hereinafter, the present invention will be explained in more detail with reference to Examples. Examples 1 to 3, Comparative Examples 1 and 2 (1) Preparation of silanol-containing epoxy compound 236.0 g of γ-glycidoxypropyltrimethoxysilane and γ-glycidoxypropylmethyldiethoxy were placed in a reactor equipped with a rotor. Silane 436.5g
Add 0.01N hydrochloric acid aqueous solution 117.4 while stirring.
Add g at once. Immediately after addition, the solution is opaque, but soon becomes a homogeneous solution. Then about 1 more
Stirring was continued for hours to obtain a hydrolyzate. This hydrolyzate was treated at 50° C. for 2 hours under a reduced pressure of 3 mmHg to obtain a concentrate. The water content of the concentrate was approximately 3% by weight as determined by the Karl Fischer method. Molecular sieve for 100g of the above concentrate
After adding 20 g of 5A and leaving it at room temperature for 24 hours, a silanol-containing epoxy compound was obtained. (2) Preparation of thermosetting resin composition Various titanium compounds (hereinafter referred to as component C) are added to 100 parts by weight of the silanol-containing epoxy compound.
Add the amount shown in Table 1, under reduced pressure of 3 mmHg,
After treatment at 50° C. for 1 hour, an aluminum chelate compound (hereinafter referred to as component B) and additives were added in amounts shown in Table 1 to obtain a thermosetting resin composition. As a comparative example, a composition in which component B and component C were not added was also prepared at the same time. (3) Preparation of plano lens for coating A plano lens with a center thickness of 2.1 mm was made by cutting and polishing using a thermosetting acrylic resin polymer having the following monomer composition as a material. Monomer composition tetramethylolmethanetetraacrylate
15g Methacrylic acid 3g Methyl methacrylate 82g Benzoyl peroxide 0.08g Dicumyl peroxide 0.3g n-dodecyl mercaptan 0.4g Tinuvin-P 0.02g Polymerization was performed by cast polymerization, and the polymerization conditions were 45°C, after heating for 48 hours, It was heated at 80°C for 30 minutes and at 130°C for 2 hours, and then taken out after cooling. (4) Curing and performance evaluation of thermosetting resin composition Using one plano lens obtained in (3) above and two chemically strengthened glasses each having the same curvature,
Approximately 3g of the above resin composition was injected and fixed by sandwiching it in a sandwich shape, and then heated at 80°C for 16 hours.
Furthermore, raise the temperature to 110℃ while keeping it as it is.
Heating continued for an hour. Thereafter, the lens was cooled and removed from the glass mold, and then further heated and dried at 110°C for 10 minutes. The following tests were conducted on the obtained lenses. In addition, as a result of visually inspecting the appearance, no defects such as foreign objects were observed in any of them. (a) Abrasion resistance test Rub with steel wool #0000 to check the resistance to scratches. Judgment was made as follows. A...It won't get scratched even if it is rubbed strongly. B... If you rub it quite strongly, it will get a little scratched. C...Even weak friction can cause damage. In addition, untreated thermosetting acrylic resin lenses are C
It was hot. Comparative Example 3 The same procedure as in Example 2 was carried out except that the silanol-containing epoxy compound was not completely added. As a result, the surface of the obtained lens was only covered with insufficiently cured polymer, was easily scratched by fingernails, and could not withstand the friction test with #0000 steel wool. . 【table】

Claims (1)

[Scope of Claims] 1. A thermosetting resin composition characterized by containing the following components A, B and C. A: A silane compound having at least one epoxy group and a hydroxyl group bonded to a silicon atom in the molecule. B Aluminum chelate compound represented by the general formula Al・X ¹ _o・Y ¹ _3-o . Here, X ¹ is a C ₁ to C ₈ alkoxy group, and Y ¹ is
A ligand derived from a compound selected from the group consisting of M ¹ COCH ₂ COM ² and M ³ COCH ₂ COOM ⁴ , where M ¹ , M ² , M ³ and M ⁴ are lower alkyl groups, and n is 0, 1 Or 2. C A titanium compound represented by the general formula Ti.X ² _n.Y ² _4-n or a condensate thereof. Here, X ² is a hydroxyl group or a C ₁ to C ₈ alkoxy group, Y ² is M ⁵ COCH ₂ COM ⁶ ,
M ⁷ COCH ₂ COOM ⁸ , HOR ^a COOH and N(R ^b
OH) is a ligand derived from a compound selected from the group consisting of ₃ , where M ⁵ , M ⁶ , M ⁷ and M ⁸ are lower alkyl groups, and R ^a and R ^b are C ₁ to C ₈ hydrocarbon groups. , m is 2, 3 or 4.