JP5449713B2 - Aqueous paint composition - Google Patents

Description

  The present invention relates to an aqueous paint composition having excellent antiseptic and antifungal properties and excellent dispersion stability of pigments.

  Water-based paint compositions used as watercolor paints and emulsion paints including poster colors are particularly susceptible to spoilage over time due to microorganisms present in the environment, since the resin component serves as a nutrient source for the microorganisms. Conventionally, these aqueous paint compositions are blended with antibacterial substances, that is, antiseptic / antifungal agents.

As such antiseptic / antifungal agents, phenol, BIT (1,2-benzisothiazolin-3-one) and the like have been used so far, but these have problems in safety. Thus, recently, it has been proposed to use a combination of phenoxyethanol and sodium fluoride as an antiseptic / antifungal agent (see Patent Document 1), but sodium fluoride still has a problem in safety.
JP 2006-036966 A

  The present invention has been made to solve the above-mentioned problems in aqueous paint compositions, and has excellent antiseptic and antifungal properties, excellent dispersion stability of pigments, and thus long-term storage stability. An object of the present invention is to provide an excellent aqueous paint composition.

  According to the present invention, there is provided an aqueous paint composition characterized by containing at least a pigment, an aqueous resin, a wetting agent, a surfactant, and water, and also containing phenoxyethanol and benzyl alcohol.

  In particular, the aqueous paint composition according to the present invention comprises phenoxyethanol and benzyl alcohol in the range of 50/50 to 90/10 by weight ratio of phenoxyethanol / benzyl alcohol and 0.1 to 1 in total based on the aqueous paint composition. It is preferable to contain in the range of weight%.

  According to the present invention, a watercolor paint composition in which the aqueous resin is a water-soluble resin and an emulsion paint composition in which the aqueous resin is a synthetic resin emulsion are provided individually.

  The aqueous paint composition according to the present invention contains phenoxyethanol and benzyl alcohol as a preservative and antifungal agent, preferably in a predetermined weight ratio, based on the aqueous paint composition, and has antiseptic and antifungal properties. Not only is it excellent, but also the dispersion stability of the pigment, that is, there is no curing of the paint composition or separation of the components even during storage over a long period of time, and in addition, it is excellent in the kneadability of the mixture of raw material components. Yes.

  In the aqueous paint composition according to the present invention, the pigment (that is, the colorant) includes carbon black, aniline black, iron black, titanium oxide, alumina, silica, talc and other inorganic pigments, azo pigments, naphthol pigments, phthalocyanines Pigments, selenium pigments, quinacridone pigments, ultramarine, bitumen, anthraquinone pigments, dioxane pigments, dioxazine pigments, indigo pigments, thioindigo pigments, perinone pigments, perylene pigments, indolenone pigments, azomethine In addition to organic pigments such as pigments, metal powder pigments such as aluminum powder and bronze powder, fluorescent pigments, pearl pigments, and glitter pigments can be used. In addition, plastic pigments (synthetic resin particle pigments) having various shapes such as a spherical shape, a flat shape, and a hollow shape are also used.

  According to the present invention, the pigment is usually used in the range of 60% by weight or less based on the aqueous paint composition. When an excessive amount of pigment is used, the viscosity of the resulting aqueous paint composition is too high, and the elongation of the paint composition is poor at the time of drawing. On the other hand, when the amount of the pigment is too small, the resulting aqueous paint composition lacks coloring power and cannot be used for its original purpose. Preferably, the ratio of the pigment in the aqueous paint composition is in the range of 5 to 40% by weight.

  Furthermore, the aqueous paint composition according to the present invention may contain extender pigments as necessary. Specific examples of extender pigments include calcium carbonate, talc, precipitated barium sulfate, alumina silicate, silicon oxide, bentonite, and clay. In the aqueous paint composition, the proportion of such extender pigment is usually in the range of 40% by weight or less, and preferably in the range of 5 to 40% by weight.

  For example, when the aqueous paint composition is a watercolor paint, a water-soluble resin is used as the aqueous resin. In watercolor paints, water-soluble resins help disperse pigments in paints, and also act as a film-forming agent to form a film while forming a film while containing the pigment when drawn on the drawing surface. . Examples of such water-soluble resins include cellulose resins such as carboxymethylcellulose, hydroxymethylrose, and methylcellulose, acrylic resins, styrene-acrylic copolymer resins, polyvinyl alcohol, polyvinylpyrrolidone, gum arabic, and dextrin. Can do.

  In the watercolor paint, the ratio of the water-soluble resin is usually in the range of 0.1 to 50% by weight, preferably 0.5 to 30% by weight in terms of solid content in the total amount of the paint. In a watercolor paint, when the ratio of the water-soluble resin is less than 0.1% by weight in terms of solid content, the film-forming property is not sufficient, and it is difficult to form a coating film containing a pigment when drawn. On the other hand, when the proportion of the water-soluble resin is more than 50% by weight in terms of solid content, the resulting paint is inferior in coloring power.

  On the other hand, when the aqueous paint composition is an emulsion paint, a synthetic resin emulsion is used as the aqueous resin. The emulsion paint is an aqueous paint that forms a film by forming a film while the synthetic resin contained in the emulsion contains a pigment by evaporating water as a solvent.

  As the synthetic resin emulsion, acrylic resin emulsions, vinyl acetate-acrylic resin emulsions, styrene-acrylic resin emulsions, alkyd resin emulsions, urethane resin emulsions and the like are usually used. Specifically, examples of the acrylic resin emulsion include a trade name “MOVINYL DM772” (manufactured by Nichigo Movinyl Co., Ltd.), a trade name “MOVINYL LDM7520” (manufactured by Nichigo Movinyl Co., Ltd.), and the like. . As the vinyl acetate-acrylic resin emulsion, the trade name “MOVINYL DM5” (manufactured by Nichigo Movinyl Co., Ltd.), the trade name “Nicazole FX138Y” (manufactured by Nippon Carbide Industries Co., Ltd.), and the trade name “Nicazole RX242A”. (Nippon Carbide Industries Co., Ltd.). Examples of the styrene-acrylic resin emulsion include “Boncoat NST100” (Dainippon Ink Chemical Co., Ltd.), “Movinyl 972” (Nichigo Movinyl Co., Ltd.), and the like. The trade name “Watersol CD520” (manufactured by Dainippon Ink & Chemicals, Inc.) is used as the alkyd resin emulsion, and the trade name “Superflex 500” (produced by Daiichi Kogyo Seiyaku Co., Ltd.) is used as the urethane resin emulsion Etc. In particular, in the present invention, an acrylic resin emulsion or a vinyl acetate-acrylic resin emulsion is preferably used.

  These synthetic resin emulsions are usually used in an emulsion paint in the range of 1 to 50% by weight, preferably 3 to 40% by weight in terms of solid content. In the emulsion paint, when the ratio of the synthetic resin emulsion is less than 1% by weight in terms of solid content, the film forming property is not sufficient, and it is difficult to form a coating film when drawn. On the other hand, when the ratio of the synthetic resin emulsion is more than 40% by weight in terms of solid content, the resulting emulsion paint is inferior in stability over time.

  In addition, the emulsion paint may contain a film-forming aid as necessary so as to form a uniform coating film. Examples of the film-forming aid include glycols having a relatively high boiling point and monoethers thereof. And monoacetate are preferably used. Therefore, as an example of the film forming aid, for example, dipropylene glycol monopropyl ether can be mentioned.

  The aqueous paint composition according to the present invention contains a wetting agent. As the wetting agent, for example, water-soluble polyhydric alcohols such as glycerin, propylene glycol, ethylene glycol and sorbitol are preferably used. The aqueous paint composition according to the present invention contains such a wetting agent in the range of 0.1 to 20% by weight, preferably 0.5 to 10% by weight, based on the aqueous paint composition. When the proportion of the wetting agent in the aqueous paint composition exceeds 20% by weight, when the drawing, the drying of the coating film is slow. On the other hand, when the proportion of the wetting agent is less than 0.1% by weight, Drying is brittle.

  In the aqueous paint composition according to the present invention, a surfactant is used as a pigment dispersion aid. Examples of such surfactants include nonionic surfactants such as polyethylene glycol alkyl ether and polyethylene glycol alkylphenyl ether, sodium naphthalene sulfonate / formalin condensate, higher alcohol sulfate sodium ester, sodium alkyl benzene sulfonate, and the like. Anionic surfactants can be exemplified.

  These surfactants are usually used in an amount of 0.01 to 10% by weight, preferably 0.1 to 3% by weight, based on the aqueous paint composition. When the ratio of the surfactant in the aqueous paint composition is more than 10% by weight, the obtained aqueous paint composition easily penetrates into the drawing surface and has poor elongation. On the other hand, when the ratio of the surfactant in the aqueous paint composition is less than 0.01% by weight, the dispersibility of the pigment is poor and the resulting aqueous paint composition is inferior in stability over time.

  The aqueous paint composition according to the present invention contains a combination of phenoxyethanol and benzyl alcohol as a preservative and antifungal agent having a broad antibacterial spectrum, and as a dispersant that improves the pigment wettability and enhances the pigment dispersion stabilizer. Thus, the aqueous paint composition according to the present invention is not only excellent in antiseptic and antifungal properties, but also excellent in the dispersion stability of the pigment, and thus in the storage stability over a long period of time. Furthermore, according to the present invention, since a combination of phenoxyethanol and benzyl alcohol is used as an antiseptic / antifungal agent and as a dispersant, it is excellent in kneadability of a mixture of raw material components in the production of an aqueous paint composition. Thus, the excellent kneadability of the mixture of raw material components also contributes to enhancing the storage stability of the resulting aqueous paint composition.

  The action of phenoxyethanol and benzyl alcohol as a dispersant will be described in more detail. Both phenoxyethanol and benzyl alcohol are alcoholic compounds that are liquid at room temperature and have a certain degree of solubility in water. By dissolving in a water-based paint composition containing a resin and a pigment, the surface tension of water as a solvent can be lowered. Thus, if the surface tension of water as a solvent is lowered, it is dispersed in water. The air layer on the surface of the pigment is easily replaced by water containing a resin, so that the surface of the pigment is easily wetted, and thus acts as a dispersant that enhances the dispersion stabilizer of the pigment.

  On the other hand, the antiseptic and antifungal properties of the combination of phenoxyethanol and benzyl alcohol will be described in more detail. First, in the aqueous paint composition, benzyl alcohol having high solubility in water penetrates into the pigment and is adsorbed. This is expected to sterilize pigment-derived microorganisms. Next, phenoxyethanol is adsorbed on the surface of the pigment and appears to have a bactericidal effect against external microorganisms. Further, since phenoxyethanol has fluidity even when adsorbed on the surface of the pigment, it suppresses aggregation between the pigment particles, which is considered to contribute to the dispersion stability of the pigment.

  In general, the storage stability of an aqueous paint composition largely depends on the milling (kneading property) and wetting of the pigment at the time of production. That is, when the pigment is not sufficiently ground and wetted during the production of the aqueous paint composition, there is a high possibility that the aqueous resin will not be sufficiently adsorbed on the surface of the pigment, and thereafter the pigment will aggregate. Accordingly, when the obtained aqueous paint composition is stored in the production of the aqueous paint composition while the pigment is not sufficiently ground and wetted, the aggregation of the pigment proceeds and the pigment and solvent are cured. Separation will proceed.

  Here, the aqueous paint composition according to the present invention thus contains a combination of phenoxyethanol and benzyl alcohol, which not only has excellent antiseptic and antifungal properties, but also improves the dispersion stability of the pigment. Even during long-term storage, it is difficult for the pigment to harden or separate from the pigment and the solvent. Thus, the storage stability over a long period of time is excellent.

  According to the present invention, phenoxyethanol and benzyl alcohol are usually used in a total amount of 0.1 to 1% by weight, preferably 0.2 to 0.7% by weight, based on the aqueous paint composition. % Range. In particular, according to the present invention, phenoxyethanol and benzyl alcohol are preferably included in the range of 50/50 to 90/10, and in the range of 55/45 to 85/15, by weight ratio of phenoxyethanol / benzyl alcohol. Most preferred.

  Even if phenoxyethanol and benzyl alcohol are each used alone, the resulting aqueous paint composition does not have sufficient antiseptic and antifungal properties. On the other hand, when used in an amount exceeding 1% by weight, the resulting aqueous composition The paint composition lacks storage stability, and in addition, the kneadability is inferior when the aqueous paint composition is produced. Further, when drawing, the paint composition may be repelled on the drawing surface.

  On the contrary, when the ratio of phenoxyethanol and benzyl alcohol is less than 0.1% by weight in total, the resulting aqueous paint composition is not sufficient in antiseptic and antifungal properties and the wettability of the pigment is not sufficient. The resulting aqueous paint composition lacks storage stability.

  Furthermore, according to the present invention, when the weight ratio of phenoxyethanol / benzyl alcohol is out of the above range, an aqueous paint composition excellent in both antiseptic and antifungal properties and storage stability cannot be obtained.

  In the aqueous paint composition according to the present invention, a thickener is used as necessary in order to adjust the viscosity. Many of the above-described water-soluble resins also act as thickeners. For example, polyacrylic acid or cross-linked polyacrylic acid is used in addition to these water-soluble resins as necessary.

  The water-based paint composition according to the present invention may contain an appropriate amount of additives such as a rust preventive, a dispersant, and an antifoaming agent in addition to conventionally used antiseptic / antifungal agents, if necessary. . Examples of the antiseptic include Coatside H (manufactured by Nippon Envirochemicals), and examples of the antifungal agent include “Proxel XL-2” (benzisothiazoline, manufactured by Avicia). Can do.

  The water-based paint composition according to the present invention is not subject to any restrictions in its production method. However, in the case of a watercolor paint, first, an aqueous solution of a water-soluble resin is prepared, and this is used as a pigment, wetting agent, antiseptic. It can be obtained by mixing with a glaze, a surfactant, water and the like to obtain a raw material mixture, which is sufficiently stirred and kneaded until uniform using a dissolver, and further kneaded using a roll mill.

  In the case of an emulsion paint, a pigment, a wetting agent, an antiseptic / antifungal agent, a surfactant and the like are mixed with water to obtain a raw material mixture, which is sufficiently stirred and kneaded until uniform using a dissolver, It can be obtained by kneading using a roll mill, further adding a synthetic resin emulsion and an antifoaming agent, and stirring under vacuum.

  EXAMPLES The present invention will be described below with reference to examples, but the present invention is not limited to these examples.

  An aqueous paint composition was prepared using the components shown in Table 1 in the amounts shown in Table 1. The types and color development of the aqueous pigment compositions obtained in the respective examples and comparative examples are as follows. Example 1 (watercolor, yellow), Example 2 (watercolor, white), Example 3 (poster color, yellowish green), Example 4 (poster color, black), Example 5 (emulsion, white), Comparative Example 1 (Watercolor, yellow), Comparative Example 2 (Watercolor, Yellow), Comparative Example 3 (Watercolor, Yellow), Comparative Example 4 (Watercolor, Yellow), Comparative Example 5 (Poster Color, Yellow Green), Comparative Example 6 (Poster) Color, black), Comparative Example 7 (emulsion, white). Details of the components described in Table 1 are as follows.

Pigment Hansa Yellow G: CI Pigment Yellow 1
Hansa Yellow 10G: CI Pigment Yellow 3
Phthalocyanine Green: CI Pigment Green 7
Titanium oxide: CI Pigment White 6
Carbon black: CI Pigment Black 7
Light calcium carbonate: CI Pigment White 18
NO67 Carplex: hydrous amorphous silicon dioxide, manufactured by DSL Japan

Surfactant Labelin FC-P: Anionic surfactant, manufactured by Daiichi Kogyo Seiyaku Co., Ltd. Prisurf A-212E: Nonionic surfactant, manufactured by Daiichi Kogyo Seiyaku Co., Ltd.

Antifoaming agent Nopco 8034-L: San Nopco

Antiseptic and antifungal agent Densil P: manufactured by Arch Chemicals Japan Co., Ltd. Suneyeback SA: manufactured by Sanai Oil Co., Ltd. Courtside H: manufactured by Nippon Enviro Chemicals Co., Ltd.

Water-soluble resin Tyroze H-4000P: Hydroxyethyl cellulose, manufactured by Clariant Japan

Synthetic Resin Emulsion Mobile DM-5: Vinyl Acetate-Acrylic Resin Emulsion, Nichigo Mo Vinyl Co., Ltd.

  Each of the obtained aqueous pigment compositions was examined for storage stability and antiseptic and antifungal properties. In addition, the kneadability of the mixture of raw material components was examined during the production of the aqueous paint composition. The kneadability, storage stability and antiseptic and antifungal properties were evaluated as follows.

Kneadability When the mixture of raw material components is mixed and stirred using a dissolver during the production of the aqueous paint composition, the mixture of the raw material components is fluid and can be easily kneaded. The case where the fluidity of the mixture of raw material components was small and kneading was difficult was evaluated as Δ, and the case where the material component mixture was not fluid and could not be kneaded was evaluated as x.

Storage stability After the obtained aqueous paint composition was stored in a thermostatic bath at 50 ° C. for one month, when there was no change compared to the aqueous paint composition before storage, it was slightly cured or separated. When it was recognized, Δ was marked, and when it was completely cured or separated, x was marked.

Antiseptic and antifungal properties The obtained aqueous paint composition was used as a test specimen, and 4 types of inoculum suspension or sputum was inoculated 1% every prescribed day (2 to 7 days). As bacteria, Escherichia coil, Pseudomonas aeruginosa, Bacillus subtilis and Staphylococcus aureus are used. The scissors used in “Test” were used. The inoculated test specimen was subjected to a culture test in a constant temperature bath at 28 ± 2 ° C., and then the number of viable bacteria was measured. This operation was repeated for 3 weeks to examine antiseptic and antifungal properties. ○ when the growth of bacteria or mycelium is not observed in the test sample, slightly, when the growth of bacteria or mycelium is observed in the test sample, △, when the growth of many bacteria or mycelium is observed in the test sample It was.

  Each of Comparative Examples 1 and 5 does not contain a combination of phenoxyethanol and benzyl alcohol, and is inferior in antiseptic and antifungal properties and in storage stability. Comparative Examples 2 and 3 contain only one of phenoxyethanol and benzyl alcohol, and are inferior in both antiseptic and antifungal properties and storage stability. Comparative Examples 4 and 6 contain a combination of phenoxyethanol and benzyl alcohol, and are excellent in antiseptic and antifungal properties, but their amount is excessive, so that the storage stability is inferior. Furthermore, the kneadability of the mixture of components is inferior during the production.

  In Comparative Example 7, the amount of the combination of phenoxyethanol and benzyl alcohol is within the range specified by the present invention, but the weight ratio of phenoxyethanol / benzyl alcohol is not within the range specified by the present invention. Is not sufficient in both antiseptic and antifungal properties and storage stability.

On the other hand, all of the aqueous paint compositions according to the examples are excellent in antiseptic and antifungal properties and storage stability, and also in the kneadability of the mixture of components at the time of production.

Claims (4)

An aqueous paint composition containing at least a pigment, an aqueous resin, a water-soluble polyhydric alcohol as a wetting agent , a surfactant and water, and containing phenoxyethanol and benzyl alcohol, wherein the weight ratio of phenoxyethanol and benzyl alcohol is phenoxyethanol / benzyl alcohol. A water-based paint composition comprising: 50/50 to 90/10 at a total amount of 0.1 to 1% by weight based on the water-based paint composition. The watercolor paint composition according to claim 1 , wherein the aqueous resin is a water-soluble resin. The emulsion paint composition according to claim 1 , wherein the aqueous resin is a synthetic resin emulsion. The watercolor paint composition according to claim 1, wherein the water-soluble polyhydric alcohol is glycerin, propylene glycol, ethylene glycol or sorbitol.