WO2020261798A1 - 消臭剤含有加工液及びそれを用いた消臭製品の製造方法 - Google Patents

消臭剤含有加工液及びそれを用いた消臭製品の製造方法 Download PDF

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WO2020261798A1
WO2020261798A1 PCT/JP2020/019349 JP2020019349W WO2020261798A1 WO 2020261798 A1 WO2020261798 A1 WO 2020261798A1 JP 2020019349 W JP2020019349 W JP 2020019349W WO 2020261798 A1 WO2020261798 A1 WO 2020261798A1
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Prior art keywords
deodorant
processing liquid
acid
containing processing
phosphate
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PCT/JP2020/019349
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English (en)
French (fr)
Japanese (ja)
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雄輝 上杉
喜直 山田
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東亞合成株式会社
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Priority to CN202080033246.2A priority Critical patent/CN113784786B/zh
Priority to JP2021527467A priority patent/JPWO2020261798A1/ja
Priority to KR1020217037640A priority patent/KR20220027056A/ko
Publication of WO2020261798A1 publication Critical patent/WO2020261798A1/ja

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    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
    • A61L9/00—Disinfection, sterilisation or deodorisation of air
    • A61L9/01—Deodorant compositions
    • A61L9/014—Deodorant compositions containing sorbent material, e.g. activated carbon
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
    • A61L9/00—Disinfection, sterilisation or deodorisation of air
    • A61L9/01—Deodorant compositions
    • A61L9/012—Deodorant compositions characterised by being in a special form, e.g. gels, emulsions
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/30—Processes for preparing, regenerating, or reactivating
    • B01J20/32—Impregnating or coating ; Solid sorbent compositions obtained from processes involving impregnating or coating
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
    • A61L2101/00—Chemical composition of materials used in disinfecting, sterilising or deodorising
    • A61L2101/02—Inorganic materials
    • A61L2101/16—Inorganic materials containing phosphorus
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
    • A61L2209/00—Aspects relating to disinfection, sterilisation or deodorisation of air
    • A61L2209/20—Method-related aspects
    • A61L2209/22—Treatment by sorption, e.g. absorption, adsorption, chemisorption, scrubbing, wet cleaning

Definitions

  • the present invention relates to a deodorant-containing processing liquid suitable for producing a deodorant product having deodorant performance against ammonia gas.
  • a deodorant mask which is an example of a deodorant product, that is, a chemically adsorbed deodorant such as CuO / SiO 2 composite oxide and zirconium phosphate is bonded to the surface of a fiber by an adhesive composition
  • a deodorant mask having a main body portion including a deodorant fiber layer containing a composite fiber (impregnated) is disclosed.
  • a deodorant-containing processing liquid containing a chemisorption type deodorant, an adhesive composition and the like is used.
  • deodorant filter media contain, for example, a deodorant containing a deodorant and an adhesive resin after a base cloth such as a non-woven cloth is unwound from a base cloth sheet roll wound in a roll shape on a winding core.
  • a base cloth such as a non-woven cloth is unwound from a base cloth sheet roll wound in a roll shape on a winding core.
  • the base cloth with a coating film is generally dried while being moved laterally or diagonally from the feeding side of the base cloth to the winding side of the deodorant cloth.
  • a deodorant cloth or deodorant filter medium having stable deodorizing performance is particularly applied to a processing liquid containing a phosphate of a tetravalent metal such as zirconium phosphate, which has deodorizing performance of a basic gas such as ammonia gas. It has been desired to consider whether it is possible to improve the production of gas efficiently.
  • a phosphate of a tetravalent metal such as zirconium phosphate which chemically adsorbs a basic gas such as ammonia gas, can be sufficiently adhered to a substrate, which is excellent in processability and particularly deodorizes to ammonia gas.
  • An object of the present invention is to provide a deodorant-containing processing liquid capable of efficiently producing a deodorant product having excellent performance.
  • the present inventors use a tetravalent metal such as zirconium phosphate to adhere 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.
  • a deodorant-containing processing liquid containing a phosphate a surfactant and an adhesive component are further contained to have a specific viscosity, so that the deodorizing performance against basic gas, particularly ammonia gas is excellent.
  • the present invention was completed by finding that the deodorant product can be efficiently produced.
  • the present invention is shown below.
  • Item 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 with respect to 100 parts by mass of the deodorant. 4.
  • the deodorant-containing processing liquid according to any one of the above items 1 to 7 which contains water.
  • a method for manufacturing a deodorant product which comprises. 11. It comprises a base material and a deodorant-containing portion bonded to at least a part of the surface of the base material, and the deodorant-containing part contains a phosphate of a tetravalent metal, a surfactant and an adhesive component.
  • the deodorant-containing processing liquid of the present invention has excellent dispersibility and stability of the contained components, and has a high amount of the deodorant containing a tetravalent metal phosphate, and deodorizes a basic gas, particularly ammonia gas. Suitable for manufacturing deodorant products with excellent performance.
  • a deodorant-containing processing liquid containing a tetravalent metal phosphate selected from Zr, Hf, Ti and Sn it is possible to efficiently produce a deodorant product having excellent deodorizing performance against ammonia gas. it can.
  • a deodorant product having high deodorizing performance against a basic gas such as ammonia gas can be efficiently produced.
  • Example 1 It is an enlarged image of one side (surface) of the deodorant fiber sheet obtained in Example 1. It is an enlarged image of one side (back side) of the deodorant fiber sheet obtained in Example 1. It is an enlarged image of one side (surface) of the deodorant fiber sheet obtained in Comparative Example 1. It is an enlarged image of one side (back side) of the deodorant fiber sheet obtained in Comparative Example 1.
  • 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 of 50 mPa ⁇ s or more at 25 ° C. by a B-type viscometer. It is characterized by that.
  • the deodorant-containing processing liquid of the present invention is based on a deodorant containing at least a tetravalent metal phosphate by an adhesive component after applying the deodorant-containing processing liquid to a base material and drying the formed coating film. It is intended to manufacture deodorant products in which materials are adhered.
  • Phosphate of tetravalent metal such as zirconium phosphate is a deodorant having chemical adsorption performance for basic gas such as ammonia gas, and the deodorant-containing processing liquid of the present invention is at least ammonia gas. On the other hand, it provides a deodorant product with high deodorant performance.
  • the deodorant-containing processing liquid of the present invention may further contain other deodorants (described later) that chemically adsorb basic gas or other malodorous gas, and additives, if necessary.
  • 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.
  • Deodorant containing a phosphate of a valent metal contains a phosphate of a tetravalent metal as an essential component and has a chemical adsorption performance for at least a basic gas. It is an agent. Further, as described in detail later, the deodorant may contain a deodorant other than the tetravalent metal phosphate (hereinafter, referred to as “other deodorant”), if necessary.
  • other deodorant tetravalent metal phosphates and other deodorants will be described.
  • the phosphate of tetravalent metal is preferably a compound represented by the following general formula (1), and is insoluble or sparingly soluble in water.
  • M in the general formula (1) include Zr, Hf, Ti, Sn, etc.
  • M in the compound of the general formula (1) is a combination of two or more kinds of atoms even if it is a single atom. Is also good.
  • Preferred specific examples of the tetravalent metal phosphate include zirconium phosphate, hafnium phosphate, titanium phosphate, tin phosphate and the like. These compounds include crystalline compounds having various crystal systems such as ⁇ -type, ⁇ -type, and ⁇ -type, and amorphous compounds, and any of them can be preferably used. Among these, zirconium phosphate is particularly preferable because it has a high chemical adsorption power of ammonia and is easily available industrially.
  • the zirconium phosphate is preferably a compound represented by the following formula (2).
  • X in the above formula (2) is preferably 0.005 ⁇ x ⁇ 0.1 because the chemical adsorption power of ammonia is particularly high.
  • the shape of the phosphate of the tetravalent metal is not particularly limited, but is usually granular, and the median diameter measured by a laser diffraction type particle size distribution measuring machine is preferably 0.1 to 100 ⁇ m, more preferably 0. .2 to 50 ⁇ m, more preferably 0.3 to 10 ⁇ m.
  • specific surface area measured by the BET method of calculating the amount of nitrogen adsorbed, from the viewpoint of deodorant, such as ammonia gas preferably 0.1 ⁇ 100m 2 / g, more preferably 0.5 ⁇ 100 m 2 / g, more preferably 1 to 100 m 2 / g.
  • the deodorant-containing processing liquid of the present invention may contain other deodorants that are deodorants other than tetravalent metal phosphate.
  • Other deodorants can be blended in a type and proportion in which the obtained deodorant product does not deteriorate the deodorizing performance of the basic gas.
  • Other deodorants are basic gases such as ammonia gas and trimethylamine; acid gases such as acetic acid and isovaleric acid; aldehyde gases such as formaldehyde, acetaldehyde, and nonenal; and sulfur gases such as hydrogen sulfide and methyl mercaptan. It can have deodorizing performance against malodorous gas such as.
  • Deodorants 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 amorphous composite oxide of K 2 O, and the like.
  • Examples of the deodorant for acid gas include zirconium hydride, zirconium oxide, and hydrotalcite compounds such as magnesium-aluminum hydrotalcite.
  • Examples of the deodorant for aldehyde-based gas include hydrazine-based compounds such as adipic acid dihydrazide, carbohydrazide, dihydrazide succinate, and dihydrazide oxalate, aminoguanidine hydrochloride, aminoguanidine sulfate, and amino such as aminoguanidine bicarbonate. Examples include guanidine salt and the like.
  • Examples of the deodorant for sulfur-based gas include copper silicate, copper zirconium phosphate hydrate, zinc oxide, zinc aluminum oxide, zinc silicate, zinc aluminum silicate, and layered zinc aluminosilicate.
  • the proportion of the tetravalent metal phosphate used is preferably 1 to 10000 parts by mass, more preferably 5 to 2000 parts by mass with respect to 100 parts by mass. ..
  • the surfactant is not particularly limited, and any of an anionic surfactant, a cationic surfactant, a nonionic surfactant and an amphoteric surfactant may be used. Of these, anionic surfactants and nonionic surfactants are particularly preferable from the viewpoint of dispersibility of the phosphate of the tetravalent metal.
  • the preferable surfactant contained in the deodorant-containing processing liquid of the present invention may be either an anionic surfactant or a nonionic surfactant, or both.
  • anionic surfactant examples include carboxylic acid-based anionic surfactants, sulfonic acid-based anionic surfactants, sulfuric acid-based anionic surfactants, and phosphoric acid-based anionic surfactants.
  • anionic surfactants will be specifically exemplified, but the “salt” is an alkali metal salt (lithium salt, sodium salt, potassium salt, etc.), alkaline earth metal salt (magnesium salt, calcium salt, etc.), ammonium.
  • a salt or amine salt (monoethanolamine salt, diethanolamine salt, triethanolamine salt, monoisopropanolamine salt, etc.).
  • carboxylic acid-based anionic surfactant examples include polycarboxylic acid salts, aliphatic carboxylates, alkyl ether carboxylates, alkenyl succinates, N-acyl amino acid salts, amide ether carboxylates, and acyl lactates. Can be mentioned. Of these, polycarboxylic acid salts are preferable.
  • polycarboxylic acid salt examples include salts of homopolymers or copolymers containing structural units derived from acrylic acid, methacrylic acid, maleic acid, fumaric acid, itaconic acid, maleic anhydride and the like. Specifically, polyacrylic acid, polymethacrylic acid, polymaleic acid, polymaleic anhydride, maleic acid / isobutylene copolymer, maleic anhydride / isobutylene copolymer, maleic acid / diisobutylene copolymer, maleic anhydride.
  • aliphatic carboxylic acid salt examples include capronate, caprylate, caprinate, laurate, myristate, palmitate, stearate, and oleate having 8 to 8 carbon atoms.
  • examples thereof include aliphatic carboxylates containing 20 alkyl groups.
  • alkyl ether carboxylate examples include (poly) oxyethylene alkyl ether acetate and (poly) oxyethylene alkyl ether propionate. Specifically, oxyethylene oleyl ether acetate, polyoxyethylene lauryl ether acetate, polyoxyethylene stearyl ether acetate, polyoxyethylene hexylphenyl ether acetate, polyoxyethylene tridecyl ether acetate, polyoxyethylene lauryl.
  • Alkyl ether carboxylates containing alkylene groups having 14 to 60 carbon atoms, such as ether propionate and alkyl glycol acetate, can be used.
  • alkenyl succinate examples include an alkenyl succinate (monosalt or disalt) containing an alkenyl group having 8 to 22 carbon atoms.
  • alkenyl succinate examples include an alkenyl succinate (monosalt or disalt) containing an alkenyl group having 8 to 22 carbon atoms.
  • N-acylamino acid salt examples include N-acylglutamic acid salt, N-acylaspartate, N-acyl- ⁇ -alanine salt, N-acylmethylalanine salt, N-acylglycine salt, and N-acylproline salt. And N-acylsarcosine salt and the like.
  • N-lauroyl- ⁇ -alanine arginine, N-lauroyl- ⁇ -alanine potassium, N-lauroyl- ⁇ -alanine triethanolamine, N-lauroyl-N-carboxymethyl- ⁇ -alanine sodium, N- Sodium lauroyl glutamate, disodium N-stearoyl-L-glutamate, sodium N-lauroyl sarcosine and the like can be used.
  • amide ether carboxylate examples include fatty acid alkanol amide ether carboxylic acid salt and polyoxyalkyleneized alkyl amide ether carboxylic acid salt.
  • sulfonic acid-based anionic surfactant examples include alkane sulfonate, ⁇ -olefin sulfonate, alkylbenzene sulfonate, alkylnaphthalene sulfonate, alkyldiphenyl ether disulfonate, alkylglycidyl ether sulfonate, and lignin sulfonic acid.
  • Examples thereof include salts, ⁇ -sulfo fatty acid ester salts, acyl ISEthionates, alkyl sulfosuccinates, alkyl sulfoacetates, N-acylmethyl taurine salts, formalin condensation sulfonates, and melamine sulfonates.
  • alkane sulfonate examples include 1-octane sulfonate, 2-octane sulfonate, 1-decane sulfonate, 2-decane sulfonate, 1-dodecane sulfonate, 2-dodecane sulfonate and the like.
  • Alcan sulfonates having 8 to 18 carbon atoms can be mentioned.
  • Examples of the ⁇ -olefin sulfonate examples include ⁇ -olefin sulfonates having 8 to 18 carbon atoms such as tetradecene sulfonate.
  • alkylbenzene sulfonate examples include p-toluene sulfonate and dodecylbenzene sulfonate.
  • alkylnaphthalene sulfonate examples include monoalkylnaphthalene sulfonate and dialkylnaphthalene sulfonate.
  • Acidates diisopropylnaphthalene sulfonates, dibutylnaphthalene sulfonates, diisobutylnaphthalene sulfonates, methylnonylnaphthalene sulfonates and the like can be used.
  • alkyl diphenyl ether disulfonate examples include alkyl diphenyl ether disulfonates containing an alkyl group having 1 to 20 carbon atoms. Specifically, nonyldiphenyl ether disulfonate, dodecyl diphenyl ether disulfonate, stearyl diphenyl ether disulfonate and the like can be used.
  • ⁇ -sulfofatty acid ester salt include an ⁇ -sulfofatty acid alkyl ester salt 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 acetylate salt include lauroyl citionate and coconut oil fatty acid ethyl ester sulfonate.
  • Examples of the alkyl sulfosuccinate include alkylsulfosuccinates containing an alkyl group having 8 to 18 carbon atoms, such as dioctyl sulfosuccinate, di-2-ethylhexyl sulfosuccinate, and lauryl sulfosuccinate; polyoxyethylene. Examples thereof include polyoxyethylene alkyl sulfosuccinates having 8 to 18 carbon atoms, such as lauryl sulfosuccinic acid salts.
  • alkyl sulfoacetate examples include alkyl sulfoacetates containing an alkyl group having 8 to 18 carbon atoms, such as lauryl sulfo acetate.
  • N-acylmethyl taurine salt examples 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.
  • formalin condensation type sulfonate examples include formalin condensates of naphthalene sulfonate, formalin condensate of alkylnaphthalene sulfonate, formalin condensate of melamine sulfonic acid, formalin condensate of alkyl melamine sulfonic acid and the like. ..
  • sulfate-based anionic surfactant examples include alkyl sulfates, alkyl ether sulfates, alkylaryl ether sulfates, fatty acid alkanolamide sulfates, and fatty acid monoglyceride sulfates.
  • alkyl sulfate examples include lauryl sulfate, stearyl sulfate, cetyl sulfate and the like.
  • alkyl ether sulfate examples include POE lauryl ether sulfate and POE tridecyl ether sulfate.
  • alkylaryl ether sulfate examples include polyoxyethylene nonylphenyl ether sulfate and the like.
  • fatty acid alkanolamide sulfate examples include polyoxyethylene alkyl coconut oil fatty acid monoethanolamide sulfate.
  • fatty acid monoglyceride sulfate examples include hardened coconut oil fatty acid glyceryl sulfate.
  • Examples of the phosphate-based anionic surfactant include alkyl phosphates, polyoxyalkylene alkyl ether phosphates, alkylaryl ether phosphates, fatty acid amide ether phosphates, glycerin fatty acid ester monophosphates, and the like. ..
  • Examples of the alkyl phosphate include lauryl phosphate, myristyl phosphate, palmityl phosphate, stearyl phosphate and the like.
  • polyoxyalkylene alkyl ether phosphate examples include polyoxyethylene lauryl ether phosphate, polyoxyethylene alkyl (C12 to 15) ether phosphate, polyoxyethylene cetyl ether phosphate, and polyoxyethylene oleyl ether phosphorus. Examples thereof include phosphates and polyoxyethylene stearyl ether phosphates. Examples of the alkylaryl ether phosphate include polyoxyethylene nonylphenyl ether phosphate and the like. Examples of the fatty acid amide ether phosphate include polyoxyethylene alkyl monoethanolamide phosphate and the like.
  • anionic surfactant a sulfonic acid-based anionic surfactant is preferable, and an alkylsulfosuccinate is particularly preferable.
  • nonionic surfactant examples include polyoxyalkylene alkyl ether which is an alkylene oxide adduct to an aliphatic alcohol; and polyoxyalkylene phenyl ether or polyoxyalkylene alkyl phenyl ether which is an alkylene oxide adduct to an aromatic alcohol.
  • Polyoxyalkylene aryl ether Polyoxyalkylene aryl ether); glycerin fatty acid ester; polyoxyalkylene glycerin fatty acid ester which is an alkylene oxide adduct to glycerin fatty acid ester; polyoxyalkylene pentaerythritol fatty acid ester which is an alkylene oxide adduct to pentaerythritol fatty acid ester; fatty acid Polyoxyalkylene fatty acid ester which is an alkylene oxide adduct to sorbitan; sorbitan fatty acid ester; polyoxyalkylene sorbitan fatty acid ester which is an alkylene oxide adduct to sorbitan fatty acid ester; sorbitan fatty acid ester; sucrose fatty acid ester; pentaerythritol fatty acid ester; Polyoxyalkylene alkylamine, which is an alkylene oxide adduct to an aliphatic amine
  • the content ratio of the surfactant contained in the deodorant-containing processing liquid of the present invention is the tetravalent metal phosphate 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 salt is 100 parts by mass, it is preferably 0.01 to 30 parts by mass, more preferably 0.05 to 15 parts by mass, and further preferably 0.1 to 10 parts by mass. ..
  • the adhesive component is a component that adheres a deodorant containing a tetravalent metal phosphate to a substrate containing at least one of an inorganic material and an organic material in the manufacture of a deodorant product, and is preferably a polymer. It is a compound and may be any of a synthetic polymer, a semi-synthetic polymer and a natural polymer. Examples of the polymer compound include resins and polysaccharides, and resins are preferable.
  • the adhesive component contained in the deodorant-containing processing liquid of the present invention may be one type or two or more types.
  • the resin may be either a water-soluble resin or a water-insoluble resin, and is an ethylene / vinyl acetate copolymer or a modified product thereof (acid-modified product, etc.), an ethylene / vinyl chloride copolymer, or a vinyl chloride / vinyl acetate copolymer.
  • the polyester resin may be either an aromatic polyester or an aliphatic polyester, and these may be used in combination. Further, the polyester may be either a saturated polyester or an unsaturated polyester.
  • an acid component the saturated polyester is preferably composed of a polycondensate obtained by using the hydroxyl group-containing component, -SO 3 H, -SO 3 Na , -SO 3 -, - COOH, -COO It may be a polyester to which a hydrophilic group such as ⁇ , ⁇ OPO (OH) 2 and ⁇ OPO (OH) O ⁇ is bonded.
  • the acid components 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-.
  • Examples of the acid component having a hydrophilic group include sodium isophthalic acid 5-sulfonate, ammonium isophthalic acid 5-sulfonate, sodium isophthalic acid 4-sulfonate, ammonium isophthalic acid 4-methylsulfonate, and sodium 2-sulfonate.
  • Examples thereof include sulfonate compounds such as terephthalic acid, potassium isophthalic acid 5-sulfonate, potassium isophthalic acid 4-sulfonate, and potassium terephthalic acid 2-sulfonate.
  • hydroxyl group-containing component examples include ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, propylene glycol, dipropylene glycol, 1,3-propanediol, 2-methyl-1,3-propanediol, and 1,4-.
  • the polyester resin can be obtained by a known method such as a melt polymerization method, a solution polymerization method, and a solid phase polymerization method.
  • the hydrophilic group can be introduced by a known method, but when -COO- is introduced, for example, trimellitic anhydride, trimellitic acid, pyromellitic anhydride, pyromellitic acid, trimesic acid, etc.
  • a method of subjecting to a neutralization reaction using an amino compound, ammonia or an alkali metal salt is applied.
  • the molecular weight of the resin is not particularly limited, and known adhesives can be used, but the number average molecular weight is, for example, 1,000 to 1,000,000, and for example, 2,000 to 500,000. Also, for example, 3,000 to 100,000, and for example, 4,000 to 50,000.
  • the adhesive component is preferably water-soluble or hydrophilic (in the case of being water-insoluble).
  • the content ratio of the adhesive component contained in the deodorant-containing processing liquid of the present invention is the total amount of the deodorant containing the phosphate of the tetravalent metal from the viewpoint of the adhesiveness of the deodorant in the obtained deodorant product.
  • it is 100 parts by mass, it is preferably 5 to 1000 parts by mass, more preferably 10 to 500 parts by mass, and further preferably 15 to 100 parts by mass.
  • the deodorant-containing processing liquid of the present invention contains the above-mentioned deodorant containing a tetravalent metal phosphate, a surfactant and an adhesive component as essential components, but is necessary. Other ingredients may be included accordingly.
  • the deodorant-containing processing liquid of the present invention usually contains a medium.
  • the medium include water alone or a mixed solution of water and a water-soluble organic solvent, and water is preferable.
  • the water-soluble organic solvent include alcohols such as methyl alcohol, ethyl alcohol, and isopropyl alcohol.
  • the content ratio of the medium contained in the deodorant-containing processing liquid of the present invention is not particularly limited, but the medium contains the deodorant containing a tetravalent metal phosphate in the deodorant-containing processing liquid. On the other hand, it is preferably contained in an amount of 0.1 to 50% by mass, more preferably 0.5 to 40% by mass, and further preferably 1 to 30% by 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, and more preferably 100 mPa ⁇ s. That is all. Normally, No.
  • the viscosity can be measured at a rotation speed of 60 rpm or 30 rpm using two rotors, but a processing liquid having a viscosity so high that it cannot be measured under the above conditions can also be used. In that case, an appropriate rotor and rotation speed can be appropriately combined for measurement.
  • the upper limit of the viscosity can be preferably 1000 mPa ⁇ s.
  • the deodorant-containing processing liquid of the present invention is suitable for producing a deodorant product having a high amount of a deodorant containing a tetravalent metal phosphate.
  • the viscosity of the deodorant-containing processing liquid of the present invention is appropriately adjusted from the type, structure, particle size, molecular weight, composition ratio, concentration, etc. of each component consisting of the deodorant, the surfactant, the adhesive component, the medium, and the like.
  • a thickener or the like described later as a viscosity modifier for adjustment.
  • the deodorant-containing processing liquid of the present invention may further contain additives as other components.
  • additives include viscosity modifiers such as thickeners, defoamers, colorants, fragrances, antibacterial agents, antiviral agents, antiallergen agents, preservatives and the like.
  • Known thickeners can be used and are 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. Specifically, examples of the polysaccharide 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-based copolymer, sodium salt of acrylic acid-based copolymer, ammonium salt of acrylic acid-based copolymer, and crosslinked type.
  • the amount of the processing liquid component such as the deodorant can be set to an appropriate amount so as not to be excessive, for example. In this case, the productivity of the deodorant processing is improved, which is preferable.
  • the content ratio of the thickener is preferably 0.1 to 10 parts by mass, more preferably 0.7 to 7 parts by mass, when the total amount of the deodorant containing the phosphate of the tetravalent metal is 100 parts by mass. Parts, more preferably 0.5 to 5 parts by mass.
  • the deodorant processing liquid of the present invention As a method for producing the deodorant processing liquid of the present invention, a conventional method may be followed. For example, it can be produced by mixing a medium such as a deodorant containing a tetravalent metal phosphate, a surfactant, an adhesive component, and water. In this case, a deodorant containing a tetravalent metal phosphate, a surfactant and an adhesive component can be added and mixed in a medium such as water for production. As the surfactant, it is preferable to use it as an aqueous solution or an aqueous dispersion. When producing the deodorant processing liquid of the present invention, the raw material components can be agitated under heating, if necessary.
  • the deodorant-containing processing liquid of the present invention is suitable as a material for manufacturing a deodorant product by adhering a deodorant containing a tetravalent metal phosphate to the surface of a base material. ..
  • the method for producing a deodorant product of the present invention is a step of applying a deodorant-containing processing liquid to a base material to form a coating film composed of the deodorant-containing processing liquid on the surface of the base material (hereinafter, "coating film”).
  • a step of drying the coating film hereinafter referred to as a “drying step”.
  • the coating film forming step padding, dipping, coating, spraying, printing, etc. are applied according to the shape of the base material, and a deodorant-containing processing liquid is applied to the surface of the base material to apply the coating film.
  • the base material is not particularly limited, and may be an article containing an inorganic material, an organic material, or a material combining these, and the shape thereof is not particularly limited.
  • resin molded products such as films, granules and general molded products (including foamed resin molded products); fibers; non-woven fabrics containing fibers, sheet-shaped articles such as woven fabrics and the like can be used.
  • the viscosity of the deodorant-containing processing liquid used is 50 mPa ⁇ s or more, the desired amount of the deodorant can be applied without the need for multi-layer coating.
  • 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 the like, and is preferably 100 to 150 ° C.
  • phosphorus of the tetravalent metal can be used.
  • the deodorant product of the present invention is an article comprising a base material and a deodorant-containing portion containing 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.
  • the amount of the phosphate of the tetravalent metal attached is preferably 0.1 g / m 2 or more, more preferably 0.5 g / m 2 or more, from the viewpoint of deodorizing a basic gas such as ammonia gas. is there.
  • the preferred base material in the present invention is a sheet-like article containing fibers, and for example, a deodorant filter medium using a non-woven fabric as a base material is a typical deodorant product.
  • the deodorant filter medium may be one in which tetravalent metal phosphate is adhered only to one side of the non-woven fabric, or one in which tetravalent metal phosphate is adhered to both sides of the non-woven fabric. it can.
  • the fiber (only) is also a preferable base material, and a deodorant fiber in which a tetravalent metal phosphate is attached to the surface of the fiber is also a typical deodorant product.
  • a woven fabric or a non-woven fabric can be produced and used as a deodorant fiber sheet for use as a deodorant filter medium or the like. It can also be applied to clothing such as underwear, socks, and aprons; nursing clothing; daily necessities such as cushions, duvets, blankets, rugs, sofas, curtains, and covers; and processed products such as vehicle seat materials.
  • Deodorant (1) Zirconium phosphate ⁇ -zirconium phosphate, the median diameter measured by Malvern's laser diffraction type particle size distribution measuring device "MS2000" (model name) is 1 ⁇ m, and the BET specific surface area is 10 m 2 Particles that are / g. (2) Copper silicate Particles having a median diameter of 3 ⁇ m and a BET specific surface area of 500 m 2 / g. (3) Zeolite Particles having a median diameter of 3 ⁇ m and a BET specific surface area of 350 m 2 / g. (4) Active zinc oxide Particles having a median diameter of 2 ⁇ m and a BET specific surface area of 100 m 2 / g. (5) Zirconium hydride A particle having a median diameter of 2 ⁇ m and a BET specific surface area of 300 m 2 / g.
  • Adhesive component Saturated polyester resin (number average molecular weight 16,000) was used.
  • Aqueous solution of surfactant or aqueous dispersion (1) Di (2-ethylhexyl) Anionic surfactant "Ricasurf M-30” (trade name) manufactured by New Japan Chemical Co., Ltd., which is an aqueous solution mainly containing sodium sulfosuccinate, is used. There was. (2) “BYK-349” (trade name) manufactured by Big Chemie Japan Co., Ltd., which is an aqueous dispersion mainly containing a polyether-modified siloxane as a nonionic surfactant, was used. (3) A water-soluble acrylic acid-based dispersant "T-50" (trade name) manufactured by Toagosei Co., Ltd. containing an anionic surfactant was used. (4) "DISPERBYK-193" (trade name) manufactured by BYK, which is a nonionic surfactant, was used.
  • Example 2-1-1 Example 1 Zirconium phosphate particles, copper silicate particles, saturated polyester resin, xanthan gum aqueous solution, an aqueous solution of an anionic surfactant (Ricasurf M-30), and pure water are mixed to eliminate the composition shown in Table 1.
  • a processing liquid containing an odorant was produced.
  • the viscosity at 25 ° C. and 60 rpm was measured using a B-type viscometer (No. 2 rotor) manufactured by Toki Sangyo Co., Ltd.
  • a deodorant fiber sheet was produced using this deodorant-containing processing liquid by the method described above, and the deodorant property was evaluated (see Table 1).
  • FIG. 1 is a photograph (300 times) of the state of adhesion of the deodorant to the deodorant fiber sheet manufactured in this manner observed with a scanning electron microscope "S-4800" (hereinafter abbreviated as SEM) manufactured by Hitachi High-Technologies Corporation. And shown in FIG.
  • S-4800 scanning electron microscope
  • Example 2 Zirconium phosphate particles, zeolite particles, saturated polyester resin, CMC aqueous solution, aqueous dispersion of nonionic surfactant (BYK-349), and pure water are mixed to deodorize the composition shown in Table 1.
  • An agent-containing processing liquid was produced. Then, the viscosity was measured in the same manner as in Example 1. Then, a deodorant fiber sheet was manufactured and deodorant property evaluation was performed (see Table 1). Incidentally, impregnated amount of the deodorizing agent in the deodorant fibrous sheet is a zirconium phosphate particles 12 g / m 2 and zeolite particles 12 g / m 2.
  • Example 3 Zirconium phosphate particles, active zinc oxide particles, saturated polyester resin, CMC aqueous solution, an aqueous solution of an anionic surfactant (Ricasurf M-30), and pure water are mixed to eliminate the composition shown in Table 1.
  • a processing liquid containing an odorant was produced. Then, the viscosity was measured in the same manner as in Example 1. Then, a deodorant fiber sheet was manufactured and deodorant property evaluation was performed (see Table 1). Incidentally, impregnated amount of the deodorizing agent in the deodorant fibrous sheet is a zirconium phosphate particles 3 g / m 2 and the active zinc oxide particles 3 g / m 2.
  • Example 4 Zirconium phosphate particles, zirconium hydride particles, saturated polyester resin, CMC aqueous solution, aqueous dispersion of nonionic surfactant (BYK-349), and pure water are mixed and have the configuration shown in Table 1.
  • a processing liquid containing a deodorant was produced. Then, the viscosity was measured in the same manner as in Example 1. Then, a deodorant fiber sheet was manufactured and deodorant property evaluation was performed (see Table 1). The amount of the deodorant attached to the deodorant fiber sheet is 4.5 g / m 2 of zirconium phosphate particles and 14 g / m 2 of zirconium hydride particles.
  • Example 5 Zirconium phosphate particles, copper silicate particles, saturated polyester resin, zirconium hydride particles, xanthan gum aqueous solution, an aqueous solution of an anionic surfactant (Ricasurf M-30), and pure water are mixed and shown in the table.
  • a deodorant-containing processing liquid having the constitution shown in 1 was produced. Then, the viscosity was measured in the same manner as in Example 1. Then, a deodorant fiber sheet was manufactured and deodorant property evaluation was performed (see Table 1).
  • the amount of the deodorant attached to the deodorant fiber sheet is zirconium phosphate particles 4 g / m 2 , copper silicate particles 8 g / m 2, and zirconium hydride particles 4 g / m 2 .
  • Example 6 Zirconium phosphate particles, zirconium hydride particles, active zinc oxide particles, saturated polyester resin, CMC aqueous solution, aqueous dispersion of nonionic surfactant (BYK-349), and pure water are mixed.
  • a deodorant-containing processing liquid having the constitution shown in Table 1 was produced. After that, when the viscosity was measured in the same manner as in Example 1, the viscosity was so high that the measurement was impossible. Therefore, the conditions were set to 25 ° C., 30 rpm, No. Viscosity measurement was performed using 2 rotors. Then, a deodorant fiber sheet was manufactured and deodorant property evaluation was performed (see Table 1).
  • impregnated amount of the deodorizing agent in the deodorant fibrous sheet zirconium phosphate particles 8 g / m 2, a zirconium hydroxide particles 12 g / m 2 and the active zinc oxide particles 6 g / m 2.
  • Example 7 Table 1 shows a mixture of zirconium phosphate particles, copper silicate particles, zeolite particles, saturated polyester resin, xanthan gum aqueous solution, an aqueous solution of an anionic surfactant (Ricasurf M-30), and pure water.
  • a deodorant-containing processing liquid having the composition shown was produced. Then, the viscosity was measured in the same manner as in Example 6. Then, a deodorant fiber sheet was manufactured and deodorant property evaluation was performed (see Table 1). The amount of the deodorant attached to the deodorant fiber sheet is zirconium phosphate particles 3 g / m 2 , copper silicate particles 6 g / m 2, and zeolite particles 12 g / m 2 .
  • Example 8 Zirconium phosphate particles, zirconium hydride particles, zeolite particles, saturated polyester resin, an aqueous solution of xanthan gum, an aqueous dispersion of a nonionic surfactant (BYK-349), and pure water are mixed, and Table 1 A deodorant-containing processing liquid having the composition shown in the above was produced. Then, the viscosity was measured in the same manner as in Example 6. Then, a deodorant fiber sheet was manufactured and deodorant property evaluation was performed (see Table 1).
  • impregnated amount of the deodorizing agent in the deodorant fibrous sheet zirconium phosphate particles 4g / m 2, a zirconium hydroxide particles 10 g / m 2 and zeolite particles 10 g / m 2.
  • 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 have the configuration shown in Table 1.
  • a processing liquid containing a deodorant was produced. Then, the viscosity was measured in the same manner as in Example 1. Then, a deodorant fiber sheet was manufactured and deodorant property evaluation was performed (see Table 1). The amount of the deodorant attached to the deodorant fiber sheet is 2 g / m 2 of zirconium phosphate particles and 6 g / m 2 of copper silicate particles.
  • Example 10 Zirconium phosphate particles, copper silicate particles, saturated polyester resin, an aqueous solution of xanthan gum, an aqueous dispersion of a nonionic surfactant (DISPERBYK-193), and pure water are mixed and have the configurations shown in Table 1.
  • a processing liquid containing a deodorant was produced. Then, the viscosity was measured in the same manner as in Example 1. Then, a deodorant fiber sheet was manufactured and deodorant property evaluation was performed (see Table 1). The amount of the deodorant attached to the deodorant fiber sheet is 2 g / m 2 of zirconium phosphate particles and 6 g / m 2 of copper silicate particles.
  • Example 11 A mixture of zirconium phosphate particles, copper silicate particles, saturated polyester resin, an acrylic thickener (A-20L), an aqueous solution of an anionic surfactant (Ricasurf M-30), and pure water is mixed. , A deodorant-containing processing liquid having the constitution shown in Table 1 was produced. Then, the viscosity was measured in the same manner as in Example 1. Then, a deodorant fiber sheet was manufactured and deodorant property evaluation was performed (see Table 1). The amount of the deodorant attached to the deodorant fiber sheet is 2 g / m 2 of zirconium phosphate particles and 6 g / m 2 of copper silicate particles.
  • Comparative Example 2-2-1 Comparative Example 1 Zirconium phosphate particles, copper silicate particles, saturated polyester resin, and pure water were mixed to produce a deodorant-containing processing liquid having the constitution shown in Table 2. Then, the viscosity was measured in the same manner as in Example 1. Then, a deodorant fiber sheet was manufactured and the deodorant property was evaluated (see Table 2). The amount of the deodorant attached to the deodorant fiber sheet is 2 g / m 2 of zirconium phosphate particles and 6 g / m 2 of copper silicate particles.
  • FIGS. 3 and 4 show photographs (300 times) of the state of adhesion of the deodorant to the deodorant fiber sheet produced in this manner observed by SEM.
  • Comparative Example 5 Zirconium phosphate particles, zirconium hydride particles, saturated polyester resin, an aqueous solution of an anionic surfactant (Ricasurf M-30), and pure water are mixed and processed to contain a deodorant having the composition shown in Table 2. The liquid was produced. Then, the viscosity was measured in the same manner as in Example 1. Then, a deodorant fiber sheet was manufactured and the deodorant property was evaluated (see Table 2). The amount of the deodorant attached to the deodorant fiber sheet is 4.5 g / m 2 of zirconium phosphate particles and 14 g / m 2 of zirconium hydride particles.
  • Comparative Example 8 Zirconium phosphate particles, copper silicate particles, zeolite particles, saturated polyester resin, xanthan gum aqueous solution, and pure water were mixed to produce a deodorant-containing processing liquid having the constitution shown in Table 2. Then, the viscosity was measured in the same manner as in Example 6. Then, a deodorant fiber sheet was manufactured and the deodorant property was evaluated (see Table 2). The amount of the deodorant attached to the deodorant fiber sheet is zirconium phosphate particles 3 g / m 2 , copper silicate particles 6 g / m 2, and zeolite particles 12 g / m 2 .
  • impregnated amount of the deodorizing agent in the deodorant fibrous sheet zirconium phosphate particles 4g / m 2, a zirconium hydroxide particles 10 g / m 2 and zeolite particles 10 g / m 2.
  • Comparative Examples 2, 4, 7 and 8 are examples of a deodorant-containing processing liquid having a viscosity of 50 mPa ⁇ s or more, but are examples in which a surfactant is not used, and the corresponding Examples 1 and 8, respectively. Compared with 3, 6, 7, 9, 10 and 11, the deodorizing property of ammonia gas by zirconium phosphate was not sufficient. Further, Comparative Examples 1, 3, 5, 6 and 9 are examples of deodorant-containing processing liquids having a viscosity of less than 50 mPa ⁇ s, and the appearance of the deodorant fiber sheet is not good, and they correspond to each other. Compared with Examples 2, 4, 5 and 8, the deodorizing property of ammonia gas by zirconium phosphate was not sufficient.
  • FIGS. 1 to 4. 3 and 4 are SEM images of the deodorant fiber sheet of Comparative Example 1 of the deodorant processing liquid having a viscosity of less than 50 mPa ⁇ s, and the deodorant is remarkably on the back surface (FIG. 4) of the deodorant fiber sheet. It is localized and adheres to the fiber surface is non-uniform.
  • the deodorant is present evenly on both the front and back surfaces, and the uniformity of adhesion to the fiber surface is high.
  • the deodorant-containing processing liquid of the present invention is a deodorant product (deodorant filter medium, deodorant paper, deodorant film, etc.) that can be easily applied to various substrates and has excellent deodorizing performance of ammonia gas. Suitable for production.
  • the deodorant filter medium is used as a component of a deodorant mask, a deodorant filter, a deodorizing device, etc., for example, a medical / nursing / excretion site, a sewage treatment plant, a waste treatment plant (incinerator). ), Fertilizer factory, chemical factory, etc.
  • the deodorant product of the present invention can be suitably used for environmental purification in the field where a material that generates ammonia gas from itself is handled.
PCT/JP2020/019349 2019-06-27 2020-05-14 消臭剤含有加工液及びそれを用いた消臭製品の製造方法 WO2020261798A1 (ja)

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