JPS6183263A - Oxidative drying-type paint - Google Patents

Abstract

PURPOSE:The title paint quickly drying and curing at normal or low temp. and giving a coat with excellent adhexion, which contains a specified fatty acid-modified, nitrogen-contg. alkyd resin as the vehicle. CONSTITUTION:A polybasic acid component such as succinic acid, a polyhydric alcohol component comprising an alkanolamine such as diethanolamine having at least two hydroxyl groups or comprising it and another polyhydric alcohol such as ethylene glycol, and a (semi) drying oil such as safflower oil are reacted to obtain a vehicle comprising a fatty acid-modified, nitrogen-contg. alkyd resin of a hydroxyl number <=200. After the vehicle is dispersed in water or an org. solvent, an amino resin, coloring pigment, loading pigment, UV absorber, anti-sagging agent and the like are compounded to obtain an oxidative drying- type paint.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a paint that can be oxidized and dried at room temperature or low temperature heating (below 130°C). This relates to an oxidation-drying paint containing the main component.

Oxidation-drying paints whose main component is alkyd resin modified with drying oil fatty acids are used in a wide range of fields, and are low-cost and have excellent coating workability, adhesion, and texture (especially in solid colors). There is. However, in today's era of rapid technological innovation, the functional level required of paints has inevitably increased, and when looking at oxidation-curing paints, the finished appearance (gloss, sharpness, etc.)
There is a strong demand for further improvements in adhesion, corrosion resistance, chemical resistance, and removability.

The present invention has been made to meet these demands, and as a result of research efforts from various perspectives, it has been discovered that all of the above demands can be met by including a nitrogen atom in the main skeleton of a fatty acid-modified alkyd resin. It was done.

That is, the present invention relates to an oxidation-drying paint whose main component is a fatty acid-modified nitrogen-containing alkyd resin that is oxidatively dried and is made of an alkanolamine having at least two hydroxyl groups in part or all of the polyhydric alcohol component.

The present invention is characterized by an oxidation-drying fatty acid-modified nitrogen-containing alkyd resin that uses, as the fatty acid-modified alkyd resin, an alkanolamine having at least two hydroxyl groups in some or all of the polyhydric alcohol components constituting the resin. This is where the .

As a result, all of the above-mentioned defects could be eliminated and the object of the wooden invention could be fully achieved.

That is, the paint of the present invention can be heated at room temperature or at low temperature (1
It quickly dries and hardens through an oxidative polymerization reaction even at temperatures below 30 degrees Celsius, and the resulting coating film has excellent adhesion. It has excellent adhesion to materials treated with chromate, etc. (including soldered parts), plastics (especially polyamide resins), glass, wood, inorganic substrates, etc., so it is necessary to prepare the surface with a primer etc. There isn't. Furthermore, since it has excellent recoatability, the paint of the present invention can be coated over and over again without sanding. Furthermore, it has excellent adhesion with paint films made of other compositions such as primer (undercoat), intermediate coat, and top coat, so even if a multilayer paint film is formed with these, there is almost no interlayer peeling, and it is suitable for repair. It is also useful as a paint. Furthermore, the fatty acid-modified nitrogen-containing alkyd resin used in the present invention has excellent adsorption properties on the pigment surface, making it easy to disperse pigments, especially for acidic pigments, which are often difficult to disperse uniformly and finely. Certain carbon blacks could also be easily and uniformly and finely dispersed. As a result, paints in which carbon black and other inorganic, organic pigments, extender pigments, etc. ,
There is almost no deterioration in image sharpness.

Furthermore, compared to conventional oxidation drying type paints, the paint of the present invention has
Corrosion resistance, chemical resistance, and flexibility were also significantly improved.

Next, the coating material of the present invention will be explained in more detail.

The fatty acid-modified nitrogen-containing alkyd resin is made by using an alkanolamine having at least two hydroxyl groups in some or all of the polyhydric alcohol components constituting the resin. That is, regarding the alkyd resin, at least two of the hydroxyl groups contained in the alkanolamine are esterified with a polybasic acid component, and both components form most or all of the main skeleton of the resin, and the nitrogen contained in the alkanolamine is esterified with a polybasic acid component. It is important to position the atoms in the main skeleton, and this allows the above-mentioned defects to be eliminated. Therefore, it is not the intention of the present invention to add the amine to a pre-formed alkyd resin and bond it pendantly to the terminal or side chain of the main skeleton of the resin.

The fatty acid-modified nitrogen-containing alkyd resin used in the present invention contains a polybasic acid component, a polyhydric alcohol component consisting of an alkanolamine and another polyhydric alcohol, and a drying oil (fatty acid) (semi-alkanolamine). (including dryness) by a conventional method.

The polybasic acid component consists of a polyvalent carboxylic acid compound having two or more carboxyl groups in one molecule, and examples of such compounds include cono-phosphoric acid, adipic acid, azelaic acid, cepacic acid, and dodecylsuccinic acid. And aliphatic saturated dibasic acids, such as their anhydrides! leic acid, fumaric acid,
Aliphatic unsaturated dibasic acids such as itaconic acid and their anhydrides, aromatic polybasic acids such as phthalic acid, isophthalic acid, terephthalic acid, trimellitic acid, pyromellitic acid and their anhydrides, tetrahydrophthalic acid, Methyl cyclohexentricarboxylic acid, hexahydrophthalic acid, hemic acid, het acid, tetrachlorophthalic acid, cyclohexane dicarboxylic acid, methyl hexahydrophthalic acid,
Examples include alicyclic polybasic acids such as hexahydrotrimellitic acid and anhydrides thereof, and one type or two or more types selected from these may be used.

The polyhydric alcohol component is composed of only an alkanolamine having at least two hydroxyl groups or a mixture of these and a polyhydric alcohol.

Of these, alkanolamines are functional groups (
A compound having at least one diN-),
For example, jetanolamine, triethanolamine,
These include diisopropanolamine, triisopropanolamine, cyclohexylsitbrobanolamine, methyldiisopropanolamine, etc., and these can be used alone or in combination, and among these, jetanolamine, triethanolamine, etc. etc. are preferable.

The polyhydric alcohol that can be used in combination with the above alkanolamine as a component of the polyhydric alcohol component is
It has two or more hydroxyl groups in one molecule, such as ethylene glycol, diethylene glycol-/l/,)
Liethylene glycol, propylene glycol, dipropylene glycol, butanediol, neopentyl glycol, 1.2-, 1.3-, 2.3-, 1.4-butylene glycol, bentanediol, 2.3-dimethylpropanediol , 1.6-, 2.5-hexanediol, tetramethylene glycol, hexamethylene glycol, trimethylolethane, trimethylolpropane, glycerin, diglycerin, dipentaerythritol, sorbitol, etc.; Used in plural.

In the present invention, "fatty acid modification" in the fatty acid-modified nitrogen-containing alkyd resin melts, drying oil (including semi-drying oil, the same shall apply hereinafter) or drying oil fatty acid (including semi-drying oil fatty acid),
The same applies hereafter). These drying oils and drying oil fatty acids have oxidatively polymerizable unsaturated bonds, and preferably have an iodine value of 80 or more, more preferably 100 or more. Drying oils (including semi-drying oils) include, for example, safflower oil, linseed oil, soybean oil, sesame oil, poppy seed oil, eno oil, hempseed oil, corn kernel oil, corn oil, sunflower oil, oitica oil, cottonseed oil, and walnut oil. oil, rubber seed oil, tung oil, dehydrated castor oil, tall oil, rice bran oil and their keys.

These can be used alone or in combination of two or more types. Among these, dehydrated castor oil, safflower oil, linseed oil, soybean oil, tall oil and the like are particularly suitable. In addition, examples of drying oil fatty acids (including semi-drying oil fatty acids) include safflower oil fatty acids, linseed oil fatty acids, soybean oil fatty acids, sesame oil fatty acids, poppy oil fatty acids, eno oil fatty acids, hempseed oil fatty acids, pudoku kernel oil fatty acids, Examples include horse sorghum oil fatty acid, tall oil fatty acid, castor oil fatty acid, cottonseed oil fatty acid, walnut oil fatty acid, rubber seed oil fatty acid, tung oil fatty acid, dehydrated castor oil fatty acid, rice bran oil fatty acid, oiticica oil fatty acid, and their dimer acids. These can be used alone or in combination of two or more. Among these, especially safflower oil fatty acids,
Dehydrated castor oil fatty acids, linseed oil fatty acids, soybean oil fatty acids, tall oil fatty acids, and the like are suitable. Furthermore, if necessary, aromatic basic acids such as benzoic acid and P-terbutylbenzoic acid can also be used in combination.

The fatty acid-modified nitrogen-containing alkyd resin used in the present invention contains the above-mentioned polybasic acid component, polyhydric alcohol component, and drying oil (!
or drying oil fatty acids) according to a conventional method. The polybasic acid component/polyhydric alcohol component (molar ratio) is 0.5 to 1.2, particularly 0.7 to 1.
The content of the alkanolamine used as the sweet and polyhydric alcohol component is preferably 0.5, based on the total amount of the polybasic acid component, polyhydric alcohol component, and drying oil (or drying oil fatty acid). ~20% by weight is suitable;
0.5 to 10% by weight, particularly preferably 2 to 1% by weight
It is 0% by weight. Additionally, drying oils (or drying oil fatty acids)
The blending amount (oil length) is 25 to 75% by weight, preferably 25 to 60% by weight, based on the total amount of the polybasic acid component, polyhydric alcohol component, and the drying oil (drying oil fatty acid).
It is suitable to use within the range of % by weight. Furthermore, the paint of the present invention can be used in either an organic solvent system or an aqueous system; in the case of an organic solvent system, the acid value of the fatty acid-modified nitrogen-containing alkyd resin may be adjusted to 30 or less, and in the aqueous system, the acid value may be adjusted to 10 to 200. preferable. In aqueous systems, fatty acid-modified nitrogen-containing alkyd resins are further combined with basic compounds (e.g. ammonia, monoethylamine, diethylamine, trimethylamine, triethylamine, isopropylamine, diisopropylamine, monoethanolamine, jetanolamine, triethanolamine, dimethylethanolamine, It is neutralized (partially or completely) with morpholine, ethylenediamine, ethylenetriamine, etc.) and then dissolved or dispersed in water.

Further, the hydroxyl value is preferably 200 or less, particularly preferably 100 or less. In particular, when the paint of the present invention is used as a water-based paint,
The acid value of fatty acid-modified nitrogen-containing alkyd resins can be lowered compared to conventional alkyd resins without impairing water dilution stability, for example, up to about 30 for water-soluble systems and 1 for water-dispersed systems.
The acid value could be lowered from 0 to 30, and as a result, the water resistance of the coating film could be improved.

In the present invention, it is necessary to add a desiccant to improve the oxidative drying properties of the fatty acid-modified nitrogen-containing alkyd resin. Metal salts of fatty acids are used as desiccant agents, such as naphthenic acid, linseed oil fatty acids, soybean oil fatty acids, tall oil, rosin, and diethylhexanic acid.The metals include cobalt, manganese, calcium, and zinc. , iron, zirconitum, ceritum, copper, etc.

The paint examples of the present invention containing the fatty acid-modified nitrogen-containing alkyd resin as a main component may contain amino resins, coloring pigments, extender pigments, metallic pigments, ultraviolet absorbers, anti-sagging agents, etc. as necessary. I can do it. Among these, amino resins are useful for further improving the curability of the coating film.
Methylolated or monohydric alcohol (1 to 5 carbon atoms)
Alkyl etherified melamine resin, urea resin, benzoguanamine resin, etc. modified with one or more selected from the following are used, and the blending amount is 1 to 1 of the above alkyd resin in terms of solid content ratio.
It is preferably 1 to 25 parts by weight per 00 parts by weight.

The paint of the present invention is a liquid paint that uses an organic solvent and/or water as a solvent or dispersion medium, and the organic solvent-based paint is a liquid paint in which each of the above components is mixed with a conventional organic solvent for paints, such as (i) luene,
Hydrocarbons such as xylene, naphtha, mineral spirits, octane, cyclohexane, alcohols such as methanol, ethanol, butanol, cyclohexanol, heptatool, etc., ethers such as dioxane, methyl cellosolve, butyl cellosolve, methyl calpitol, butyl carpitol, etc. , ethyl acetate, butyl acetate, methyl cellosolve acetate, cellosolve acetate, carpitol acetate, and other esters; methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, isophorone, and other organic solvents. is obtained by neutralizing the alkyd resin as described above and dissolving or dispersing it together with other components in water (which may contain an organic solvent). These paints can be applied by brush coating, flow coating, spray (air, airless) coating, electrostatic coating, dipping coating, curtain flow coater, electrodeposition coating, etc., and the non-volatile content of the paint at the time of coating is 10
-70% by weight is suitable, and the thickness of the coating film is preferably 5 to 40μ even if it is a dry coating film, and the coating film is dried at room temperature (
(below 40°C) or by heating at a low temperature of 40 to 130°C. The surface to be coated is not particularly limited, and includes, for example, untreated metal, metal whose surface has been treated with phosphate or chromate, articles that have already been coated with a primer, intermediate coat, or top coat, plastics, and wood. , glass, and inorganic products.

Below, production examples, examples, and comparative examples of the fatty acid-modified nitrogen-containing alkyd resin used in the present invention will be explained F3A.

Production Example 1 A mixture consisting of 25.5 parts by weight of trimethylolpropane, 2.5 parts by weight of triethanolamine, 30 parts by weight of phthalic anhydride, 42 parts by weight of linseed oil fatty acid and 3 parts by weight of xylene was heated in a nitrogen gas atmosphere. , 160~ while stirring
The reaction was carried out at 230° C. for about 12 hours to obtain a fatty acid-modified nitrogen-containing alkyd resin (A-1) used in the present invention. Regarding the resin (A-1), the hydroxyl value is 30, the acid value is 10,
The polybasic acid/polyhydric alcohol (molar ratio) was 0.95, the alkanolamine content was 2.5% by weight, and the fatty acid content was 45% by weight.

Production Example 2 A mixture consisting of 27.8 M parts of neopentyl glycol, 10 parts by weight of triethanolamine, 35 parts by weight of phthalic anhydride, 27.2 parts by weight of soybean oil fatty acid, and 3 parts by weight of xylene was prepared in the same manner as in Production Example 1 above. A fatty acid-modified nitrogen-containing alkyd resin (A-2) used in the present invention was prepared by reacting the resin. Regarding the resin (A-2), the hydroxyl value is 100,
The acid value was 3, the polybasic acid component/polyhydric alcohol component (molar ratio) was 0.71, the fatty acid content (oil length) was 30% by weight, and the alkanolamine content was 10% by weight.

Production Example 3 Phthalic anhydride 27.3 parts by weight, linseed oil fatty acid 43.9 parts by weight
A mixture consisting of 22.7 parts by weight of trimethylolpropane, 2.7 parts by weight of triethanolamine, 3 parts by weight of xylene, and 0.1 parts by weight of diptyltin oxide was heated to 160 to 160 parts by weight while stirring in an atmosphere of nitrogen gas. After reacting at 230°C for 12 hours, maleic anhydride 3.
4 parts by weight was added by esterification at -200°C for 2.5 hours to obtain a fatty acid-modified nitrogen-containing alkyd resin (A-3) used in the present invention. Regarding the resin (A-3), the hydroxyl value was 16.6, the acid value after ring opening of the acid anhydride group was 45, the alkanolamine content was 2.9% by weight, and the fatty acid content was 47% by weight.

Production Example 4 11.6 parts by weight of benzoic acid, 25.3 parts by weight of phthalic anhydride, 33.8 parts by weight of sour oil fatty acid, 20.8 parts by weight of trimethylolpropane, 5.7 parts by weight of triethanolamine.
After reacting a mixture consisting of 1 part by weight, 3 parts by weight of xylene and 0.1 part by weight of diptyltin oxide at 160 to 230°C for 12 hours while stirring in a nitrogen gas atmosphere, 2.8 parts by weight of maleic anhydride was further added. 200℃
The addition was carried out by esterification for 2 and a half hours to obtain a fatty acid-modified nitrogen-containing alkyd resin (A-4) used in the present invention.

Regarding the resin (A-4), the hydroxyl value is 10.0, the acid value after ring opening of the acid anhydride group is 35, and the alkanolamine content is 6.
The fatty acid content was 35% by weight.

Production Example 5 A mixture consisting of 27.8 parts by weight of neopentyl glycol, 9 parts by weight of trimethylolpropane, 35 parts by weight of fucuric anhydride, 27.2 parts by weight of soybean oil fatty acid and 3 parts by weight of xylene was prepared in the same manner as in Production Example 2. A reaction was conducted to prepare an alkyd resin for comparative examples.

Example 1 To the nitrogen-containing alkyd resin (A-1) obtained in Production Example 1, 0.5 parts by weight of copal naphthenate and 0 parts by weight of manganese naphthenate were added per 10 parts by weight (solid content) of the resin (A-1). .5 parts by weight, butoxymelamine resin (manufactured by Mitsui Toatsu ■, trade name Kneepan 208E) 15 parts by weight (solid content), 125 parts by weight of titanium white pigment, and organic solvent (butanol, xylene)
6L, mixed and dispersed with a sand mill, non-volatile content 5
A white oxidation-drying paint 1 containing 0% by weight was obtained.

Example 2 Nitrogen alkyd resin (A-2) solid content 1 obtained in Production Example 2
0.5 parts by weight of cobalt naphthenate per 00 parts by weight,
0.5 parts by weight of manganese naphthenate, 6.25 parts by weight of Carbon Black 600E (trade name, Nagashio Sangyo), and a solvent (isobutanol, xylene) were mixed and dispersed in a ball mill, and the non-volatile content was 55 parts by weight. % colored paint 2 was produced.

Example 3 The nitrogen-containing alkyd resin (A-3) obtained in Production Example 3 was neutralized in an equivalent amount with diethylaminoethanol to obtain a water-solubilized product, and then the resin (A-3) (10,000 weight solids) was mixed with naphthenic acid. Cobalt 0.5 parts by weight, manganese naphthenate 0
．． 5 parts by weight, titanium white pigment (manufactured by Teikoku Kako Co., Ltd., trade name J
1-25 parts of R-600E), butyl cellosolve and water were mixed and dispersed in a ball mill to produce colored paint 3 having a non-volatile content of 50% by weight.

Example 4 The nitrogen-containing alkyd resin (A-4) obtained in Production Example 4 was neutralized in an equivalent amount with diethylaminoethanol to obtain a water-solubilized product, and then naphthenic acid was added per 100 parts by weight (solid content) of the resin (A-4). Kobal) 0.5] ifi part, manganese naphthenate 0.5 part by weight, carbon black 600E 6.2
5 parts by weight, butyl cellosolve and water were mixed and dispersed in a ball mill to obtain a non-volatile content of 50% by weight.
Colored paint 4 was produced.

Comparative Example 1 Colored paint 5 was produced in the same manner as in Example 2, except that the nitrogen-containing alkyd resin (A-2) in Example 2 was replaced with the comparative alkyd resin obtained in Production Example 5.

Performance test results Colored paints 1 to 5 obtained in the above Examples and Comparative Examples were applied to iron plates whose surface had been treated with iron phosphate, and various coating film performance tests were conducted on the coated plates made by oxidation drying.The results are as follows. It was as shown in the table.

(Concern 1) Judgment by second visual inspection of painted surface condition. Smoothness, repellency,
The presence or absence of dents was investigated.

(*2) Corrosion resistance: Cross-cut the coating film to reach the substrate, and after testing with Tsuruto Spray for 120 hours, apply adhesive cellophane tape to the cut area, scratch it, and remove the coating from the cut area. Both sides of the membrane were examined during peeling.

(*3) Acid resistance: N/10 sulfuric acid aqueous solution was dropped onto a horizontally supported painted surface, and the condition of the painted surface was examined after leaving it for 24 hours. ○ indicates that no abnormality is observed.

(*4) Alkali resistance: Same as above (*3) except that N/10 caustic soda aqueous solution was used. ○ indicates that no abnormality was observed; △ indicates that whitening and glossy pixelation were observed.

(*5) Bending resistance: The condition of the painted surface was examined when the paint was bent with the paint film on the outside with a radius of curvature of 3 mm. ○ indicates that no abnormality was observed; △ indicates that cracking and peeling were observed.

(*6) Solvent resistance: The coated plate was immersed in toluene (20°C) for 5 hours and the condition of the coated surface was examined. ○ indicates that no abnormality is observed.

(*7) Adhesion: The coated plate was immersed in warm water at 40°C for 24 hours, then pulled up and left for 1 hour, and cut in the same manner as in (*8) to examine adhesion.

(*8) Recoatability: Paint each colored paint on the iron plate so that the cured film thickness is 30μ, and bake it at 180'C for 130 minutes.The same paint is coated again so that the cured thickness is 20μ. Please re-bake at 120℃ for 30 minutes.

Next, use a razor to reach the substrate to make 100 goblets of 1 x 1 mm in size, stick adhesive cellophane tape on the surface, and after removing it, remove the remaining gobun marks. Check the number and next.

Claims (1)

[Claims] An oxidation-drying paint whose main component is a fatty acid-modified nitrogen-containing alkyd resin obtained by using an alkanolamine having at least two hydroxyl groups in part or all of the polyhydric alcohol component.