JPH1176832A - Antibacterial deodorant composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To control the decomposition, deterioration of physical property, and coloring of a binder by making a composition containing composite particles in which a granular semiconductor photocatalyst and granular amorphous calcium phosphate are integrated and a binder. SOLUTION: An antibacterial deodorant composition consists of composite particles in which a granular semiconductor photocatalyst and granular amorphous calcium phosphate are combined/integrated and a binder. Slurry containing amorphous calcium phosphate(ACP) particles of prescribed particle size is added with a semiconductor photocatalyst of particle size smaller than that of the PCP particles and agitated to make a kind of mixed slurry in which the aggregation of respective particles is controlled. By granulating and drying the slurry, composite particles in which particles made by the adhesion of the semiconductor photocatalyst particles to the peripheries of the ACP particles are combined/ integrated are obtained. The binder is not restricted in particular and uses a organic resin such as a synthetic resin, an inorganic substance, and others.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an antibacterial deodorant composition comprising a binder and a composite particle in which a semiconductor photocatalyst capable of exhibiting deodorant and antibacterial effects utilizing photocatalytic activity and amorphous calcium phosphate are integrated. The present invention relates to an antibacterial deodorant composition which can be applied to various materials such as painting, printing, spraying and the like.

[0002]

2. Description of the Related Art Semiconductor photocatalysts such as titanium oxide and zinc oxide are known as semiconductor photocatalysts having photocatalytic activity. This photocatalytic activity means that the oxide semiconductor particles are excited by absorbing light (generally, ultraviolet light) having energy equal to or more than the band gap, and the generated electrons and holes are transferred to and from a substance adsorbed on the particle surface. Is performed to decompose the adsorbed substance by oxidation or reduction.

Many applications utilizing such photocatalytic activities have been filed, but when applied to commonly used binders, strong oxidative action due to photocatalytic activity would occur if semiconductor photocatalysts were used alone. As a result, the binder which comes into contact with the semiconductor photocatalyst may be decomposed or deteriorated to cause discoloration, so that it cannot withstand industrial use.

In order to solve these problems, for example, Japanese Patent Laid-Open No.
Japanese Patent No. 164334 discloses that a titanium oxide having an average particle diameter of 0.001 to 0.5 μm, a hydrolyzate of a special hydrolyzable silicon compound, and a solvent are used to determine the weight ratio of titanium and silicon. And a titanium oxide coating film moldable composition for photocatalysts having a ratio of 1%.

[0005]

However, in the above method, the composition for forming a titanium oxide coating film for a photocatalyst requires the use of a hydrolyzate of a special hydrolyzable silicon compound. It is not easy to form a coating film using a hydrolyzate of such a special hydrolyzable silicon compound. In addition, the method using a hydrolyzate of such a special hydrolyzable silicon compound is not versatile, so that there is a problem that manufacturing and processing costs are increased. The present invention has been made in order to solve the above problems, and even when applied to a commonly used binder, the binder is decomposed by a strong oxidizing action due to photocatalytic activity, resulting in deterioration of physical properties. And photo-catalytic activity of the semiconductor photocatalyst can be exhibited, and the specific gravity of the semiconductor photocatalyst such as titanium oxide, which is easy to separate, does not disperse. An object of the present invention is to provide a sex deodorant composition.

[0006]

According to the present invention, there is provided an antibacterial deodorant composition comprising a composite particle in which a particulate semiconductor photocatalyst and a particulate amorphous calcium phosphate are combined and integrated, and a binder. It is. Further, the particle diameter of the particulate semiconductor photocatalyst contained in the composite particles is smaller than the particle diameter of the particulate amorphous calcium phosphate, or the composite particles, the particulate semiconductor photocatalyst is a particle of amorphous calcium phosphate Is an antibacterial and deodorizing composition obtained by integrally integrating particles formed by fixing semiconductor photocatalyst particles around the composition.

As the semiconductor photocatalyst in the present invention, titanium oxide, zinc oxide, cerium oxide, CdS, CdS
e, WO ₃ , Fe ₂ O ₃ , SrTiO ₃ , KNbO and the like, and these can be used alone or in combination of two or more. In addition, in order to achieve the object of the present application, particularly, as a semiconductor photocatalyst, titanium oxide is preferable because its photocatalytic activity is strong, and any of anatase-type titanium oxide and rutile-type titanium oxide can be preferably used as such titanium oxide. .

In order to enhance the activity of these semiconductor photocatalysts, the above-mentioned semiconductor photocatalysts can be made to adhere to metals such as platinum, palladium, rhodium and ruthenium and metals such as silver, copper and zinc. In this case, 1 depending on the activity
-20% by weight of metal can be used as appropriate. Since the photocatalytic activity of the semiconductor photocatalyst increases as the particle diameter decreases, that is, as the specific surface area increases, the average particle diameter of the semiconductor photocatalyst particles is preferably 0.001 to 1 μm, and particularly preferably 0.001 to 1 μm. It is preferably about 0.1 μm. Further, the particle diameter of the semiconductor photocatalyst particles is desirably smaller than the particle diameter of the particulate amorphous calcium phosphate.
Although the reason for this is not clear, it is because various substrates can be prevented from decomposing and coloring due to strong oxidizing action due to photocatalytic activity, and the photocatalytic activity possessed by the semiconductor photocatalyst can be exhibited.

Amorphous Calcium Phosphate (ACP) used in the present invention is prepared by adding a neutral or weakly alkaline water-soluble polymer to a suspension of calcium hydroxide under stirring. A dispersant, for example, a weakly alkaline ammonium triacrylate is added to obtain a mixed solution, and then the aqueous solution of phosphoric acid is added dropwise while stirring the mixed solution to adjust the pH to 11 to 5. ACP having a large specific surface area can be obtained. In particular, by adding the above-mentioned water-soluble polymer dispersant to a calcium hydroxide suspension under stirring to synthesize ACP, the average particle diameter of particles in the obtained slurry containing ACP is 0.01 to It can be 10 μm.
The amount of the water-soluble polymer dispersant added is 0.1 to 10% by weight, preferably 0.1 to 10% by weight, based on the calcium hydroxide suspension (hereinafter sometimes referred to as slurry).
It is desirable to set it to ３3% by weight.

In synthesizing ACP, maintaining the slurry temperature at 50 ° C. or lower is advantageous for obtaining a porous ACP having a larger specific surface area. In the slurry containing the ACP particles thus obtained,
Since the ACP particles are easily aggregated, the slurry in which the particulate ACP is dispersed can be maintained by stirring using a high-speed stirrer, more preferably a convection-type high-speed stirrer. The particle size in the present specification is measured by a laser diffraction method.

The ACP used in the present invention is characterized in that it is not fired. By not firing, very fine particles can be obtained and the specific surface area of the particles can be kept large. It can exhibit an excellent adsorption effect. The ACP used in the present invention
Is obtained from a diffraction pattern obtained by powder X-ray analysis, based on tricalcium phosphate containing water of crystallization [formula: Ca ₃ (PO ₄ ) ₂ .nH
₂ O], and the pattern was broad, indicating that it was amorphous.
Further, since the ACP particles contain water of crystallization, they are considered to be electrostatically active substances, and various kinds of bacteria and viruses whose surfaces are charged, off-odor substances having aldehyde groups, ammonia groups, etc. It is assumed that SOx, NOx and the like are easily adsorbed.

[0012] An antibacterial metal ion may be added to the slurry, and the antibacterial metal ion may be adsorbed to the ACP particles to impart antibacterial properties to the obtained porous particles. Such antibacterial metal ions include gold, silver, zinc,
Copper, tin, lead, arsenic, platinum, iron, antimony, nickel,
Aluminum, barium, cadmium, ions such as manganese, and the like, may be used alone,
A mixture thereof, a metal compound, or an aqueous solution thereof may be used.

In the above slurry, 50 parts by weight of the slurry
By mixing an antibacterial metal powder, an antibacterial metal compound, or an aqueous solution thereof so as to be less than or equal to% by weight,
Amorphous calcium phosphate to which antibacterial metal ions are adsorbed is one of the preferred embodiments of the amorphous calcium phosphate of the present invention. The particle size of the antibacterial metal powder and the antibacterial metal compound powder is desirably 10 μm or less in order to increase reactivity. Also, the slurry, antibacterial metal powder,
It is desirable to mix with the antibacterial metal compound powder or the antibacterial metal aqueous solution at room temperature under alkaline conditions.

Further, in order to produce a composite particle in which the ACP and the semiconductor photocatalyst used in the present invention are combined and integrated, the particle diameter of the particulate semiconductor photocatalyst should be smaller than the particle diameter of the particulate amorphous calcium phosphate. Is desirable. Specifically, AC slurry is added to a slurry containing ACP particles having a predetermined particle size.
A semiconductor photocatalyst having a particle diameter smaller than the particle diameter of the P particles is added, and the mixed slurry containing the ACP and the semiconductor photocatalyst is stirred by using a high-speed stirrer, more preferably a convection high-speed stirrer. Further, since the mixed slurry contains the water-soluble polymer dispersant described above, a mixed slurry in which aggregation of each particle is suppressed can be obtained. By mixing and drying the mixed slurry in which the aggregation of such particles is suppressed, for example, by a method such as a spray drying granulation method,
It is possible to obtain composite particles obtained by integrally integrating particles obtained by fixing semiconductor photocatalyst particles around amorphous calcium phosphate particles. Further, even when the obtained composite particles are applied to a commonly used binder, the binder is decomposed by a strong oxidizing action due to photocatalytic activity, and it is possible to suppress deterioration of physical properties or coloring. In addition, the photocatalytic activity of the semiconductor photocatalyst can be exhibited.

The total content of the ACP and the semiconductor photocatalyst in the mixed slurry is preferably adjusted to be 1 to 90% by weight, particularly preferably 5 to 50% by weight. preferable. When the total content of the ACP and the semiconductor photocatalyst in the slurry exceeds 90% by weight, the viscosity of the slurry increases, and the composite particles in which the semiconductor photocatalyst particles are fixed around the amorphous calcium phosphate particles are formed. This is because it becomes inappropriate. Further, the total content of ACP and semiconductor photocatalyst in the slurry was 1
By changing the content in the range of 90 to 90% by weight, it is possible to produce composite particles in which ACP having a desired average particle size and a semiconductor photocatalyst are combined and integrated, but it promotes adsorption and decomposition of off-odor substances and bacteria. Therefore, the specific surface area of the composite particles is 1
Since it is preferable to use a porous body of 0 m ² / g or more,
From this point, the average particle size of the composite particles is 0.1 to 200 μm.
It is preferred that

The composite particles in which the semiconductor photocatalyst and the ACP used in the present invention are complexed and integrated have a semiconductor photocatalyst of 30 to 9%.
Preferably, the composition contains 5% by weight and 5 to 70% by weight of ACP, and more preferably 50 to 95% by weight of the semiconductor photocatalyst and 5 to 50% by weight of ACP. The reason is that when the proportion of the semiconductor photocatalyst in the composite particles exceeds 95% by weight, the binder is easily decomposed due to the strong oxidizing action due to the photocatalytic activity, and when the proportion of the semiconductor photocatalyst is less than 30% by weight, it is not sufficient. This is because the photocatalytic activity of the semiconductor photocatalyst may not be expected.

The composite slurry used in the present invention can be obtained by granulating and drying the mixed slurry in which the particles of the ACP and the semiconductor photocatalyst are suppressed from being aggregated. Spray drying granulation method, granulation method of pulverization after freeze drying, high speed stirring type granulation method, etc. can be used. In particular, the spray drying granulation method is preferable, because the specific surface area of the composite particles obtained by compositely integrating the particles of the ACP and the semiconductor photocatalyst can be easily made into a porous body having a specific surface area of 10 m ² / g or more. . Such porous particles having a specific surface area of 10 m ² / g or more of the composite particles include various bacterial cells and viruses, off-odor substances having aldehyde groups, ammonia groups, etc., SOx, N
It has a high ability to adsorb Ox and the like, and is one of the most excellent embodiments.

The antibacterial deodorant composition of the present invention comprises a composite particle in which a particulate semiconductor photocatalyst and a particulate amorphous calcium phosphate are combined and integrated, and a binder. The binder referred to in the present invention is one that forms a molding material or a film-forming material together with the composite particles in which the particulate semiconductor photocatalyst and the particulate amorphous calcium phosphate are combined and integrated. There is no particular limitation as long as it is usually used as a molding material or a film forming material. Specific examples include organic resins such as synthetic resins and natural resins, and inorganic substances.
When the antibacterial composition of the present invention is used as a film-forming material, the binder is a portion that solidifies or cures to form a coating film.

Examples of the synthetic resin include polyethylene resin, polypropylene resin, polyurethane resin, polyester resin, polyacryl resin, polyamide resin, polystyrene resin, polyvinyl chloride resin, fluorine resin, silicone resin, and solvent drying commonly used as a paint. Mold resins, various curable resins, and the like.

Examples of the curable resin include thermosetting, photocurable, and electron beam curable resins, and are not particularly limited as long as they are commonly used as paints. When a coating film is required to have chemical resistance and surface hardness, it is preferable to polymerize a polyfunctional (meth) acrylate compound or an unsaturated polyester resin by light or heat. Examples used are given below.

The polyfunctional (meth) acrylate compounds include ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, and nonaethylene glycol. Di (meth) acrylate, polyethylene glycol di (meth) acrylate, tripropylene glycol di (meth) acrylate, tetrapropylene glycol di (meth) acrylate, nonapropylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, 2 , 2-Bis [4- (acryloxydiethoxy) phenyl] propane, 2,2-bis [4- (methacryloxydiethoxy) phenyl] propane, 3-phenoxy 2-propanoyl acrylate,
Examples include bifunctional (meth) acrylates such as 1,6-bis (3-acryloxy-2-hydroxypropyl) -hexyl ether, which are also used for adjusting the viscosity of a coating material.

Further, pentaerythritol tri (meth)
Acrylate, trimethylolpropane tri (meth) acrylate, glycerol tri (meth) acrylate,
Trifunctional (meth) acrylates such as tris- (2-hydroxyethyl) -isocyanuric acid ester (meth) acrylate, other pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate Caprolactone-modified dipentaerythritol hexaacrylate (DPCA series: Nippon Kayaku) obtained by reacting (meth) acrylic acid with a polyol obtained by adding ε-caprolactone to acrylate and dipentaerythritol;
Tetrafunctional or higher (meth) acrylates such as 1,3,3,5,5-hexa ((meth) acryloylalkylenedioxy) cyclotriphosphazene are suitably used for improving the surface hardness.

Further, when an acrylic urethane oligomer having a urethane bond in the molecule of the acrylic monomer is used, the abrasion resistance of the obtained coating film is further improved. Adjustment of such a urethane oligomer having an acryloyl group or a methacryloyl group at the molecular end can be performed, for example, by reacting a compound having two or more isocyanate groups in one molecule with an acrylate or methacrylate having active hydrogen. it can. Compounds having two or more isocyanates in one molecule include m-phenylene diisocyanate, p-phenylene diisocyanate, toluene-2,4-diisocyanate, toluene-2,6-diisocyanate, toluene-2,5-diisocyanate, toluene -3,5-diisocyanate, m-xylylene diisocyanate, p-xylylene diisocyanate, hexamethylene diisocyanate, trimethylhexamethylene diisocyanate, isophorone diisocyanate, 4,4'-diphenylmethane diisocyanate,
4,4'-diisocyanate-3,3'-dimethylbiphenyl, 4,4'-diisocyanate-3,3'-dimethylbiphenylmethane and the like can be mentioned.

Examples of the acrylate or methacrylate containing active hydrogen include 2-hydroxyethyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, glycerin di (meth) acrylate, and 1,6-bis (3-acryloxy-2-acrylate). (Hydroxypropyl) -hexyl ether, pentaerythritol tri (meth) acrylate, tris- (2-hydroxyethyl) -isocyanurate (meth) acrylate, (meth) acrylic acid and the like.

An ordinary unsaturated polyester resin obtained by dissolving an unsaturated polyester in a polymerizable monomer can be used. The unsaturated polyester is obtained by a known method of reacting an unsaturated polybasic acid or its anhydride with a polyhydric alcohol.

Examples of the unsaturated polybasic acid or anhydride thereof include maleic anhydride, maleic acid, fumaric acid, itaconic acid, carboxylic acid, carboxylic acid anhydride and the like.
If necessary, a saturated polybasic acid such as phthalic anhydride, isophthalic acid, terephthalic acid, monochlorophthalic acid, adipic acid, succinic acid and sebacic acid may be added. When forming a bathtub or the like that requires hot water resistance, an isophthalic acid-based unsaturated polyester resin, a hydrogenated bisphenol-based unsaturated polyester resin, a bisphenol A-based unsaturated polyester resin, or the like is preferably used.

Examples of the polyhydric alcohol component include glycols such as ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, triethylene glycol, butanediol, neopentyl glycol, hydrogenated bisphenol A, and bisphenol A ethylene oxide adduct. And trihydric or higher alcohols such as pentaerythritol, glycerin and trimethylolpropane.

The unsaturated polyester is used by dissolving it in a polymerizable monomer having a double bond in the molecule.
As the polymer monomer, styrene, vinyl toluene, divinylbenzene, methyl (meth) acrylate, ethyl methacrylate and the like are preferably used. In addition, the above 2
A functional or higher functional (meth) acrylate compound may be used. In the case of the bifunctional or higher functional (meth) acrylate compound having a high viscosity, it is usually used simultaneously with the low-viscosity polymerizable monomer.

When these synthetic resins and the like are used, the following polymerization initiators can be added as required. As the polymerization initiator, a thermal polymerization initiator, a photopolymerization initiator, or the like is used. The following is an example. Examples of the photopolymerization initiator include sulfides such as sodium methyl dithiocarbamate sulfide, diphenyl monosulfide, dibenzothiazoyl monosulfide, and disulfide; thioxanthone, 2-ethylthioxanthone,
Thioxanthone derivatives such as chlorothioxanthone and 2,4-diethylthioxanthone; azo compounds such as hydrazone and azobisisobutyronitrile; diazo compounds such as benzenediazonium salt; benzoin, benzoin methyl ether, benzoin ethyl ether, benzophenone and dimethylamino Benzophenone, Michler's ketone,
Benzylanthraquinone, t-butylanthraquinone,
Aromatic carbonyl compounds such as 2-methylanthraquinone, 2-ethylanthraquinone, 2-aminoanthraquinone, 2-alloloanthraquinone; methyl p-dimethylaminobenzoate, ethyl p-dimethylaminobenzoate;
dialkylaminobenzoic acid esters such as butyl p-dimethylaminobenzoate and isopropyl p-diethylaminobenzoate; peroxides such as benzoyl peroxide, di-t-butyl peroxide, dicumyl peroxide, cumene hydroperoxide; 9 Acridine derivatives such as -phenylacridine, 9-p-methoxyphenylacridine, 9-acetylaminoacridine, benzacridine; 9,10-dimethylbenzphenazine, 9
Phenazine derivatives such as -methylbenzphenazine, 10-methoxynesphenazine; quinoxaline derivatives such as 6,4 ', 4 "-trimethoxy-2,3-diphenylquinoxaline; 2,4,5-triphenylimidazoyl dimer; 2-nitrofluorene, 2,4,6-triphenylpyrylium boron tetrafluoride, 2,4,6-tris (trichloromethyl) -1,3,5-triazine, 3,3 ′
-Carbonylbiscoumarin, thiomichler ketone and the like.

An amine compound may be added to the photopolymerization initiator in order to prevent a decrease in sensitivity due to oxygen inhibition. The amine compound is not particularly limited as long as it is a nonvolatile compound such as an aliphatic amine and an aromatic amine.

Examples of the thermal polymerization initiator include organic peroxides such as methyl ethyl ketone peroxide, benzoyl peroxide, cumene hydroperoxide and lauroyl peroxide, and azo compounds such as azobisisobutyronitrile. Simultaneously with the above thermal polymerization initiator, as a curing accelerator, metal soaps such as cobalt naphthenate, cobalt octenoate and manganese naphthenate, aromatic tertiary amines such as dimethylaniline, and quaternary such as dimethylbenzylammonium chloride. Ammonium salts and the like may be used.

When the antibacterial deodorant composition of the present invention is used as a paint, an organic solvent can be used separately from the binder. The organic solvent is not particularly limited, but those having a low boiling point and those having a high volatility have a problem that the viscosity changes due to evaporation during construction, and those having a high boiling point require a long time for the drying step. Therefore the boiling point is 70-16
A solvent at about 0 ° C. is preferred. Examples of the organic solvent include cyclohexanone, ethylene glycol monomethyl ether (methyl cellosolve), ethylene glycol monoethyl ether (ethyl cellosolve), diethylene glycol dimethyl ether, butyl acetate, isopropyl acetone, methyl ethyl ketone, toluene, xylene, and anisole.

Known antioxidants and polymerization inhibitors can be used in the antibacterial deodorant composition of the present invention. Examples of the antioxidant include a phenolic antioxidant, a phosphorus antioxidant, and a sulfur antioxidant. Examples of the polymerization inhibitor include hydroquinone and p-methoxyphenol.

As the binder used in the present invention, inorganic substances can be used in addition to the above. Examples of such inorganic substances include cements, metals, products of the sol-gel method, and the like. Examples of the cement include Portland cement, magnesia cement, white cement, alumina cement, silica cement, blast furnace cement, fly ash cement and the like.

The amount of the composite particles in which the particulate semiconductor photocatalyst and the particulate amorphous calcium phosphate are combined and integrated into the binder is limited to 1 to 1000 parts by weight based on 100 parts by weight of the binder. If the amount is less than 1 part by weight, the antibacterial properties and deodorizing properties are not sufficient. More preferably, it is 2 to 500 parts by weight. When a molded article is obtained by adding or dry blending to a binder, the amount of addition is preferably 100 parts by weight or less from the viewpoint of the strength and workability of the molded article.

The antibacterial deodorant composition of the present invention may contain, in addition to the above components, commonly used coloring agents, surface modifiers, fillers, plasticizers, spreading agents, flame retardants, antistatic agents, and the like. Additives can be used. Further, the following dispersants may be used to improve the dispersibility of the composite particles in which the particulate semiconductor photocatalyst and the particulate amorphous calcium phosphate are combined and integrated.

As the dispersant, a silane coupling agent,
Examples include titanate coupling agents, aluminate coupling agents, zirconate coupling agents, surfactants, and organic acids. Examples of these dispersing aids include the following.

Examples of the silane coupling agent include vinyltriethoxysilane, vinyltrimethoxysilane, vinyltris (β-methoxyethoxy) silane, γ-methacryloxypropyltrimethoxysilane, and β- (3,4-epoxycyclohexyl) ethyltrisilane. Methoxysilane, γ
-Glycidoxypropyltrimethoxysilane, γ-mercaptopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, N-β- (aminoethyl) -γ
-Aminopropyltrimethoxysilane, γ-ureidopropyltriethoxysilane, phenyltriethoxysilane, methyltriethoxysilane, methyltrimethoxysilane, polyethylene oxide-modified silane monomer, polymethylethoxysiloxane, hexamethyldisilazane, and the like. .

As the titanate coupling agent, isopropyl triisostearoyl titanate, tetraisopropyl bis (dioctyl phosphite) titanate,
Tetraoctylbis (ditridecylphosphite) titanate, tetra (2,2'-diallyloxymethyl-1)
-Butyl) bis (di-tridecyl) phosphite titanate, isopropyltridecylbenzenesulfonyl titanate, bis (dioctylpyrophosphate) oxyacetate titanate, bis (dioctylpyrophosphate) ethylene titanate, isopropyltrioctanoyl titanate, isopropyldimethacrylisostearoyl Titanate, isopropyl isostearyl diacryl titanate, isopropyl tri (dioctyl phosphate) titanate, isopropyl tricumyl phenyl titanate, isopropyl tri (N-aminoethyl-aminoethyl) titanate and the like can be mentioned.

Examples of the aluminate coupling agent include acetoalkoxyaluminum diisopropylate and acetoalkoxyaluminum diisobutyrate. The zirconate coupling agent has a neopentyl (diallyl) oxy group and a reactive functional group. Zirconate compounds and the like (noopentyl (diallyl) oxytrinedecanoyl zirconate, neopentyl (diallyl) oxytri (dioctyl) phosphate zirconate and the like).

Examples of the surfactant include sodium dialkylsulfosuccinate and sodium alkylnaphthalenesulfonate as anionic surfactants, stearyltrimethylammonium chloride as a cationic surfactant, and sorbitan monostearate as an ester surfactant. Include oleic acid, acetic acid, (meth) acrylic acid and the like.

In producing the antibacterial deodorant composition of the present invention, a commonly used method for producing a binder can be applied. When the binder is a thermoplastic resin, a molded article can be obtained by directly molding with an injection molding machine, an extrusion molding machine or the like. Further, an antibacterial deodorant composition containing composite particles in which a high concentration of a semiconductor photocatalyst and ACP are compositely integrated may be used as a master batch.

The antibacterial deodorant composition of the present invention can be used as a film forming material. By forming a coating film or film on the surface of a molded article, a plate, or the like, a composite particle in which a very small amount of the particulate semiconductor photocatalyst and the particulate amorphous calcium phosphate are combined and integrated is equivalent to the above-described molded article. It is possible to exhibit antibacterial and deodorant performance. The coating material as the film forming material, the composite particles,
The curable resin is prepared by adding an additive such as a polymerization initiator and a solvent, if necessary, and mixing.

For the mixing, a device usually used for dispersing or blending the paint is used to sufficiently disperse the composite particles in the paint. Examples include a sand mill, a ball mill, an attritor, a bead mill, a high-speed rotary stirrer, and a three-roll mill. The coating material thus prepared is applied to various materials and the surface of a molded product by a general application method such as a spray method, a bar coating method, a doctor blade method, and a roll coating method.

Materials used include plastic plates such as styrene resin, polypropylene, polyethylene, vinyl chloride, polycarbonate, polymethyl methacrylate (acrylic resin), ABS resin, polyimide, polyether sulfone, and polyether ketone, and plastic films. And inorganic materials such as glass and the like, and are used indoors and outdoors, windows and inner surfaces of water tanks.

In addition, antibacterial treatment of ceilings, walls, etc. can be performed by using it for various building materials. It is used in the manufacture of FRP molded products and artificial marble by a general gel coat forming method such as a hand lay-up method, a spray-up method, a compression molding method, etc., together with a reinforcing layer made of a thermosetting resin fibrous reinforcing material as necessary. You. Further, it can be used by coating it on the surface of the molded product or by laminating it on the surface of the molded product to be press-molded, followed by pressing and curing, and is used for antibacterial and fungicide prevention of bathtubs, kitchen counters, wall materials and the like. In addition to the FRP molded body, it is used for the same purpose on the surface of artificial marble and the like.

As described above, the composite particles used in the antibacterial deodorant composition of the present invention are composed of a semiconductor photocatalyst and an ACP.
Is a composite particle integrated into a complex, so even when applied to a commonly used binder, the binder is decomposed by strong oxidizing action due to photocatalytic activity, and it does not cause deterioration in physical properties or coloration Since the photocatalytic activity of the semiconductor photocatalyst as described above can be exerted, effects such as deodorization and antibacterial can be exerted. Further, as compared with the case where the semiconductor photocatalyst particles and the ACP particles are blended, the semiconductor photocatalyst having a higher specific gravity is not disperse | distributed and it is an antibacterial deodorant composition which is easy to handle.

[0048]

DESCRIPTION OF THE PREFERRED EMBODIMENTS Hereinafter, the present invention will be described in detail with reference to examples, but the present invention is not limited to these examples. (Production Example 1) Composite particles obtained by compositely integrating the particulate semiconductor photocatalyst and the particulate amorphous calcium phosphate used in the present invention were produced as follows. The apparatus used for producing the composite particles is schematically shown in FIG. In FIG.
Reference numeral 9 denotes an air filter, and 10 denotes an electric heater. Hot air heated by the electric heater 10 through the air filter 9 enters the spray drier 5 from the hot gas chamber 11 and is sprayed by the atomizer 6 of the spray drier 5. The slurry 3 flows out from the discharge hole 12 toward the cyclone 8 while being dried and granulated.

For the calcium hydroxide suspension under stirring,
A mixed solution was obtained by adding 0.5% by weight of weakly alkaline ammonium triacrylate as a water-soluble polymer dispersant. A phosphoric acid aqueous solution was added dropwise while the obtained mixed solution was stirred using a convection high-speed stirrer, and the pH was adjusted to 10 to obtain a slurry containing ACP particles having an average particle diameter of about 0.1 μm. . While the obtained slurry was continuously stirred using a convection type high speed stirrer, titanium oxide having an average particle diameter of about 0.007 μm (trade name: ST-01, manufactured by Ishihara Sangyo Co., Ltd.) was added to ion exchange water at a convection type high speed. The solution dispersed by stirring using a stirrer is added, and titanium oxide and A are added.
A mixed slurry having a weight ratio of CP to 50:50 was obtained.

The obtained titanium oxide particles 1 and ACP particles 2
Is mixed using a convection high-speed stirrer.
The mixture slurry 3 was further stirred for 15 minutes, and the mixed slurry 3 was spray-dried by a metering pump 4 (L, manufactured by Okawara Kako Kikai Co., Ltd.).
-8) It was supplied to the atomizer 6 of 5. The atomizer 6 was rotated at a high speed, and the mixed slurry 3 was sprayed into a hot air stream for drying in the spray dryer 5, and was granulated and dried by a spray granulation drying method. By this granulation drying,
Composite particles 7 were obtained. The obtained composite particles were spherical, and the average particle size was 10 μm. When the specific surface area was measured by the BET method, the specific surface area was 80 m ² / g.

As is clear from the electron micrograph shown in FIG. 2, the composite particles were confirmed to be composite particles in which titanium oxide particles were fixed around amorphous calcium phosphate particles. In addition, for the resin degradation test described below, mixed and kneaded with low-density polyethylene, even after inflation processing, the composite particles of the present invention,
It was confirmed that the titanium oxide particles did not detach from around the amorphous calcium phosphate particles, and that the titanium oxide particles were fixed around the amorphous calcium phosphate particles.

Further, in order to clarify the particles of titanium oxide and the particles of amorphous calcium phosphate in the electron micrograph, FIG. 3 shows a photograph of secondary aggregated particles of titanium oxide, and FIG. A photograph of the secondary aggregated particles of amorphous calcium phosphate is shown. From the electron micrograph of FIG.
Secondary aggregated particles of spherical titanium oxide are observed. Also,
From the electron micrograph of FIG. 4, particles obtained by agglomerating amorphous calcium phosphate having a substantially rod shape are observed.

The operating conditions in the above granulation were as follows. The supply amount of the mixture slurry 3 by the metering pump 4 is 1 to 3 kg / h, and the temperature of the hot air heated by the electric heater 10 through the air filter 9 is such that the inlet temperature of the hot gas chamber 11 is 150 to 250 C., the outlet temperature at the discharge hole 12 diverging in the cyclone 8 is 80 ° C.
℃, and the atomizer 6
Was set in the range of 10,000 to 37000 rpm.

(Production Example 2) To a calcium hydroxide suspension under stirring, 0.5% by weight of a weakly alkaline ammonium triacrylate as a water-soluble polymer dispersant was added to obtain a mixed solution. . While stirring the obtained mixed solution, an aqueous solution of phosphoric acid was added dropwise to adjust the pH to 10, whereby a slurry containing ACP particles having an average particle diameter of about 0.1 μm was obtained. The obtained slurry was used in the same spray dryer as in Production Example 1 to obtain amorphous calcium phosphate particles. The obtained ACP particles have an average particle diameter of 12 μm.
m, the specific surface area was measured by the BET method and found to be 70 m ² / g. The obtained ACP particles and the same titanium oxide used in Example 1 were mixed in a weight ratio of 5%.
The particles were mixed at a ratio of 0:50 to obtain blend particles of ACP particles and titanium oxide.

(Example 1) Using the composite particles obtained in Production Example 1, a coating film was formed by the following method. Specifically, a treatment liquid having the following composition was applied to a base material obtained by coating a Teflon-coated polyester resin plate with a thickness of about 20 by a doctor blade method.
μm and then dried at 80 ° C. for about 1 hour.
The composition of the treatment liquid was a polycarbonate resin emulsion (manufactured by Sanyo Chemical Industries, Ltd., trade name: Bermarin UA-3)
10) 2 parts of the composite particles obtained in Production Example 1 were added to 100 g
A treatment liquid obtained by adding 0 g and 20 g of water and stirring was used.

(Example 2) Using the composite particles obtained in Production Example 1, an acrylic-silicon resin emulsion (manufactured by Sanyo Chemical Industry Co., Ltd., trade name: Sunmol SW)
-131) A coating film was prepared in the same manner as in Example 1 except that the amount of the composite particles obtained in Production Example 1 was changed to 20 g and water to 20 g with respect to 100 g.

Comparative Example 1 A coating film was prepared in the same manner as in Example 1 except that the composite particles used in Example 1 were blended with the ACP particles obtained in Production Example 2 and titanium oxide.

Comparative Example 2 A coating film was formed in the same manner as in Example 1 except that the composite particles used in Example 1 were changed to 10 g of the same titanium oxide as that used in Example 1.

Comparative Example 3 A coating film was prepared in the same manner as in Example 1 except that the composite particles used in Example 2 were blended with the ACP particles obtained in Production Example 2 and titanium oxide.

Comparative Example 4 A coating film was prepared in the same manner as in Example 1 except that the composite particles used in Example 2 were changed to 10 g of the same titanium oxide as that used in Example 1.

(Degradation Test of Coating Film) The coating films obtained in Examples 1 and 2 and Comparative Examples 1 to 4 were exposed to the sun under a temperature of about 31.
An exposure test was carried out by allowing the film to stand at ℃, and the state of deterioration of the coating film was observed. As a result, the coating films of Examples 1 and 2 showed almost no discoloration and no deterioration was observed. On the contrary,
In Comparative Examples 1 and 3, the coating film was partially yellowed and deteriorated. This is presumed that the titanium oxide was knitted and dispersed. In Comparative Examples 2 and 4, the coating film turned yellow as a whole, and deterioration of the coating film was observed.

Next, an antibacterial test was carried out using the coating film obtained in Example 1. (Antibacterial test method) The coating film (thickness: about 20 μm) obtained in Example 1 was cut into a size of 30 × 40 mm, placed in a 200 ml Erlenmeyer flask containing 70 ml of sterilized water, and added with a previously prepared bacterial solution. The number of viable cells was measured by shaking at 120 rpm. In addition, Escherichia coli K1
Two strains (IFON N3301) were used and the ultraviolet light was 0.5
Irradiation was performed using a mW / cm ² black light. Table 1 shows the results. In addition, the control does not add the above-mentioned coating film.

[0063]

[Table 1]

Next, an ammonia gas adsorption decomposition test was carried out using the coating film obtained in Example 1. (Ammonia gas adsorption decomposition test method) The coating film (thickness: about 20 μm) obtained in Example 1 was 70 × 150 mm
And sealed in a 3 liter Tedlar bag. Thereafter, the following ammonia gas was charged, and the residual concentration of the test gas was measured at each elapsed time. In addition, the filling of ammonia gas is performed at the time of the first filling at 0 minutes,
After 20 minutes, the test was performed by adding the same concentration of ammonia gas as that charged at 0 minutes. In the above test, 460 μW / cm ² was applied to each evaluation sample.
Was carried out under ultraviolet irradiation using a black light. Test gas: ammonia gas concentration 30 ppm (N ₂ Balance) test temperature: room temperature Assay method: manufactured by Gas Tech ammonia gas detector tube (No3
L) The results show that ammonia gas can be adsorbed and decomposed below the threshold (4 ppm for ammonia), which is the concentration at which humans do not perceive the smell, and the test results performed after 10 minutes and 20 minutes have been added. It was confirmed that ammonia gas was adsorbed and decomposed.

[0065]

The antibacterial and deodorant composition of the present invention comprising a binder and a composite particle in which the particulate semiconductor photocatalyst and the particulate amorphous calcium phosphate are combined and integrated is used as a binder commonly used. Even in the case of application, the binder is decomposed due to strong oxidizing action due to photocatalytic activity, which suppresses deterioration of physical properties and coloring, and exhibits the photocatalytic activity of the semiconductor photocatalyst. In addition, since the amorphous calcium phosphate particles are compositely integrated with the particles of the amorphous calcium phosphate particles, the amorphous calcium phosphate particles adsorb various bacteria, viruses, off-odor substances having aldehyde groups, ammonia groups, etc., SOx, NOx, and the like. However, since a synergistic effect that the semiconductor photocatalyst is decomposed effectively can be expected, a coating film or a molded article having excellent antibacterial properties and deodorant properties can be obtained. Further, since the semiconductor photocatalyst such as titanium oxide having a high specific gravity and being easily separated does not disperse, the antibacterial deodorant composition is easy to handle.

[Brief description of the drawings]

FIG. 1 is a schematic configuration diagram of an apparatus used for producing composite particles.

FIG. 2 is an electron micrograph (× 100,000) of the composite particles obtained in Example 1.

FIG. 3 is an electron micrograph (100,000) of titanium oxide particles.
Times).

FIG. 4 is an electron micrograph (× 100,000) of amorphous calcium phosphate particles.

[Explanation of symbols]

 DESCRIPTION OF SYMBOLS 1 ... Titanium oxide particle 2 ... ACP particle 3 ... Mixed slurry 4 ... Metering pump 5 ... Spray dryer 6 ... Atomizer 7 ... ACP porous particle 8 ... Cyclone 9 ... Air filter 10 ... Electric heater 11 ... Hot gas chamber 12 ... Discharge hole

Claims (3)

[Claims] 1. An antibacterial deodorant composition comprising a binder and a composite particle in which a particulate semiconductor photocatalyst and a particulate amorphous calcium phosphate are combined and integrated. 2. The antibacterial deodorant composition according to claim 1, wherein the particle diameter of the particulate semiconductor photocatalyst contained in the composite particles is smaller than the particle diameter of the particulate amorphous calcium phosphate. Stuff. 3. The composite particle according to claim 1, wherein the particulate semiconductor photocatalyst is obtained by integrally integrating particles obtained by fixing semiconductor photocatalyst particles around amorphous calcium phosphate particles. Item 3. An antibacterial deodorant composition according to Item 2.