KR20220027056A - Processed liquid containing deodorant and manufacturing method of deodorant product using same - Google Patents

Abstract

The deodorant-containing processing liquid of the present invention contains a deodorant containing a tetravalent metal phosphate, a surfactant, and an adhesive component, and has a viscosity at 25°C of 50 mPa·s or more by a type B viscometer. The tetravalent metal is preferably at least one selected from Zr, Hf, Ti and Sn. The specific surface area of the tetravalent metal phosphate is preferably 0.1 to 100 m 2 /g, and the median diameter is preferably 0.1 to 100 μm. The surfactant is preferably anionic or nonionic, and the adhesive component is preferably a polymer compound.

Description

Processed liquid containing deodorant and manufacturing method of deodorant product using same

The present invention relates to a deodorant-containing processing liquid suitable for manufacturing a deodorizing product having deodorizing performance against ammonia gas.

Various gaseous pollutants such as odors and harmful gases exist in the air in the living environment and work environment, and in order to create a comfortable environment, a deodorant for removing these gaseous pollutants or a deodorizing product including the same is widely used. .

In Patent Document 1, a deodorizing mask as an example of a deodorizing product, that is, a deodorizing fiber layer comprising a composite fiber in which a chemical adsorption type deodorant such as CuO·SiO ₂ composite oxide and zirconium phosphate is bonded (attached) to the surface of the fiber with an adhesive composition. There is disclosed a deodorizing mask having a body portion having a. In order to form this deodorizing fiber layer, a deodorant containing processing liquid containing, for example, a chemical adsorption type deodorant, an adhesive composition, etc. is used.

International Publication No. 2015/194334

When there is only one deodorizing filter medium constituting the deodorizing mask and one deodorizing filter medium constituting the deodorizing filter, it is considered preferable that the adhering deodorant is uniformly distributed in the thickness direction. These deodorizing filter media are prepared by, for example, drawing out air bubbles such as a nonwoven fabric from a base sheet roll wound on a core and then applying a deodorant-containing processing liquid containing a deodorant and an adhesive resin to the base fabric and drying the coating film. , a roll-shaped deodorant cloth to which a deodorant is impregnated, and then the deodorant cloth is cut to a predetermined size and manufactured. At this time, it is common to dry, while moving the foam|bubble to which the coating film adhered in a horizontal direction or an oblique direction from the blowing side of a bubble to the winding-up side of a deodorizing cloth. However, it was found that, when such a manufacturing method is applied using a conventionally known deodorant-containing processing liquid, a problem arises in that the deodorant adhering to the deodorant cloth or the deodorizing filter medium obtained is unevenly distributed. So, in particular, with respect to a processing liquid containing a phosphate of a tetravalent metal such as zirconium phosphate having a deodorizing performance of a basic gas such as ammonia gas, it is possible to efficiently produce a deodorizing cloth or a deodorizing filter medium having a stable deodorizing performance. A review was requested as to whether the

According to the present invention, a phosphate of a tetravalent metal such as zirconium phosphate, which chemically adsorbs a basic gas such as ammonia gas, can be sufficiently attached to a substrate, and a deodorizing product having excellent processability and, in particular, excellent deodorizing performance for ammonia gas, efficiently An object of the present invention is to provide a deodorant-containing processing liquid that can be manufactured.

The present inventors have found that a deodorant-containing processing liquid containing a phosphate of a tetravalent metal such as zirconium phosphate is used to attach a phosphate of a tetravalent metal such as zirconium phosphate to a substrate in a state where a basic gas such as ammonia gas is easily adsorbed. And, by containing a surfactant and an adhesive component to have a specific viscosity, it was found that a deodorizing product excellent in deodorizing performance against a basic gas, particularly ammonia gas, was efficiently produced, and the present invention was completed.

The present invention is shown below.

1. A deodorant-containing processing liquid containing a deodorant containing a tetravalent metal phosphate, a surfactant, and an adhesive component, and having a viscosity at 25°C of 50 mPa·s or more according to a B-type viscometer.

2. The deodorant-containing processing liquid according to Item 1, wherein the tetravalent metal is at least one selected from Zr, Hf, Ti and Sn.

3. The deodorant-containing processing liquid according to Item 1 or 2, wherein the content of the surfactant is 0.01 to 30 parts by mass based on 100 parts by mass of the deodorant.

4. The deodorant-containing processing liquid according to any one of Items 1 to 3, wherein the surfactant is at least one selected from anionic surfactants and nonionic surfactants.

5. The deodorant-containing processing liquid according to any one of Items 1 to 4, wherein the tetravalent metal phosphate has a specific surface area of 0.1 to 100 m 2 /g.

6. The deodorant-containing processing liquid according to any one of Items 1 to 5, wherein the tetravalent metal phosphate has a median diameter of 0.1 µm to 100 µm.

7. The deodorant-containing processing liquid according to any one of Items 1 to 6, wherein the adhesive component contains a polymer compound.

8. The deodorant-containing processing liquid according to any one of items 1 to 7, further comprising water.

9. The deodorant-containing processing liquid according to any one of items 1 to 8, further comprising a thickener.

10. A deodorizing product comprising the steps of: applying the deodorant-containing processing liquid according to any one of items 1 to 9 to a substrate to form a coating film on the surface of the substrate; and drying the coating film. manufacturing method.

11. A deodorant product comprising a substrate and a deodorant-containing portion bonded to at least a portion of the surface of the substrate, wherein the deodorant-containing portion contains a tetravalent metal phosphate, a surfactant, and an adhesive component.

12. The deodorizing product according to the above item 11, wherein the base material has a fiber-containing sheet shape, and the deodorizing product is a deodorizing filter medium.

The deodorant-containing processing liquid of the present invention is excellent in dispersibility and stability of the components contained therein, and the amount of the deodorant containing a tetravalent metal phosphate is high. Suitable. By using a deodorant-containing processing liquid containing a phosphate of a tetravalent metal selected from Zr, Hf, Ti and Sn, a deodorizing product having excellent deodorizing performance for ammonia gas can be efficiently manufactured.

According to the manufacturing method of the deodorizing product of this invention, the deodorizing product which has high deodorizing performance with respect to basic gases, such as ammonia gas, can be manufactured efficiently.

1 is an enlarged image of one side (surface) of a deodorizing fiber sheet obtained in Example 1. FIG.
2 is an enlarged image of one side (back side) of the deodorizing fiber sheet obtained in Example 1. FIG.
3 is an enlarged image of one side (surface) of the deodorizing fiber sheet obtained in Comparative Example 1. FIG.
4 is an enlarged image of one side (back side) of the deodorizing fiber sheet obtained in Comparative Example 1. FIG.

The deodorant-containing processing liquid of the present invention contains a deodorant containing a tetravalent metal phosphate, a surfactant, and an adhesive component, and has a viscosity at 25°C of 50 mPa·s or more by a type B viscometer.

The deodorant-containing processing liquid of the present invention is to prepare a deodorant product in which a deodorant containing at least a tetravalent metal phosphate and a substrate are adhered to each other by means of an adhesive component by applying the deodorant-containing processing liquid to a substrate and then drying the formed coating film. Phosphate of a tetravalent metal such as zirconium phosphate is a deodorant having chemical adsorption performance with respect to basic gas such as ammonia gas, and the deodorant-containing processing liquid of the present invention provides a deodorant product having high deodorization performance with respect to at least ammonia gas. In addition, the deodorant-containing processing liquid of the present invention may further contain other deodorants (described later) or additives that chemically adsorb basic gas or other malodorous gases, if necessary.

Hereinafter, a deodorant containing a tetravalent metal phosphate, a surfactant, an adhesive component, other components, a method for producing a deodorant-containing processing liquid, and a method for producing a deodorant product will be described.

1. Deodorant containing tetravalent metal phosphate

The deodorant according to the present invention contains a tetravalent metal phosphate as an essential component, and is a deodorant having chemical adsorption performance for at least basic gas.

In addition, as described in detail later, the deodorant may contain a deodorant other than a tetravalent metal phosphate (hereinafter, referred to as "other deodorant") as needed.

Hereinafter, tetravalent metal phosphates and other deodorants will be described.

1-1. Phosphates of tetravalent metals

The tetravalent metal phosphate is preferably a compound represented by the following general formula (1), and is insoluble or sparingly soluble in water.

(Wherein, M is a tetravalent metal atom, a, b and c are numbers satisfying the formula: a+4b=3c, and n is 0 or a positive number.)

Zr, Hf, Ti, Sn, etc. are mentioned as M in the said General formula (1), M in the compound of the said General formula (1) may be a single atom, or a combination of 2 or more types of atoms may be sufficient as it.

Preferred specific examples of the tetravalent metal phosphate include zirconium phosphate, hafnium phosphate, titanium phosphate, and tin phosphate. These compounds include crystalline and amorphous compounds having various crystal systems such as α-form, β-form, and γ-form, and any of these compounds can be preferably used. Among these, a zirconium phosphate is especially preferable at the point which the chemical adsorption power of ammonia is high and it is easy to obtain also industrially.

The zirconium phosphate is preferably a compound represented by the following formula (2).

(Wherein, 0≤x≤0.2, 2<b≤2.1, a is a number satisfying 3b-a=4, and 0≤n≤2.)

Since x in said Formula (2) has especially high chemical-adsorption power of ammonia, Preferably it is 0.005<=x<=0.1.

Although the shape of the tetravalent metal phosphate is not particularly limited, it is usually granular, and the median diameter measured by a laser diffraction particle size distribution analyzer is preferably 0.1 to 100 µm, more preferably 0.2 to 50 µm, still more preferably It is preferably 0.3 to 10 μm.

In addition, the specific surface area measured by the BET method calculated from the nitrogen adsorption amount is preferably 0.1 to 100 m 2 /g, more preferably 0.5 to 100 m 2 /g, still more preferably from the viewpoint of deodorization of ammonia gas or the like. is 1 to 100 m 2 /g.

1-2. Other deodorants

The deodorant-containing processing liquid of the present invention may contain other deodorants that are deodorants other than tetravalent metal phosphates.

The other deodorant can be blended in a ratio and the type of the deodorant product obtained by not reducing the deodorizing performance of the basic gas.

Other deodorants include basic gases such as ammonia gas and trimethylamine; acid gases such as acetic acid and isovaleric acid; aldehyde-based gases such as formaldehyde, acetaldehyde, and nonenal; And it can be set as what has deodorizing performance with respect to odor gases, such as sulfur-type gas, such as hydrogen sulfide and methyl mercaptan.

Examples of the deodorant for basic gas include zeolite, Al ₂ O ₃ , SiO ₂ , MgO, CaO, SrO, BaO, ZrO ₂ , TiO ₂ , WO ₂ , CeO ₂ , Li ₂ O, Na ₂ O and K ₂ O. and an amorphous composite oxide. Examples of the deodorant for acid gas include hydrotalcite-based compounds such as zirconium hydroxide, zirconium oxide, and magnesium-aluminum hydrotalcite.

Examples of the deodorant for aldehyde gas include hydrazine-based compounds such as adipic acid dihydrazide, carbohydrazide, succinic acid dihydrazide, and oxalic acid dihydrazide, and aminoguanidine salts such as aminoguanidine hydrochloride, aminoguanidine sulfate and aminoguanidine bicarbonate. and the like.

Examples of the deodorant for sulfur-based gas include copper silicate, copper zirconium phosphate hydrate, zinc oxide, aluminum zinc oxide, zinc silicate, aluminum zinc silicate, and layered zinc aluminosilicate.

When using another deodorant, as the usage ratio, with respect to 100 mass parts of usage-amounts of the tetravalent metal phosphate, Preferably it is 1-10000 mass parts, More preferably, it is 5-2000 mass parts.

2. Surfactant

Surfactant is not specifically limited, Any of anionic surfactant, cationic surfactant, nonionic surfactant, and amphoteric surfactant may be used. Of these, from the viewpoint of dispersibility of the tetravalent metal phosphate, anionic surfactants and nonionic surfactants are particularly preferable. The preferred surfactant contained in the deodorant-containing processing liquid of the present invention may be either an anionic surfactant or a nonionic surfactant, or both.

Examples of the anionic surfactant include carboxylic acid-based anionic surfactants, sulfonic acid-based anionic surfactants, sulfuric acid-based anionic surfactants, and phosphoric acid-based anionic surfactants.

Hereinafter, anionic surfactants are specifically exemplified, but "salt" is an alkali metal salt (lithium salt, sodium salt, potassium salt, etc.), alkaline earth metal salt (magnesium salt, calcium salt, etc.), ammonium salt or amine salt (monoethanolamine) salts, diethanolamine salts, triethanolamine salts, monoisopropanolamine salts, etc.).

Examples of the carboxylic acid-based anionic surfactant include polycarboxylate, aliphatic carboxylate, alkyl ether carboxylate, alkenyl succinate, N-acylamino acid, amide ether carboxylate, and acyl lactate. . Among these, polycarboxylate is preferable.

As said polycarboxylate, the salt of the homopolymer or copolymer containing the structural unit derived from acrylic acid, methacrylic acid, maleic acid, fumaric acid, itaconic acid, maleic anhydride, etc. is mentioned. Specifically, polyacrylic acid, polymethacrylic acid, polymaleic acid, polymaleic anhydride, maleic acid/isobutylene copolymer, maleic anhydride/isobutylene copolymer, maleic acid/diisobutylene copolymer, Maleic anhydride/diisobutylene copolymer, acrylic acid/itaconic acid copolymer, methacrylic acid/itaconic acid copolymer, maleic acid/styrene copolymer, maleic anhydride/styrene copolymer, acrylic acid/methacrylic acid copolymer, Salts such as acrylic acid/methyl acrylic acid ester copolymer, acrylic acid/vinyl acetate copolymer, acrylic acid/maleic acid copolymer, and acrylic acid/maleic anhydride copolymer can be used.

Examples of the aliphatic carboxylate include an aliphatic acid salt containing an alkyl group having 8 to 20 carbon atoms, such as caproate, caprylate, caprate, laurate, myristate, palmitate, stearate and oleate. carboxylate.

As said alkyl ether carboxylate, (poly) oxyethylene alkyl ether acetate, (poly) oxyethylene alkyl ether propionate, etc. are mentioned. Specifically, oxyethylene oleyl ether acetate, polyoxyethylene lauryl ether acetate, polyoxyethylene stearyl ether acetate, polyoxyethylene hexylphenyl ether acetate, polyoxyethylene tridecyl ether acetate, polyoxy Alkyl ether carboxylates containing an alkylene group having 14 to 60 carbon atoms, such as ethylene lauryl ether propionate and alkyl glycol acetate, can be used.

As said alkenyl succinate, the alkenyl succinate (monosalt or disalt) containing a C8-C22 alkenyl group is mentioned.

Examples of the N-acylamino acid salt include N-acylglutamate, N-acyl aspartate, N-acyl-β-alanine salt, N-acylmethylalanine salt, N-acylglycine salt, N-acylproline salt and N- and acyl sarcosinitis. Specifically, N-lauroyl-β-alanine arginine, N-lauroyl-β-alanine potassium, N-lauroyl-β-alanine triethanolamine, N-lauroyl-N-carboxymethyl-β -Sodium alanine, sodium N-lauroyl glutamate, N-stearoyl-L-disodium glutamate and sodium N-lauroyl sarcosine can be used.

Examples of the amide ether carboxylate include fatty acid alkanolamide ether carboxylate and polyoxyalkylenated alkylamide ether carboxylate.

Examples of the sulfonic acid-based anionic surfactant include alkanesulfonates, α-olefinsulfonates, alkylbenzenesulfonates, alkylnaphthalenesulfonates, alkyldiphenyletherdisulfonates, alkyl glycidylethersulfonates, ligninsulfonates, α- sulfo fatty acid ester salts, acyl ethionate, alkyl sulfosuccinate, alkyl sulfo acetate, N-acyl methyl taurine salt, formalin condensed sulfonate, melamine sulfonate, and the like.

Examples of the alkanesulfonate include 1-octanesulfonate, 2-octanesulfonate, 1-decanesulfonate, 2-decanesulfonate, 1-dodecanesulfonate and 2-dodecanesulfonate, having 8 carbon atoms. to 18 alkanesulfonates.

Examples of the ?-olefin sulfonate include ?-olefin sulfonate having 8 to 18 carbon atoms, such as tetradecene sulfonate.

As said alkylbenzenesulfonate, p-toluenesulfonate, dodecylbenzenesulfonate, etc. are mentioned.

Examples of the alkyl naphthalene sulfonate include monoalkyl naphthalene sulfonate and dialkyl naphthalene sulfonate. Specifically, methylnaphthalenesulfonate, ethylnaphthalenesulfonate, propylnaphthalenesulfonate, isopropylnaphthalenesulfonate, butylnaphthalenesulfonate, isobutylnaphthalenesulfonate, dimethylnaphthalenesulfonate, diethylnaphthalenesulfonate, diisopropyl Naphthalenesulfonate, dibutylnaphthalenesulfonate, diisobutylnaphthalenesulfonate, methylnonylnaphthalenesulfonate, etc. can be used.

Examples of the alkyldiphenyletherdisulfonate include alkyldiphenyletherdisulfonate containing an alkyl group having 1 to 20 carbon atoms. Specifically, nonyldiphenyletherdisulfonate, dodecyldiphenyletherdisulfonate, stearyldiphenyletherdisulfonate, and the like can be used.

Examples of the α-sulfo fatty acid ester salt include α-sulfo fatty acid alkyl ester salts having 8 to 18 carbon atoms in the fatty acid residue. Specifically, methyl 2-sulfolaurate, polyoxyethylene fatty acid methyl ester, and the like can be used.

Examples of the acyl acetionate include lauroyl cethionate and palm oil fatty acid ethyl ester sulfonate.

Examples of the alkyl sulfosuccinate include alkyl sulfosuccinates containing an alkyl group having 8 to 18 carbon atoms, such as dioctyl sulfosuccinate, di-2-ethylhexyl sulfosuccinate and lauryl sulfosuccinate; and polyoxyethylene alkylsulfosuccinates having 8 to 18 carbon atoms, such as polyoxyethylene sulfosuccinic acid lauryl salt.

Examples of the alkylsulfoacetate include alkylsulfoacetate salts containing an alkyl group having 8 to 18 carbon atoms, such as laurylsulfoacetate.

Examples of the N-acylmethyl taurine salt include lauroyl methyl taurine salt, myristoyl methyl taurine salt, palmitoyl methyl taurine salt, stearoyl methyl taurine salt, and coconut oil fatty acid methyl taurine salt.

As said formalin condensed sulfonic acid salt, the formalin condensate of naphthalene sulfonate, the formalin condensate of alkylnaphthalene sulfonate, the formalin condensate of melamine sulfonic acid, the formalin condensate of alkylmelamine sulfonic acid, etc. are mentioned.

Examples of the sulfate-based anionic surfactants include alkyl sulfates, alkyl ether sulfates, alkylaryl ether sulfates, fatty acid alkanolamide sulfates, and fatty acid monoglyceride sulfates.

Examples of the alkyl sulfate include lauryl sulfate, stearyl sulfate and cetyl sulfate.

As said alkyl ether sulfate, POE lauryl ether sulfate, POE tridecyl ether sulfate, etc. are mentioned.

Polyoxyethylene nonylphenyl ether sulfate etc. are mentioned as said alkylaryl ether sulfate.

Examples of the fatty acid alkanolamide sulfate include polyoxyethylene alkyl palm oil fatty acid monoethanolamide sulfate.

Examples of the fatty acid monoglyceride sulfate include hydrogenated palm oil fatty acid glyceryl sulfate.

Examples of the phosphate-based anionic surfactants include alkyl phosphates, polyoxyalkylene alkyl ether phosphates, alkylaryl ether phosphates, fatty acid amide ether phosphates, and glycerin fatty acid ester monophosphates.

Examples of the alkyl phosphate include lauryl phosphate, myristyl phosphate, palmityl phosphate and stearyl phosphate.

Examples of the polyoxyalkylene alkyl ether phosphate include polyoxyethylene lauryl ether phosphate, polyoxyethylene alkyl (C12 to 15) ether phosphate, polyoxyethylene cetyl ether phosphate, polyoxyethylene oleyl ether phosphate, and polyoxyethylene stearyl. Ether phosphate, etc. are mentioned.

Polyoxyethylene nonylphenyl ether phosphate etc. are mentioned as said alkylaryl ether phosphate.

Examples of the fatty acid amide ether phosphate include polyoxyethylene alkyl monoethanol amide phosphate.

As the anionic surfactant, a sulfonic acid-based anionic surfactant is preferable, and an alkylsulfosuccinate is particularly preferable.

Examples of the nonionic surfactant include polyoxyalkylene alkyl ethers which are alkylene oxide adducts to aliphatic alcohols; polyoxyalkylenephenylether or polyoxyalkylenealkylphenylether (polyoxyalkylenearylether) which is an alkyleneoxide adduct to an aromatic alcohol; glycerin fatty acid esters; polyoxyalkyleneglycerin fatty acid esters which are alkyleneoxide adducts to glycerin fatty acid esters; polyoxyalkylenepentaerythritol fatty acid esters which are alkyleneoxide adducts to pentaerythritol fatty acid esters; polyoxyalkylene fatty acid esters which are alkyleneoxide adducts to fatty acids; sorbitan fatty acid esters; polyoxyalkylenesorbitan fatty acid esters which are alkyleneoxide adducts to sorbitan fatty acid esters; sorbitan fatty acid esters; sucrose fatty acid esters; pentaerythritol fatty acid esters; polyoxyalkylenealkylamines which are alkyleneoxide adducts to aliphatic amines; polyoxyalkylene fatty acid amides which are alkyleneoxide adducts to fatty acid amides; polyoxyalkylene (hardened) castor oil; polyoxyalkylene-modified polysiloxane; polyglyceryl-modified silicone; glyceryl-modified silicone; sugar-modified silicone; perfluoropolyether surfactants; polyoxyethylene/polyoxypropylene block copolymer; and alkyl polyoxyethylene/polyoxypropylene block copolymer ether. Among these, polyoxyalkylene-modified polysiloxane is preferable.

The content of the surfactant contained in the deodorant-containing processing liquid of the present invention is 100 parts by mass, from the viewpoint of the stability of the deodorant-containing processing liquid and the dispersibility of the tetravalent metal phosphate, the total amount of the deodorant containing the tetravalent metal phosphate In one case, Preferably it is 0.01-30 mass parts, More preferably, it is 0.05-15 mass parts, More preferably, it is 0.1-10 mass parts.

3. Adhesive component

The adhesive component is a component that adheres a deodorant containing a tetravalent metal phosphate to a base material containing at least one of an inorganic material and an organic material, preferably a polymer compound, and a synthetic polymer, semi-synthetic, when manufacturing a deodorant product Any of a polymer|macromolecule and a natural polymer may be sufficient.

Resins, polysaccharides, etc. are mentioned as a high molecular compound, Preferably it is resin. In addition, the adhesive component contained in the deodorant containing processing liquid of this invention can be made into 1 type, or 2 or more types.

The resin may be either a water-soluble resin or a water-insoluble resin, and an ethylene/vinyl acetate copolymer or a modified product thereof (acid modified product, etc.), an ethylene/vinyl chloride copolymer, a vinyl chloride/vinyl acetate copolymer, or polyvinyl acetate , polyvinyl chloride, modified olefin resin (chlorinated polyolefin, etc.), polyvinyl alcohol, alkyl cellulose, carboxyalkyl cellulose, carboxyalkyl hydroxyalkyl cellulose, polyacrylic acid, polyacrylate, acrylic resin, polyester resin, urethane resin, styrene ㆍButadiene copolymer, styrene/isoprene copolymer, styrene/butadiene/styrene block copolymer, styrene/ethylene/butylene/styrene block copolymer, styrene/ethylene/propylene/styrene block copolymer, hydrogenated styrene/butadiene/styrene A block copolymer, a hydrogenated styrene/ethylene/butylene/styrene block copolymer, a hydrogenated styrene/ethylene/propylene/styrene block copolymer, and a styrene/maleic anhydride copolymer etc. are mentioned.

Among these, a polyester resin is preferable at the point with few odors derived from resin.

Any of aromatic polyester and aliphatic polyester may be sufficient as a polyester resin, and it may use it combining these. Moreover, any of saturated polyester and unsaturated polyester may be sufficient as the said polyester. The polyester is preferably a saturated polyester comprising an acid component and a polycondensate obtained using a hydroxyl group-containing component, -SO ₃ H, -SO ₃ Na, -SO ₃ -, -COOH, -COO Polyester to which hydrophilic groups, such as -, -OPO(OH) ₂ and -OPO(OH)O-, couple|bonded may be sufficient.

Examples of the acid component include terephthalic acid, isophthalic acid, orthophthalic acid, naphthalenedicarboxylic acid, 4,4'-diphenyldicarboxylic acid, trimellitic acid, trimesic acid, pyromellitic acid, benzoic acid, p-oxybenzoic acid, p-(hydroxyethoxy)benzoic acid, succinic acid, adipic acid, azelaic acid, sebacic acid, glutaric acid, suberic acid, dodecanedicarboxylic acid, fumaric acid, maleic acid, itaconic acid, 1,4-cyclohexane dicarboxylic acid, 1,3-cyclohexanedicarboxylic acid, cyclobutanetetracarboxylic acid, dimethylolpropionic acid, tricyclodecanedicarboxylic acid, tetrahydroterephthalic acid, tetrahydroorthophthalic acid, hexahydroorthophthalic acid, and The methyl ester of these di, tri, or tetracarboxylic acid, or an anhydride, etc. are mentioned.

Examples of the acid component having a hydrophilic group include sodium 5-sulfonate isophthalic acid, 5-sulfonate ammonium isophthalic acid, 4-sulfonate sodium isophthalic acid, 4-methylsulfonate ammonium isophthalic acid, 2-sulfonate sodium terephthalic acid, and 5-sulfonate potassium isophthalic acid. , sulfonate-based compounds such as potassium 4-sulfonate isophthalic acid and 2-sulfonate potassium terephthalic acid.

Examples of the hydroxyl group-containing component include ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, propylene glycol, dipropylene glycol, 1,3-propanediol, 2-methyl-1,3-propanediol, 1, 4-butanediol, 1,2-butanediol, 1,5-pentanediol, 2-methyl-1,5-pentanediol, 1,6-hexanediol, neopentyl glycol, 2-ethyl-2-butyl-1,3 -Propanediol, 1,8-octanediol, 1,9-nonanediol, 1,10-decanediol, 2,2,4-trimethyl-1,3-pentanediol, polyethylene glycol, polypropylene glycol, polytetramethylene Glycol, trimethylolpropane, trimethylolethane, glycerin, pentaerythritol, bisphenol ethylene oxide adduct, bisphenol propylene oxide adduct, 1,4-cyclohexanedimethanol, 1,4-cyclohexanediol, 1 ,3-cyclohexanedimethanol, 1,3-cyclohexanediol, hydrogenated bisphenol A, spiroglycol, tricyclodecanediol, tricyclodecanedimethanol, resorcinol and 1,3-bis(2-hydroxy oxy) benzene and the like.

The polyester resin may be obtained by a known method such as a melt polymerization method, a solution polymerization method, and a solid phase polymerization method.

In addition, the hydrophilic group can be introduced by a known method. When -COO- is introduced, for example, trimellitic anhydride, trimellitic acid, pyromellitic anhydride, pyromellitic acid, trimesic acid, cyclobutane After the polycondensation reaction using tetracarboxylic acid, dimethylolpropionic acid, or the like, a method of subjecting the polycondensation reaction to a neutralization reaction using an amino compound, ammonia or an alkali metal salt or the like is applied.

The molecular weight of the resin is not particularly limited and a known adhesive may be used, but the number average molecular weight is, for example, 1,000 to 1,000,000, or, for example, 2,000 to 500,000, or, for example, 3,000 to 100,000, or For example, 4,000 to 50,000.

Since the deodorant-containing processing liquid of the present invention contains a surfactant, the adhesive component preferably has water solubility or hydrophilicity (in the case of water insolubility).

The content of the adhesive component contained in the deodorant-containing processing liquid of the present invention is preferably from the viewpoint of the adhesiveness of the deodorant in the deodorant product obtained when the total amount of the deodorant containing the tetravalent metal phosphate is 100 parts by mass. is 5-1000 mass parts, More preferably, it is 10-500 mass parts, More preferably, it is 15-100 mass parts.

4. Deodorant-containing processing liquid

The deodorant-containing processing liquid of the present invention contains, as essential components, the above-described deodorant containing a tetravalent metal phosphate, a surfactant, and an adhesive component, but may contain other components as necessary.

The deodorant-containing processing liquid of the present invention usually contains a medium. As a medium, only water or the liquid mixture of water and the organic solvent which has water solubility is mentioned, Water is preferable.

As an organic solvent which has water solubility, alcohol, such as methyl alcohol, ethyl alcohol, and isopropyl alcohol, is mentioned.

Although the content ratio of the medium contained in the deodorant-containing processing liquid of the present invention is not particularly limited, the medium preferably has a content ratio of the deodorant containing a tetravalent metal phosphate of 0.1 to 50% by mass relative to the deodorant-containing processing liquid. , More preferably, it is 0.5-40 mass %, More preferably, it is contained so that it may become 1-30 mass %.

The deodorant-containing processing liquid of the present invention has a viscosity at 25° C. (hereinafter simply referred to as “viscosity”) measured by a B-type viscometer of 50 mPa·s or more, preferably 70 mPa·s or more, more preferably 100 mPa·s or more. More than that.

In addition, although the No. 2 rotor is usually used and the viscosity can be measured at a rotation speed of 60 rpm or 30 rpm, a processing fluid having a high viscosity that cannot be measured under the above conditions may be used. In that case, it can measure by combining an appropriate rotor and rotation speed appropriately. However, from the viewpoint of productivity of the deodorizing product, for example, the upper limit of the viscosity can be preferably 1000 mPa·s.

Even if the viscosity of the deodorant-containing processing liquid of the present invention is 50 mPa·s or more, since it contains a surfactant, the dispersibility of the components is excellent, handling is easy, and the coating property to the substrate is excellent. Therefore, the deodorant-containing processing liquid of the present invention is suitable for manufacturing a deodorant product with a high amount of the deodorant containing a tetravalent metal phosphate.

The viscosity of the deodorant-containing processing liquid of the present invention can be appropriately adjusted from the type, structure, particle size, molecular weight, composition ratio and concentration of each component including the deodorant, surfactant, adhesive component and medium, etc. It is preferable to adjust using as a viscosity modifier.

The deodorant-containing processing liquid of the present invention may further contain additives as other components.

As an additive, viscosity modifiers, such as a thickener, an antifoamer, a coloring agent, a fragrance|flavor, an antibacterial agent, an antiviral agent, an antiallergic agent, a preservative, etc. are mentioned.

A known thickener can be used and is not particularly limited, and examples thereof include polysaccharides, acrylic polymers, associative polyurethanes, carboxyvinyl compounds, and clay minerals. Of these, polysaccharides and acrylic polymers are preferred. Specific examples of polysaccharides include xanthan gum, alginate, gum arabic, starch, tamarind seed gum, guar gum, carboxymethyl cellulose, and the like. Examples of the acrylic polymer include polyacrylic acid, sodium polyacrylate, ammonium polyacrylate, acrylic acid copolymer, sodium salt of acrylic acid copolymer, ammonium salt of acrylic acid copolymer, crosslinked polyacrylic acid, crosslinked sodium polyacrylate and crosslinked type. An acrylic polymer etc. are mentioned.

By adding the thickener, the amount of the processing liquid component such as the deodorant can be set to an appropriate amount that does not become excessive, for example. In this case, the productivity of the deodorant processing is improved, which is preferable.

The content of the thickener is preferably 0.1 to 10 parts by mass, more preferably 0.7 to 7 parts by mass, still more preferably 0.5 to 5 parts by mass, when the total amount of the deodorant containing the tetravalent metal phosphate is 100 parts by mass. is the mass part.

A conventional method may be followed as a method for producing the deodorant processing liquid of the present invention.

For example, it can be prepared by mixing a deodorant containing a tetravalent metal phosphate, a surfactant, an adhesive component, and a medium such as water.

In this case, it can also be produced by adding and mixing a deodorant containing a tetravalent metal phosphate, a surfactant, and an adhesive component in a medium such as water.

As surfactant, it is preferable to use it as an aqueous solution or aqueous dispersion.

When preparing the deodorant processing liquid of the present invention, if necessary, the raw material components may be stirred under heating.

5. Manufacturing method of deodorant products

The deodorant-containing processing liquid of the present invention is suitable as a material for manufacturing a deodorant product by attaching a deodorant containing a tetravalent metal phosphate to the surface of a substrate.

The method for manufacturing a deodorant product of the present invention includes a step of applying a deodorant-containing processing liquid to a substrate, and forming a coating film containing the deodorant-containing processing liquid on the surface of the substrate (hereinafter referred to as “coating film formation step”), and the coating film A drying step (hereinafter, referred to as a “drying step”) is provided.

In the coating film forming process, padding, dipping, coating, spraying, printing, etc. are applied according to the shape of the substrate to apply a deodorant-containing processing liquid to the surface of the substrate, and a coating film is formed.

The said base material is not specifically limited, It can be set as the article containing an inorganic material, an organic material, or a material combining these, The shape is not specifically limited, either. Examples of the substrate include resin molded articles (including foamed resin molded articles) such as films, granules, and general molded articles; fiber; Sheet-like articles, such as a nonwoven fabric containing a fiber, a woven fabric, etc. can be used.

In the above-mentioned coating film forming step, since the viscosity of the deodorant-containing processing liquid to be used is 50 mPa·s or more, multi-layer coating is not required, and a desired amount of the deodorant can be added.

In the drying step, sealing heating, hot air heating, etc. are applied depending on the shape of the substrate, the medium is removed from the coating film, and a deodorant-containing portion (deodorant film) is formed on the surface of the substrate.

The drying temperature is not particularly limited, and is appropriately selected depending on the type of medium contained in the deodorant-containing processing liquid, and is preferably 100 to 150°C.

As described above, in the embodiment of the present invention, a deodorant-containing processing liquid having excellent dispersibility can be used by increasing the content of the tetravalent metal phosphate, so that the deodorant containing the tetravalent metal phosphate contains the desired content. It is not necessary to repeat the coating film forming process and the drying process in order to manufacture the deodorizing product included in the ratio, and the target deodorizing product can be efficiently manufactured.

A deodorant product of the present invention is an article comprising a base material and a deodorant-containing portion comprising a tetravalent metal phosphate bonded to the surface of the base material. The deodorant-containing portion contains a surfactant and an adhesive component contained in the deodorant-containing processing liquid. From the viewpoint of the deodorizing property of a basic gas such as ammonia gas, the amount of the phosphate adhering to the tetravalent metal is preferably 0.1 g/m 2 or more, and more preferably 0.5 g/m 2 or more.

In the present invention, a preferred base material is a sheet-like article containing fibers, and for example, a deodorizing filter medium using a nonwoven fabric as a base material is a representative deodorizing product. This deodorizing filter medium can be formed by attaching a tetravalent metal phosphate to only one side of the nonwoven fabric, or by attaching a tetravalent metal phosphate to both surfaces of the nonwoven fabric.

In addition, fibers (only) are preferred substrates, and deodorizing fibers in which tetravalent metal phosphates are attached to the surface of fibers are also representative deodorizing products. A woven or nonwoven fabric can be manufactured using this deodorizing fiber, and it can be set as a deodorizing fiber sheet for use as a deodorizing filter medium. In addition, clothing, such as underwear, socks, and an apron; Nursing Care Clothing; daily necessities such as cushions, quilts, blankets, carpets, sofas, curtains, and covers; It can also be applied to processed products such as seat material for vehicles.

Example

Hereinafter, although an Example demonstrates embodiment of this invention more concretely, this invention is not limited to these Examples. In addition, in the following, unless otherwise indicated, "part" and "%" are based on mass.

1. Raw material of processing liquid containing deodorant

The raw materials used for manufacture of the deodorant containing processing liquid are shown below.

1-1. deodorant

(1) zirconium phosphate

Particles which are α-zirconium phosphate and have a median diameter of 1 µm and a BET specific surface area of 10 m 2 /g as measured by a laser diffraction particle size distribution analyzer "MS2000" (model name) manufactured by Malvern Corporation.

(2) copper silicate

Particles having a median diameter of 3 μm and a BET specific surface area of 500 m 2 /g.

(3) zeolite

Particles having a median diameter of 3 μm and a BET specific surface area of 350 m 2 /g.

(4) activated zinc oxide

Particles having a median diameter of 2 μm and a BET specific surface area of 100 m 2 /g.

(5) zirconium hydroxide

Particles having a median diameter of 2 μm and a BET specific surface area of 300 m 2 /g.

1-2. adhesive component

A saturated polyester resin (number average molecular weight 16,000) was used.

1-3. Aqueous or aqueous dispersion of surfactant

(1) An anionic surfactant "Likasurf M-30" (trade name) manufactured by New Japan Rica Corporation, which is an aqueous solution mainly containing sodium di(2-ethylhexyl)sulfosuccinate, was used.

(2) "BYK-349" (trade name) manufactured by Bic Chemie Japan, which is an aqueous dispersion mainly containing polyether-modified siloxane as a nonionic surfactant, was used.

(3) A water-soluble acrylic acid dispersant "T-50" (trade name) manufactured by Toagosei Corporation containing an anionic surfactant was used.

(4) "DISPERBYK-193" (trade name) manufactured by BYK which is a nonionic surfactant was used.

1-4. thickener

(1) An aqueous solution of xanthan gum was used.

(2) An aqueous solution of carboxymethyl cellulose (hereinafter referred to as "CMC") was used.

(3) An acrylic thickener "A-20L" (trade name) manufactured by Toagosei Co., Ltd. was used.

2. Preparation and evaluation of processing liquid containing deodorant

A deodorant-containing processing solution was prepared by using a deodorant, an adhesive component, an aqueous solution or dispersion of a surfactant, water, and a thickener in the ratios shown in Tables 1 and 2. Thereafter, the deodorant-containing processing liquid and the nonwoven fabric containing PET fibers were immersed and dried at 130° C. to obtain a rectangular deodorizing fiber sheet. And it cut to a predetermined size, the deodorization rate was computed with the following method, and deodorization property was evaluated.

Using a resin film test bag, a gas bag of ammonia (initial concentration: 200 ppm), methyl mercaptan (initial concentration: 70 ppm), acetaldehyde (initial concentration: 30 ppm), hydrogen sulfide (initial concentration: 120 ppm) or acetic acid (initial concentration: 100 ppm) prepared. Cut the deodorizing fiber sheet into a micro syringe holder size of φ 25 mm, set one in the holder, let the gas pass through the deodorizing fiber sheet by the suction force of the gas extractor, and measure the odor gas concentration after passing with a detection tube to determine the deodorization rate calculated.

2-1. Example

2-1-1. Example 1

Zirconium phosphate particles, copper silicate particles, saturated polyester resin, xanthan gum aqueous solution, aqueous solution of anionic surfactant (Likasurf M-30), and pure water are mixed, and a deodorant having the composition shown in Table 1 is contained. A processing liquid was prepared. Next, the viscosity in 25 degreeC and 60 rpm was measured using the B-type viscometer (No. 2 rotor) made by Toki Sangyo.

Thereafter, by the method described above, a deodorizing fiber sheet was prepared using this deodorant-containing processing liquid, and deodorization was evaluated (see Table 1). In addition, the adhering amount of the deodorant in the deodorizing fiber sheet is 2 g/m<2> of zirconium phosphate particles and 6 g/m<2> of copper silicate particles. 1 and 2 are photographs (300 times) observed with a scanning electron microscope "S-4800" (hereinafter abbreviated as SEM) manufactured by Hitachi High-Technologies Co., Ltd. of the state of attachment of the deodorant to the deodorant fiber sheet produced in this way. is shown in

2-1-2. Example 2

Zirconium phosphate particles, zeolite particles, saturated polyester resin, CMC aqueous solution, aqueous dispersion of nonionic surfactant (BYK-349), and pure water were mixed to prepare a deodorant-containing processing solution having the composition shown in Table 1 did Then, it carried out similarly to Example 1, and measured the viscosity. And the deodorizing fiber sheet was manufactured, and deodorizing property was evaluated (refer Table 1).

In addition, the adhering amount of the deodorant in the deodorizing fiber sheet is 12 g/m<2> of zirconium phosphate particles and 12 g/m<2> of zeolite particles.

2-1-3. Example 3

Zirconium phosphate particles, active zinc oxide particles, saturated polyester resin, CMC aqueous solution, aqueous solution of anionic surfactant (Likasurf M-30), and pure water are mixed, and deodorant-containing processing of the composition shown in Table 1 liquid was prepared. Then, it carried out similarly to Example 1, and measured the viscosity. And the deodorizing fiber sheet was manufactured, and deodorizing property was evaluated (refer Table 1).

In addition, the adhering amount of the deodorant in the deodorizing fiber sheet is 3 g/m<2> of zirconium phosphate particles and 3 g/m<2> of activated zinc oxide particles.

2-1-4. Example 4

Zirconium phosphate particles, zirconium hydroxide particles, saturated polyester resin, CMC aqueous solution, aqueous dispersion of nonionic surfactant (BYK-349), and pure water are mixed, and the deodorant-containing processing liquid having the composition shown in Table 1 prepared. Then, it carried out similarly to Example 1, and measured the viscosity. And the deodorizing fiber sheet was manufactured, and deodorizing property was evaluated (refer Table 1).

In addition, the adhering amount of the deodorant in the deodorizing fiber sheet is 4.5 g/m<2> of zirconium phosphate particles and 14 g/m<2> of zirconium hydroxide particles.

2-1-5. Example 5

Zirconium phosphate particles, copper silicate particles, saturated polyester resin, zirconium hydroxide particles, xanthan gum aqueous solution, aqueous solution of anionic surfactant (Licasurf M-30), and pure water were mixed, A deodorant-containing processing liquid having the structure shown was prepared. Then, it carried out similarly to Example 1, and measured the viscosity. And the deodorizing fiber sheet was manufactured, and deodorizing property was evaluated (refer Table 1).

In addition, the adhering amount of the deodorant in the deodorizing fiber sheet is 4 g/m<2> of zirconium phosphate particles, 8 g/m<2> of copper silicate particles, and 4 g/m<2> of zirconium hydroxide particles.

2-1-6. Example 6

Zirconium phosphate particles, zirconium hydroxide particles, active zinc oxide particles, saturated polyester resin, CMC aqueous solution, aqueous dispersion of nonionic surfactant (BYK-349), and pure water are mixed, and the composition shown in Table 1 of a deodorant-containing processing solution was prepared. Thereafter, when the viscosity was measured in the same manner as in Example 1, the viscosity was high and the measurement was impossible. And the deodorizing fiber sheet was manufactured, and deodorizing property was evaluated (refer Table 1).

In addition, the adhering amount of the deodorant in the deodorizing fiber sheet is 8 g/m<2> of zirconium phosphate particles, 12 g/m<2> of zirconium hydroxide particles, and 6 g/m<2> of activated zinc oxide particles.

2-1-7. Example 7

Zirconium phosphate particles, copper silicate particles, zeolite particles, saturated polyester resin, xanthan gum aqueous solution, aqueous solution of anionic surfactant (Licasurf M-30), and pure water are mixed, A deodorant-containing processing liquid of the composition was prepared. Then, it carried out similarly to Example 6, and measured the viscosity. And the deodorizing fiber sheet was manufactured, and deodorizing property was evaluated (refer Table 1).

In addition, the adhering amount of the deodorant in the deodorizing fiber sheet is 3 g/m<2> of zirconium phosphate particle|grains, 6 g/m<2> of copper silicate particles, and 12 g/m<2> of zeolite particle|grains.

2-1-8. Example 8

The composition shown in Table 1 by mixing zirconium phosphate particles, zirconium hydroxide particles, zeolite particles, saturated polyester resin, xanthan gum aqueous solution, aqueous dispersion of nonionic surfactant (BYK-349), and pure water of a deodorant-containing processing solution was prepared. Then, it carried out similarly to Example 6, and measured the viscosity. And the deodorizing fiber sheet was manufactured, and deodorizing property was evaluated (refer Table 1).

In addition, the adhering amount of the deodorant in the deodorizing fiber sheet is 4 g/m<2> of zirconium phosphate particles, 10 g/m<2> of zirconium hydroxide particles, and 10 g/m<2> of zeolite particles.

2-1-9. Example 9

Zirconium phosphate particles, copper silicate particles, saturated polyester resin, xanthan gum aqueous solution, aqueous dispersion of anionic surfactant (T-50), and pure water are mixed, and deodorant-containing processing of the configuration shown in Table 1 liquid was prepared. Then, it carried out similarly to Example 1, and measured the viscosity. And the deodorizing fiber sheet was manufactured, and deodorizing property was evaluated (refer Table 1).

In addition, the adhering amount of the deodorant in the deodorizing fiber sheet is 2 g/m<2> of zirconium phosphate particles and 6 g/m<2> of copper silicate particles.

2-1-10. Example 10

Zirconium phosphate particles, copper silicate particles, saturated polyester resin, xanthan gum aqueous solution, aqueous dispersion of nonionic surfactant (DISPERBYK-193), and pure water are mixed, and deodorant-containing processing of the composition shown in Table 1 liquid was prepared. Then, it carried out similarly to Example 1, and measured the viscosity. And the deodorizing fiber sheet was manufactured, and deodorizing property was evaluated (refer Table 1).

In addition, the adhering amount of the deodorant in the deodorizing fiber sheet is 2 g/m<2> of zirconium phosphate particles and 6 g/m<2> of copper silicate particles.

2-1-11. Example 11

Zirconium phosphate particles, copper silicate particles, saturated polyester resin, acrylic thickener (A-20L), an aqueous solution of anionic surfactant (Likasurf M-30), and pure water are mixed, and the composition shown in Table 1 of a deodorant-containing processing solution was prepared. Then, it carried out similarly to Example 1, and measured the viscosity. And the deodorizing fiber sheet was manufactured, and deodorizing property was evaluated (refer Table 1).

In addition, the adhering amount of the deodorant in the deodorizing fiber sheet is 2 g/m<2> of zirconium phosphate particles and 6 g/m<2> of copper silicate particles.

2-2. comparative example

2-2-1. Comparative Example 1

Zirconium phosphate particles, copper silicate particles, saturated polyester resin, and pure water were mixed to prepare a deodorant-containing processing liquid having the configuration shown in Table 2. Then, it carried out similarly to Example 1, and measured the viscosity. And the deodorizing fiber sheet was manufactured, and deodorizing property was evaluated (refer Table 2).

In addition, the adhering amount of the deodorant in the deodorizing fiber sheet is 2 g/m<2> of zirconium phosphate particles and 6 g/m<2> of copper silicate particles. 3 and 4 show photographs (300 times) observed by SEM of the state of attachment of the deodorant to the deodorant fiber sheet produced in this way.

2-2-2. Comparative Example 2

Zirconium phosphate particles, copper silicate particles, saturated polyester resin, xanthan gum aqueous solution, and pure water were mixed to prepare a deodorant-containing processing liquid having the configuration shown in Table 2. Then, it carried out similarly to Example 1, and measured the viscosity. And the deodorizing fiber sheet was manufactured, and deodorizing property was evaluated (refer Table 2).

In addition, the adhering amount of the deodorant in the deodorizing fiber sheet is 2 g/m<2> of zirconium phosphate particles and 6 g/m<2> of copper silicate particles.

2-2-3. Comparative Example 3

Zirconium phosphate particles, zeolite particles, a saturated polyester resin, an aqueous solution of a nonionic surfactant (BYK-349), and pure water were mixed to prepare a deodorant-containing processing solution having the configuration shown in Table 2. Then, it carried out similarly to Example 1, and measured the viscosity. And the deodorizing fiber sheet was manufactured, and deodorizing property was evaluated (refer Table 2).

In addition, the adhering amount of the deodorant in the deodorizing fiber sheet is 12 g/m<2> of zirconium phosphate particles and 12 g/m<2> of zeolite particles.

2-2-4. Comparative Example 4

Zirconium phosphate particles, active zinc oxide particles, saturated polyester resin, CMC aqueous solution, and pure water were mixed to prepare a deodorant-containing processing solution having the configuration shown in Table 2. Then, it carried out similarly to Example 1, and measured the viscosity. And the deodorizing fiber sheet was manufactured, and deodorizing property was evaluated (refer Table 2).

In addition, the adhering amount of the deodorant in the deodorizing fiber sheet is 3 g/m<2> of zirconium phosphate particles and 3 g/m<2> of activated zinc oxide particles.

2-2-5. Comparative Example 5

Zirconium phosphate particles, zirconium hydroxide particles, a saturated polyester resin, an aqueous solution of an anionic surfactant (Likasurf M-30), and pure water were mixed to prepare a deodorant-containing processing solution having the configuration shown in Table 2. Then, it carried out similarly to Example 1, and measured the viscosity. And the deodorizing fiber sheet was manufactured, and deodorizing property was evaluated (refer Table 2).

In addition, the adhering amount of the deodorant in the deodorizing fiber sheet is 4.5 g/m<2> of zirconium phosphate particles and 14 g/m<2> of zirconium hydroxide particles.

2-2-6. Comparative Example 6

Zirconium phosphate particles, copper silicate particles, zirconium hydroxide particles, saturated polyester resin, and pure water were mixed to prepare a deodorant-containing processing liquid having the configuration shown in Table 2. Then, it carried out similarly to Example 1, and measured the viscosity. And the deodorizing fiber sheet was manufactured, and deodorizing property was evaluated (refer Table 2).

In addition, the adhering amount of the deodorant in the deodorizing fiber sheet is 4 g/m<2> of zirconium phosphate particles, 8 g/m<2> of copper silicate particles, and 4 g/m<2> of zirconium hydroxide particles.

2-2-7. Comparative Example 7

Zirconium phosphate particles, zirconium hydroxide particles, activated zinc oxide particles, saturated polyester resin, CMC aqueous solution, and pure water were mixed to prepare a deodorant-containing processing solution having the configuration shown in Table 2. Then, it carried out similarly to Example 6, and measured the viscosity. And the deodorizing fiber sheet was manufactured, and deodorizing property was evaluated (refer Table 2).

In addition, the adhering amount of the deodorant in the deodorizing fiber sheet is 8 g/m<2> of zirconium phosphate particles, 12 g/m<2> of zirconium hydroxide particles, and 6 g/m<2> of activated zinc oxide particles.

2-2-8. Comparative Example 8

Zirconium phosphate particles, copper silicate particles, zeolite particles, saturated polyester resin, xanthan gum aqueous solution, and pure water were mixed to prepare a deodorant-containing processing solution having the configuration shown in Table 2. Then, it carried out similarly to Example 6, and measured the viscosity. And the deodorizing fiber sheet was manufactured, and deodorizing property was evaluated (refer Table 2).

In addition, the adhering amount of the deodorant in the deodorizing fiber sheet is 3 g/m<2> of zirconium phosphate particle|grains, 6 g/m<2> of copper silicate particles, and 12 g/m<2> of zeolite particle|grains.

2-2-9. Comparative Example 9

Zirconium phosphate particles, zirconium hydroxide particles, zeolite particles, a saturated polyester resin, an aqueous solution of a nonionic surfactant (BYK-349), and pure water are mixed to prepare a deodorant-containing processing liquid having the composition shown in Table 2 did Then, it carried out similarly to Example 1, and measured the viscosity. And the deodorizing fiber sheet was manufactured, and deodorizing property was evaluated (refer Table 2). In addition, the adhering amount of the deodorant in the deodorizing fiber sheet is 4 g/m<2> of zirconium phosphate particles, 10 g/m<2> of zirconium hydroxide particles, and 10 g/m<2> of zeolite particles.

2-3. evaluation

From Table 1 and Table 2, the following is clear. Comparative Examples 2, 4, 7 and 8 are examples of processing liquids containing a deodorant having a viscosity of 50 mPa·s or more, but are examples in which a surfactant is not used, and corresponding Examples 1, 3, 6, 7, 9, and 10, respectively and 11, the deodorization of ammonia gas by zirconium phosphate was not sufficient.

Comparative Examples 1, 3, 5, 6 and 9 are examples of processing liquids containing a deodorant having a viscosity of less than 50 mPa·s, and the appearance of the deodorant fiber sheet is not good and the corresponding Examples 2, 4 and 5, respectively. and 8, the deodorization of ammonia gas by zirconium phosphate was not sufficient.

From Figs. 1 to 4, the following is clear. 3 and 4 are SEM images of the deodorant fiber sheet of Comparative Example 1 of a deodorant processing liquid having a viscosity of less than 50 mPa·s, and the deodorant is remarkably localized on the back surface of the deodorant fiber sheet ( FIG. 4 ), and adhesion to the fiber surface is also non-uniform. On the other hand, in the corresponding Example 1, as shown in Figs. 1 and 2, the deodorant is present without being biased on the front and back surfaces, and the uniformity of adhesion to the fiber surface is also high.

The deodorant-containing processing liquid of the present invention is suitable for the manufacture of deodorizing products (deodorizing filter media, deodorizing paper, deodorizing film, etc.) that are easy to apply to various substrates and have excellent deodorizing performance of ammonia gas.

Among the deodorizing products of the present invention, the deodorizing filter material is useful as a constituent member of a deodorizing mask, a deodorizing filter, a deodorizing device, etc., for example, in a medical care/nursing care/discharge site, a sewage treatment plant, a waste treatment plant (incineration plant), a fertilizer plant, a chemical plant, etc. Do.

In addition, the deodorizing product of the present invention can be suitably used for environmental purification in the field where materials that generate ammonia gas from themselves are handled.

Claims (12)

A deodorant-containing processing liquid comprising a deodorant containing a tetravalent metal phosphate, a surfactant, and an adhesive component, and having a viscosity at 25°C of 50 mPa·s or more according to a B-type viscometer. The deodorant-containing processing liquid according to claim 1, wherein the tetravalent metal is at least one selected from Zr, Hf, Ti and Sn. The deodorant-containing processing liquid according to claim 1 or 2, wherein the content of the surfactant is 0.01 to 30 parts by mass based on 100 parts by mass of the deodorant. The deodorant-containing processing liquid according to any one of claims 1 to 3, wherein the surfactant is at least one selected from anionic surfactants and nonionic surfactants. The deodorant-containing processing liquid according to any one of claims 1 to 4, wherein the tetravalent metal phosphate has a specific surface area of 0.1 to 100 m 2 /g. The deodorant-containing processing liquid according to any one of claims 1 to 5, wherein the tetravalent metal phosphate has a median diameter of 0.1 µm to 100 µm. The deodorant-containing processing liquid according to any one of claims 1 to 6, wherein the adhesive component contains a high molecular compound. The deodorant-containing processing liquid according to any one of claims 1 to 7, further comprising water. The deodorant-containing processing liquid according to any one of claims 1 to 8, further comprising a thickener. 10. A process comprising: applying the processing liquid containing the deodorant according to any one of claims 1 to 9 to a substrate to form a coating film on the surface of the substrate; and drying the coating film; The manufacturing method of the product. A deodorant product comprising: a substrate; and a deodorant-containing portion bonded to at least a portion of the surface of the substrate, wherein the deodorant-containing portion contains a tetravalent metal phosphate, a surfactant, and an adhesive component. The deodorizing product according to claim 11, wherein the base material has a sheet-like shape including fibers, and the deodorizing product is a deodorizing filter medium.

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