WO2014017412A1

WO2014017412A1 - Coating film and coating material having long-lasting weather resistance

Info

Publication number: WO2014017412A1
Application number: PCT/JP2013/069733
Authority: WO
Inventors: 光夫樋口; 元熊谷; 泰史川村
Original assignee: 住化エンビロサイエンス株式会社
Priority date: 2012-07-27
Filing date: 2013-07-22
Publication date: 2014-01-30

Abstract

Provided is a method for improving the weather resistance of a coating film formed on the surface of a base material for the protection thereof. This method comprises adding to a coating film a fatty acid metal salt amounting to at least 0.001% of the weight of a base resin constituting the coating film. Also provided is a coating material composition for forming a coating film of improved weather resistance, the coating material composition comprising a base resin, a solvating medium or dispersing medium for the base resin, and a pigment, and further comprising a fatty acid polyvalent metal salt amounting to at least 0.001% of the weight of the base resin.

Description

Coating film and paint having long-lasting weather resistance

The present invention relates to a coating film having weather resistance that lasts for a long time and a coating material for forming such a coating film.

Among the main roles of paints are the protection of the substrate that is applied to the substrate and protects against corrosion, deterioration, decay, etc. and the surface of the substrate is chemically, electrical, optical, thermal and biological Includes the addition of various functions. In order to protect the substrate, it is required to have a long-term weather resistance that does not cause cracking, blistering, peeling, etc. due to deterioration of the coating film over a long period of time. Even when a function such as an insect repellent function or a fungicidal function is added, long-term weather resistance is required so that the active ingredient supporting ability is not lost due to deterioration of the coating film before the active ingredient exhibiting the function is lost. It is done.

The deterioration factor that affects the weather resistance of the coating film is basically light, and in addition to this, it is affected by secondary factors such as oxygen, ozone, environmental pollutants, rainfall, and temperature. As a method for improving the weather resistance, a method of adding a pigment such as carbon black or titanium oxide having a light shielding effect, and a light stabilizer such as an ultraviolet absorber, a quencher and a hindered amine light stabilizer (HALS) alone are used. Alternatively, there is a method of adding in combination.

For example, the wood protective paint disclosed in Japanese Patent Application Laid-Open No. 2005-145900 is a group comprising red iron oxide, yellow iron oxide and carbon black in a paint containing a wood preservative and fungicide and a wood insect repellent as active ingredients. At least one pigment selected from the following is added.

UV stabilizers, quenchers, and light stabilizers such as HALS are known to exhibit satisfactory effects at an early stage, but their effects decrease over time. For this reason, in Japanese Patent Application Laid-Open No. 1-297179, ultraviolet absorbing glass powder is used in place of the ultraviolet absorber. Both UV absorbers and UV-absorbing glass absorb UV rays of harmful wavelengths contained in sunlight and convert them into harmless heat energy and release them. It is difficult to protect the coating film from light deterioration only with glass.

There is a method of using a resin that is less deteriorated by light, oxygen, moisture, etc. as a resin component constituting the coating film, instead of improving the weather resistance by an additive. For example, in Japanese Patent Application Laid-Open Nos. 58-89662 and 58-89663, the weather resistance can be improved by using an oxyalkylene ester of a tertiary carboxylic acid as a part of the constituent of the alkyd resin. . However, this technique is limited to alkyd resins.

In view of the above, an object of the present invention is to provide a method for imparting long-lasting weather resistance to a coating film regardless of the base resin component constituting the coating film, and a coating material for realizing the method. .

In one aspect, the present invention provides a method for imparting long-lasting weather resistance to a coating film, comprising adding a fatty acid polyvalent metal salt known as metal soap to the coating film formed on the substrate surface. .

In another aspect, the present invention provides a coating composition comprising a base resin that forms a coating film, a solvent or dispersion medium for the base resin, a pigment, and a fatty acid polyvalent metal salt.

According to a preferred specific example, the metal species of the fatty acid polyvalent metal salt is selected from cobalt, manganese, copper or zinc, and the fatty acid is selected from octylic acid (2-ethylhexanoic acid), naphthenic acid or versatic acid.

According to another preferred embodiment, the base resin is an alkyd resin or an acrylic resin.

The present invention can also be applied to a protective coating for protecting a substrate (substrate) or a coating containing an active ingredient for imparting a biological function such as an antifungal function and an insect repellent function. .

In general, the anionic portion of metal soap is composed of rosin and tall oil fatty acids, saturated and unsaturated natural long chain aliphatic monocarboxylic acids having 7 to 22 carbon atoms, naphthenic acid, 2-ethylhexanoic acid, synthetic tertiary carboxylic acids ( Versatic acid). The cationic moiety is a polyvalent light metal and heavy metal. The main use of metal soaps is paint dryers that use polyvinyl chloride resin stabilizers, lubricant additives, catalysts, drying oils and alkyd resins as film-forming components.

Generally, the cation part of metal soap is Al, Ba, Bi, Ca, Ce, Co, Cr, Cu, Fe, Ga, Ge, In, La, Mg, Mn, Mo, Ni, Pb, Pd, Rh, Ru, Anionic moieties such as Sn, Sr, Ti, V, Y, Zn, and Zr are saturated and unsaturated long chain natural fatty acids, rosin and tall oil fatty acids, naphthenic acid, octylic acid (2-ethylhexanoic acid), synthetic third Examples of fatty acid polyvalent metal salts, such as secondary carboxylic acids (versatic acid), suitable for the purposes of the present invention are cobalt octylate, manganese octylate, zinc octylate, copper octylate, zirconium octylate, naphthenic acid Includes calcium, cobalt naphthenate, manganese naphthenate, zinc naphthenate, and copper naphthenate. Zinc octylate is particularly preferred. The valence of the polyvalent metal is 2 or more, and divalent or trivalent is particularly preferable.

By adding the fatty acid polyvalent metal salt, the weather resistance of the coating film of the paint to which this is added lasts for a longer period of time compared to the coating film of the paint to which this is not added. This fact has never been known. Here, “weather resistance lasts for a long time” means that the initial weather resistance does not change significantly for a long time. For example, the useful life of a wood protective paint, which has been effective for about 2 years, is extended to 3 years or more.

The method of blending the fatty acid polyvalent metal salt into the paint is arbitrary. For example, a pigment and a conventional additive can be added to the base resin varnish and dispersed at the same time. Alternatively, it may be added to the prepared paint before use.

Although the fatty acid polyvalent metal salt which is liquid at normal temperature can be used as it is for mixing with the paint, it is preferably used in the form of a preparation convenient for mixing with the paint or its base resin varnish. As the form of these preparations, liquid agents such as solutions and dispersions are suitable, and the solvent is an organic solvent for paint.

Although the fatty acid polyvalent metal salt that is liquid or solid at room temperature can be used as it is for mixing with the paint, it is preferably used in the form of a formulation convenient for mixing with the paint or its base resin varnish. . For example, oil agent, emulsion, emulsion agent, microemulsion agent, flowable agent, suspoemulsion agent and the like can be mentioned. The solvent used in this preparation is not particularly limited as long as the paint and the fatty acid polyvalent metal salt are dissolved or dispersed.

Solvents used in the preparation of the fatty acid metal salt of the present invention include aromatic or aliphatic hydrocarbons (xylene, toluene, alkylnaphthalene, phenylxylylethane, kerosene, terpenes, light oil, white kerosene, hexane, cyclohexane, etc.) , Halogenated hydrocarbons (chlorobenzene, dichloromethane, dichloroethane, trichloroethane, etc.), alcohols (methanol, ethanol, 2-propanol, butanol, hexanol, benzyl alcohol), glycols (ethylene glycol, etc.), ethers (diethyl ether, Ethylene glycol dimethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, propylene glycol monomethyl ether, tetrahydrofuran, dioxane ), Esters (ethyl acetate, butyl acetate, etc.), ketones (acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, etc.), nitriles (acetonitrile, isobutyronitrile, etc.), sulfoxides (dimethyl sulfoxide, etc.), amides (N, N-dimethylformamide, N, N-dimethylacetamide, N-methyl-pyrrolidone, etc.), alkylidene carbonates (propylene carbonate, etc.), vegetable oils (soybean oil, cottonseed oil, etc.), plant essential oils (orange oil, hyssop oil) , Lemon oil, etc.), and water. These may be used alone or in combination of two or more.

Base resin components constituting the coating film are acrylic resin, vinyl chloride-vinyl acetate copolymer resin, vinylidene fluoride resin, polyvinyl alcohol, polyvinyl acetal, nitrocellulose, cellulose acetate butyrate and other thermoplastic resins, and alkyd resins, Thermosetting resins such as amino alkyd resins, silicone resins, epoxy resins, unsaturated polyester resins, thermosetting acrylic resins, polyurethane resins, phenol resins, urea resins, and melamine resins. Further, from the viewpoint of the drying or curing mechanism of the coating film, a normal drying type, a baking type, an ultraviolet curing type, an electron beam curing type, and the like are included. There is also a two-component paint in which the base resin and its curing agent are provided separately and mixed immediately before use. Since the composition of the paint is well known in the industry, no further detailed explanation will be necessary.

The present invention can be applied to a paint that protects a material with a coating film itself, or a paint that contains an active ingredient for imparting a specific function. The material of the object to be coated is metal, particularly steel, wood, plastic, concrete, glass, and the like, and is particularly applicable to buildings, facilities, furniture, etc. using these materials outdoors. When the material is wood, specifically, outdoor shutters, window frames, window lattices, verandas, gates, fences, log houses, balconies, wooden shelves, pergola, wooden decks, lattices, garden tables, garden chairs, wood Plant wood, and interior wood such as walls, ceilings, pillars, window frames, doors, door frames, etc.

In particular, a significant effect can be obtained when applied to a paint for protecting wood from decay, mold, pests and the like. Previous wood protective paints had a useful life of at most about 2 years when applied to products used outdoors. On the other hand, recent drugs that protect wood from decay, mold, pests, etc. have an effective life of more than 10 years. Therefore, the useful life of a functional wood paint containing a drug is governed by the useful life of a protective paint containing no drug. According to the present invention, it is possible to extend the useful life of a wood protective paint containing no drug and a functional paint containing a drug to at least 3 years.

The term “wood” as used herein includes not only lumber such as pillars and boards, but also laminated wood, plywood, veneer laminate, particle board, fiber board, strand board, and the like. It does not matter whether the tree type is coniferous or hardwood.

The amount of fatty acid polyvalent metal salt added to the paint does not adversely affect the performance of the paint, and significantly increases the duration of the weather resistance of the formed coating film compared to the paint without addition. Must be sufficient. This amount is at least 0.001% by weight of the base resin (as a solid content) constituting the coating film as the fatty acid metal salt. The amount added to a specific paint varies depending on the type of base resin, the drying or curing method, the composition of the fatty acid polyvalent metal salt, etc., but is usually about 5% by weight, preferably about 3% by weight, more preferably about 2% by weight. Will.

Of course, the paint may contain a solvent, a pigment and a conventional paint additive in addition to the fatty acid polyvalent metal salt and the agent for imparting functionality. Examples of conventional additives are dispersants, plasticizers, leveling agents, antifoaming agents, thickeners, stabilizers, anti-skinning agents, antifungal agents, antiseptics, antifreeze agents, antioxidants, etc. . The fatty acid polyvalent metal salt is not necessary because it is effective for improving weather resistance alone, but an ultraviolet absorber or HALS may be used in combination.

The weather resistance of the paint is determined by exposing the test panel coated with the test paint to the natural environment for at least one year, changing appearance, degree of discoloration (△ E), decreasing rate of gloss (60 ° gloss), peeling It is common to evaluate by a peeling test. Even in the accelerated weather resistance test, the evaluation items are basically the same. The present inventors have found that weather resistance can be evaluated by measuring changes in water repellency and contact angle of the coating film over time in addition to or instead of these items. This is because the water repellency and the contact angle decrease in proportion to the progress of the deterioration of the coating film.

The invention is illustrated by the following non-limiting examples. In the examples, “parts” and [%] are by weight unless otherwise specified.

As fatty acid polyvalent metal salt preparation and paint fatty acid polyvalent metal salt, Octlife (registered trademark) ZnS (Zinc octylate-free solvent, Zn content 22.5%, manufactured by Sumika Enviro Science Co., Ltd.) and A zinc octylate solution (zinc concentration 10%) obtained by stirring and mixing 50 parts of the active ingredient and 50 parts of Pegasol AS-100 (mineral spirit, manufactured by ExxonMobil) was used.

Test paint 1
99.98 parts of commercially available wood protective paint Sadrine Classic (alkyd resin 25.7%, solvent 66.8%, pigment 2.0%, additive 5.5%, manufactured by Genren Chemical Industry Co., Ltd.) zinc octylate 0.02 part of the raw material was added and mixed with stirring.

Test paint 2
Same as Test Paint 1 except that 0.02 part zinc octylate solution was used instead of 0.02 part zinc octylate base.

Test paint 3
0.02 part of zinc octylate base is added to 99.98 parts by weight of commercially available wood protective paint xyladecol (Parisanda color, alkyd resin 20%, other components 80%, manufactured by Nippon Enviro Chemicals Co., Ltd.), and mixed by stirring. did.

Test paint 4
Same as Test Paint 3 except that 0.02 part zinc octylate solution was used instead of 0.02 part zinc octylate base.

Comparative paint 1
The commercially available wood protective paint Sadlin Classic was used as the comparative paint 1 as it was.

Comparison paint 2
A commercially available wood protective paint, xyladecol, was used as the comparative paint 2 as it was.

1. Outdoor Exposure Test create test paint 1 of the test coated plate 4 and the comparative coatings 1-2 respectively cedar plate (length 200 mm, width 90 mm, thickness 18 mm) to all one side of, brushing the coating amount of 75 g / ^{m 2} And dried at room temperature overnight to prepare a test coating plate.

Each test coating plate was fixed on a horizontal test stand installed outdoors, exposed to the natural environment for 1 year and 6 months, and evaluated for changes in appearance, water repellency and contact angle after visual exposure.

1) Evaluation of visual appearance Visual deterioration of the appearance such as cracking, peeling, blistering, and discoloration of the coating film was judged by visual observation and evaluated in the following five stages.
1: Deterioration is observed in less than 20% of the coating film area.
2: Deterioration is observed in 20% or more and less than 40% of the coating film area.
3: Deterioration is observed in 40% or more and less than 60% of the coating film area.
4: Deterioration is observed in 60% or more and less than 80% of the coating film area.
5: Deterioration is observed in 80% or more of the coating film area.

2) Evaluation of water repellency 1 g of distilled water was dropped on the coating film surface of the coated plate, left to stand for 1 minute, and then wiped off with a tissue paper (absorbent paper or filter paper). Water repellency% = 100− (water absorption amount × 100)) was calculated.

3) Contact angle evaluation The contact angle of the coating surface was measured using a contact angle meter (Kyowa Interface Science Co., Ltd. (image processing type) CA-X150 type). By comparing the contact angles, a microscopic difference can be determined for a case where the difference cannot be determined by macroscopic evaluation such as visual observation or water repellency.

4) Results Table 1 shows the results.

2. Weathering accelerated test test coatings of creating test paints 1 and Comparative Paint 1 respectively cedar plate (length 60 mm, width 90 mm, thickness 18 mm) one side of the half of the area (length 60 mm, width 45 mm) of the, 75 g A brush was applied at a coating amount of / m ² and dried overnight at room temperature to prepare a test coating film.

Using a metal halide lamp type weathering acceleration test apparatus (SUV-W151 type, manufactured by Iwasaki Electric Co., Ltd.) for each test film, a 150-hour weathering acceleration test was performed under the following conditions to visually evaluate the appearance and repel The water content and contact angle were measured. The same items were evaluated for the coated plate before the test.
Light source: Metal halide lamp (irradiation light wavelength: 295 to 450 nm)
Irradiance: 1000 W / cm ² (control wavelength: 300 to 400 nm)
Black panel temperature: 63 ° C
On-site humidity: 50% RH
Spray: None

目視 Visual appearance evaluation and contact angle measurement are the same as those for the outdoor exposure test. The measuring method of the water repellency is the same as the measuring method in the outdoor exposure test except that the amount of distilled water dripped onto the coating surface is changed to 0.5 g.

The results are shown in Table 2.

As shown Discussion of Results Table 1 and Table 2 are by adding the fatty acid polyvalent metal salts in the coating, it is clear that can improve the weather resistance of the coating film formed on a coating object surface.

Claims

A method for improving the weather resistance of a coating film formed on a substrate surface, comprising adding at least 0.001% of a fatty acid polyvalent metal salt of a base resin constituting the coating film on a weight basis to the coating film.
The method of claim 1, wherein the metal species of the fatty acid polyvalent metal salt is selected from the group consisting of cobalt, manganese, copper and zinc.
The method according to claim 1 or 2, wherein the fatty acid of the fatty acid polyvalent metal salt is selected from the group consisting of octylic acid, naphthenic acid and versatic acid.
4. The method according to claim 1, wherein the base resin constituting the coating film is an alkyd resin or an acrylic resin.
The method according to any one of claims 1 to 4, wherein the substrate is wood.
An improvement comprising a base resin constituting the coating film, a solvent or dispersion medium for the base resin, and a pigment, and further containing at least 0.001% fatty acid polyvalent metal salt of the base resin on a weight basis Coating composition having improved weather resistance.
The coating composition according to claim 6, wherein the metal species of the fatty acid polyvalent metal salt is selected from the group consisting of cobalt, manganese, copper and zinc.
The coating composition according to claim 6 or 7, wherein the fatty acid of the fatty acid polyvalent metal salt is selected from the group consisting of octylic acid, naphthenic acid and versatic acid.
The coating composition according to any one of claims 6 to 8, wherein the base resin constituting the coating film is an alkyd resin or an acrylic resin.
The coating composition according to any one of claims 6 to 9, comprising an organic solvent in which a base resin constituting the coating film is dissolved.
The coating composition according to any one of claims 6 to 9, wherein the base resin constituting the coating film contains water dispersed as emulsion particles.