JPS606369B2 - Manufacturing method of anti-fog transparent composite - Google Patents

Description

[Detailed description of the invention] The present invention relates to a method for producing an anti-fog transparent composite.

More specifically, the present invention applies a specific coating agent to various transparent substrates such as transparent plastics and glass,
The present invention relates to a method for producing a cloud-proofing transparent composite material, which is characterized in that the cured film is made cloud-proof by further hydrolysis treatment after heating and curing. Conventionally, window glass for buildings, vehicle glass, aircraft glass, etc., made of glass or transparent plastic moldings,
Attempts have been made to provide cloud-proofing properties to the surfaces of doors, mirrors, eyeglass lenses, goggles, optical lenses, etc. by coating them with hygroscopic resin, and this has already been put to practical use in some applications.

However, such conventional hygroscopic resins have a drawback in terms of surface hardness that should be improved.
In general, films with anti-cloud properties are hydrophilic, so they have been prevented from decreasing in hardness. This is because in high humidity conditions where cloud-proofing properties are to be exhibited, a large amount of water molecules are absorbed inside the membrane, so the resin tends to swell due to high humidity and reduce surface hardness. Therefore, there has been a strong desire in the industry for a technology that maintains surface hardness and simultaneously improves anti-fog properties.

As a result of intensive research, the present inventors succeeded in improving two contradictory properties, namely, improving surface hardness and improving anti-fogging properties, by using a specific coating agent and performing a specific treatment.

Therefore, the main object of the present invention is to provide a method for producing a cloud-proof transparent composite that maintains surface hardness and has improved fog-proofing properties.

Still another object of the present invention is to provide a coachwag material that can be applied to a transparent substrate such as glass or transparent plastics to provide antifogging properties.

The objects and advantages of the present invention will be made clear in the following.

The present invention provides a reaction modified product of one or more alkoxy group-containing silane compounds represented by the general formula: 60 to 9 parts by weight; A coating agent consisting of 40 to 2 parts by weight of two or more epoxy group-containing polymerizable vinyl monomers or (co)polymers thereof and 50 to 15 parts by weight of a solvent is applied to a transparent substrate such as glass or transparent plastic. The cured film obtained by coating and curing by heating at a temperature of 30q0 to 200oo, preferably 60oo to 150oo for several minutes to 5 hours is hydrolyzed at a temperature of 50 to 10,000℃ for several hours using an acid catalyst if necessary. However, in the above general formula, R is an alkylene group having 2-4 carbon atoms; R2 is an alkyl group having 1-4 carbon atoms; R3 is OR2 or an alkylene group having 1-3 carbon atoms; an alkyl group; and X is hydrogen or a methyl group.

Examples of the alkoxy group-containing silane compounds used in the present invention include methacryloxymethyltrimethoxysilane, methacryloxymethyltriethoxysilane, methacryloxymethyltripropoxysilane, methacryloxymethyltributoxysilane, methacryloxyethyltrimethoxysilane, and methacryloxymethyltrimethoxysilane. Ethyltriethoxysilane, methacryloxyethyltripropoxysilane, methacryloxyethyltributoxysilane, methacryloxypropyltrimethoxysilane, methacryloxypropyltriethoxysilane, methacryloxypropyltripropoxysilane, methacryloxypropyltributoxysilane, acryloxymethyl Trimethoxysilane, acryloxymethyltriethoxysilane, acryloxymethyltripropoxysilane, acryloxymethyltributoxysilane, acryloxyethyltrimethoxysilane, acryloxyethyltriethoxysilane, acryloxyethyltripropoxysilane, acryloxyethyltri Butoxysilane, acryloxypropyltrimethoxysilane, acryloxypropyltriethoxysilane, acryloxypropyltripropoxysilane, acryloxypropyltriptoxysilane, a substitute for the trialkoxysilane group of the above silane compounds.This is dimethoxymethylsilane. , dimethoxyethylsilane, dimethoxypropylsilane, diethoxymethylsilane, diethoxyethylsilane, diethoxypropylsilane, dimethoxybutylsilane, diethoxybutylsilane, dipropoxymethylsilane, dipropoxyethylsilane, dipropoxypropylsilane, Examples include propoxybumethylsilane, diptoxymethylsilane, dibutoxyethylsilane, diptoxypropylsilane, and compounds substituted with dibutoxybutylsilane groups.

The polymerizable vinyl compounds containing an epoxy group used in the present invention include methallyl glycidyl phenol, glycidyl methacrylate, and chrycidyl acrylate.

In the present invention, the transparent substrate is glass or polyvinyl chloride resin, polyvinylidene chloride resin, polycarbonate resin, oak resin made of a polymer or copolymer of methacrylic acid or acrylic acid ester, poly(diethylene glycol bisallyl carbonate) resin, polystyrene resin, It is useful as a primer for transparent plastic substrates such as styrene-acrylonitrile copolymer resin, polyvinyl phthral resin, cellulose acetate resin, and polyester resin, among which polycarbonate resin, polymethyl methacrylate resin, cellulose acetate resin, etc. are exemplified. .

The first feature of the present invention is that the above-mentioned alkoxysilane compound and vinyl monomer are used together.

That is, when using only an alkoxysilane compound, emphasis is placed only on improving hardness, and the resulting film is brittle and does not have sufficient adhesion. However, the above problems could be solved by reacting the vinyl monomer with the alkoxysilane compound. This fact is proven in Example 3. The antifogging and bending properties obtained by applying the above coating agent to a transparent substrate such as glass or transparent plastic and hydrolyzing the cured film after curing it are more effective when alkoxy groups and amino groups coexist. It was found from Example 1 that an excellent product could be obtained.

. Furthermore, when obtaining antifogging properties by hydrolyzing the cured film, the reaction will not proceed sufficiently unless the hydrolysis temperature is 5000 or higher, resulting in insufficient antifogging properties. In this case, the presence of an acid catalyst is more effective. This hydrolysis treatment slightly reduces the initial hardness of the film, so it is necessary to increase the hardness as much as possible at the stage of obtaining the initial cured film. By the way, if hydroxyl groups are generated by hydrolysis, it may be possible to perform the hydrolysis from the beginning, but this is not possible. This is because all of these hydroxyl groups are involved in the condensation reaction during heat curing, and the result is that they do not contribute to cloud-proofing properties at all, but only improve hardness. In the cured film state, the degree of freedom of the alkoxy groups present on the film surface is suppressed, making it difficult for them to contribute to the condensation reaction. The performance test of the obtained cloud-proof cured film was as follows.

Adhesiveness to the substrate Pocket test, i.e. with a razor blade on the coating.
Ten incisions reaching the base material were made per square millimeter, cellophane tape was pasted onto the incisions, and when the tape was strongly peeled upward 900 mm, the number of coatings remaining was determined.

When there is no peeling at all, it is displayed as loo/100.
Surface hardness Measured by pencil hardness test according to JISK5651.

Hereinafter, the present invention will be explained more specifically based on Examples.

Note that "parts" used in the examples are by weight unless otherwise specified. Example 1 A modified product obtained by mixing 10 parts of vinyltriethoxysilane, 5 parts of glycidyl methacrylate, and overflowing to 70 qo. - Add 4 parts of methacryloxypropyltrimethoxysilane, 10 parts of ethyl cellosolve, and add 5 parts of y-ray from cobalt-60.
Irradiation was carried out in an air atmosphere for 4 hours at a dose rate of ×1 and R/hr.

This solution was applied to the surface of a diethylene glycol bisallyl carbonate substrate and heated at 11,000 for 3 hours to cure it. The cured film obtained was a colorless, transparent, uniform film, with a hardness of 7 days and a peeling test result of 100.
/100, no cloud-proofing property was observed. However, the above cured film (thickness: 10 French) was mixed with 50 q containing 0.1% hydrochloric acid.
When treated for 3 hours in warm water of
No clouding occurred on the surface even when exhaled air was blown outdoors at 0°C. The hardness of this coating film was uneven, the result of the grid test was 100/100, and no change in appearance was observed. Example 2 After reacting 10 parts of vinyltrimethoxysilane and 10 parts of 3,4-epoxycyclohexylpropyltrimethoxysilane for 3 hours in an oil bath containing 1,100 ml of silane, 8 parts of the resulting modified product were obtained. In advance, a mixture of 5 parts of allyl glycidyl ether, 5 parts of hydroxyethyl acrylate, 5 parts of vinyl triethoxysilane, and 0.5 parts of isopropyl peroxide was added to 75 oo to bring the liquid viscosity to 300-35 p. After that, prepolymer composition liquid 2 to which 85 parts of methanol had been added was added and mixed.

Apply this solution to the surface of the polycarbonate base material for 130 minutes.
It was cured by heating at qo for 2 hours. The obtained cured film was a colorless transparent uniform film, the hardness was fine, the result of the grid peeling test was 100/100, and it was not observed in the outdoor breath test of Boun Ouma 1oo○. However, the above cured film (thickness 13A) was
When treated in warm water at 0° C. for 2 hours, this coating film did not develop any clouding on the surface even when air was blown on it outdoors. The performance of the coating film after treatment is
The result of the grid test was 100/100. Example 3 10 parts of 3,4-epoxycyclohexylpropyltrimethoxysilane and 10 parts of y-glycidoxypropyltrimethoxysilane were reacted for 4 hours in an oil bath controlled at 100:00. A mixture of 15 parts of glycidyl methacrylate, 15 parts of 2-hydroxyethyl methacrylate, and 1 part of penzoyl peroxide was added to 75 parts of the modified product at 80:00 to bring the viscosity of the solution to 350-4.
After adjusting the ratio to 0 p, 25 parts of a prepolymer composition solution containing 7 parts of ethyl cellosolve was added and mixed.

Claims (1)

[Claims] 1 (A) Reaction-modified product 60 of one or more alkoxy group-containing silane compounds represented by the general formula of group [I]
~98 parts by weight; (b) 1 represented by the general formula of group [II]
A coating agent consisting of 40 to 2 parts by weight of a species or two or more epoxy group-containing polymerizable vinyl monomers or (co)polymers thereof and (c) 50 to 150 parts by weight of a solvent is applied to a transparent substrate. A method for producing an anti-fogging transparent composite consisting of heating and curing the coating film and hydrolyzing the resulting cured film using an acid catalyst if necessary; [I] Group ▲ Includes mathematical formulas, chemical formulas, tables, etc. ▼ [II] Group ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ However, R_1 is an alkylene group with 2-4 carbon atoms; R_
2 is an alkyl group having 1-4 carbon atoms; R_3 is OR_2
or an alkyl group having 1 to 3 carbon atoms; and X is hydrogen or a methyl group. 2. The method according to claim 1, wherein the hydrolysis is carried out in hot water at 50°C to 100°C. 3. Heat curing of the coating film at 30°C to 200°C, preferably the method according to claim 1. 4. Transparent base material is glass or polyvinyl chloride resin, polyvinyl chloride resin, polycarbonate resin, resin consisting of polymer or copolymer of methacrylic acid or acrylic acid ester, poly(diethylene glycol bisallyl carbonate) resin, polystyrene resin, styrene resin.
A patent for a transparent plastic selected from the group consisting of acrylonitrile copolymer resins, polyvinyl butyral resins, cellulose acetate resins and polyester resins, among others, polycarbonate resins, polymethyl methacrylate resins, cellulose acetate resins, etc. The method according to claim 1.