JPS58122972A - Silicon resin-based coating for glare protection - Google Patents

Abstract

PURPOSE:To provide a glare shielding silicone resin coating excellent in surface hardness, resistance to abrasion and solvent and superior in adhesion, prepared by adding a specified thermoplastic or thermosetting resin to a silicone resin component contained in a condensed hydrolyzate of a specified silicon compd. CONSTITUTION:A glare shielding resin component (B) is added to a silicone resin component (A) in an amount of 0.1-30PHR. (A) is a silicone resin component contained in a hydrolyzate of a silicon compd. of the formula (where R is a 1-4C hydrocarbon group, to which amino, glycidoxy or methacryloxy may be added; R' is a 1-5C hydrocarbon group or 1-4C acyl; x is 0, 1 or 2). (B) is at least one thermoplastic resin selected from among polyvinyl chloride, polyethylene, polystyrene and poly(methacrylic acid) or at least one thermosetting resin selected from among melamine and epoxy resins. The silicon compd. includes methyltrimethoxysilane, vinyltriethoxysilane, N-(trimethoxysilylpropyl)ethylenediamine, etc.

Description

[Detailed Description of the Invention] This invention can be applied to the surface of plastic molded products such as optical parts, automobile panel parts, electrical product filter cover cases, cosmetic cases, etc. to provide anti-reflection and matte properties, so-called anti-corrosion properties. This invention relates to anti-glare silicone resin paints that are not effective.

As eye protection paints, acrylic resin paints, vinyl chloride resin paints, urethane resin paints, epoxy resin paints, melamine resin paints, nitrocellulose paints, silicone resin paints, etc. are commercially available. However, no material has yet emerged that has excellent surface hardness, abrasion resistance, and solvent resistance, as well as sufficient adhesion to the molded product.

In view of L, it is an object of the present invention to provide a silicone resin paint that has excellent surface hardness, abrasion resistance, and solvent resistance, and has sufficient adhesion to the body of the molded product. purpose.

The anti-glare silicone resin paint of the present invention contains silicon and an anti-glare resin component selected from thermosetting plastic resins or thermosetting resins from a specific group with respect to silicon and resin components. By blending, the above purpose is achieved.

Hereinafter, the anti-glare silicone resin paint of the present invention will be explained in detail. .

Here, the silicon resin component used (hereinafter referred to as 1" (A) component") has the general formula -8 RxSi (OR') p-y
It is included in the hydrolyzed condensate of silicon compounds represented by . In the formula, R is a hydrocarbon group with carbon number / ~ da, or a hydrocarbon group with amino group, glycidoxy group or methacryloxy group added thereto, R' carbon number / ~ S hydrocarbon group or carbon number / ~ μ each represents an acyl group, x is O1
/ straddle 2.

Specific examples of the above silicon compounds include methyltrimethoxysilane, methyltributoxysilane, ethyltrimethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, N-()rimethoxysilylbrobyl)ethylenediamine, and aminomethyltrimethoxysilane. Silane, 3
- Trifunctional silanes such as aminopropyltrimethoxysilane, r-glycidoxypropyltrimethoxysilane, r-methacryloxypropyltrimethoxysilane, r-methacryloxypropyltrimethoxysilane, tetramethoxysilane, tetraethoxysilane, tetra There are tetrafunctional silanes such as propoxysilane and tetrabutoxysilane.

": At least seven of the silicon compounds mentioned above are dissolved in an alcohol, ester, ketone, ether, etc. N) to form a hydrolyzed condensate ((A) component liquid). At this time, a curing catalyst, a curing accelerator, and a gelling inhibitor are added as necessary.

Specific examples of the above-mentioned curing catalysts and curing accelerators include alkali metal salts of organic carboxylic acids, alkali metal carbonates, alkali metal thiocyanates, alkali metal sulfites, amines, imidazole compounds, acetylacetone metal salts,
Among these are Reinegg's salt, dicyandiamide, guanidine, polycarboxylic acids and their acid anhydrides, etc., but a combination of a particularly preferred silicone resin component, curing catalyst, and curing accelerator that satisfies the adhesion required for plastic molded products. Ru. For example, for polymethyl methacrylate molded articles, a combination of an alkyltrialkoxysilane hydrolyzed condensate and an alkali metal salt of an organic carboxylic acid, an alkali metal carbonate, an amine, guanidine, etc. is preferable, and for a polycarbonate molded article, , a combination of a hydrolyzed condensate of a quinine compound containing an epoxy group, an imidazole compound, an acetylacetone metal salt, dicyandiamide, a polyhydric carboxylic acid, and its acid anhydride.

In addition, the protective resin component (hereinafter referred to as 1-' (B) component) is a thermoplastic resin consisting of the group of polyvinyl chloride, polyethylene, polystyrene, polymethacrylic acid, or a group of melamine resin and epoxy resin. At least one selected from thermosetting resins is used. Here, whether to select a thermoplastic resin or a thermosetting resin as component (B) is determined by the fact that the former has better impact resistance than the latter, and the latter has better surface hardness and solvent resistance than the latter. excellent at
5- Therefore, the law should be applied as appropriate depending on the material and purpose of the plastic molded product to be coated.

Although this (B) component can be mixed into the (A,) component liquid even in the form of a fine powder, the dispersion stability is poor, so (B) is usually used.
Component 1 is dissolved in a soluble solvent to form a solution, or dispersed in an insoluble solvent to form a dispersion and mixed with the component (A) liquid. (B
) The blending amount of component (A) is 02/~10P
HR, more preferably 0. ! ; -20P HR. 0. /P Less than HR, the eye protection effect is small, 3
0. Exceeding the PHR will adversely affect the surface hardness, abrasion resistance, solvent resistance, etc. of the coating film.

The anti-AT silicone resin paint containing components (A) and (B) obtained by mixing and adjusting as described above is applied to the surface of a plastic molded product and cured by heating, so that the transparency is not significantly reduced. A coating film having an anti-glare effect can be obtained on the surface of a plastic molded product without causing any glare. Here, the coating means is not particularly limited, but spray coating is suitable because it allows easy adjustment of the coating thickness. In addition, the heat curing conditions are not constant depending on the type and amount of the curing catalyst, but are usually 60 to 15
0°C1 preferably L< is 70 to ioo''C.

Plastic molded products to which the anti-accumulation silicone resin paint of the present invention can be applied include polymethyl methacrylate, polycarbonate, cellulose acetate, CP (cellulose propionate), AS resin, /A 13 S resin,
Examples include those made of diethylene glycol bisallyl carbonate resin. However, the coating material of the present invention can also be applied to plastic products made of materials other than oak and stiff materials by performing appropriate pretreatment or undercoating.

In order to confirm the effects of this invention, a comparative example is given together with an example, and the results of a soft straw performance test are shown. In the examples, "1 part" indicates "part by weight."

Test method> Each paint prepared in each of the following Examples and Comparative Examples was spray applied (film thickness: !; pm) (Example/~7, Comparative Example/~t
) or immersion method (pulling speed 1.2 tsm/sec,)
(Examples ~//) was applied to the indicated plastic molded product, heated and cured under the indicated conditions, and the following physical property tests were conducted for each item. The results are shown in Tables 1 to 3.

(A) Abrasion resistance test - The surface was rubbed with #oooo steel wool, and the scratch resistance formula was determined by W and V.

The judgment criteria are as follows.

a: No scratches even if rubbed strongly.

b: Scratches occur if rubbed very strongly.

C: Scratches occur even if rubbed gently.

(b) Surface hardness...JIS-K-J IIo
According to 0.0, the highest pencil hardness without scratches was measured using a pencil scratch hardness tester (load/to 9).

(c) Appearance: Coloring of the film, foreign surface condition, etc. were checked by visual observation.

(d) Adhesion..., T I S-D -020,! Accordingly, 100 squares were made and a peel test was performed three times using cellophane adhesive tape, and the number of squares remaining was indicated.

(e) Eye resistance test: A test was conducted under the optical conditions of Method 2 of J-Technical Engineering 5-Z-J'7 Da/, and the glossiness of the 60-part bell surface was measured.

(f) Transparency...Measure the transmittance with a spectrophotometer,
'I The average value of the transmittance of 00 mm-700ff was defined as the transparency.

(g) Solvent resistance...Apply acetone at room temperature,
Its appearance was examined by visual observation.

<Example/~t, Comparative Example/~2> Mixing 10 parts of methyltrimethoxysilane with 75 parts of isopropyl alcohol 1-. Hydrolysis is carried out by gradually adding 35 parts of a 0.02N hydrochloric acid aqueous solution with stirring.

After being left at room temperature for 72 hours, parts of triethylenetetraamine O and II and 30 parts of acetic acid to prevent gelation were added to form a component (A) solution, and polymethacrylic acid was added to the component solution (A). A milky white product obtained by adding the parts shown in Table 1 of the (B) component solution prepared by dissolving 10 parts of methyl (Dianal BR-1rO, manufactured by Mitsubishi Rayon Co., Ltd.) in 90 parts of acetone while stirring at room temperature. dispersion paint. The numbers in parentheses in the FA number column of (B) component liquid indicate the (A') number of FA in component liquid.
) The PHR of component (B) (resin content) in the (B) component solution (9-) relative to component (resin content) is shown. Knead the second
The same applies to Tables 3 to 3. In addition, Comparative Example 1 is (B)
Ingredients are 0. / P HR, and Comparative Example 2 has component (B) of 301? This is a case where the HR is exceeded.

<Example S> 700 parts of r-glycidoxypropyltrimethoxysilane, 50 parts of f-dipropyl alcohol, and 20 parts of methyl alcohol were mixed, and 30 parts of a 0.02N hydrochloric acid aqueous solution was gradually added while stirring. 2 parts of the hydrolyzate at room temperature
Time release t1. After that, anhydrophthalic! ! 120 parts, no-ethyl-7-methylimidazolda part was added (A)
A polyethylene dispersion (L) was added to the component liquid as the (B) component liquid.
3-Ofl-a, 1; W; produced by Toyo Ink Manufacturing Co., Ltd.) IIo parts.

Comparative Example 3 Commercially available acrylic lacquer (T, S-/, 23;
A paint prepared by adding 41.0 parts of component (B) in Example J to 130 parts (manufactured by B Chemical Co., Ltd.).

Comparative example Silver silicon resin matte paint (commercially available).

<Example 6> 92,250 parts of methyltriethoxy and 65 parts of r-glycidoxyprobyltrimethoxysilane were mixed with 70 parts of isopropyl alcohol. 0.02N aqueous acid solution 3.
Hydrolysis is carried out by gradually adding 2 parts with stirring. After standing for 21 parts at room temperature, melamine resin (as component (B)) was added to the component (1) solution to which 1 part of dicyandiamide, 1 part of 2-methylimidazole O, and 30 parts of vinegar were added.
A dispersion paint obtained by adding 73 parts of Smelon (manufactured by Natco Paint Co., Ltd.) with stirring.

<Example 7> 5 parts of isopropyl alcohol were mixed with 2j parts of methyltrimethoxysilane and rj parts of γ-glycidoxypropyltrimethoxysilane 1-. Gradually add 35 parts of a 0.02 N aqueous acid solution while stirring to perform hydrolysis, and leave it at room temperature for 21 parts.
Add 0, a part of acetyl-7ton cobalt salt and 11 to 32 parts of vinegar to obtain the (A) component solution, and add 5 parts of epoxy resin (AEI-?-337; manufactured by Asahi Kasei Industries, Ltd.) to 20 parts of acetone.
Part was dissolved to obtain 2j parts of component (B) solution. Dispersion paint obtained by adding component (B) to component (A) while stirring at room temperature <Examples g to II> 0. After adding 23 parts of IN aqueous hydrochloric acid solution and stirring for 7 hours, 20 parts of methyl alcohol and 10 parts of ethylene glycol monoethyl ether were mixed as diluents, stirred for further 7 hours, and left to stand for 12 hours. To this was added 3 parts of maleic anhydride, and after stirring at room temperature for 1 hour, 11 parts of ammonium Reineke salt was added and the mixture was further stirred for 2 hours.
(A) Component liquid. To this (A) component liquid, add the indicated parts of the (B) component or (B) component liquid shown in Table 3 IJ[]
Dispersion paint obtained by

As shown in Tables 1 to 3, the anti-glare silicone resin paint of this invention has excellent surface hardness, abrasion resistance, and solvent resistance, and also has sufficient adhesion to the molded product body. It also has a good anal prevention effect.

That is, from Table 1, it can be seen that the amount of component (B) relative to component (A) is 0. It can be seen that if it is less than /P HR, the 0h prevention effect will be weak, and if it exceeds 30 PHR, it will have an adverse effect on the surface hardness, appearance, adhesion, and transparency. From Tables 2 and 3, it can be seen that the coating films formed with the paints of the examples all had good island-visiting effects, and also had various physical properties on the surface of the molded product (abrasion resistance, surface hardness, adhesion, solvent resistance). It can be seen that it improves one's sex (sexuality).

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Claims (1)

[Scope of Claims] A silicone resin paint for anal prevention, characterized in that the following anti-breathing resin component (B) is blended with O0/~30 PHR of the monolithic silicone resin component (A). (A) A silicon resin component contained in a hydrolyzed condensate of a silicon compound represented by the general formula Ry, Si (OF')lI-x. I. In the formula, R is a hydrocarbon group having carbon number/-1, or one to which an ami7 group, a glycidoxy group ML<k methacryloxy group is added, R' is a hydrocarbon group having carbon numbers l to j, or Each represents an acyl group having l-da carbon atoms, and X is 0. /
Or -. (B) An anti-glare resin component selected from at least seven thermoplastic resins from the group of polyvinyl chloride, polyethylene, polystyrene, and polymethacrylic acid, or thermosetting resins from the group of melamine resins and epoxy resins. 1-