JPH11256041A - Inorganic resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a resin composition which can form a high-hardness thin coating film by heat treatment at a relatively low temperature by mixing an epoxy-containing alkoxysilane (co)hydrolyzate with an aminosilane and a zirconium chelate compound. SOLUTION: It is desirable that a silane compound derivative based on 100 pts.wt. epoxy-containing alkoxysilane hydrolyzate or cohydrolyzate and 10-100 pts.wt. aminosilane is mixed with a zirconium chelate compound. The zirconium chelate compound used is desirably is one represented by the formula: Zr(lig)n (OR)4-n (wherein lig is a chelate-forming group such as acetylacetone or ethyl acetoacetate; R is an alkyl; and n is 1-4). The amount of the zirconium chelate compound used is usually desirably 0.5-25 pts.wt. (in terms of zirconium oxide) per 100 pts.wt. epoxy-containing alkoxysilane hydrolyzate or cohydrolyzate.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an inorganic resin composition capable of forming a thin film having high hardness by heat treatment at a relatively low temperature. According to the composition of the present invention, it is possible to easily form a high-hardness thin layer coating on the surface of glass, ceramics, metal, synthetic resin, etc. by applying abrasion resistance. Is possible.

[0002]

2. Description of the Related Art Generally, PMMA (polymethyl methacrylate), PC (polycarbonate), PVC (polyvinyl chloride), PET (polyethylene terephthalate)
Products molded with thermoplastic resins (hereinafter referred to as "resins") are widely used because they are inexpensive and easy to mold, and are lighter and have better impact resistance and transparency than glass products. I have.

However, the surface hardness of the above resin is generally inferior to that of glass products, so that the surface of the resin is damaged during transportation of the product, during installation, during use, and the like, resulting in a decrease in product yield and a decrease in product yield. Since there was a problem of lowering the value, there was a demand to improve the surface hardness of these products. Such a request exists not only for the above resin products but also for those made of glass or a metal material. Therefore, a number of methods for increasing the surface hardness of a product by forming a film by applying and curing a resin composition on the surface of the product have been proposed.

A well-known method is as follows.
(1) A method of forming a thermosetting film in which a coating material containing alkoxysilane as a main component and optionally colloidal silica is applied to the surface of a resin product and heated, and (2) two or more ( A method of forming a UV-cured film by applying a coating mainly composed of a polyfunctional monomer (monomer) having a (meth) acrylic group to the surface of a resin product and irradiating the surface with an active energy ray such as ultraviolet light. It is.

[0005]

However, (1)
Because the method of forming a thermosetting film is mainly made of a material having a relatively high ratio of inorganic components, the effect of improving abrasion resistance is great, but the hardness is increased by polycondensation of alkoxysilane by thermosetting. In addition, the treatment must be performed at a relatively high temperature for a long time, and this high-temperature long-time treatment is not preferable for a product using a resin material having poor heat resistance such as PMMA. Although the method (2) of forming an ultraviolet-cured coating film has the advantage of being able to be cured at a low temperature for a short time, at present the performance of the cured coating film such as abrasion resistance, durability and adhesion is not sufficient. is there.

[0006] The present invention provides a thin layer having good abrasion resistance, durability, adhesion, and abrasion resistance, which adheres well to the surface of various resins including PMMA, glass, ceramics, and metals. An object of the present invention is to obtain an inorganic resin composition capable of easily forming a coating film, thereby solving the above-mentioned problems.

[0007]

That is, the present invention provides an inorganic resin comprising one or more hydrolyzed or co-hydrolyzed products of epoxy group-containing alkoxysilane, aminosilane and zirconium chelate. Related to the composition.

In the above, 100 parts by weight of one or more hydrolyzates or co-hydrolysates of an epoxy group-containing alkoxysilane, 10 to 100 parts by weight of aminosilane, and zirconium chelate of 0.5 to 25 as zirconium oxide. It is suitable that the amount is from 1 to 10 parts by weight.

The zirconium chelate is preferably a zirconium chelate represented by the following general formula. Zr (lig) _n (OR) _4-n where lig represents a chelate-forming group such as acetylacetone or ethyl acetoacetate, R represents an alkyl group, and n represents an integer of 1 to 4.

The present inventor has analyzed the components of the conventional thermosetting inorganic resin composition and the functions of the components, and provided a specific silane compound derivative with a low-temperature curability and a hardness improving property. As a result of diligent studies based on the finding that the above problem can be solved by combining the catalysts described in
100 parts by weight of one or more hydrolyzed or co-hydrolyzed products of epoxy group-containing alkoxysilanes and aminosilanes 10 to 100 described in US Pat.
It has been found that a silane compound derivative whose main component is parts by weight can be preferably used, and a specific catalyst for imparting low-temperature curability and hardness improvement properties is represented by the general formula Zr (lig) _n (OR) _4-n , Lig represents a chelating group such as acetylacetone or ethyl acetoacetate, R represents an alkyl group, and n represents an integer of 1 to 4. Have been found to be suitable.

The silane compound derivative which can be used in the present invention is obtained by preparing in advance one or more hydrolyzate or co-hydrolyzate of an epoxy group-containing alkoxysilane and adding an amino group-containing silane thereto. Are preferred.

Examples of the epoxy silane having an epoxy group include glycidoxymethyltrimethoxysilane, glycidoxymethyltriethoxysilane, β-glycidoxymethyltrimethoxysilane, β-glycidoxymethyltriethoxysilane, and γ-glycol. Sidoxymethyltrimethoxysilane, γ-glycidoxymethyltriethoxysilane,
3,4-epoxycyclohexylmethyltriethoxysilane, β- (3,4-epoxycyclohexyl) ethyltriethoxysilane, β- (3,4-epoxycyclohexyl) propyltrimethoxysilane, β- (3,4-
Epoxycyclohexyl) propyltriethoxysilane and the like can be exemplified.

Examples of the amino group-containing silane include aminomethyltrimethoxysilane, aminomethyltriethoxysilane, aminoethyltrimethoxysilane, aminoethyltriethoxysilane, aminopropyltrimethoxysilane, aminopropyltriethoxysilane, (β-amino Ethyl) -β-aminopropyltrimethoxysilane,
(Β-aminoethyl) -β-aminopropylmethyldimethoxysilane, (β-aminoethyl) -γ-aminopropyltrimethoxysilane and the like can be exemplified.

Specific examples of the zirconium compound include zirconium tributoxy acetylacetonate, zirconium dibutoxy bisacetylacetonate, zirconium tetraacetylacetonate,
Zirconium tributoxy ethyl acetoacetate, zirconium monobutoxy acetylacetonate bisethyl acetoacetate and the like can be exemplified.

These are generally commercially available in the form of an organic solvent solution having a concentration of about 7.5 to 15% in terms of zirconium oxide, dissolved in a solvent such as toluene and / or n-butanol.

In the present invention, the addition weight of the zirconium compound is 0.5 to 25 parts by weight as zirconium oxide with respect to 100 parts by weight of one or more hydrolyzed or co-hydrolyzed products of the above-mentioned epoxy-containing alkoxysilane. , Preferably in the range of 1 to 10 parts by weight. 0.5
When the amount is less than 25 parts by weight, the low-temperature curability is insufficient, so that sufficient hardness cannot be obtained. It is not economical.

In the inorganic resin composition of the present invention, various dyes and pigments can be added in order to enhance the decorativeness. As such a dye, an organic solvent-soluble dye, for example, a metal complex salt dye commercially available from Hodogaya Chemical Industry Co., Ltd. as an Eizenspirone dye or a UTCO color pigment for oiliness commercially available from Dainichi Seika is preferably used.

Further, in the inorganic resin composition of the present invention,
Other functional fine particles and the like can be added. Examples of the functional fine particles include silica, zirconia, etc., which improve hardness, indium oxide, tin oxide, titanium oxide, carbon, graphite, etc., which give conductivity, and magnesium oxide, alumina, etc. which give thermal conductivity. Furthermore, it is also possible to add a wetting agent, a thixotropic agent, a diluting solvent, an antifoaming agent and the like for improving the coating property.

[0019]

DESCRIPTION OF THE PREFERRED EMBODIMENTS Hereinafter, the present invention will be described with reference to Examples 1 to 10, but the present invention is not limited to these Examples.

Examples 1 to 5 and Comparative Example 1 100 parts by weight of γ-glycidoxypropyltrimethoxysilane were dissolved in 105 parts by weight of ethylene glycol monoethyl ether, and 45 parts by weight of water and 0.3% of 35% hydrochloric acid were added thereto.
The mixture was cooled to room temperature, and then 50 g of γ-aminopropyltriethoxysilane and 75 g of ethylene glycol monoethyl ether were added.
The parts by weight were added and mixed uniformly to obtain a silane compound derivative (1).

4 g of the zirconium compound solution shown in each column of Examples 1 to 5 of Table 1 was mixed with the silane compound derivative (1) 50
g was added to a solution diluted with 50 g of xylene.
To 5 were prepared.

The inorganic resin composition liquid according to each of the examples is applied to a glass plate, and firstly at 80 ° C. for 30 minutes and then for 15 minutes.
Thermal curing was performed at 0 ° C. for 30 minutes. The resulting film had a thickness of 1 to 2 μm, was a colorless and transparent uniform film, and had a pencil hardness of 7H or more (see Table 1). For comparison, when the same experiment was performed using a solution containing no zirconium compound, the pencil hardness was 5 to 6H (Comparative Example 1).

[0023]

[Table 1]

Examples 6 to 9 and Comparative Example 2 50 parts by weight of γ-glycidoxypropyltrimethoxysilane and 50 parts by weight of β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane were mixed with ethylene glycol monoethyl ether diacetone. After dissolving in 70 parts by weight of alcohol, 30 parts by weight of water and 0.2 parts by weight of 35% hydrochloric acid were added thereto, reacted at 65 ° C. for 5 hours, cooled to room temperature, and then (β-aminoethyl) -γ 25 parts by weight of -aminopropyltrimethoxysilane, 25 parts by weight of γ-aminopropyltriethoxysilane, and 125 parts by weight of ethylene glycol monoethyl ether were added and uniformly mixed to obtain a silane compound derivative (2).

50 g of this silane compound derivative (2) was diluted with 25 g of diacetone alcohol and 25 g of xylene,
4 g of the zirconium compound solution shown in Example 1 was added thereto.
8 g, 15 g, and 30 g were added to prepare inorganic resin composition liquids of Examples 6 to 9.

The inorganic resin composition liquid according to each of the examples is applied to a glass plate, first at 80 ° C. for 30 minutes, and then at 18 ° C.
Thermal curing was performed at 0 ° C. for 10 minutes. The film thickness of the obtained film was 1-2 μm, it was a colorless and transparent uniform film, and the pencil hardness was 7H, 7H, 7H, 7H in each example. For comparison, when the same experiment was performed using a solution containing no zirconium compound, the pencil hardness was 5H (Comparative Example 2).

Example 10 and Comparative Example 3 The composition described in Example 1 was applied to a PMMA plate, and heat cured at 80 ° C. for 30 minutes and then at 120 ° C. for 2 hours. The thickness of the obtained film was 1-2 μm, it was a colorless and transparent uniform film, and the pencil hardness was 7H. For comparison, when a solution containing no zirconium compound (the composition described in Comparative Example 1) was applied to a PMMA plate and cured, the pencil hardness was 4H (Comparative Example 3).

[0028]

As is apparent from the above description,
Since the inorganic resin composition of the present invention comprises one or more kinds of hydrolysis or co-hydrolysates of epoxy group-containing alkoxysilane, aminosilane and zirconium chelate, a thin layer having high hardness is obtained by heat treatment at a relatively low temperature. Since a film can be formed, a wear-resistant and high-hardness film can be easily formed on the surface of glass, ceramics, metal, resin, etc., and can be used in a very wide range of fields.

Claims (3)

[Claims] 1. An inorganic resin composition comprising one or more hydrolyzed or co-hydrolyzed products of epoxy group-containing alkoxysilane, aminosilane and zirconium chelate. 2. 100 parts by weight of a hydrolyzate or co-hydrolyzate of one or more of epoxy group-containing alkoxysilanes, 10 to 100 parts by weight of aminosilane and 0.5 to 25 parts by weight of zirconium chelate as zirconium oxide; An inorganic resin composition comprising preferably 1 to 10 parts by weight. 3. The inorganic resin composition according to claim 1, wherein the zirconium chelate is a zirconium chelate represented by the following general formula. Zr (lig) _n (OR) _4-n where lig represents a chelate-forming group such as acetylacetone or ethyl acetoacetate, R represents an alkyl group, and n represents an integer of 1 to 4.