WO2002004569A1

WO2002004569A1 - Coating composition

Info

Publication number: WO2002004569A1
Application number: PCT/JP2001/005957
Authority: WO
Inventors: Mutsuo Himeno
Original assignee: Mutsuo Himeno
Priority date: 2000-07-10
Filing date: 2001-07-10
Publication date: 2002-01-17
Also published as: AU2001269489A1

Abstract

A coating composition which comprises at least one calcium compound selected from the group consisting of lime, gypsum, calcium phosphate and calcium silicate, a water-soluble or water-dispersible resin, an inorganic oxide having photocatalytic activity and water and optionally an inorganic pigment such as titanium oxide and zinc oxide; a package containing the coating composition; a coating material or paint for construction and civil engineering comprising the coating composition; a coated article having a coating film formed from the coating composition; and a method for carrying out or repairing the coating of an exterior or interior of a building bt the use of the coating composition. The coating composition is capable of forming a coating film which has a photocatalytic function such as deodorizing property, antibacterial activity and air clarifying action, and also self-clarification action, and thus can maintain good appearance for a long period of time.

Description

Specification

Technical field of coating composition

The present invention relates to a coating composition suitable for making or protecting architectural and civil engineering structures. More specifically, the present invention relates to a coating composition for forming a film having a function such as deodorant, antibacterial, self-cleaning, or air-purifying properties. The present invention also relates to a package containing the coating composition.

Further, the present invention relates to a coated article coated or coated with the coating composition, a method for applying the coating composition, and a method for repairing a building interior and exterior using the coating composition. Background art

Plaster has excellent functions such as humidity control (P and moisture release and moisture release), mold resistance and fire resistance, in addition to a calm and dignified finish. It is a building material that has been used since ancient times.

However, since plastering requires plastering work requiring skill, the finish is likely to vary due to the skill of the worker, and the efficiency of construction is poor due to the necessity of multiple repetitive constructions, and the construction period is long. And the construction cost is high. Attempts have been made to use quicklime instead of slaked lime, which is the main component of stucco, for this improvement, but the workability has not been improved.

For this reason, the interior wall surfaces in recent residential buildings are mainly painted with cloth or painted with synthetic resin paint, but recently, the harmful effects of chemical substances such as chemical sensitivity and sick house syndrome have been a problem. The harmless natural materials are being reviewed again. Disclosure of the invention

In order to respond to such demands, the present inventor has repeatedly studied day and night, and using slaked lime (calcium hydroxide), which is a main component of plaster, for coating that can be sprayed without impairing the texture and humidity control function peculiar to plaster. Successfully developed as a composition (Patent No. 3,083,519, Patent No. 3,094,227).

By the way, in recent years, consumers' awareness of safety and hygiene and interest in environmental issues have increased, and as a decorative coating material such as interior and exterior walls and ceiling materials, materials that do not contain volatile organic substances or organic solvents are used. In addition, there is an increasing demand for the development of decorative coating materials that have environmental purification functions such as antibacterial properties, deodorant properties, self-cleaning properties, and air purification properties.

The present invention has been made in view of the needs of society, and has an object to pay attention to calcium compounds such as slaked lime, and to provide a more functional coating composition containing these as main components. Specifically, the present invention is an aqueous coating composition containing a calcium compound as a main component, and a coating formed from the coating composition has desired design properties and coating properties (adhesion, surface strength, etc.), Another object of the present invention is to provide a coating composition having an environmental purification function such as deodorant, antibacterial, self-cleaning, or air purification. In particular, an object of the present invention is to provide a coating composition and coating material used in the fields of construction and civil engineering, and in particular, a coating composition suitable as a cosmetic.

Further, the present invention provides a coated product having a coating () formed from the coating composition, specifically, various building members (boards, panels, cloths) used as, for example, wall materials inside and outside buildings and ceiling materials. Another object is to provide various types of civil engineering members such as tunnel wall materials, guardrail materials, sound insulation wall materials, protective wall materials, and members of bridge structures. The coated article can have useful functions such as deodorant, antibacterial, self-cleaning or air-purifying properties based on the various functions of the coating composition.

The present invention also provides a method for applying the above-mentioned coating composition, that is, a method for painting the inside and outside walls of a building using the coating composition, and a method for restoring the inside and outside of a building. Aim.

The inventor of the present invention has conducted intensive studies with the aim of developing a coating composition that exhibits an environmental purification function such as deodorant, antibacterial, self-cleaning, or air purification properties. It has been found that the above object can be achieved by adding an inorganic oxide having photocatalytic activity to the coating composition to be formed. Specifically, the present inventor has found that a self-hardening calcium compound such as slaked lime or quick lime functions as an inorganic binder itself without being decomposed by a photocatalyst. It has been found that the composition is useful as a coating composition exhibiting the effect of a catalyst. In addition, when a synthetic resin was added to the coating composition containing such a calcium compound as a main component, there was a concern that the photocatalyst would initially leave the resin and reduce the strength and adhesion of the coating. On the contrary, it has been found that the composition for coating having the above-mentioned desired function can be prepared, with the decomposition of the resin by the photocatalyst hardly affecting the film performance.

That is, the present invention is a coating composition listed in the following items 1 to 9:

1. At least one calcium compound selected from the group consisting of lime, gypsum, calcium phosphate and calcium silicate, 7] a soluble or water-dispersible resin, an inorganic oxide having photocatalytic activity, and a coating containing water Composition.

2. The coating composition according to item 1, wherein the calcium compound is at least one lime selected from the group consisting of slaked lime, quicklime, calcium carbonate and dolomite.

3. The coating composition according to item 1, wherein the calcium compound is slaked lime.

4. The coating composition according to item 1, wherein the water-soluble or water-dispersible resin is a biel-based monomer copolymer or a homopolymer.

5. Bier monomers are (meth) acrylic acid ester, (meth) acrylonitrile, vinyl monomer containing amide bond, styrene or styrene derivative, vinyl monomer containing carboxyl group, vinyl halide, vinyl ester, and silyl Item 5. The covering composition according to Item 4, which is at least one member selected from the group consisting of group-containing vinyl monomers.

6. As a water-soluble or water-dispersible resin, instead of or together with a vinyl monomer copolymer or homopolymer, a fluororesin, polysiloxane resin, urethane resin, silicone resin, phenolic resin, urea resin, melamine metaphor and phthalic acid resin Item 5. The coating composition according to Item 4, comprising at least one member selected from the group consisting of fats and oils.

7. The coating composition according to item 1, wherein the inorganic oxide having photocatalytic activity is titanium oxide.

8. The coating composition according to item 1, further comprising an inorganic pigment.

9. The coating composition according to item 8, wherein the inorganic pigment is at least one selected from the group consisting of titanium oxide, zinc white, zinc sulfide, lithon, lead white, antimony white, and zirconium. Further, the present invention provides a package filled with the coating composition described in the following Items 10 to 13:

10. A package formed by sealingly filling the coating composition according to item 1 in a flexible container in an airtight state, preferably in a light-shielded state.

1 1. Flexible container, alkali resistance, low C_〇 ₂ permeability, and TeiToru package of claim 1 0 wherein is made of wet material.

1 2. The package according to item 11, wherein the flexible container further has a heat-fusing property.

Item 3. The package according to item 10, wherein the coating composition is an ironing coating material containing slaked lime as a main component.

Further, the present invention is a coating material or a paint listed in the following items 14 to 15:

1 4. A coating material or paint for construction and civil engineering, comprising the coating composition according to item 1.

1 5. A coating material or paint for an inner or outer wall of a building, comprising the coating composition according to item 1.

Further, as described in the following items 16 to 17, the present invention is applied to a painted product having a coating film (coating film) formed from the above coating composition, for example, a wall material for a building and a ceiling material. Building materials for interior and exterior, as well as civil engineering materials used as tunnel wall materials, guardrail materials, sound insulation wall materials, protective wall materials and bridge structures:

1 6. A coated article having a coating formed from the coating composition according to item 1.

17. The coated article according to item 16, which is used as a building member or a civil engineering member.

Further, the present invention provides a method of using the coating composition (a coating method, an application method, and a repair method) described in the following item 18-21:

1 8. A coating method characterized by applying the coating composition according to claim 1 to the surface of a building base material or a base material, drying and, if necessary, polishing and polishing the coating surface.

19. (i) The process of connecting a plurality of building members as described in Item 17 to the building base material or base material,

(i i) a step of filling or applying the coating composition according to item 1 to the joints of the building members and drying them; and

(i i i) If necessary, polishing the coated surface

Including, construction method of building interior and exterior. 20. (i) The process of connecting a plurality of building members described in Item 17 to the building base material or base material in a row,

(i i) a step of filling or applying the coating composition according to item 1 to the joint of each building member, if necessary;

(i i i) a step of covering the joint with a reinforcing member,

(iv) a step of applying and coating the coating composition according to item 1 on the reinforcing member, and (V) a step of polishing and polishing the coating surface, if necessary.

Including, construction method of building interior and exterior.

21. A method for repairing a damaged portion of a building interior / exterior surface having a coating layer formed on the surface thereof by applying the coating composition according to item 1.

(0 a step of shaving off the coating layer of the damaged part if necessary,

(i i) a step of filling or applying the coating composition according to item 1 to the damaged wall surface and drying the coating composition, and

(i i i) polishing the surface of the coating, if necessary

Including, how to repair the interior and exterior surfaces of buildings. BRIEF DESCRIPTION OF THE FIGURES

FIG. 1 is an external view (a) showing an example of a package body filled with the coating composition of the present invention, and an AA ′ cross-sectional view (b) thereof. In the figures, reference numeral 1 denotes a flexible container, and reference numeral 2 denotes a coating composition.

FIG. 2 is a cross-sectional view showing a method of arranging a building member on a base material (base) according to the present invention. In the figures, reference numeral 1 denotes a panel base material, reference numeral 2 denotes a coating layer, reference numeral 3 denotes a nail, and reference numeral 5 denotes a base material under the wall (hereinafter the same in FIGS. 3 to 5).

FIG. 3 is a new view showing a continuous arrangement of building members (panels) according to the present invention. (A) shows the striking, (b) shows the striking V-shaped groove, and (c) shows the eye-opening with a phased joint. In the figure, reference numeral 6 indicates a joint portion of the panel base material.

FIG. 4 is a cross-sectional view showing a panel joint, which has been treated by the panel construction method (using a tape material such as cold gauze as a reinforcing member). In the figure, reference numeral 4 denotes a coating composition, and reference numeral 7 denotes a tape material (reinforcing member). FIG. 5 is a cross-sectional view showing the panel joint, which has been treated by the panel construction method (using a substantially T-shaped joiner as a reinforcing member). In the figure, reference numeral 8 denotes a joiner (reinforcing member).

FIG. 6 is a graph showing the results showing the formaldehyde adsorptivity (time-dependent change in formaldehyde concentration) of the film formed with the coating composition of Example 3 tested in Experimental Example 4.

FIG. 7 is a graph showing the results of the carbon dioxide absorption (time-dependent change in carbon dioxide concentration) of the film formed with the coating composition of Example 3 tested in Experimental Example 4. Figure 8 is a diagram showing an outline of evaluation test apparatus NOx removal photocatalyst utilizing NO, N0 ₂ sensor constant potential electrolysis method. MF means mass flow 'sensor. FIG. 9 is a diagram showing the adsorption, decomposition and removal effects of NO and NO ₂ on a film formed with the coating composition of the present invention (Experimental Example 5). BEST MODE FOR CARRYING OUT THE INVENTION

(1) Coating composition

The coating composition of the present invention is characterized by containing a calcium compound, a water-soluble or water-dispersible resin, an inorganic oxide, and water.

The calcium compound in the present invention broadly means a compound containing calcium in the molecule. Although not particularly limited, specifically, quicklime containing calcium oxide as a main component, slaked lime mainly containing 7K calcium oxide, calcium carbonate (calcite, aragonite, paterite, basic calcium carbonate, amorphous calcium carbonate, etc.) precipitated calcium carbonate, heavy calcium carbonate) and dolomite (CaMg (C0 ₃₎ ₂₎ lime and the like; Secco © (dihydrate Sekkou mainly composed of calcium sulfate (CaS0 ₄ '2 0), hemihydrate Sekkou (alpha , / 3), anhydrous Sekkou (III type (alpha,] 3), II-type, I-type)); calcium phosphate [Apataito _{_{(Ca l () (P0 4}} ) 6 F 2, Ca 10 (P0 4) 6 (OH _{_{_{) 2, Ca 10 (P0 4}}} ) 6 C1 2), octacalcium phosphate, amorphous calcium phosphate, arsenic - _{_{or; 6 - Ca 3 (P0 4}} ) 2, Ca 4 (P0 4) 2 0 , and hydrogen phosphate Calcium and the like. ]; Kei calcium [Tobamorai bets _{_{_{(Ca 5 (Si 6 0 ls}}} ) '4H 2 0), and including xonotlite _{_{_{(Ca 6 (Si 6 0 17}}} ) (0H) 2) or the like. ]; And Ca ₃ Si0 _5, Ca Si0 ₄ or Ca ₃ Al ₂ 0 containing cement _6, and the like. Examples of these calcium compounds include calcium compounds recovered from various types of waste materials such as construction materials (eg, concrete waste materials, Secco waste materials) and industrial waste materials (eg, paper sludges). Can also be used. Preferably, lime, gypsum, calcium gayate and cement, which themselves have hydration hardening, 7K thermosetting or air setting properties, are preferably used, and more preferably, lime such as quick lime, slaked lime and calcium carbonate, semi-hydrated gypsum ( , J3) and type II anhydrous gypsum, etc., and calcium silicate. These calcium compounds may be used alone or in any combination of two or more.

Here, the slaked lime is not particularly limited as long as it is usually used as a component of the plaster wall material. For example, various types of calcium hydroxide including industrial slaked lime (JIS A6902) can be used. it can. Slaked lime that has been subjected to a treatment such as coloring can also be used. The particle size is not particularly limited. In addition to the particle size that is usually used as industrial slaked lime, one having a particle size even smaller than the particle size can be arbitrarily used. In addition, calcium hydroxide, which is a main component of slaked lime, has the property of becoming calcium carbonate over time under the influence of carbon dioxide in the air, so calcium carbonate is used instead of part or all of the slaked lime. It can also be used.

The mixing ratio of the calcium compound contained in the coating composition of the present invention is such that the coating formed by the coating composition of the present invention has a desired coating performance and does not hinder the effects of the present invention. If it is, there is no particular limitation. For example, the mixing ratio of the calcium compound at a solid content of 100% by weight or less in the coating composition is usually in the range of 5 to 90% by weight, and can be appropriately selected and adjusted according to the type of the calcium compound to be used. it can. For example, Table 1 shows an example of such a range. Particularly preferred ranges are indicated by <> (the same applies hereinafter). <Table 1>

Examples of the water-soluble or water-dispersible metaphor used in the present invention include a wide range of known water-soluble or water-dispersible resins conventionally used in the field of building and civil engineering coating materials or building and civil engineering coatings. it can.

Although not limited, examples thereof include vinyl-based synthetic resins and vinyl-based synthetic resin emulsions. The Bier synthetic resin is not particularly limited as long as it is a polymer of a vinyl monomer capable of emulsion polymerization.

Such vinyl monomers include, for example, (meth) acrylic acid ester, (meth) acrylonitrile, amide bond-containing Bier monomer, styrene or styrene derivative, carboxyl group-containing vinyl monomer, vinyl halides, vinyl esters, silyl group And vinyl monomers.

More specifically, (meth) acrylates include, for example, methyl acrylate, ethyl acrylate, n-propyl acrylate, isopropyl acrylate, n-butyl acrylate, isobutyl acrylate, t-butyl acrylate, Alkyl groups such as hexyl acrylate, n-octyl acrylate, -2-ethylhexyl acrylate, lauryl acrylate, stearyl acrylate, palmityl acrylate or cyclohexyl acrylate have 1 to 18 carbon atoms Acrylic acid alkyl esters of methyl methacrylate, methacrylate, n-propyl methacrylate, isopropyl methacrylate, n-butyl methacrylate, isoptyl methacrylate, t-butyl methacrylate, methacryl Hexyl acid, methacrylic acid Le, hexyl methacrylate monobasic 2-Echiru, methacrylic acid lauryl, main Yua Alkyl methacrylates having an alkyl group of about 1 to 18 carbon atoms, such as stearyl acrylate, palmityl methacrylate, and methylhexyl methacrylate; hydroxyethyl acrylate, hydroxyethyl methacrylate, and hydrate acrylate Alkyl esters having a hydroxyl group in the side chain of (meth) acrylic acid, such as roxypropyl, hydroxypropyl methacrylate, hydroxybutyl acrylate, hydroxybutyl methacrylate; methoxybutyl acrylate, methoxybutyl methacrylate Alkyl esters having an alkoxyl group in the side chain of (meth) acrylic acid, such as methoxyethyl acrylate, methoxyethyl methacrylate, ethoxybutyl acrylate, ethoxybutyl methacrylate, etc .; acrylyl methacrylate Alkenyl esters of (meth) acrylic acid, such as acrylic acid; alkenyloxyalkyl esters of (meth) acrylic acid, such as acryloxyethyl acrylyldiaryloxyshetyl methacrylate; daricidyl acrylate, glycidyl methacrylate, and acrylyl Alkyl esters having an epoxy group on the side chain of acrylic acid, such as methyldaricidyl methacrylate ゃ methyldaricidyl methacrylate; getylaminoethyl acrylate, getylaminoethyl methacrylate, methylaminoethyl acrylate, Mono- or dialkylaminoalkyl esters of (meth) acrylic acid such as methylaminoethyl methacrylate; silicone-modified (meth) having silyl group, alkoxysilyl group or hydrolyzable alkoxysilyl group as side chain Acrylic acid esters and the like.

Examples of the amide bond-containing pinyl monomer include, for example, acrylamide, methacrylamide; α-ethylacrylamide, Ν, Ν-dimethylacrylamide, Ν, Ν-dimethylmethacrylamide, Ν-methylacrylamide, and Ν-methylmethacrylamide. (Meth) acrylamide having an alkyl group such as Ν-methylol acrylamide, Ν-methylol methacrylamide, etc. (methyl) acrylamide having a methylol group; Ν-alkoxymethyl acrylamide (for example, Ν-iso (Meth) acrylamide having an alkoxymethyl group such as butoxymethylol acrylamide) and Ν-alkoxymethylol methacrylamide (eg, イソ -isobutoxymethylol methacrylamide). ; Nyu- butoxymethylacrylamide Ya Nyu- butoxymethyl methacrylate § (Meth) acrylamide having an alkoxyalkyl group such as amide; N-substituted (meth) acrylamide dimer such as methylene bisacrylamide / methylene bismethacrylamide; and N-vinylpyrrolidone.

Examples of styrene or a styrene derivative include styrene, α-methylstyrene, ρ-tert-butylstyrene, biertoluene, and monochlorostyrene. Examples of the propyloxyl group-containing pinyl monomer include acrylic acid, methacrylic acid, maleic acid, half-esterified maleic acid, fumaric acid, half-esterified fumaric acid, itaconic acid, half-esterified itaconic acid, crotonic acid, and cay Β-unsaturated carboxylic acids such as cinnamic acid; carboxyshethyl (meth) acrylate の carboxyalkyl (meth) acrylates such as carboxypropyl (meth) acrylate; monohydroxyethyl acrylate succinate monohydroxysuccinate Ester of dicarboxylic acid such as ethyl acrylate and monohydroxyalkyl acrylate.

Examples of the vinyl halides include vinyl chloride and vinylidene chloride. Examples of the vinyl esters include vinyl acetate, vinyl lactate, vinyl butyrate, vinyl piperate, vinyl V acid (versatic acid), vinyl benzoate, and vinyl propionate.

Examples of silyl group-containing vinyl monomers include, for example, divinyldimethoxysilane, divinyldi) 3-methoxyethoxysilane, vinyltriethoxysilane, vinyltris-iS-methoxyethoxyethoxysilane, and 7- (meth) acryloxypropyl silane. Rutrimethoxysilane, 7- (meth) acryloxypropyltriethoxysilane, Ύ- (meth) acryloxypropylmethyljetoxysilane and the like. These vinyl monomers can be used alone or in any combination of two or more. That is, the water-soluble or water-dispersible resin used in the present invention is, for example, a homopolymer composed of one kind of the various monomer components listed above or a copolymer composed of any combination of two or more kinds. It may be hot. If necessary, other components such as butadiene, divinylbenzene, and diarylphthalate can be used as the polymerization monomer, if necessary. Such a vinyl polymer can be prepared by a known method. It can be prepared by subjecting the combined monomer component to emulsion polymerization in the presence of an emulsifier in a conventional manner.

Specific examples of such a vinyl-based synthetic resin or vinyl-based synthetic resin emulsion include styrene-noacrylic copolymers such as styrene-acrylic ester, styrene-acrylonitrile, and styrene-acrylamido-ethyl acrylate, and vinyl acetate acrylic acid. Vinyl acetate / acrylic copolymers such as esters and biel acetate-methacrylic acid esters; butadiene Zacrylic copolymers such as butadiene-acrylonitrile; vinyl chloride Z acrylic copolymers; vinylidene chloride Z acrylic copolymers; PA Z acrylic copolymer, acrylic copolymer, pinyl chloride Z ethylene copolymer, vinyl chloride Z vinyl acetate copolymer, vinyl chloride / vinylidene chloride copolymer, pinyl chloride / veoba copolymer, vinyl acetate Ethylene copolymer, vinyl acetate Z-beoba copolymer, vinegar Vinyl / fumarate (eg, vinyl acetate / dibutyl fumarate), vinyl acetate Z maleate (eg, vinyl acetate Z, dibutyl maleate); Beoba / ethylene, acrylic-modified · Alkyd resin, acrylic- Examples thereof include vinyl acetate Z-pinyl chloride copolymer resin and fluorine-modified acryl resin. Further, in the present invention, 7) as the soluble or water-dispersible resin, a resin known as a forming component in the art can be used instead of or together with the vinyl resin. Examples of such a coating film forming component include a fluorine resin, a polysiloxane resin, a urethane resin, a silicone resin, a phenol resin, a urea resin, a melamine resin, and a phthalic acid resin.

Here, as the fluororesin, polyvinyl fluoride, polyvinylidene fluoride, polytetrafluoroethylene, polytetrafluoroethylene, polytetrafluoroethylene, hexafluoropropylene copolymer, ethylene-polytetrafluoroethylene copolymer, Crystalline fluororesins such as ethylene monochloride trifluoride ethylene copolymer and tetrafluoroethylene-fluoro-alkyl vinyl ether copolymer; non-fluorinated polymers such as perfluorocyclic polymer, vinyl ether-fluoroolefin copolymer, and pinyl ester-fluoroolefin copolymer Amorphous fluororesin; a copolymer of fluororefin and a vinyl monomer (fluoroolefin copolymer) can be mentioned. Here, the vinyl monomer is a monomer copolymerizable with fluoroolefin. It is not particularly limited as long as it is a component, and examples thereof include olefins such as ethylene, propylene, and isobutylene; ethyl vinyl ether, cyclohexyl vinyl ether, hydroxybutyl pinyl ethyl, butyl vinyl ether, isobutyl vinyl ether, Vinyl ethers such as methyl vinyl ether and polyoxylene ethylene vinyl ether; polyoxyethylene aryl ether, ethyl aryl ether, hydroxyethyl aryl ether, aryl alcohol, aryl ether Alkenyl such as vinyl acetate, vinyl lactate, vinyl butyrate, vinyl pivalate and vinyl benzoate; and ethylenically unsaturated carboxylic acids such as itaconic anhydride, succinic anhydride and crotonic acid. .

The polysiloxane resin has the general formula:

R “Si (0R ₂ ) (0R ₃ ) — [— 0-Si (0R ₄ ) (0R ₅ ) _] n -0R ₆

Can be suitably used.

Wherein, in the formula, each represents independently a hydrogen atom; a linear or branched alkyl group such as a methyl group, an ethyl group, an n-propyl group, or an isopropyl group, preferably a C ₆ alkyl group; And an aryl group such as a phenyl group or a naphthyl group. Note that they may be the same or different, and ^ n represents an integer of 1 to 100. More specific examples of the polysiloxane resin include polyhydroxysiloxane, polymethoxysiloxane, polyethoxysiloxane, and polybutoxysiloxane.

Examples of the urethane resin include a hard urethane resin conventionally used as a component of a coating material, particularly, a urethane resin emulsion. Examples of such emulsions include, as diol compounds, oil-modified alkyd resins containing a polyester bond in the main chain, oil-free polyesters, polyester polyols such as polycaprolactone polyol, and polycaprolactone polyol; Acrylic polyols, vinyl polymers containing hydroxyl groups, fluorine resins containing hydroxyl groups, polyether polyols, epoxy polyols, hydroxyl-terminated polybutadienes containing a double bond in the main chain or side chain, etc. Specifically, polyoxyethylene glycol , Polyoxyethylene propylene glycol copolymer, diol obtained by adding propylene oxide or ethylene oxide to bisphenol A, polyethylene adenylate Polyol compounds such as polypropylene adipate, polybutylene adipate, polyethylene terephthalate, ethylene glycol, propylene glycol, 1,4-butanediol, 1,6-hexanediol, and acid groups such as dimethylolpropionic acid Diols and the like, and as diisocyanate compounds, for example, hexamethylene diisocyanate, tolylene diisocyanate, 4,4 'diphenyl / methane diisocyanate, xylylene diisocyanate, 4 , 4 'and the like.

Examples of silicone resins include linear silicone resins, acrylic silicone resins (acryl-modified silicone resins), alkyd-modified silicone resins, urethane-modified silicone resins, polyester-modified silicone resins, epoxy-modified silicone resins, and various other silicone rubbers. be able to.

Here, as the acryl silicone resin, one obtained by compounding silicon and acrylate, one obtained by block copolymerization of both, one obtained by partially acryl-modified silicon, and another cross-linking agent obtained by using silicon and acrylate And the like can be mentioned. Examples of the cross-linking agent include an amino resin, a phenol resin, an epoxy resin, an alkyd resin, an unsaturated polyester resin, an isocyanate compound, a block isocyanate compound, a polyhydric alcohol, an aziridine compound, a metal, and a metal. And the like.

The acrylate components include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, n-butyl (meth) acrylate, i-butyl (meth) acrylate, t-butyl (meth) acrylate, and amyl. Monomers such as acrylic acid, i-amyl (meth) acrylate, hexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, and n-butyl methyl (meth) acrylate; Oligomers and polymers obtained by the polymerization reaction of hydroxymethyl (meth) acrylate, hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, hydroxybutyl (methyl) acrylate, hydroxyamyl (meth) acrylate , Hydroxyhexyl (meth) acryle DOO, styrene, alpha-methyl styrene, 4-methylstyrene, 2-methylstyrene, 3-methylstyrene, 4-methoxystyrene, 2-hydroxymethylstyrene, 4-ethylstyrene, 4-ethoxystyrene, 4-dimethylstyrene, 2-chlorostyrene, 3-chlorostyrene, 4-chlorostyrene 1-Methylstyrene, 4-t-butylstyrene, 2,4-dichlorostyrene, 2,6-dichlorostyrene, 1-vinylnaphthylene, methacrylic acid, divinylbenzene, fumaric acid, itaconic acid, monoalkyl Itaconate, maleic acid, crotonic acid, 2-methacryloyloxhetylhexahydrophthalic acid, arylglycidyl ether, glycidyl (meth) acrylate, dibibenzenebenzene, methyldaricidyl (meth) acrylate, ethylene glycol Di (meth) acrylate, diethylene glycol (meta) Acrylate, triethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, tripropylene glycol di (meth) acrylate, dipropylene glycol di (meth) acrylate , Tetrapropylene glycol di (meth) acrylate, butanediol di (meth) acrylate, hexanediol di (meth) acrylate, trimethylolpropanetri (meth) acrylate, penyu erythritol tetra (meth) acrylate, (meta) ) Acrylamide, N-methylol (meth) acrylamide, N-methoxymethyl (meth) acrylamide, N-butoxymethyl (meth) acrylamide, Ν, Ν'-methylenebisacrylamide, tylacetone acrylic Amide, maleic amide, maleimide, vinyl chloride, vinylidene chloride, fatty acid vinyl ester, trifluoroethyl (meth) acrylate, pendudecorfluorooctyl (meth) acrylate, r-methacryloylpropanetrimethoxysilane, etc. Preferable examples include copolymers of the above monomers, oligomers or polymers with monomers copolymerizable with the polymer. Silicon components include tetramethoxysilane, tetraethoxysilane, tetrapropoxysilane, tetrabutoxysilane, methyltrimethoxysilane, methyltriethoxysilane, ethyliletrimethoxysilane, and n-propyltrimethoxysilane.

Piltrimethoxysilane, Archloropropyltriethoxysilane, Biertri Methoxysilane, Biertriethoxysilane, 3,3,3-Trifluoropropyltrimethoxysilane, glycidoxypropyltrimethoxysilane, arg

"3,3,3-Trifluoropropyl acryloxypropyl triethoxysilane, r. Orchid, phenyltriethoxysilane, α-"

Lejetoxysilane, getyldimethoxysilane, hexaphenylcyclotrisiloxane, octaphenylcyclotetrasiloxane, tetravinyltetramethylcyclotetrasiloxane, hexamethylcyclotetrasiloxane, octamethylcyclotetrasiloxane, pentamethylcyclotetrasiloxane, hexamethylcyclotetrasiloxane Clotetrasiloxane, tetramethylcyclotetrasiloxane, decamethylcyclohexapentasiloxane, dodecamethylcyclohexaoxaxane, trimethyltriphenylcyclotrisiloxane, and (partly) hydrolysates thereof, condensates of the hydrolyzates, and the like are preferable. Can be exemplified.

The content of the silicon component in the resin is sufficient as long as it is resistant to degradation due to photocatalysis. In general, the more the acrylic component, the better the adhesion when applied to the surface of the synthetic resin, making it difficult to peel off, and the higher the siloxane content, the better the weather resistance. Therefore, the siloxane content can be appropriately selected from the range of 1 to 70% in consideration of such a tendency. Further, for the purpose of increasing the surface strength and the flexibility, silica may be added to the acrylic silicon resin, two or more kinds of acrylic silicon resins may be mixed, or a silicon-based resin may be added.

The type of the resin used in the present invention, the mixing ratio of each monomer component, the degree of polymerization, and the like are determined based on the working temperature (curing temperature) of the obtained coating composition of the present invention, compatibility with other components such as a calcium compound, In addition, it is appropriately selected in consideration of, for example, the glass transition point (T g) of the obtained resin in consideration of the adhesion of the coating film (coating layer) and the film forming property. The form of the resin used is not particularly limited. It may be in any form such as aqueous emulsion or dispersion form such as dispersion, powder form such as re-emulsified powder resin, and liquid form such as liquid polymer. Preferred is an emulsion mode. When formulated as an emulsion, the emulsion may be obtained by emulsion polymerization of a monomer having a polymerizable unsaturated double bond, or may be prepared by dispersing a previously synthesized resin in an aqueous dispersion medium using a dispersant. Further, there may be mentioned those prepared by dispersing a powder type polymer in water or the like.

The resin used in the present invention increases the adhesive strength between calcium compounds in the coating composition, the adhesive strength between the calcium compound and the additives described below, and the adhesive strength between the coating composition and the object to be coated. It is thought that it has the function of preventing cracking of the coating layer (m layer) formed on the surface of the object to be coated and improving the toughness of the building material. When the calcium compound to be used has a self-hardening property such as lime, gypsum, calcium silicate, cement or the like, the self-hardening effect causes the adhesive strength or the adhesive strength to develop over time. Therefore, the resin only needs to have a function of maintaining at least the initial adhesive strength or adhesive strength at the beginning of coating.

The mixing ratio of the water-soluble or water-dispersible resin satisfies the performance required for water-based coating materials or coatings, such as coating (coating and construction) workability and film forming properties, or compounding stability (compatibility). There is no particular limitation as long as it is within the range, and it can be appropriately determined according to the type of resin used. Specifically, the mixing ratio of the water-soluble or water-dispersible resin (solid content) contained in 100% by weight (solid basis) of the coating composition is usually in the range of 1 to 85% by weight (solid basis). Can be selected and adjusted. Table 2 shows the range as an example.

The inorganic oxide used in the present invention is not particularly limited as long as it has photocatalytic activity. Not limited to Specifically, titanium oxide, reledium oxide, cobalt oxide, cesium oxide, oxidized chromium, rhodium oxide, vanadium oxide, zinc oxide, manganese oxide, rhenium oxide, ferric oxide, tungsten trioxide, zirconium oxide, oxide Examples include tin, bismuth oxide, ruthenium oxide, strontium titanate, molybdenum oxide, germanium oxide, lead oxide, cadmium oxide, copper oxide, niobium oxide, and tantalum oxide. These can be used singly or as a combination of two or more kinds, for example, as a composite. Conventionally, these photocatalytic inorganic oxides exhibit a strong oxidizing ability by photoexcitation when irradiated with energy light having a band gap or more (for example, ultraviolet light of sunlight or artificial illumination light). It is known to remove chemicals such as bacteria and formalin. The inorganic oxides of the present invention include those that exhibit an oxidizing ability and exhibit a photocatalytic function not only by energy light such as sunlight or ultraviolet light but also by light such as visible light.

Titanium oxide or zinc oxide is preferable as the inorganic oxide from the viewpoint of safety and economy. Titanium oxide is classified into three types, rutile type and anatase type belonging to tetragonal system, and wurtzite type belonging to orthorhombic type. Regardless of such crystal type, it is sufficient if it has photocatalytic activity. . As an titanium oxide having photocatalytic activity, anatase-type titanium oxide is well known.

The particle diameter of the inorganic oxide having photocatalytic activity is not particularly limited. Preferably, the average particle size is within a range of 10 m or less from the viewpoints of photocatalytic activity, resistance to organic compound decomposition, dispersibility in the coating composition, and storage stability when blended in the coating composition. It can be selected and used. The average particle size is more preferably 3 / xm or less, and still more preferably 1 m or less. Among them, a powder having an average particle diameter in the range of 1 to 800 nm can be suitably mentioned. Generally, the smaller the average particle size, the larger the specific surface area and the higher the photocatalytic activity tends to be. In the present invention, the particle size can be appropriately selected and used in consideration of a balance between a desired environmental purification function based on photocatalytic activity and organic compound resistance (resin decomposability).

The inorganic oxide has Pt, Pd, Ir, Fe, Mo, Ru, Os, Re, Ni, Cd, Co, V, Rh, Ag, Oxide conversion of metal components such as Cu and Zn Alternatively, the photocatalytic activity can be further enhanced by supporting the compound in the form of metal ions. Accordingly, the inorganic oxide used in the present invention includes Pt; Pd, Ir, Fe, Mo, Ru, 〇s, Re, Ni, Cd, Co, V, R Inorganic oxides carrying at least one metal component selected from the group consisting of h, Ag, Cu and Zn are also included. Among them, Ag, Cu and Zn are more preferable metal components because they exhibit antibacterial properties themselves. As a method for supporting these metal components, a conventionally known method can be adopted. For example, as a method for supporting Ag, silver oxide is dissolved in aqueous ammonia to form an aqueous solution of an amine complex salt of silver, and the inorganic oxide is put in the aqueous solution. After stirring, a method of heating and drying the filtered residue at 150 ° C. for 48 hours can be exemplified.

Even in the case where the inorganic oxide that does not support metal ions as described above is used, the same effect can be obtained by blending a metal salt or the like composed of these metal ions into the coating composition. Can be obtained. Examples of such metal salts include salts of the above metals with inorganic acids such as nitric acid, sulfuric acid, hydrochloric acid and bromic acid, and oxides of the above metals, 7K oxides, oxyhydroxides and halides. Can be mentioned. Such a metal salt or the like is preferably incorporated into the coating composition of the present invention as a solution dissolved in a 7J-soluble or hydrophilic solvent.

Such an inorganic oxide may be directly mixed in powder form with other components constituting the coating composition of the present invention, or may be previously dispersed in a hydrophilic solvent such as water, isopropanol, or ethanol. It can also be blended in the form of a dispersion. Subsequently, the mixture is dispersed and mixed in the coating composition with a stirrer such as a disperser, a sand mill, and a shaker. Another method of mixing is to mix an inorganic oxide with the resin component, disperse the mixture in a resin having an appropriate viscosity (50 to 100Κϋ) to form a paste, and then form a coating material or a paint as necessary. You can also mention.

The coating composition of the present invention can also be prepared using a solution containing a powder of an inorganic oxide and colloid particles. The method of blending the inorganic oxide as a colloidal solution does not require the above-mentioned dispersion step, and can be blended into the aqueous composition in a finer powder state. It is. Examples of the inorganic oxide colloid solution are disclosed in, for example, JP-A-6-80527, JP-A-7-33616, and the like. ₂ simple Colloidal particles and _{_{S i 0 2 · A 1 2}} 0 of ₃ · T i 0 ₂ composite oxide such as roller I de particles monoxide thereof. These can be made into colloidal particles by adhering the aforementioned antibacterial metal component to the surface of the colloidal particles, or by mixing them with an inorganic oxide.

According to the inorganic oxide having a medium activity, it is contacted or adsorbed on the coating film by a reaction that occurs as a result of being excited by absorbing ultraviolet light or visible light emitted from sunlight or indoor lighting equipment. Contamination components and malodorous components can be oxidized and made non-toxic. Therefore, the film formed by the coating composition of the present invention containing the inorganic oxidized product has a deodorizing function, an antibacterial function (anti-mold function), a self-cleaning function (browning due to adhesion of hand marks, etc., It can exhibit environmental purification functions such as yellowing prevention function) or air purification (decomposition and removal of NOx and SOX).

The proportion of the inorganic oxide to be incorporated into the coating composition 100% by weight (solid basis) can be adjusted to a desired value without affecting the film forming property of the formed film and the adhesion to the substrate. There is no particular limitation as long as it has an environmental purification function such as deodorant, antibacterial, self-cleaning or air purification. Usually, taking into account the effect on the film forming properties of the coating and the adhesion to the substrate, the type of the calcium compound and the water-soluble or water-dispersible resin are used.

It can be appropriately selected from the range of 590% by weight (solid basis). Table 3 shows the range as an example.

The coating composition of the present invention may further contain an inorganic pigment. Preferable examples of the inorganic pigment include an inorganic white pigment which does not itself have photocatalytic activity or is subjected to a reduction treatment. Specific examples include titanium oxide, zinc white, zinc sulfate, lithobone, lead white, antimony white, and zirconia. The titanium oxide used here is preferably a rutile type or a force recite type. Preferably, it is rutile-type titanium oxide having no or reduced photocatalytic activity. These inorganic pigments may be used alone or in combination of two or more. They can be used in any combination. Preferably, titanium oxide is used alone or in a combination of titanium oxide and one or more other inorganic pigments. The mode of combination is not particularly limited, but a combination of titanium oxide and at least one of zinc, zinc sulfide, lithopone, lead white, antimony white and zirconia can be suitably exemplified. Preferably, a combination of titanium oxide and zinc white or a combination of titanium oxide and zinc sulfide is used.

In addition, these inorganic pigments include those having various shapes (granular, spherical, amorphous, fine particle, plate-like, etc.) and particle diameters according to the type of the pigment. From the viewpoint of the opacity and dispersion stability in the coating composition, the particle size is preferably in the range of 0.1 to 0.5 m, and more preferably in the range of 0.1 to 0.3 m. However, there is no particular limitation. When the inorganic pigment is blended with the coating composition of the present invention, the blending ratio is not particularly limited, but is usually 0.1 to 85 as a blending ratio in 100% by weight (solid basis) of the coating composition. The range of weight% can be exemplified. The ratio can be selected and adjusted according to the use mode and the application method of the coating composition to be used. For example, when used in the form of a paint, it is preferable to blend a white pigment in such a ratio that a predetermined hiding power is exhibited. An example of the mixing ratio of the inorganic pigment is as shown in Table 4 below.

An extender pigment can be further added to the coating composition of the present invention. By using such an extender in combination with the inorganic pigment, the hiding power of the inorganic pigment can be improved. Extenders include talc, kaolin clay, aluminum hydroxide, calcium carbonate (heavy calcium carbonate, light (precipitable) calcium carbonate), bentonite, barium sulfate (precipitable barium sulfate, pearlite powder), Bonn, silica and the like can be exemplified. Preferably talc, calcium carbonate, Barium sulfate and clay are more preferable, and talc and calcium carbonate are more preferable. As calcium carbonate, porous calcium carbonate can be suitably used in addition to light calcium carbonate.

When the extender is blended with the coating composition of the present invention, the blending ratio is not particularly limited, but is usually 0.1 to 85 as a blending ratio in 100% by weight (solid basis) of the coating composition. It can be used by selecting from the range of weight%. An example is shown in Table 5 below.

In the coating composition of the present invention, the above-mentioned inorganic pigment or Z and extender are optional components. However, by blending these components, the hiding power of the coating is increased, and the coating can be made thinner or thinner. That is, the coating composition of the present invention containing an inorganic pigment and / or an extender pigment can have a potentially high coating hiding power. Here, the film hiding power is the minimum film thickness of the film that makes it impossible to recognize the color of the substrate when the coating composition is applied to the substrate, and specifically, is applied on a black and white plate. It means the minimum thickness of the coating that makes it impossible to distinguish the black and white of the base when observed with the naked eye through the coated coating. For example, the coating composition may have a film hiding power (minimum film thickness) of 1 mm or less, 500 m or less, 300 / m or less, 200 m or less, or 100 m or less, as necessary. It can be prepared as follows. Therefore, the coating composition of the present invention containing such an inorganic pigment or Z and an extender pigment can be thinly coated by a usual coating method such as spraying, brushing or a roller, particularly when the coating composition is used in a paint form. This is useful when performing construction, or when finishing with one or two or three constructions.

However, the above-mentioned film hiding power is a potential property of the coating composition, and is not limited by this film thickness at the time of use. The coating composition of the present invention may further contain a colored pigment and various additives as necessary.

The colored pigment is not particularly limited, and any pigment can be employed, but is preferably an inorganic pigment. Examples of such colored pigments include black pigments such as bonbon black and iron oxide: red pigments such as cadmium red, red iron oxide, molybdenum red, and lead red pigments: yellow lead (chrome yellow), titanium yellow, cadmium yellow, and yellow. Yellow pigments of iron oxide, tan, antimony yellow, vanadium tin yellow, vanadium zirconium yellow: chromium oxide, pyridian, titanium cobalt green, cobalt green, cobalt chrome green, Victoria Darine, etc. green pigments: ultramarine, navy blue, kozolto blue, cerulean Inorganic pigments such as blue pigments such as Blue, Cosolt Silica Blue, and Cobalt Zinc Silica Blue. The proportion of these colored pigments to be incorporated into the coating composition of the present invention is not particularly limited, and can be appropriately selected and adjusted according to a desired color (lightness, chromaticity, saturation). Additives include, for example, pigment dispersants, wetting agents, antifoaming agents, thickeners, freeze-thaw stabilizers, film forming aids such as film forming aids and rheology modifiers, inorganic fillers, and pH adjustment Agents, ion exchange resins, surfactants, plasticizers, water reducing agents, fluidizing agents, water retention agents, preservatives, waterproofing agents, antibacterial agents, coagulants or coagulation accelerators. As the pigment dispersant and the wetting agent, those which are generally used by being blended into paints and coating materials can be widely used.For example, formalin condensates of sodium alkylnaphthalenesulfonate, low molecular weight ammonium polyacrylate, Examples thereof include low molecular weight styrene-ammonium maleate copolymer, fatty acid ester of polyoxetylene, alkylphenol ether, sulfosuccinic acid derivative, block polymer of polyethylene oxide and polypropylene oxide, and the like.

The defoaming agent is not particularly limited as long as it is generally used by being blended into a paint, a coating material or a spraying material for construction, and any of them can be employed. Examples include various foaming inhibitors and foaming agents such as octyl alcohol, glycoderivatives, cyclohexane, silicon, pull nick surfactants, and polyoxetylene alkylphenyl ether. be able to.

Thickeners include methylcellulose, hydroxyethylcellulose, hydroxy Cellulosics such as propylmethylcellulose; polysaccharides such as saccharose and glucose; acrylics; and others, such as aluminum stearate, zinc stearate, organic bentonite, silica gel, polyvinyl alcohol, sodium alginate, silicate, bentonite, sodium caseinate, etc. Can be exemplified.

Inorganic fillers include, for example, inorganic aggregates (fine aggregates) such as silica sand, cold water sand, perlite, balmikilite, shirasu spheres and recycled aggregates such as sludge fired aggregates, as well as kaolin, halloysite, montmorillonite, Natural inorganic materials such as bentonite, gibbsite, my strength, ceramic sand, glass beads, pearlite, acid clay, pottery stone, dolomite, feldspar, limestone, gypsum, dolomite, magnesite, talc; normous oxide, magnesium hydroxide Water-insoluble metal hydroxides such as natural calcium; calcium silicate hydrates such as tobermonite zonotorite; hydrates of various oxides such as calcium aluminate hydrate and calcium sulfoaluminate hydrate; Alumina, silica, hydrous silicate, magnesia, zinc oxide, spinel, alloy Synthetic carbonic acid powders, fibrous or granular inorganic materials such as synthetic minerals such as calcium, calcium phosphate, magnesium carbonate, barium sulfate, and potassium titanate.

Examples of the waterproofing agent include, but are not particularly limited to, silicone oil, silicone resin, and organoalkoxysilane. These components can generally improve the waterproofness, chemical resistance, weatherability, etc. of the coating, but when the coating is required to have humidity control properties, it can be used within a range that does not hinder the humidity control properties. preferable. There is no particular limitation on the setting agent or setting accelerator. For example, when calcium sulfate is used as the calcium compound, it is preferable to use a compound having an action of assisting or enhancing the expression of hydration hardening of the calcium sulfate. Specific examples of such a substance having such an action include potassium sulfate, myrrh pan, fine powder of dihydrated sesame, and organic acids such as oxalic acid.

The water retention agent is not particularly limited, and examples thereof include water-soluble polymers such as polyvinyl alcohol and methyl cellulose.

The coating composition of the present invention may further contain diatomaceous earth or zeolite (including synthetic zeolite). Diatomaceous earth is a natural material that does not contain harmful substances. It is a material that has been attracting attention.By adding diatomaceous earth zeolite, it is possible to impart various functions such as humidity control, dew condensation prevention, heat insulation or deodorizing effect to the film, or Functions can be improved and improved.

The coating composition of the present invention contains a calcium compound in an amount of 5 to 90% by weight, and the resin and the inorganic oxide are added to 100 parts by weight of the calcium compound, respectively. To 70 parts by weight and 2 to: 100 parts by weight of L (all in terms of solids). The mixing ratio of the resin and the inorganic oxide to 100 parts by weight of the calcium compound can be appropriately adjusted within such a range. For example, the following ranges can be exemplified.

Table 6>

1) 100% by weight of nocalcium compound

2) Incorporation ratio of inorganic oxide 100% by weight of Z calcium compound

When an inorganic white pigment is blended as an optional component, the following range can be exemplified as the blending ratio with respect to 100 parts by weight of the calcium compound contained in the coating composition. <Table 7>

100% by weight of Z calcium compound

The above-mentioned various components are mixed with water so that the total solid content of the coating composition is 100 to 100% by weight of the composition, 40 to 90% by weight, preferably 40 to 80% by weight. More preferably, the content can be adjusted so as to be 50 to 70% by weight.

The coating composition of the present invention is obtained by mixing the above components with water and mixing them using a conventional method for coating materials or paints, for example, using a paint blending device (mixer, shaker, mill, kneader, or the like). It can be prepared as a coating material or paint in various forms such as liquid (spray), slurry or putty.

In this case, the coating composition may be, for example, spray coating (air spray, airless spray, etc.), brush coating, roller coating, putty coating, coat coating (curtain flow coater, mouth-luko overnight), trowel coating It can be prepared so as to have a desired viscosity according to various kinds of coating or coating method. In this case, a preferable viscosity range can be appropriately selected and adjusted in consideration of coating workability, leveling, observation, and the like. Usually, it is prepared to be in the range of 100 to 60,000 cP at room temperature (25 ° C soil 5). For example, the viscosity of the liquid coating composition is 300 to 8000 cP at room temperature, preferably 500 to 5000 cP, more preferably 1000 to 4500 cP at room temperature so as to be suitable for brush coating, roller coating, coat coating or spray coating. Preferably, the range of 2000 to 4000 can be mentioned. The viscosity of the putty-like coating composition is not limited, but may be in the range of 8,000 to 30,000 cP at room temperature (25 ° C. ± 5), preferably 8,000 to 20,000 cP. The coating composition of the present invention is useful as an architectural or civil engineering coating or paint. There are no restrictions, but specifically, painting (coating) of interior and exterior surfaces such as ceilings and walls (inner and outer walls) of various buildings; ceiling and walls (inner and outer walls) of buildings Base material Of various architectural components (cloths, panels, boards) used as materials and decorative materials; surface of road structures such as tunnel walls, guard rails, sound insulation walls and protection walls, and surfaces of bridge structures, etc. Coating (coating); and various wall materials such as tunnel walls, sound insulation walls, protective walls, etc .; and civil engineering members (panels, boards, pillars) such as various members of bridge structures (painting). it can. Further, the coating composition of the present invention can be further applied with a design finish by painting or coating according to a conventional method, followed by patterning with an uneven patterning roller or a trowel, or treating the film surface. Wear.

An example of a preferred embodiment of the coating composition of the present invention is a paint. Such a coating material preferably satisfies at least the requirement of the concealment ratio for one kind of paint specified in Japanese Industrial Standard JIS K 5663-1995, and more preferably the properties of the coating liquid and the appearance of the dried coating film. And at least two paints whose physical properties are specified in ISK 5663-1995 (1) State in a container, (2) Paint workability, (3) Low temperature stability, (4) Appearance of coating film, It is desirable to meet the requirements of (5) Alkali resistance, (6) Wash resistance and (7) Concealment ratio.

More preferred coating compositions in the form of paints have at least the following qualities (JIS 5663-1995) when measured according to the method of JIS 5400 in accordance with JIS K 5663-1995. Is:

(1) Condition in the container: When stirred, there is no lump and the whole contents become uniform: (2) Painting workability: Two coats do not hinder painting work:

(3) Low temperature stability: No deterioration when cooled to 15 ° C:

(4) Appearance of coating film: Appearance of coating film is normal:

(5) Alkali resistance: No abnormality when immersed in a calcium hydroxide solution (20 ± 1 ° C) for 18 hours:

(6) Washing resistance: Withstand 100 washes:

(7) Concealment ratio: 0.95 or more

Further, the coating composition of the present invention has no problem even when immersed in deionized water for 96 hours with respect to water resistance (8.19 of JIS K 5400) 0131 (5.9 of 5663-1995). Regarding weather resistance (9.8.1 of JIS K 5400), the degree of chalk is 8 points or more, and there is no blister It is preferable that the degree of color change is not large compared to the sample (5.12 in JIS K 5663-1995), and the concealment ratio is 0.93 or more (5.8 in JIS K 5663-1995). In addition, the weather resistance (JIS K 540 (^ 9.9) was not swelled, peeled or cracked after a 12-month test period, and the degree of color change and the degree of chalk were larger than those of the sample. It is preferable to satisfy the requirement that there is no (JIS K 5663-1995, 5.13).

Examples of another preferred embodiment of the coating composition of the present invention include a coating material suitable for ironing. There is no limitation as long as the viscosity is suitable for ironing, but examples thereof include coating materials having a temperature in the range of 10,000 to 50,000 cP, preferably 10,000 to 30,000 cP at room temperature (25 ° C. ± 5). In addition, such a coating material can be provided as a package body in which a single use (for example, about 1 to 5 kg) is subdivided and filled into a container. The container used is preferably a flexible container, for example, an air-tight and liquid-tight bag made of a plastic film or sheet. Further, it is preferable to have a light shielding property. The material and thickness of the film or sheet can be appropriately selected according to the type of calcium compound used in the coating composition.For example, when slaked lime is used as the calcium compound, it is alkali-resistant, It is also necessary to select materials that have no or low gas permeability (especially co ₂ permeability) so that they do not harden due to the action of air, especially carbon dioxide, and that have no or low moisture permeability so that they do not dry. preferable. In addition, it preferably has durability and heat sealing properties. In such a package, the covering composition of the present invention prepared to have a viscosity suitable for trowel coating is applied to an air-tight and liquid-tight flexible container (bag), for example, under degassing conditions. It can be prepared by filling hermetically under vacuum conditions or N ₂ gas replacement conditions, and then closing the filling port with a heat seal or an inspired seal. FIG. 1 shows an example of such a packaging composition-filled package. According to the package, since the coating material is prepared in advance to have a viscosity suitable for ironing, the user does not need to mix and knead the materials with water at the construction site. Can be used. In addition, since it is refilled after each use, there is no need to dispose of the remaining material.

(2) Painted object

The present invention also provides a coated article obtained by applying the coating composition. The substrate (object to be coated) to which the 'coating composition of the present invention is applied' is not particularly limited, but is preferably a base material for a ceiling or a wall (inner 'outer wall) of a building.ゃ Various building materials used as decorative materials, such as cloths, boards and panels. The surface of such a substrate may be subjected to various treatments such as a sealer treatment. Also, various civil engineering members used as tunnel wall materials, guard rail materials, sound insulation wall materials, protective wall materials, and bridge structures, such as panels and boards, may be mentioned.

Examples of the cloth include a wide variety of cloth materials used for building interiors (such as indoor walls and ceilings). Examples of the cloth material include paper and fibrous sheets such as nonwoven cloth or woven cloth made of various fibers. Specifically, the paper may be any of Japanese paper, Western paper (high quality paper, medium quality paper), kraft paper, thin paper, backing paper, resin impregnated paper, pole paper, cardboard, etc. Also includes treated paper that is suitable for wallpaper construction, such as flame-resistant backing paper and non-combustible paper. Examples of the fibrous sheet include a porous woven fabric, a nonwoven fabric, and a knitted fabric obtained by using natural fibers; glass fibers; or synthetic fibers such as polypropylene, acrylic, nylon, polyester, polyamide, and vinylon as constituent materials. be able to. The above materials may be used alone or in any combination of two or more.

Examples of the pods and panels include a wide range of pod materials and panel materials used for building interiors (such as indoor walls and ceilings) and exteriors. Concretely, wood board, plywood, medium density fiber board, plastic board, cement mortar, asbestos cement calcium silicate board, hollow cement board, wood wool cement board, steel sheet panel, concrete board, PC panel, AL Examples include C panel, asbestos slate, gypsum board, particle board, foam cement board, wood chip cement board, calcium gayate board, and siding pod. Preferably, the gypsum port one de, gypsum particle board, wood board, medium density fiberboard, calcium silicate boards, plastic plates, rhinoceros ^ ⁵ queuing board (metal-based, including ceramic-based), and the like. Pod materials and panel materials used as tunnel wall materials, guard rail materials, sound insulation wall materials, protective wall materials, and various members of bridge structures can also be mentioned. The method of applying the coating composition to these base materials (construction members, civil engineering members) is not particularly limited, and may be a roll, a roller, a roller, a trowel, or the like. And a conventional method such as a spraying method using a spray or various guns. The coating composition applied to the substrate is then dried to be hardened. For drying, any of natural drying method, ventilation drying method, forced drying method and heat drying method can be used. At this time, the calcium compound contained in the coating composition is bonded together with the resin component to form a coating layer, and adheres to the surface of the substrate to be integrated with the substrate. The coated product of the present invention can be finished by applying a design to the surface of the formed coating layer with a roller with a concavo-convex pattern, or by sanding with a file or various types of polishing machines, if necessary.

The thickness of the coating formed from the coating composition of the present invention is not particularly limited as long as the coating surface of the substrate is sufficiently concealed and coated, and usually has a thickness of 0.1 to 5 mm. Can be selected as appropriate.

When a lime (eg, slaked lime, quicklime, calcium carbonate), gypsum or calcium silicate is used as a calcium compound, for example, a coated article having a coating formed from the coating composition of the present invention is prepared based on its porosity. It has excellent wettability (P and moisture release properties) and can exhibit a high dew condensation preventing effect. In addition, when lime (eg, slaked lime, quicklime, calcium carbonate, etc.) {secco} is used as the calcium compound, plaster-specific or plaster-like texture (color, gloss, fineness, etc., appearance and texture) can be exhibited. .

Further, a coated article having a coating formed from the coating composition of the present invention can have deodorant properties, antibacterial properties, self-cleaning properties, or air purification properties based on the photocatalytic action of the coating. Such properties of painted objects include various building materials such as inner and outer wall materials, roofing materials and ceiling materials, as well as guardrails placed facing the road. Sound insulation walls, protective walls, tunnel walls or bridges. It is useful for various civil engineering members such as members.

In the case of architectural members such as boards (panels) and cloth, treatment of joints and joints between building materials after construction tends to be a problem. According to the coated material prepared by applying the coating composition of the present invention, after being applied to a wall or the like, the coating surface of a joint or a joint of a building member is polished and polished to almost distinguish it from the surrounding coating layer. Continuous and even It is also possible to finish in one. Further, according to the coated product prepared by applying the coating composition of the present invention, there is also an advantage that repair after the application to a wall or the like can be easily performed. That is, when the building member is damaged or stained after the construction, it is possible to partially repair only the damaged portion by using the coating composition of the present invention. Such repairs can be made by applying a coating composition of the same color to the repaired area, or by polishing the damaged area first if necessary and filling or applying the coating composition of the same color to the area. It can be carried out.

In addition, the coating composition of the present invention can be usefully used for construction members (construction of interior and exterior). That is, when nailing or screwing the painted object of the present invention, particularly the interior / exterior panel to the wall base material, the putty-like coating composition is filled into the nail head recesses on the surface of the building material formed by nailing. Further, if necessary, a liquid or slurry-like coating composition is further applied thereon to cure and harden, and if necessary, the surface of the film is polished. It is possible to carry out the work so that the struck part is hardly visible (see Fig. 2). In this way, it is possible to avoid sticking the building material with the adhesive.

(3) Application method of coating composition

Furthermore, the present invention relates to a method for constructing a building interior and exterior using the above coating composition or coating (construction member). Examples of the construction method of the present invention include the following embodiments.

A. A coating method comprising applying the coating composition of the present invention to the surface of a building base material, drying the surface, and optionally polishing the surface after drying.

B. (0 a process of continuously providing a plurality of building members of the present invention to a building base material,

(i i) a step of filling or applying the coating composition of the present invention to the joints of the building materials and drying them, and

(iv) Polishing the coated surface as necessary

Including, construction method of building interior and exterior.

C. (i) a step of arranging a plurality of building materials of the present invention in a building base

(ii) If necessary, fill the joint of each building member with the coating composition of the present invention. Or coating process,

(i i i) a step of covering the joint with a reinforcing member,

(iv) a step of applying the coating composition of the present invention on the reinforcing member and drying; and (V) a step of polishing and polishing the coating surface if necessary.

Including, construction method of building interior and exterior.

The construction method of the interior and exterior of the building according to the present invention includes: (1) a method of coating and laminating the coating composition of the present invention on the inner and outer walls of the building and the roof material; The method of attaching or arranging the architectural members (cloths, panels, and pods) of the present invention to the inner and outer wall base materials is included.

The construction method of ① is, specifically, the surface of the base material (base material) of the inner and outer walls and ceiling of the building is directly or undercoated with a sealer or primer, etc., and then the coating of the present invention is applied. A coating composition having a viscosity of 100 to 400 centivoise at room temperature (25 ± 5. C), preferably at room temperature (25 ± 5.C), is applied and dried at room temperature or air until it solidifies. Then, if necessary, the polishing can be performed by polishing and polishing the surface of the coating layer laminated on the inner and outer wall base materials.

The base material (base material) of a building to which the coating composition of the present invention can be applied is not particularly limited, and examples thereof include concrete, cement mortar, gypsum blaster, dolomite plaster, asbestos slate, and gypsum pond. Cement-based and gypsum-based substrates such as plaster walls, pulp cement boards, asbestos cement calcium silicate boards, wool and wood chip cement boards, GRC glass fiber reinforced concrete panels and asbestos cement hollow extrusion boards; veneer boards , Laminated materials, plywood, wood fiber board and particle pods; plastic base made from vinyl resin such as vinyl chloride versatile or vinyl acetate; other metal bases Can be. Further, the building base material targeted by the present invention may be one in which a cloth is stuck or various paints are applied. That is, according to the coating composition of the present invention, the inner and outer walls and ceiling of the building can be reformed by applying to the cross or the painted surface.

When the building base material contains an organic material such as a plastic base material or a paint-coated surface, the undercoating treatment of the present invention is performed after the undercoating treatment with the coating composition containing no photocatalyst. It is preferred to apply the composition for use. The coating composition not containing a photocatalyst is not limited, and examples thereof include a composition comprising the same components as the coating composition of the present invention except that it does not contain a photocatalyst. Specifically, the coating composition used for undercoating includes a coating composition containing at least a calcium compound, a water-soluble or water-dispersible resin, and water, and, if necessary, further containing an inorganic pigment and / or an extender pigment. Things can be mentioned. Preferably, a coating composition containing a calcium compound, a zK-soluble or water-dispersible resin, a white pigment such as titanium oxide, and water, wherein the mixing ratio of the calcium compound is 10 to 90% by weight, Preferably 30 to 80% by weight (in terms of solids); the blending ratio of 5 to 70 parts by weight, preferably 10 to 50 parts by weight (in terms of solids) with respect to 100 parts by weight of the calcium compound; And a coating composition in which the white pigment such as titanium oxide is used in an amount of 2 to 30 parts by weight, preferably 2 to 16 parts by weight (as solid), based on 100 parts by weight of the calcium compound. be able to. The specific examples and mixing ratios of the above components, and other optional components are as described above for the coating composition of the present invention.

As shown in Experimental Example 2 described below, the coating composition composed of the above composition is resistant to an inorganic oxide having photocatalytic activity. Therefore, a coating having film performance and a photocatalytic function can be formed by applying an arbitrary coating agent having photocatalytic activity on the coating layer formed by the undercoating coating composition. It is possible.

The construction method of ② is based on the inner and outer walls of the building, the inner and outer wall frames provided on the base material (base material) or the base material (base material) of the roof and ceiling. Arranging objects (architectural members such as crosses, panels, boards, etc.) by abutting each side end face, and coating the coating composition of the present invention on the surface area of the joint of each architectural member, preferably A coating composition having a viscosity at room temperature of 300 to 8000 cP, preferably 500 to 5000 cP, more preferably 1000 to 4000 cP, is applied and dried until solidified, and then, if necessary, the surface of the layer is polished. You can do this by doing

When the interior and exterior panels are used as building members, the form of continuous connection of the panels is not particularly limited, and an example of the connection method shown in FIG. 2 can be given. More specifically, a flat panel is formed by abutting the side surfaces of a panel having vertical side surfaces so as to be continuous. A flanging method for forming a flannel surface (Fig. 3 (a)), in which interior and exterior panels having chamfered slopes at least on the surface side are connected side by side to each other, and a V-shaped V-grooving method (Fig. 3 (b)), which forms a panel surface with grooves of the type shown in Fig. 3 (b). The interior and exterior panels are constructed with their side surfaces in contact with each other, and a bumping or eye-opening method (FIG. 3 (c)) for forming a panel surface having a square groove in the continuous portion can be exemplified.

When a groove is formed at the joint portion of the panel as shown in FIGS. 3 (b) and (c), the same as the coating composition applied to the groove portion of the joint portion prior to the application of the coating composition described above. A high-viscosity (low water content) coating composition, preferably a coating composition having a viscosity of 8,000 to 30,000 cP at room temperature, preferably 10,000 to 20,000 cP, is filled as a sealing material, It is preferable to apply a coating composition having a viscosity of 300 to 8000 cP at room temperature from above. Prior to filling or application of the coating composition, the joint between the panels can be covered with a reinforcing member (FIGS. 4 and 5).

Examples of the reinforcing member include tape-shaped members such as woven fabric, non-woven fabric, ceramic paper, synthetic paper, mesh, and cold gauze, and these can be used as they are or by applying a filling paint, resin, or the like, or Films can be laminated and used (Figure 4). Also, a plastic or metal joiner having a substantially T-shaped or substantially D-shaped cross section can be used as the reinforcing member (FIG. 5). According to the construction method of the present invention, the joints of architectural members, such as cloths and panels, are not particularly noticeable at the joints of architectural members, such as cloths and panels, in the finishing step, and the surface of the architectural members is substantially uniform to A continuous and beautiful state can be achieved, and interior and exterior with good aesthetic appearance can be provided.

In addition, in addition to the above-described method, a conventional method used for construction of civil engineering members such as sound insulation walls and protective walls can be used for construction of civil engineering members.

(4) Restoration method of building interior and exterior

The present invention also relates to a method for restoring a construction surface of a building interior / exterior using the building member or the coating composition. The following are examples of such repair and repair methods. Things can be mentioned.

Damaged wall surface having a coating layer formed on the surface by applying the coating composition of the present invention containing at least a calcium compound, a water-soluble or water-dispersible resin, an inorganic oxide having photocatalytic activity and water. A method of repairing

(i) removing the coating layer of the damaged part if necessary,

(i i) a step of filling or applying the coating composition of the present invention to the damaged wall portion and drying the coating composition, and

(i i i) a step of polishing and polishing the coating surface if necessary

Repair method for building interior and exterior walls.

Can be exemplified. Example

Hereinafter, the contents of the present invention will be specifically described using the following examples. However, these examples are only aspects of the present invention, and the present invention is not limited to these examples.

Example 1

Lime 6 0.0

Acrylic silicone resin emulsion (solid resin content) 7.0

Photocatalytic titanium oxide (ST-21, Ishihara Sangyo) 20.0

Extender pigment (calcium carbonate) 5.0

White pigment (titanium oxide (EP_498, Dainichi Seika)) 5.0

Thickener (SP-600, Daicel Chemical) 1.5

Dispersant 1.5

100 parts by weight (solid content) 10.0 parts by weight The above component (solid content) was put into a paint mixing mixer together with water and stirred to stably disperse the solid content in water. Object (viscosity 3900cps (25 ° C)

B-type viscometer; solid content: about 60%). Slaked lime was used as lime.

Example 2 Lime 50.0

Acrylic silicone resin emulsion (solid resin) 7.0

Photocatalytic titanium oxide (ST-21, Ishihara Sangyo) 20.0

Extender pigment (calcium carbonate) 20.0

Thickener (SP-600, Daicel Chemical) 1.5

Dispersant 1.5

Total amount (solid content) 100.0 parts by weight The above component (solid content) was put into a paint mixing mixer together with water and stirred to stably disperse the solid content in water, and the coating composition of the present invention (viscosity 3000 cps (25) Β-type viscometer; solid content about 60%) was prepared. Slaked lime or quick lime was used as lime.

Example 3

Lime 50.8

Acryl resin emulsion (resin solids) 16.0

Photocatalytic titanium oxide (ST-21, Ishihara Sangyo) 15.0

White pigment (titanium oxide (ΕΡ-498, Dainichi Seika)) · 8.0

Extender pigment (talc) 7.2

Inorganic thickener 0.8

Silicon defoamer 0.8

Dispersant (Anionic surfactant) 1.4

Total amount (solid content) 100.0 parts by weight The above component (solid content) is put into a paint mixing mixer together with water and stirred to stably disperse the solid content in water, and the coating composition of the present invention (viscosity 1200 cps (25 ° C) B-type viscometer; solids content about 63%). Slaked lime or quick lime was used as lime.

Example 4

Lime 50.8

Acryl resin emulsion (solid resin content) 16.0

Photocatalytic titanium oxide (ST-21, Ishihara Sangyo) 8.0 White pigment (titanium oxide (EP-498, Dainichi Seika)) 8.0

Extender pigment (talc) 14.2

Inorganic thickener 0.8

Silicon defoamer 0.8

Dispersant (Anionic surfactant) 1.4

Example 5 Plastering Coating Material

Lime 60.0

Acryl silicone resin emulsion (solid resin content) 7.0

Photocatalytic titanium oxide (ST-21, Ishihara Sangyo) 20.0

Extender pigment (calcium carbonate) 5.0

White pigment (titanium oxide (EP-498, Dainichi Seika)) 5.0

Thickener (SP-600, Daicel Chemical) 1.5

Dispersant L_5

Total amount (solid content of paint) 100.0 parts by weight The above component (solid content) was put into a paint mixing mixer together with water and stirred to obtain a coating composition of the present invention (viscosity 18000 cps (25 ° C) B-type viscometer Solids content about 90%). As the lime, a mixture of slaked lime and quick lime was used.

Example 6

The coating composition prepared in Example 1 was put in an airless spray, and evenly sprayed on one side of a gypsum board (20 cm × 20 cm × thickness lcm, made by Yoshino Gypsum), and the film was dried by ventilation drying (total). The applied amount (total amount of paint) was 500 g / m ² , and the dried coating was 0.35 thigh. The gypsum panel had a uniform appearance with no unevenness of blowing, color, or gloss with respect to various lights such as direct sunlight, oblique light, and illumination. The panel has excellent moisture absorption and release properties, and dew condensation occurs even in an environment with a humidity of 80%. Was significantly prevented. Further, it was confirmed that even when an open flame was approached to the surface of the EE layer of the panel, it did not ignite, did not generate smoke, and had excellent flame resistance. Next, the obtained gypsum panel was used as an interior wall material in a room and nailed with a coating layer on a wall base material. The nail head is hit until it sinks into the inside of the coating layer, and into the nail head recess formed thereby, 100 parts by weight of slaked lime, a composition consisting of acrylic silicone resin emulsion, photocatalytic titanium oxide and a thickener Insert a putty-like coating material (viscosity: 8000 cps) that was slightly kneaded and mixed with water and filled. After solidification, the coating composition of Example 1 was applied again to the nailing area and its surrounding area to finish. . The interior material used as the wall material was finished in such a way that the surface of the nailed part (repair part) could not be distinguished from the surrounding area and integrated. Moreover, the coating film formed on the interior panel had sufficient toughness and flexibility without cracking even after being applied to the indoor wall.

Experimental example 1

Using the coating composition prepared in Example 1, the adhesive strength and the strength of the dried coating film were measured.

(1) Adhesive strength

The coating composition prepared in Example 1 was put into an airless spray, and a sidewalk plate (two types with primer treatment and without primer treatment) and a plywood plate (without primer treatment) (300 XI 50 X 5) The panel (test plate) with a coating thickness of 0.5 mm was created by spraying it evenly on one side of the cafeteria) and solidifying it by ventilation drying. A test was conducted using three such samples in accordance with the test (tensile strength) specified in JIS K5400-1990 8.8, and the adhesion of the coating film was evaluated. In addition, ADHESION TESTER ELC0METER was used as a bow I tension tester. Specifically, the tensile strength was calculated by measuring the load (kgf) at the time when the adhesive surface fracture or internal surface fracture occurred (JIS K5400-1990 8.8). As a result, Table 8 shows the average of three samples performed on each test plate.

Tensile strength

Sidewalk board (without lymer) 15 kg / cm ²

Sidewalk board (with priming) 18 kg / cm ²

Veneer board (without lymer treatment) 12 kg / cm ² (2) Dry film strength

The test plate prepared above was subjected to a test according to the pencil scratch value measurement method (hand drawing method) specified in JIS K5400-1990 8.4, and the strength of the coating was evaluated. Specifically, the surface of the coating formed on the test board (sidewalk board) prepared above is drawn with a pencil, and the core density of the pencil (H) is such that the coating has two or more scratches in five tests. Therefore, the strength of the coating formed from the coating composition of the present invention was evaluated as HB.

Experimental example 2

The coating formed with the coating composition prepared in Example 3 was irradiated with ultraviolet rays for 250 hours, and the adhesion strength of the coating after the irradiation was measured. As a comparative experiment, a coating composition (comparative coating composition) prepared using a pigment oxidized titanium (EP-498, Dainichi Seika) instead of the photocatalytic titanium oxide in the formulation of Example 3 The film formed in step 2 was irradiated with ultraviolet rays in the same manner, and the adhesion strength of the film after irradiation was measured. Specifically, the experiment was performed as follows.

The coating composition prepared in Example 3 or the coating composition for comparison was placed in an airless sprayer, and sprayed onto one side of a sidewalk board (with primer treatment) (300 XI 50 X 5 cruises) without exhaustion. It was solidified by drying to prepare a panel (test specimen: 2 specimens each) with a coating thickness of 0.5 mm. Ultraviolet irradiation (255 ± 45 w / m ² ) was performed on the two samples of each of the panels for 250 hours using a sunshine weather meter (power Bon Arc lamp type). After irradiation with ultraviolet rays, a test was performed in accordance with the test (tensile strength) specified in JIS K5400-1990 8.8 in the same manner as in the method of Experimental Example 2 (1) to evaluate the adhesion of the coating. Table 9 shows the results.

As can be seen, the coating formed with the coating composition of the present invention (Example 3), despite containing the organically active titanium oxide together with the organic resin, has an ultraviolet light. Adhesion strength was not affected by the radiation, and it adhered strongly to the underlying substrate (sidewalk board). Although not restricted, one of the reasons is that in the coating composition of the present invention (Example 3), slaked lime (calcium hydroxide), which is the main component, becomes calcium carbonate over time by curing. As a result, it is conceivable that they adhere more firmly to the base material. That is, the coating composition of the present invention means that even if the resin in the coating composition is separated by the action of a photocatalyst, the adhesion strength required for practical use as a coating film can be sufficiently ensured. This means that the coating composition of the present invention, which is mainly composed of a self-curable power compound, has the ability to ensure at least the initial adhesion and adhesion of the resin to be incorporated therein. It suggests that something is acceptable.

Further, the surface of the coating formed with the coating composition containing the photocatalytically active titanium oxide (Example 3) had a unique plaster like the coating composition without the photocatalytically active titanium oxide (comparative example). No change (deterioration or discoloration) was observed even after irradiation with ultraviolet light, confirming that the product had excellent weather resistance.

Experimental example 3 Moisture absorption. Moisture release (condensation prevention)

The coating composition prepared in Example 1 was put into an airless spray, sprayed evenly on one side of a gypsum board (40 cm x horizontal 25 cm x thickness 5 mm), and solidified by ventilation drying. Thus, a panel having a coating thickness of 0.6 mm was prepared.

A humidity control test was performed using six such panels. In order to properly evaluate the humidity control of the coating layer, a moisture-proof seal was applied to the side surface and the back surface of the panel (the surface on which the coating composition was not applied) to prevent water vapor from permeating. Specifically, the building material panel of the present invention is left in an environment with a relative humidity of 65% and a temperature of 2 and weighed 7 to 8 minutes after the absorption amount has almost reached equilibrium. 9 8% temperature 2 0 and transferred to an environment of ° C, was determined water absorption of the panel per unit surface area (1 m ²⁾ was枰量after 48 hours again reaches near equilibrium moisture absorption rate . Next, the sample after the moisture absorption test was similarly transferred to an environment with a relative humidity of 65% and a temperature of 2, and after standing for 24 hours, it was weighed to determine the water absorption of the panel per unit surface area (lm ² ). Was. Then, the difference in the amount of water absorbed in these experiments was evaluated as the amount of absorbed moisture and the amount of released moisture, respectively.

Wallpaper made of vinyl chloride (vertical 40 c mX horizontal 25 c Table 10 shows the humidity control effect of m).

The indications in the table mean the following.

20 ° C 65% weight (g / m ² ) ": Weight per 1 m ² after standing at 20 ° C 65 ° RH for 48 hours

20 ° C65¾S * (g / m ² ) * ² : Weight per 1 in ² after standing at 20 ° C65% RH for 24 hours ”

20 ° C 98% weight (g / m ² ) 20 ° C 98 ° RH Weight per 1 m ² after standing for 48 hours

Hygroscopicity (g / m ² ) 98% weight at 20 ° C ― 65% weight at 20 ° C

Moisture release (g / m ² ) 20 ° C 98% weight-20 ° C 65% weight * ²

From this, it was confirmed that a film formed by applying the coating composition of the present invention has an excellent humidity control function (moisture absorption and release properties), which is useful for preventing dew condensation on indoor walls. It was considered.

Experimental Example 4 Indoor Air Pollutant Adsorption.

Of the indoor air pollutants, formaldehyde in particular causes carcinogenicity, allergic asthma, sickness! 1 Intense, headache, fatigue and sleep disorders, etc., and carbon dioxide is a respiratory disease such as asthma. It is known to cause impaired lung function, reduced resistance to infection, decreased immune function and impaired health of the respiratory tract. Therefore, a panel (test piece) having a coating thickness of 0.6 mm (coating amount of 30 g) was prepared using the coating composition prepared in Example 3 in the same manner as in Experimental Example 3 above, and formed on the panel. The film (coated film) was examined for formaldehyde adsorption and carbon dioxide absorption. As in Experimental Example 3, the side and back surfaces of the panel were covered with a seal to properly evaluate the adsorptivity and absorbency of the coating layer.

Specifically, a test sample and formaldehyde (600 ml, initial concentration 45 ρρπι) or carbon dioxide (600 mK initial concentration 42%) were injected into a tedra bag (5 L), and after 4 hours and 25 hours, The gas concentration was measured using a detector tube (test sample gas concentration). In addition, As a control experiment, the above gas concentration was measured in the same manner without a test sample, and this was taken as the control gas concentration. The formaldehyde adsorption and carbon dioxide absorption were calculated from the following equations.

Formula>

Control gas concentration-Test sample gas concentration

Adsorption / absorption rate (%) = X 100 control gas concentration

(1) The adsorption rate of formaldehyde is shown in Table 11, and the change over time of the formaldehyde concentration is shown in Figure 6.

Based on this, で formed with the coating composition of the present invention (main component: slaked lime) contained 90% or more of formaldehyde (initial concentration of 45PPD1), a harmful chemical designated by the Ministry of Health and Welfare, in 4 hours and 100% in 25 hours. % P has been found to reach and take in.

(2) Table 12 shows the absorption rate of carbon dioxide, and Fig. 7 shows the change over time in the concentration of carbon dioxide.

Table 1 2>

From this, the coating film formed with the coating composition of the present invention (main component: slaked lime) was about 80% carbon dioxide (initial concentration of 42%) in the air for 4 hours and 100% for 25 hours. It was found to be absorbed and fixed as calcium carbonate.

Experimental example 5 Performance evaluation of photocatalyst (ΝΟχ removal ability)

Using the coating composition prepared in Example 3, a panel having a coating thickness of 0.3 mm (5 cm × 15 cm, coating area: 0.0075 m ² ) was prepared in the same manner as in Experimental Example 3 above (test specimen). Was prepared and the NOx removal ability of the film (coating film) formed on the panel was examined. The actual As in Experimental Example 3, the sides and back of the panel were covered with seals in order to properly evaluate the NO x removal ability of the coating layer. The NOx removal capability was measured using a potentiostatic electrolytic automatic measuring instrument (NO sensor: manufactured by Shin-Cosmos Electric Co., Ltd.) (COSMOS DENSER TECHNOLOGY P. 85 (1997) According to the report of the National Institute of Advanced Industrial Science and Technology (Νο. 14 (2000) p. 76-81), the procedure was as follows (see Fig. 8).

(1) Set the specimen in the photocatalytic reaction vessel.

( ₂ ) The test gas (NO, N〇2) flowing on the bypass side (between -C2) is switched to the reaction system side, and the test gas flows into the reaction system equipped with the photocatalytic reaction vessel, and the reaction system Measure the NO and NO ₂ gas concentrations in the chamber with the NO and NO ₂ sensors in the measuring section. (3) Irradiate black light when the output value of the NO sensor is saturated.

(3) After a predetermined time, stop irradiation of the black light.

The results of measurement of NO and NO ₂ gas concentration in the reaction system (ppm) shown in FIG. In the figure, * indicates the start of the flow of the test gas into the reaction system, ON indicates the start of black light irradiation, and ΔFF indicates the stop of black light irradiation. The time (minutes) on the horizontal axis was set as 0 minutes at the start of black light irradiation. The reaction container in the flows of the test gas into the reaction system proceeds substitutions from the state NO (N0 ₂₎ No, the output of NO and N_〇 ₂ sensor became gradually raised state close to saturation. However, as shown in FIG. 9, it takes a considerable time to NO and N 0 ₂ saturated, it was found that the specimen (film) itself of the present invention there is NO and NO ₂ adsorption capacity. Furthermore, since the NO concentration in the reaction system decreased (0.77-1) by irradiation with black light, it was confirmed that the test specimen (coating) of the present invention reliably exhibited NO removal ability. Was done. Although more is in either N 0 ₂ concentration II was found to decrease significantly. Therefore, the present specimen has no release of N0 _2, that also has NO ₂ resolution Conversely was confirmed.

Further, by using the coating composition of Example 4 was half the amount of the titanium oxide photocatalyst, when having conducted the same experiment, NO and N0 ₂ resolution in accordance with the reduction of the amount of the titanium oxide photocatalyst was reduced although, in the same manner as described above significantly NO and N0 ₂ decomposition removal effect it was confirmed.

From these results, the film formed by the coating composition of the present invention was probably Based on the porosity of the calcium compound itself and the porosity of the formed film, it is possible to adsorb and take in contaminants such as NOx from the surface to the inside, and contaminants trapped on the surface and inside of the film It was found that photocatalysts (organic oxides) scattered not only on the surface of the film but also inside could decompose efficiently and reliably. In particular, the property of the coating, which adsorbs and captures contaminants, suggests an efficient decomposition cycle in which contaminants accumulate when light is not irradiated, such as at night, and are decomposed and removed during light irradiation, such as during the day. It is. Furthermore, the property of the coating, which is capable of adsorbing and holding contaminants not only on the surface of the film but also inside the coating, has the effect of increasing the contact area between the contaminants and the photocatalyst. Product) It means that even a small amount of an internally added coating composition can exhibit efficient photocatalytic activity.

From these results, the coating composition of the present invention has not only an air purification effect such as NOx removal ability but also other effects known as a photocatalytic effect, that is, a deodorizing effect, an antibacterial effect, and a self-cleaning effect (contamination resistance). And antifouling properties).

Experiment 6

The coating compositions (paints 1 and 2) prepared in Examples 1 and 2 were prepared according to the method specified in Japanese Industrial Standards: ilSK5400. (1) In a container (JIS K5400) 4.1 (2)), (2) Painting workability (JIS K 5400 6.1) and (3) Low temperature stability (JIS K 5400 5.1). (4) Drying time (6.5 of JIS K5400), (5) Good appearance (7.1 of JIS K5400), (6) Concealment rate (7.2 of JISK5400), (7 ) Alkali resistance (8.21 of JIS K 5400), (Washability (8.11 of JIS K 5400), (9) Water resistance (8.19 of JIS 5400) and (10) Accelerated weather resistance (J Each item of 9.8.1) of IS K 5400 was examined, and the test method and evaluation of each item were all based on the method specified in J IS K5663-1995.

(1) Condition in container (5.3 of JIS ¾663-1995)

The paint was filled in a container (metal inner can) and allowed to stand at room temperature for 24 hours or more. Then, the container was opened and the contents were examined by stirring with a stick. "Good" means that there is no hard lump and the whole contents are uniform when mixed, "Normal" means that there is no lump but it is difficult to form, and "Poor" means that lump is recognized. "

(2) Painting workability (5.4 of J IS! 663-1995) Paint uniformly on the smooth surface of a test plate (flexible plate, 500 x 200 x 3 mm) with a brush (1st time, application amount: 10-13IM1Z 1 sheet), 6 hours later, 2nd brush Coating (coating amount: 9 to 11 rows 1 / sheet) was performed, and the coating workability was evaluated based on the presence or absence of difficulty in brush lotion during the second coating. If it is not difficult to carry the brush when applying the second coat, it is evaluated as `` Good '' as `` Do not disturb the painting work with 2 coats '', and `` Normal '', `` Poor '' according to the difficulty of carrying the brush And

(3) Low-temperature stability (5.5 of J IS 1¾663-1995)

Fill the container (metal inner coated can) with the paint almost completely, close it tightly, store it in a low temperature incubator at a temperature of -5 ° C 2 ° C for 18 hours, then take it out and leave it at room temperature for 6 hours. Repeated three times. Next, the lid of the container was opened, and the paint in the container was stirred with a stick to check whether or not they became uniform. In addition, painting workability was examined according to the method (2) described above. Specifically, the paint was applied once before being put into a low-temperature constant temperature oven, and twice applied using a treated paint whose low-temperature stability was adjusted. The difficulty of the second brush transport was evaluated. Further, the test plate after the above-mentioned coating workability test was dried for 24 hours, and the appearance of the formed coating film was evaluated. When the paint is easily uniform and there is no abnormality in the coating workability and appearance of the coating film, the evaluation is `` good '' as `` no deterioration when cooled to 15 ° C '', and `` "Normal" and "Bad".

(4) Drying time (JIS {(5.6 of 5663-1995)

Apply the paint to one side of a glass plate (200 x 100 x 2 restaurant) using a lOO im B-type film applicator, and apply it to a constant temperature and humidity of 20 soil 1 ° C, humidity 65 5 ± 5%. The time it takes to enter the room and dry until it is in a semi-cured state (a state in which the center of the coated surface is gently and gently rubbed with a fingertip to prevent scratching of the coated surface) was measured.

(5) Appearance of coating film (JIS (5.7 of の 663-1995)

Dry the test plate coated with the paint in the above test for paint workability for 24 hours, and visually observe the painted surface under diffused daylight to determine the size of the brush, the presence or absence of holes or looseness, and the paint film. The surface uniformity (unevenness) was evaluated. When there is no hole or slack with a large degree of brushing, and the coating surface is uniform (no unevenness), the evaluation is “good” as “the appearance of the coating film is normal”. “Normal” and “Poor” accordingly.

(6) Concealment ratio (JIS 1 (5.8 of 5661-1995) The opacity test paper was fixed on a glass plate, and a paint was applied thereon using a B-type film applicator with a gap of 150 xm, and left to dry for 24 hours. The luminous reflectance of the coating film formed on the white and black backgrounds of the test paper was measured at three points on the test piece using a reflectance measuring device. From the obtained luminous reflectance, the hiding ratio was determined from the following equation. 【formula】

Luminous reflectance of paint film on black ground

Concealment rate (%)

Luminous reflectance of paint film on white background

(7) Alkali resistance (J IS K5663- 1995, 5.10)

① Test piece: advance near and back Flexi Bull plate which had been wrapped 2-3 coats with paint of the same type (150 X 70 X 3 Yuzuru) surface of the paint brush 1 soil 0. lm 1/100 cm ² of After 6 hours, apply once more in the same manner and apply one more time in the same manner and dry for 5 days. Then, the periphery and the back of the test plate were covered with paraffin to obtain test pieces (three sheets were prepared, one of which was Original test specimen).

② Immerse the above test pieces in a calcium hydroxide saturated solution (20 to 48 hours for 20 to 48 hours). Observe the condition of the coating film immediately after taking out two test pieces from the solution and 2 hours later. It was evaluated in comparison with the original test specimen (swelling, cracking, peeling, hole, softening, color,

(3) Evaluation: No swelling, cracking, peeling, pitting, or softening was observed on the two coating films after 48 hours or 18 hours of immersion treatment, and there was no coloring or turbidity of the immersion solution. When the degree of change or discoloration of the gloss is not large, the evaluation is "good" as "no abnormality when soaked for 48 hours" or "good" as "no abnormality when soaked for 18 hours". did.

(8) Meta-detergency (5.11 of J IS 663-1995)

(1) Specimen: A flexible plate (430 x 170 x 5 thighs) with a long side of about 400 thighs, paint with a B-type film applicator with a gap of 150 m on the long side of about 400 thighs, with the coated surface facing upward for 7 days The dried one was used as a test piece (two pieces were prepared).

② Using a brush machine, rub the coating surface of the test pieces (2 pieces) wetted with 0.5% stone and water with a brush by reciprocating (100 to 500 times) and then testing. Test piece It was washed with water, and the center of the trace of brush scrubbing was inspected under a diffused daylight for 100 thighs. The film was visually inspected for tears or wear.

③Evaluation: When the coating on the center of both test pieces was broken or worn out by brush reciprocation of 500 times or more and the base material of the test piece was not exposed, it was evaluated as “withstand 500 washings”. Was evaluated as “good”, and when no exposure of the substrate of the specimen was observed after 100 or more round trips, it was evaluated as “withstand 100 washes” and the evaluation was “good”.

(9) Water resistance (J IS 1 (5.93--5663-1995)

(7) Using the same test specimens used for the alkali resistance test (2), immerse them in deionized water (20 ± 1 ° C) for 96 hours, The state of the coated surface was evaluated immediately after being taken out of the test piece and two hours later (skin, blistering, cracking, peeling, color, and gloss).

(10) Accelerated weathering resistance () 13 1½663-1995 5.12) (Sunshine carbon arc lamp type: JIS K 5400 9.8.1)

(1) Specimen: A flexible plate (150 x 70 x 3 wisteria) previously treated with JPIA-23 synthetic resin emulsion sealer was evenly brushed twice with paint (applied amount per application: 1.0

± 0.1 ml / cm ² ) and dried for 5 days to obtain test specimens (two specimens, one of which was an original specimen). The time between the first coating and the second coating was 6 hours.

(2) Irradiate for 200 hours using a sunshine power-bon lamp light fastness tester (black panel temperature: 63, rain cycle: 18 minutes at 120 minute intervals), and check the original and weather resistant test pieces. Visual observation was conducted to examine the degree of color unevenness and change in color gloss, and whether there was any chalking, blistering, peeling, or cracking.

③ When the degree of chalk is 8 or more, there is no swelling, peeling or cracking, and the degree of color change is not greater than that of the original test piece, the evaluation is “good” and the degree of failure is determined according to the degree of failure sequentially.

"Normal" and "Poor". Table 13 shows the results. <Table 13>

From these results, it was confirmed that the coating composition of the present invention can be prepared as a coating material that satisfies at least two types of synthetic resin emulsion paints, especially one type (JIS K5663-1995). Industrial applicability

Since the coating composition of the present invention contains a photocatalyst, organic substances (compounds and microorganisms) attached to the surface of the coating can be effectively decomposed in the presence of light. For this reason, the surface of the film formed by the coating composition of the present invention is conservative from its antibacterial properties and self-cleaning properties, and can maintain its cosmetic properties for a long period of time. In addition, since the coating has deodorizing properties and air purifying properties, it significantly decomposes and removes volatile toxic substances (such as formaldehyde) generated from building materials and pollutants such as NOx and SOx in the atmosphere. be able to. For this reason, as a paint or coating material for various types of buildings such as interior / exterior buildings (wall surfaces, roof surfaces, ceiling surfaces) where such photocatalytic functions are desired, signs and advertisement panels, tunnel walls, sound insulation walls, protective walls, bridge surfaces It can be suitably used as a coating or a coating material for various types of civil engineering such as guardrails.

Since the coating composition of the present invention is prepared mainly from an inorganic material in addition to the air purifying property by the photocatalytic function, "chemical sensitivity", "sick house syndrome", etc. In today's problematic situation, it is useful as an indoor or outdoor paint or coating that is both human and environmentally friendly.

The coating composition of the present invention is resistant to the photocatalytic activity even though a photocatalyst is internally added, and can maintain a stable coating for a long period of time. In addition, the coating composition of the present invention containing a porous calcium compound such as lime (eg, slaked lime, quicklime, calcium carbonate), secco, or calcium silicate exhibits functions such as humidity control and anti-condensation. be able to. For this reason, it is extremely useful as a cement-coated inner wall of condominiums or the like, or a paint (painting material) for indentation or building material (painting material) that becomes high in humidity.

In addition, the coating composition of the present invention containing an inorganic white pigment such as titanium oxide, in particular, has an excellent hiding power of 500 or less, more preferably 20 O or less, and contains a fiber material. Even without it, it has excellent film-forming properties (yield, crack resistance, flexibility, and appearance), and can be easily used in a coating form such as spraying, brushing, or one-coating with a roller.

Further, the coating composition of the present invention is stipulated in J IS 5663-1995 by using an air-hardened calcium compound such as slaked lime as a calcium compound and blending an inorganic white pigment for imparting hiding power. It can be prepared as a one-pack paint with at least two types of synthetic resin emulsion paint (indoor paint) and one (outdoor paint). Such paint can be prepared by filling it into a container at a factory or the like beforehand, so that the time required for compounding on site can be reduced, and the remaining material after painting can be returned to the container again. It has the advantage that it can be stored.

Further, the coating composition of the present invention can be suitably used for concealing a seam between cloths or between panels, and can be used in a coating form, so that it is also useful for repairing and repairing interior and exterior wall surfaces. It is a coating composition with high commercial value that can be widely used for new construction and renovation construction.

Claims

The scope of the claims

1. For coating containing at least one calcium compound selected from the group consisting of lime, gypsum, calcium phosphate and calcium silicate, a water-soluble or water-dispersible resin, a photocatalytically active inorganic oxide, and water. Composition.

2. The coating composition according to claim 1, wherein the calcium compound is at least one lime selected from the group consisting of slaked lime, quicklime, calcium carbonate and dolomite.

3. The coating composition according to claim 1, wherein the calcium compound is slaked lime.

4. The coating composition according to claim 1, wherein the water-soluble or water-dispersible resin is a vinyl monomer copolymer or a homopolymer.

5. The pinyl monomer is (meth) acrylic acid ester, (meth) acrylonitrile, vinyl monomer containing amide bond, styrene or styrene derivative, carboxyl group-containing beer monomer, halogenated beer, vinyl ester, and silyl The coating composition according to claim 4, which is at least one member selected from the group consisting of group-containing vinyl monomers.

6.7J As a soluble or water-dispersible resin, instead of or together with a pinyl monomer copolymer or homopolymer, a fluororesin, polysiloxane resin, urethane resin, silicone resin, phenolic resin, urea resin, melamine resin and phthalate 5. The coating composition according to claim 4, comprising at least one member selected from the group consisting of acid resins. ,

7. The coating composition according to claim 1, wherein the inorganic oxide having photocatalytic activity is titanium oxide.

8. The coating composition according to claim 1, further comprising an inorganic pigment.

9. The inorganic pigment is at least one selected from the group consisting of titanium oxide, zinc white, zinc sulfide, lithon, lead white, antimony white, and zirconia.

9. The coating composition according to 8.

10. A package in which the coating composition according to claim 1 is hermetically sealed in a flexible container.

1 1. Flexible containers made of alkali resistant, low co ₂ permeable and low moisture permeable materials 10. The package according to claim 10, wherein the package comprises:

12. The package according to claim 11, wherein the flexible container further has a heat-fusing property.

10. The package according to claim 10, wherein the coating composition is a trowel coating material containing slaked lime as a main component.

1 4. An architectural or civil engineering coating or paint comprising the coating composition according to claim 1.

1 5. A coating material or paint for an inner wall or an outer wall of a building, comprising the coating composition according to claim 1.

1 6. A coated article having a coating formed from the coating composition according to claim 1.

1 7. The coated article according to claim 16, which is used as a building member or a civil engineering member.

1 9. (i) a step of connecting a plurality of building members according to claim 17 to the building base material or the base material,

(ii) a step of filling or applying the coating composition according to claim 1 to a joint portion of each building member and drying it; and

(i i i) If necessary, polishing the coated surface

Including, construction method of building interior and exterior.

20. (i) A step of connecting a plurality of the building members according to claim 17 to the building base material or the base material,

(i i) a step of filling or applying the coating composition according to claim 1 to a joint portion of each building member, as necessary.

(i i i) a step of covering the joint with a reinforcing member,

(iv) a step of applying and drying the coating composition according to claim 1 on the reinforcing member, and

(v) polishing the surface of the coating if necessary

Including, construction method of building interior and exterior.

21. A method for repairing a damaged portion of a building interior or exterior surface having a coating layer formed by applying the coating composition according to claim 1 on the surface, (i) if necessary, a step of shaving the coating layer of the damaged portion;

(i i) a step of filling or applying the coating composition according to claim 1 to a damaged wall surface and drying the coating composition; and

(i i i) polishing the surface of the coating, if necessary

Including, how to repair the interior and exterior surfaces of buildings.