JPS60212470A - Coating resin composition - Google Patents

Abstract

PURPOSE:To provide the titled composition containing emulsion of a water- resistant polymer, a compound capable of forming a chelate, and colloidal silica, etc., and capable of imparting excellent adhesivity, rust-preventing property and storage stability to steel plate, aluminum, glass, etc. CONSTITUTION:The objective composition can be prepared e.g. by compounding (A) 10-70(wt)% emulsion of a water-resistant polymer (based on the composition), (B) 5-20% polyhydric phenol carboxylic acid polyhydric alcohol ester having adjacent hydroxyl groups and/or polynucleous polyhydric phenol having adjacent hydroxyl groups (based on the whole composition), (C) 0.5-10% phosphorus acid having P-OH bond (e.g. orthophosphoric acid), ester of a phosphorus acid or salt of a phosphorus acid and (D) 2-20% colloidal silica. EFFECT:Even a ruse steel plate or a substrate having inadequate primary coating layer can be painted.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a resin composition for paint. More specifically, the present invention relates to a rust-preventing coating composition containing an emulsion of a water-resistant polymer, a chelate-formable compound, and colloidal silica. In particular, the present invention provides excellent adhesion and rust prevention to not only rust-free steel plates and derusted steel plates, but also rusted steel plates or poorly treated steel plates, aluminum, zinc steel plates, stainless steel, glass, etc. The present invention relates to a coating composition having good properties and storage stability.

Conventionally, water-resistant polymer emulsions have been widely used as paints, but the performance of the paint film is significantly affected by the surface treatment before painting, mainly the degree of rust removal. If you paint with insufficient surface treatment,
This causes poor adhesion and significantly reduces corrosion protection performance.

The purpose of the present invention is to have excellent adhesion, corrosion resistance, and storage stability even when applied directly to rust-free steel plates, steel plates with simplified surface treatment, or rusted steel plates. An object of the present invention is to provide a resin composition for paint.

The coating resin composition of the present invention comprises an emulsion (A) containing a water-resistant polymer as an essential component, and a polyhydric phenol carboxylic acid polyhydric alcohol ester (B-1) having adjacent hydroxyl groups and/or an adjacent hydroxyl group. For paints containing polynuclear polyhydric phenol (13-II), phosphorus acid, ester of phosphorus acid or salt of phosphorus acid <c> having at least one P-OH bond, and colloidal silica (D) It is a resin composition.

Examples of the emulsion (A) containing a water-resistant polymer, which is an essential component of the composition of the present invention, include various polymer latexes, such as styrene-butadiene polymers, acrylonitrile-butadiene polymers, acrylic polymers, and vinyl chloride polymers. Examples include latexes such as polymers, acrylic acid ester polymers, and urethane polymers.

Examples of the polyhydric phenol carboxylic acid polyhydric alcohol ester (B-1) having adjacent hydroxyl groups in the molecule used in the present invention include the following.

That is, the polyhydric alcohol components include ethylene glycol, propylene glycol, butylene glycol, 1,
Diols such as 6-hexanediol, triols such as glycerin and trimethylolpropane, polyols with a valence of 4 or more such as pentaerythritol, sorbitol, glucose, etc. can be used, and as the polyhydric phenol carboxylic acid component having adjacent hydroxyl groups, Catechol-3-carboxylic acid, catechol-4-carboxylic acid (protocatechuic acid), gallic acid ('3,4.5-trioxybenzoic acid)
, m~digallic acid, pyrogallol-4-carboxylic acid, pyrogallol-4,6-dicarboxylic acid, tannic acid, etc. can be used, and a typical structure of the ester is, for example, an ester of glycerin and protocatechuic acid. , it is thought that higher-order condensation is also included.

Preferred examples of the polynuclear polyhydric phenol (B-11) having adjacent hydroxyl groups used in the present invention include the following. Formalin condensate of catechol and catechol-3 (or 4)-carboxylic acid (or its ester)
Formalin condensate of pyrogallol, formalin condensate of pyrogallol, pyrogallol-4-carboxylic acid (or its ester)
Formalin condensate of pyrogallol-4,6-dicarboxylic acid or its ester), 3.4
．． 5") formalin condensate of lyoxybenzoic acid (or its ester), tannic acid (or its ester) or its formalin condensate, formalin condensate of urushiol. Also, when polyhydric phenol is condensed with formalin, phenol, cresol , hydroquinone, salicylic acid, and other mononuclear phenols.

Examples of the phosphorus acid <C> having at least one P-○I] bond used in the present invention include orthophosphoric acid, meclic acid, pyrophosphoric acid, phosphorous acid, polyphosphoric acid, phosphonic acid, phosphinic acid, etc. orthophosphoric acid is particularly preferred.

Further, as the phosphorus acid ester (C) having at least one P-OH bond, the above-mentioned phosphorus acid ester,
Preferably, alkyl esters having up to about 8 carbon atoms (having one or more hydroxyl groups) and hydroxyalkyl esters, such as ethyl, n7''yl, 2-ethylhexyl, hydroxyethyl, hydroxydibutyl, hydroxypropyl, hydroxybenzyl, etc. Among these, mono- or di-phosphoric acid esters of n-butyl or 2-ethylhexyl are particularly preferred.

Further, as the phosphorus acid salt (C) having at least one I"OH bond, the above-mentioned phosphorus acid salts, such as salts of potassium, sodium, lithium, calcium, zinc, aluminum, tin, barium, etc. Among them, primary or secondary phosphates of potassium, sodium or calcium are particularly preferred.

Colloidal silica (D>) used in the present invention is also called silica sol, and is a colloidal aqueous dispersion of 5i02 (silica), which can be used, for example, for neutralization of sodium silicate, ion exchange treatment of sodium silicate, decomposition of silicic acid, etc. Colloidal particles can be obtained by various methods such as hydrolysis of silicon or ethyl silicate, and products include Applied (manufactured by Asahi Denka) and Ludox (manufactured by DuPont). is 5 to 100 mμ, 5i02 (silica) concentration 25 to
Generally, 50% by weight of colloidal silica can be used, but colloidal silica whose surface has been specially treated to increase the stability of the colloid is also used.

In preparing the coating resin composition of the present invention, the water-resistant polymer emulsion (A) contains 10 to 70% by weight of the water-resistant polymer as a solid content, preferably 25% by weight of the composition.
The polyhydric alcohol ester (B-I) and/or the polynuclear polyhydric phenol (B-11), which are chelate compounds, are used in an amount of 0.5 to 55% by weight based on the total weight of the composition. 20% by weight, preferably 3-10% by weight
and phosphorus acid or ester or salt (C) in an amount of 0.5 to 10% by weight, preferably 2 to 5% by weight based on the total weight of the composition, and colloidal silica (D)
is 1 to 30% by weight, preferably 2 to 30% by weight based on the total weight of the composition.
It is used in an amount of 20% by weight.

Furthermore, two or more types of water-resistant polymers can be used in the composition of the present invention, if necessary, and diluents such as ethyl cellosolve, butyl cellosolve, and acetic acid cellosolve, solvents, coloring pigments, antirust pigments, fillers, Other additives can be used in combination.

The coating composition of the present invention can be dried naturally to form a coating film, but if necessary, the desired coating film can also be obtained by forced drying by heating or the like.

The present invention will be described in detail below with reference to Examples, but the present invention is not limited to these Examples. In addition, all parts in the examples mean parts by weight.

Example 1 Styrene-butadiene polymer latex (product name
N1POL LX 119, Nippon Zeon M) 100 parts of glycerin protocatechuic acid triester (molecule [
1500), 5 parts of monoethyl phosphate, and 20 parts of ethyl cellosolve to make a homogeneous emulsion solution (
1) was obtained.

For 100 parts of this emulsion solution (1), add colloidal silica (trade name: Applied AT-30, manufactured by Asahi Denka).
10 parts were mixed to obtain a coating resin composition (I)' of the present invention.

Example 2 100 parts of modified acrylic acid ester polymer latex (trade name N1POL LX 856, manufactured by Nippon Zeon) were mixed with 5 parts of m-G gallic acid ester of glucose, 3 parts of dibasic potassium phosphate, and 15 parts of cellosolve acetate. A uniform emulsion solution (2) was obtained.

For 100 parts of this emulsion solution (2), colloidal silica (trade name Applied AT-2OA, Asahi Denka M
) 15 parts of the coating resin composition (II) of the present invention
I got it.

Example 3 Acrylonitrile-butadiene polymer latex (
Product name N1POL LX 51 parts (manufactured by Nippon Zeon) 10
0 parts formalin condensate of catechol (molecular weight 450)
A uniform emulsion solution (3) was obtained by mixing 15 parts of orthophosphoric acid, 8 parts of orthophosphoric acid, and 25 parts of butyl cellosolve.

To 100 parts of this emulsion solution (3), 5 parts of colloidal silica (trade name: Applied AT-20Q, manufactured by Asahi Denka) was mixed, and the coating resin composition of the present invention (I[[)
I got it.

Comparative Example 1 The emulsion solution (1) obtained in Example 1 was used as a coating resin composition (IV).

Comparative Example 2 The emulsion solution (2) obtained in Example 2 was used as a coating resin composition (V).

Comparative Example 3 Acrylonitrile-butadiene polymer latex (
Product name N1POL LX 511, manufactured by Nippon Zeon) 1
An emulsion solution (4) obtained by adding 10 parts of colloidal silica (trade name: Applied AT-30, manufactured by Asahi Denka Co., Ltd.) to 00 parts of the emulsion was used as a coating resin composition (VI).

The coating resin compositions (1) to (Vl) obtained in Examples 1 to 3 and Comparative Examples 1 to 3 above were respectively applied to a steel plate, and a coating test and an adhesion test were conducted under the conditions shown in Table 1 below. The physical properties of each were measured and the results shown in Table 1 were obtained. In Table 1, *1, *2, and *3 are as follows.

*1: Product name N1POL LX 51 (manufactured by Nippon Zeon) *2: Goban tape test *3: 90 degree peel test Kg/cm (8 STM D-1
876) From the results shown in Table 1, it can be seen that the resin composition for paint of the present invention has excellent adhesion and rust prevention properties.

Furthermore, as a result of examining the storage stability of the coating resin compositions (I [) and (V) of the present invention], the coating resin composition (V) to which no colloidal silica was added was found to be more stable after one week of production. However, the coating resin composition (II) of the present invention did not produce the above-mentioned precipitate even after one year, and no performance deterioration was observed. Ta.

Claims (1)

[Claims] As essential constituents, an emulsion (A) containing a water-resistant polymer, a polyhydric phenol carboxylic acid polyhydric alcohol ester having adjacent hydroxyl groups (13-1) and/or a polynuclear polyhydric phenol having adjacent hydroxyl groups (B-11) ), a phosphorus acid, an ester of a phosphorus acid, or a salt of a phosphorus acid (C) having at least one P-OH bond, and a colloidal silica (D).