JPS6021665B2 - Room temperature drying paint - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a one-component paint that dries at room temperature and has excellent adhesion to an undercoat film.

At present, two-component urethane paints are the first type of paints that dry at room temperature and have excellent adhesion.

This paint has excellent film performance other than adhesion, and does not require so-called sanding (polishing the base coat with sand vapor first grade) to improve adhesion to the base coat. Both are widely used because they can be applied directly onto the base coat and have excellent adhesion. However, there are problems during use due to the two-component type, and furthermore, due to the toxicity of the curing agent component, sufficient safety measures must be taken for the painting operator and the painting environment.

Therefore, the present inventor investigated a single-component paint that dries at room temperature, is easy to handle, and has good adhesion, and found that a specific epoxy resin phosphate ester and polyamide were used as vehicle components. They found that a room-temperature-drying paint containing an essential ingredient had excellent effects and released it.
That is, the present invention provides, as essential components of the vehicle component, 1) a compound having an epoxy group and a monomer [B-] having an epoxy group and an active unsaturated group selected from orthophosphoric acid, orthophosphorous acid, and sulfuric acid; Compounds having unsaturated resins and/or epoxy groups into which unsaturated groups are introduced by ester bonding through one or more inorganic polybasic acids 'q 1 or 2, R' is a hydrocarbon group or halogenated hydrocarbon group having 2 to 20 carbon atoms, R2 is hydrogen or a methyl group, X is P
04, P03 or S04) into which an unsaturated group is introduced through an ester bond, and a room temperature drying paint containing polyamide (0).

The compound having an epoxy group which is a component of the unsaturated resin which is an essential component in the vehicle component in the present invention is, for example, Epon 828, 1001, 1004, 100.
7,1009 (all trade names manufactured by Shell Chemical Co., Ltd.), epoxy resins with a bisphthalate skeleton, Shodine 5
Glycidyl ether resin such as 00 (trade name manufactured by Showa Kobunshi Co., Ltd.), epoxidized oil, Cardular E (
It refers to an oligomer or polymer having at least one epoxy group in one molecule, such as glycidyl methacrylate or a copolymer containing glycidyl acrylate (trade name manufactured by Shell Chemical Co., Ltd.).

Alternatively, synthetic resins such as polyester, acrylic urethane, and polybutadiene may be modified with polyepoxy compounds to introduce epoxy groups into the resin skeleton. This epoxy compound may be saturated or unsaturated. The monomer {B) having an epoxy group and an active unsaturated group refers to, for example, glycidyl acrylate, glycidyl methacrylate, allyl glycidyl enalic, and the like. The compound plate represented by the above general formula is an adduct of an inorganic polybasic acid) and a monomer having a hydroxyl group and an active unsaturated group. Examples of the monomer having a hydroxyl group and an active unsaturated group include Acrylates such as 2-hydroxyethyl, 2-hydroxypropyl, 3-hydroxypropyl, 3-chloro-2-hydroxypropyl, or methacrylates, allyl alcohol, glycidyl acrylate or glycidyl methacrylate and carboxylic acids (such as benzoic acid) and monoadducts of acrylic acid or methacrylic acid and epoxy compounds (e.g., epichlorohydrin).

Examples of such compound legs include Phosmer M (trade name, manufactured by Yushi Products Co., Ltd.). The method for introducing an active unsaturated bond into an epoxy compound is to react a compound having an epoxy group with a reaction product of a monomer (B} having an epoxy group and an active unsaturated group and an inorganic polybasic acid (C'). Alternatively, an unsaturated resin can be obtained by reacting an adduct of a compound having an epoxy group and an inorganic polybasic acid with a monomer having an epoxy group and an active unsaturated group. When a monomer having one epoxy group is used as the monomer [B', the three components described above can be reacted simultaneously.

Furthermore, an unsaturated resin can be obtained by reacting a compound having an epoxy group with a compound represented by the above-mentioned general formula. The reaction between the inorganic polybasic acid 'C' and the compound ■ and/or the epoxy group in the monomer leg, and the reaction between the compound and the compound ■, are carried out at approximately 60 to 15
The process is completed by heating at 0° C. for about 3 to 1 calm hour.

The end point of the reaction is determined by the acid value, but the reaction rate is 90% or more,
It is desirable to reduce the amount of free inorganic acid as much as possible.
In order to prevent thermal polymerization of active unsaturated groups in these reactions, it is preferable to add 50 to 100 polymerization inhibitors such as hydroquinone. As described above, the unsaturated resin which is an essential component in the vehicle component of the present invention can be obtained.

Next, polyamide, which is an essential component in the vehicle component,
It is a thermoplastic polyamide with a softening point of 90°C to 125°C, a molecular weight of 4,000 to 800, and an amine value of 5 or less, which is solid at room temperature. For example, Tomide #394, #
395, #90 (product name manufactured by Fuji Kasei Kogyo Co., Ltd.), Versamide #930, #940, #950 (Daiichi General Co., Ltd.)
Co., Ltd. product name). In the present invention, the above-mentioned unsaturated resin and polyamide are essential components of the vehicle component.

However, if only these two are used as vehicle components, although the adhesion, which is the objective of the present invention, is sufficient, other coating film performances (for example, coating film flexibility, etc.) may be inferior. Therefore, in practice, resins, plasticizers, etc. that are compatible with both components may be appropriately used in combination, taking into consideration other coating film performances required of the article to be coated. Examples of resins used in combination include lacquers, aminoalkyd resins, melamine resins, and epoxy resins that dry at room temperature. The mixing ratio of the unsaturated resin and polyamide in the vehicle component is preferably 5 to 3% by weight of the unsaturated resin and 20 to 6% by weight of the polyamide. If the unsaturated resin content is less than 5% by weight, the adhesion will be poor, and if it exceeds 3% by weight, the water resistance will be poor. Furthermore, if the polyamide content is less than 2% by weight, the adhesion will be poor, while if it exceeds 6% by weight, the uniformity of the coating film will be impaired. The desired one-component, room-temperature-drying paint can be obtained by adding pigments, various additives, etc., which are used in secondary vessels, to the vehicle components described above.

Incidentally, as the solvent component, alcohol, ketone, aromatic hydrocarbon solvent, etc. for paints can be used as appropriate. This paint can be applied using airless spray, air spray,
Brush painting etc. can be used, and spray painting is suitable for industrial painting lines. These coating methods and coating conditions are no different from conventionally used methods.For example, when using air spray, if necessary, apply the paint with a solvent for 10 to 30 seconds/200○ (Ford.Cup 200○). ), and whether the undercoat film is a competitive type or a drying type at room temperature, it can be painted immediately without sanding after drying or curing. The drying conditions for the coating film are about 1 hour to 4 hours at room temperature. Of course, if heating is performed at a temperature of about 60 to 10,000 to promote evaporation of the solvent and shorten the drying time, the drying time will be about 20 to 30 minutes. The adhesion of the paint of the present invention is comparable to or better than that of conventional two-component urethane paints, as sand does not cause unevenness on the undercoat film, and since it is a one-component type, it is easy to handle. For example, it can be supplied by circulation even in line painting, and has excellent workability.

Furthermore, since it dries at room temperature, it has the advantage of not requiring a baking oven or the like. Further, coating film performance other than adhesion can be adjusted by using other concomitant resins, plasticizers, etc. according to the purpose of the article to be coated. The paint of the present invention can be widely used for mainly metal products such as automobile interior parts, electrical products, and mechanical appliances.

The present invention will be explained below with reference to Examples and Comparative Examples.

Example 1 [Example of production of unsaturated resin] Orthophosphoric acid 980 taglycidyl methacrylate 1420 taglycidyl methacrylate 0.5 liters of tahydroquinone was put into a flask equipped with a neck strainer and a thermometer, and 100 q.
The reaction was carried out at o for 5 hours.

The reaction end point was when the acid value reached 460. After that, add 20% of Epon 828 (epoxy resin manufactured by Shell Chemical Co., Ltd.).
000 ta was added, and the reaction was carried out at 11 yen for 5 hours. acid value is 1
The reaction end point was when the temperature reached 20. As a result, a highly viscous unsaturated resin was obtained.

30% unsaturated resin solution 9 parts 30%
Polyamide solution (Versamide #930) 300 parts 20%
Nitrification wire solution 36 anchor plasticizer
2 black, paste 6
0 Ketone Solvent 57 Alcohol Solvent 45 Aromatic Hydrocarbon Solvent 951009 With the above-mentioned composition, each component was sufficiently mixed and shipped over the ocean to obtain a one-component room-temperature-drying paint of the present invention.

After adjusting the viscosity of this paint to 19 steps/2 pi○ (Ford, Cup side: 4), it was air-sprayed onto a metal slope coated with an undercoat and subjected to various tests. The test method and results are shown in Table 1. Example 2 [Production example of unsaturated resin] Orthophosphoric acid-2-hydroxyethyl methacrylate monoester (Hosmer M)
420 Yu Shodain 500
300 Tahydroquinone
The reaction was carried out at 100oC for 5 hours, and the end point was an acid value of 80.

30% unsaturated resin solution 11■Japan 30
% polyamide solution (Tomide #395) 28060%
Melamine resin solution 40 black paste
35 ketone solvent
50 alcohol solvent
38 Aromatic hydrocarbon solvent 8
0633 With the above-mentioned composition, each component was sufficiently mixed to obtain a one-component room-temperature-drying paint of the present invention.

This paint has a viscosity of 19 seconds/20oo (Ford Cup
No. 4), various tests were conducted in the same manner as in Example 1.

The test results are shown in Table 1. Comparative Example 1 In Example 1, a two-component urethane paint (manufactured by Kansai Paint Co., Ltd., trade name:
#4000) was used.

The other conditions were the same as in Example 1. The test results are in Table 1
Shown below. Comparative Example 2 In Example 1, the following formulation composition of a one-component room-temperature drying paint was used.

Other conditions were the same as in Example 1, and various tests were conducted.

The test results are shown in Table 1. Comparative Example 3 Same as Example 1 except that a 30% unsaturated resin solution was used alone as a vehicle component.

1 I1. Preparation of sample test board Sample test board ■・・・・・・Apply 30% of Amirac primer (manufactured by Kansai Paint Co., Ltd., trade name, thermosetting amino alkyd resin paint) to a polished European steel plate. Apply air spray paint, bake for 30 minutes, then apply Amirac No. 2 (manufactured by Kansai Paint Co., Ltd., trade name, thermosetting amino alkyd resin paint) was air-sprayed to a thickness of 35 mm and baked at 140° C. for 30 minutes.

Sample test board ■... KP Primer Surfacer (manufactured by Kansai Paint Co., Ltd., trade name, phthalate resin paint) was air sprayed to a thickness of 35 μm on a polished mild steel plate, and after drying at room temperature for 3 days. After sanding the surface uniformly with #360 sandpaper, it was further sanded with acrylic sandpaper. 1000 (manufactured by Kansai Paint Co., Ltd., trade name, acrylic resin paint) was air sprayed at 30 rpm and left at room temperature for one week.

Sanding process The test boards were divided into those in which a top coat was applied after sanding and those in which a top coat was applied without sanding.

When sanding, use #36 sandpaper.
0 was used. Melon Adherence to the eyes...
A 1 x 1 piece of burlap IOn was cut into the paint film so as to reach the substrate, adhesive cellophane tape was applied to the burlap, and the number of remaining burlap paint films was examined when the tape was removed.

W Cross-cut adhesion...Cut an X mark on the paint film, apply adhesive cellophane tape along the X part, and then examine the condition of the paint film in the X part when the tape is removed. Ta.

V Water resistance: Place the test plate in deionized water at 20°C.
After immersion for 4 hours, the condition of the coated surface was visually observed, and the cross-cut adhesion test described above was conducted.

Town Weather resistance: The test board was placed on a diagonal Bakuro stand at about 450 degrees south for 12 months, and then the condition of the painted surface was visually observed.
Furthermore, the above-mentioned cross-cut adhesion test was conducted.

Claims (1)

[Scope of Claims] 1. I) A compound having an epoxy group ((A) and a monomer (B) having an epoxy group and an active unsaturated group) are used as essential components in the vehicle component, such as orthophosphoric acid or orthophosphorous acid. and one or more inorganic polybasic acids (C) selected from sulfuric acid,
The compound (A) having an unsaturated resin and/or an epoxy group into which an unsaturated group has been introduced through an ester bond has a general formula ▲ mathematical formula, chemical formula, table, etc. ▼ (m and n are 1
or 2, R' is a hydrocarbon group or halogenated hydrocarbon group having 2 to 20 carbon atoms, R^2 is hydrogen or a methyl group, X
represents PO_4, PO_3 or SO_4); an unsaturated resin into which an unsaturated group is introduced through an ester bond; and II) a polyamide.