JPS58109567A - Corrosion-resistant paint composition - Google Patents

Abstract

PURPOSE:To provide the titled compsn. which exhibits a high curing rate, hardly causes amine blushing, can be used without using any solvent, and has excellent rust-inhibiting performance, containing a specified liquid epoxy resin, a specified amino compd. and a rust-inhibiting pigment as essential ingredients. CONSTITUTION:A corrosion-resistant paint compsn. contains a liquid polyhydric phenol glycidyl ether type epoxy resin (A) wherein 3-15wt% monohydric phenol is attached to the terminal epoxy groups, such as a bisphenol A diglycidyl ether type epoxy resin, an amino compd. (B) contg. at least two active hydrogen atoms per molecule such as xylylenediamine, and a rust-inhibiting pigment (C) such as red lead as essential ingredients. This compsn. exhibits a very high curing rate, hardly causes amine blushing, gives a coating film having excellent adhesion and corrosion resistance, and is useful for coating of roads, non-skid coating of concrete and wood, and protective coating of steel pipes and bridges.

Description

[Detailed Description of the Invention] The first invention relates to an anti-corrosion paint composition that has a high curing speed, is aged to cause the amine brushing phenomenon, can be made solvent-free, and has excellent anti-corrosion performance. be.

Epoxy resins are widely used as anticorrosive paints for metal fertilization, but currently, paints in which type 11a epoxy resin and a hardening agent are dissolved in a solvent are mainly used. However, in recent years, attempts have been made to make it solvent-free for the purpose of reducing pollution and coating it thickly to provide anti-corrosion properties. Solvent-free coating can be achieved by using a liquid epoxy resin, but the curing speed and amine brushing properties are poor, and there has been a strong desire for an anticorrosive paint that has a faster curing speed and is less likely to cause the amine brushing phenomenon.

The inventors investigated a coating composition that has a higher curing speed than when conventional liquid epoxy resins are used, causes amine brushing phenomenon, and has excellent anti-stain and anti-corrosion properties, and has arrived at the present invention. It is something.

That is, the present invention provides (A) a liquid polyhydric phenol glycidyl ether type epoxy resin in which 6 to 15% by weight of Yilun phenol is bonded to a terminal epoxy group; This is an anticorrosive coating composition characterized by containing the above amino compound having active hydrogen, (0) Anti-1 pigment, and (A), (B), and (C) above 1F as essential components. (Hereinafter, % by weight will simply be referred to as %.) ? of rA) used in the present invention? #The epoxy resin can be made by adding appropriate m phenols to the reaction product of a suitable polyhydric phenol and epiflurhydrin and further reacting it, or by adding a polyhydric phenol, m phenols and shrimp chlorhydrin.
Obtained by simultaneously reacting phosphorus. As a suitable medium, sodium hydroxide, lithium salt, calcium chloride, tertiary amine, quaternary ammonium salt, etc. can be used. What is not obtained is a mixture of the following formulas (1), (2), and (31).

R: Polyhydric phenol residue R' Ni-valent roughenol residue Polyhydric phenol includes resorcinol, hydroquinone, bis(
4-hydroxyphenyllamethane, 2,2-bis(4-
Hydroxyphenylnopropane (commonly known as hisphenol A)
) etc., which contain two or more phenolic hydroxyl groups in the molecule and do not contain any other functional qP groups that would interfere with the formation of glycidyl ether. A typical example is sphenol A.

The m-piece phenol contains a solid phenolic hydroxyl group in its molecule, and may be mononuclear or polynuclear, and may be substituted with other groups. Examples of the -valent phenol include phenol, P-vinylphenol, pit-dibutylphenol, P-tert-octylphenol, 3,5-dimethylphenol, P-chlorophenol, and the like.

The amount of -valent phenol is epoxy (3 to 1
It is necessary to be within the wholesale range of 5%. When it is less than 3%, the curing speed is not much different from that of ordinary epoxy resins, and when it is more than 15%, the performance of the cured product decreases. Even if epoxy trees IDf with different amounts of -valent phenols are used, there is no problem as long as the monovalent phenol content of the mixture is within the above range.

CB) used in the invention - 2 or more active waters in the molecule 2
+Amine compounds include aliphatic polyamines such as ethylenediamine, diethylenetriamine, triethylenetetramine, and tetraethylenepentamine, inphoronediamine, menthanediamine, and N-aminomethyl? Peracin@) fatty aliphatic polyamines, xylylene diamine, phenylene diamine, diaminodiphenylmethane,
Examples include aromatic amines such as diaminodiphenylsulfone, polyamines containing complex groups, modified polyamines modified from these amines, and polyamide amines synthesized from natural or synthetic dicarboxylic acid and polyamines such as ethylenediamine.

(B) has an active hydrogen equivalent of 0.5 to 2.0 equivalents, preferably 0.6 equivalents, per 1 equivalent ml of the epoxy group of (A).
It is preferable to use an amount such that the amount is 1.5 to 1.5 equivalents.

The antirust pigment (C) used in the present invention includes red lead, lead zinc oxide, lead cyanamide, cyclic lead sulfate, calcium leadate,
pt = soluble pigments such as chromate, strontium chromate, m, tt, chromium lead, lead phosphate, gold F powder such as zinc powder, aluminum powder, etc. Examples include metal oxides such as iron oxide, glass flakes, and inorganic powders such as mica powder.

The composition and product of the present invention comprising the essential components (A) to (C) above (ii) exhibits the following characteristics as compared to the #4 composition in which a conventional liquid paper epoxy resin is used in place of (A).

■Curing speed is extremely high.

■It tends to cause the so-called amine brushing phenomenon, where the paint film absorbs moisture from the air and causes whitening.

■The adhesion and corrosion resistance of the paint film are the same.

Due to its characteristics, the composition of the present invention can provide a beautiful, solvent-free coating film with excellent anticorrosion performance to metal surfaces in a short time, and is effective in preventing corrosion of steel materials, iron structures, etc.

Typical applications include pavement coverings for roads and airport runways, anti-slip civil engineering and construction materials such as concrete, asphalt, wood, and netting, steel pipes, ship furnaces, automobiles, structures, bridges, steel frames, etc. protective paints, etc.

The set p%'I of the present invention includes the previous pi'! (A) ~ (C)
In addition to the essential components, pigments, additives, and other auxiliary materials for coatings may be added as desired.

Examples of face R11 additives include glass fiber, asbestos phase separation, charcoal g fiber, cellulose, polyethylene powder, kaolin, aluminum oxide, aluminum hydroxide, seratzin, silica, pallite, zeolite, titanium nitride,
There are talc, carbon black, graphite, organic coloring pigments, and various types of dispersion presses. In addition, examples of materials for paint include asphalt, coal tar, coal tar pitch, various plasticizers, petroleum resins, coumaron resins, xylene resins, ketone resins, and the like.

Although the composition of the present invention can be used without a solvent, a solvent may be added depending on the use. As the solvent, aromatic hydrocarbons such as xylene and toluene, 1:1 ketones such as methyl ethyl ketone and methyl isobutyl ketone, esters such as ethyl acetate and isobutyl acetate, and cellosolves can be used.

Hereinafter, it will be explained in detail using examples. In the examples, parts indicate parts by weight.

Real 1 Kr-1 HWR530 (M Kasei, industrial bisphenol A diglycysol ether type engineered resin. Epoxy equivalent: 185 J
Heat and stir 100 parts of sodium hydroxide at 80°C.
0.06 part of 0% aqueous solution was added and mixed uniformly. Next, 10 parts of P-tert-butylphenol was added, and while stirring
The temperature was raised to 45° OK, and the reaction was maintained at 1- for 6 hours. The epoxy equivalent weight of the reactant was 232.

Add and mix 100 parts of glass flakes to 100 parts of the Saturday and Sunday reaction product, and add 15 parts of xylylene diamine (ψp1 ratio of 1 equivalent of epoxy group to 1 equivalent of active hydrogen of the amine.Hereinafter, the amount of amine added is the same). Add 50g of
When measuring the time to gelation at room temperature,
It was 65 minutes. When this composition was applied to a thickness of 200 μm on a mild steel plate and left to cure at room temperature for 7 days, almost no whitening caused by amine brushing was observed on the coating film.

Mitsugi Example 2 P-tert-butylphenol modified A11i obtained with 33050 parts of AgR and Suit #1! and 50 parts of R33 were uniformly mixed. The amount of monohydric phenol in the mixture amounts to 4.5%. 50 parts of zinc powder was mixed with 100 parts of this mixture, 12 parts of triethylenetetramine was added, and the gelation time was measured in the same manner as in Example 1. It was 28 minutes. When this composition was formed into a coating film in the same manner as in Example 1 and left at room temperature for 7 days, almost no whitening due to the amine brushing phenomenon was observed.

Example 3 100 parts of AIR330, 1 part of P-tertiary octylphenol
A reaction product was obtained in the same manner as in Example 1 using 4 parts.

The epoxy equivalent weight was 268.

100 parts of glass flakes were mixed with 100 parts of the reactant, 14 parts of xylylene diamine was added, and the gelation time and brushing condition were examined in the same manner as in Example 1.

Gel time was 39 minutes, 8- Almost no bleaching was observed.

Comparative Example 1 AI instead of JIR330 reacted with monovalent phenol
The same procedure as in Example 1 was conducted except that R330 was used and 18 parts of xylylene cyanine was used instead of 15 parts of xylylene cyanine, and the gelation time was 85 minutes. Also,
The coating film showed significant cloudiness due to amine brushing and staining.

Example 4 Example 1.2.3. The physical properties of the coating film of Comparative Example 1 were measured.

The results are shown in Table 1.

Examples 1, 2, and 3 showed the same performance as Comparative Example 1.

Patent applicant: Asahi Kasei Industries, Ltd.

Claims (1)

[Claims] (A) 3 to 15% monohydric phenol is bonded to terminal epoxy phenol, 1V polyhydric phenol glycidyl gother type epoxy resin, (B) - Amino compound with active hydrogen of 241-1 or more in the molecule! 1 Of course, (C) Defense/fees, Saturday and Sunday F! Anticorrosion sugar #1 composition, characterized by containing (A), (B), and (0) as essential components