WO2012049978A1 - Antibacterial fiber treatment agent, manufacturing method thereof, and antibacterial fiber manufacturing method - Google Patents

Antibacterial fiber treatment agent, manufacturing method thereof, and antibacterial fiber manufacturing method Download PDF

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Publication number
WO2012049978A1
WO2012049978A1 PCT/JP2011/072499 JP2011072499W WO2012049978A1 WO 2012049978 A1 WO2012049978 A1 WO 2012049978A1 JP 2011072499 W JP2011072499 W JP 2011072499W WO 2012049978 A1 WO2012049978 A1 WO 2012049978A1
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group
antibacterial
carbon atoms
represented
silver
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PCT/JP2011/072499
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French (fr)
Japanese (ja)
Inventor
裕幸 土手
勘藤　芳弘
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松本油脂製薬株式会社
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Priority to JP2012538628A priority Critical patent/JPWO2012049978A1/en
Priority to CN2011800489934A priority patent/CN103154356A/en
Publication of WO2012049978A1 publication Critical patent/WO2012049978A1/en

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    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M16/00—Biochemical treatment of fibres, threads, yarns, fabrics, or fibrous goods made from such materials, e.g. enzymatic
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N25/00—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests
    • A01N25/08—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests containing solids as carriers or diluents
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N25/00—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests
    • A01N25/34—Shaped forms, e.g. sheets, not provided for in any other sub-group of this main group
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N59/00—Biocides, pest repellants or attractants, or plant growth regulators containing elements or inorganic compounds
    • A01N59/16—Heavy metals; Compounds thereof
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M11/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising
    • D06M11/77—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with silicon or compounds thereof
    • D06M11/79—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with silicon or compounds thereof with silicon dioxide, silicic acids or their salts
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M11/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising
    • D06M11/83—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with metals; with metal-generating compounds, e.g. metal carbonyls; Reduction of metal compounds on textiles
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M13/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment
    • D06M13/244—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing sulfur or phosphorus
    • D06M13/282—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing sulfur or phosphorus with compounds containing phosphorus
    • D06M13/292—Mono-, di- or triesters of phosphoric or phosphorous acids; Salts thereof
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M13/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment
    • D06M13/322—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing nitrogen
    • D06M13/35—Heterocyclic compounds
    • D06M13/352—Heterocyclic compounds having five-membered heterocyclic rings
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
    • D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
    • D06M15/37—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • D06M15/53—Polyethers

Definitions

  • the present invention relates to an antibacterial processing agent for fibers used for imparting antibacterial properties to a fiber material, a method for producing the antibacterial processing agent, and a method for producing an antibacterial fiber for imparting the antibacterial processing agent to a fiber material.
  • antibacterial and deodorizing functions are one of the functions that bear that need.
  • antibacterial functions have generally permeated deeply, and it has become natural that product materials are given antibacterial properties.
  • antibacterial processing is especially attracting attention for textile materials used in clothing, bedding and living items.
  • antibacterial agents for imparting antibacterial properties to fiber materials conventionally, quaternary ammonium compounds, pyrithione organic antibacterial agents, antibacterial metals and metal oxides, and further, these are supported on a carrier such as zeolite.
  • An inorganic antibacterial agent is used.
  • inorganic antibacterial agents are widely used for antibacterial processing of fiber materials.
  • silver-based inorganic antibacterial agents are the mainstream of inorganic antibacterial agents currently used because they have a high antibacterial effect, a broad antibacterial spectrum, and high safety to the human body or the environment.
  • the present invention has been made in order to solve the problems in the antibacterial processing of such conventional fiber materials, and is a processing agent applied to the fiber material in post-processing, and imparts excellent antibacterial properties to the fiber material. It is an object of the present invention to provide an antibacterial finishing agent for fibers that can be used and has excellent washing durability, a method for producing the antibacterial finishing agent, and a method for producing an antibacterial fiber to which the antibacterial finishing agent is applied. To do.
  • the present inventors have obtained an antibacterial processing agent for fibers in which a silver-based inorganic antibacterial agent is dispersed in the presence of a specific compound (A) and water. It has been found that excellent antibacterial properties can be imparted to the fiber material and that it is also excellent in washing durability.
  • the antibacterial finishing agent for fibers of the present invention is a silver-based inorganic antibacterial agent obtained by supporting an antibacterial metal containing silver on an inorganic carrier,
  • the compound (A) represented by 1) and water are essential, the silver-based inorganic antibacterial agent is dispersed in water, and the average particle size is 0.01 to 3 ⁇ m.
  • R 1 is a hydrogen atom, a halogen atom, an alkyl group having 1 to 30 carbon atoms, an aryl group having 6 to 30 carbon atoms, an aralkyl group having 7 to 30 carbon atoms, NR 2 R 3 or OR 4 .
  • R 2, R 3 and R 4 are each independently hydrogen atom, an alkyl group having 1 to 30 carbon atoms, an aryl group or an aralkyl group having 7 to 30 carbon atoms of 6 to 30 carbon atoms .
  • M 1 Is a hydrogen atom, an alkali metal or a group represented by NR a R b R c R d , R a , R b , R c and R d are each independently a hydrogen atom, an alkyl group, an alkanol group or It is a polyoxyalkylene group.
  • the inorganic carrier is preferably at least one selected from zeolite, zirconium phosphate, silica gel, apatite, hydrous titanium oxide, montmorillonite, glass powder and potassium titanate winker.
  • the antibacterial processing agent of the present invention further includes a surfactant represented by the following general formula (2), a surfactant represented by the following general formula (3), a surfactant represented by the following general formula (4), and the following: It is preferable to include at least one surfactant (B) selected from surfactants represented by the general formula (5).
  • R 5 is an alkyl group having 1 to 30 carbon atoms, an aryl group having 6 to 30 carbon atoms, or an aralkyl group having 7 to 30 carbon atoms.
  • a 1 O is an oxyalkylene group having 2 to 4 carbon atoms.
  • N is an integer of 0 to 50.
  • m is an integer of 1 to 3.
  • M 2 is a hydrogen atom, an alkali metal, an alkaline earth metal, or a group represented by NR a R b R c R d R a , R b , R c and R d are each independently a hydrogen atom, an alkyl group, an alkanol group or a polyoxyalkylene group.
  • a 2 O is an oxyalkylene group having 2 to 4 carbon atoms, k is an integer of 2 to 70, and q is an integer of 1 to 3)
  • a 3 O is an oxyalkylene group having 2 to 4 carbon atoms, j is an integer of 2 to 70, and r is an integer of 1 to 3.
  • M 3 is a hydrogen atom, an alkali metal , Alkaline earth metal or a group represented by NR a R b R c R d R a , R b , R c and R d are each independently a hydrogen atom, an alkyl group, an alkanol group or a polyoxy group. An alkylene group.
  • a 4 O is an oxyalkylene group having 2 to 4 carbon atoms
  • h is an integer of 2 to 70
  • s is an integer of 1 to 3
  • t is an integer of 1 or 2
  • M 4 is a hydrogen atom, an alkali metal, an alkaline earth metal or a group represented by NR a R b R c R d
  • R a , R b , R c and R d are each independently hydrogen An atom, an alkyl group, an alkanol group or a polyoxyalkylene group.
  • the surfactant (B) is selected from the surfactant represented by the general formula (3), the surfactant represented by the general formula (4), and the surfactant represented by the general formula (5). It is preferable that there is at least one kind.
  • the method for producing an antibacterial processing agent of the present invention includes a step of wet-grinding a silver-based inorganic antibacterial agent in which an antibacterial metal containing silver is supported on an inorganic carrier in the presence of the compound (A) and water,
  • the average particle size of the wet-ground silver-based inorganic antibacterial agent is 0.01 to 3 ⁇ m.
  • the inorganic carrier is at least one selected from zeolite, zirconium phosphate, silica gel, apatite, hydrous titanium oxide, montmorillonite, glass powder, and potassium titanate winker. preferable.
  • the wet pulverization step is preferably a step of wet pulverizing the silver-based inorganic antibacterial agent in the presence of the surfactant (B) in addition to the compound (A) and water.
  • the surfactant (B) is selected from the surfactant represented by the general formula (3), the surfactant represented by the general formula (4), and the surfactant represented by the general formula (5). It is preferable that there is at least one kind.
  • the method for producing an antibacterial fiber of the present invention includes a step of imparting to the fiber material the antibacterial processing agent and / or the antibacterial processing agent obtained by the production method.
  • the antibacterial finishing agent for fibers of the present invention can impart excellent antibacterial properties to fiber materials and is excellent in washing durability.
  • the method for producing an antibacterial processing agent for fibers of the present invention can provide an antibacterial agent for fibers that can impart excellent antibacterial properties to fiber materials and is also excellent in washing durability.
  • the method for producing an antibacterial fiber of the present invention can provide an antibacterial fiber that is excellent in antibacterial properties and excellent in washing durability.
  • the antibacterial processing agent for fibers of the present invention essentially contains a silver-based inorganic antibacterial agent obtained by supporting an antibacterial metal containing silver on an inorganic carrier, the compound (A) represented by the above general formula (1), and water.
  • the silver-based inorganic antibacterial agent is dispersed in water. This will be described in detail below.
  • the silver-based inorganic antibacterial agent is formed by supporting an antibacterial metal containing silver on an inorganic carrier.
  • an inorganic carrier powdery ones are used, and these are commercially available.
  • the inorganic carrier include zeolite, zirconium phosphate, silica gel, apatite, hydrous titanium oxide, montmorillonite, glass powder, and potassium titanate whisker, but are not limited thereto.
  • One inorganic carrier may be used, or two or more inorganic carriers may be used in combination.
  • zeolite, zirconium phosphate, silica gel, apatite, montmorillonite, glass powder and potassium titanate whisker are preferable, and zeolite, zirconium phosphate, apatite and potassium titanate whisker are more preferable.
  • the antibacterial metal carried on the inorganic carrier contains silver essential.
  • silver alone may be supported, or an antibacterial metal other than silver and silver may be supported in combination.
  • the antibacterial metal other than silver include copper, zinc, mercury, lead, bismuth, cadmium, chromium, cobalt, nickel and the like, and one kind may be used or two or more kinds may be used in combination.
  • copper, zinc, lead, bismuth, cobalt, and nickel are preferable.
  • the method for supporting an antibacterial metal containing silver on an inorganic carrier is not particularly limited, and a known method can be adopted.
  • a method of forming an antibacterial metal thin film on the surface of an inorganic carrier by vapor deposition, dissolution precipitation reaction, sputtering, or the like are preferable.
  • the weight ratio of silver supported on the inorganic carrier is preferably 0.01 to 20 parts by weight, more preferably 0.03 to 10 parts by weight, and further 0.05 to 7 parts by weight with respect to 100 parts by weight of the inorganic carrier. preferable.
  • the weight ratio of silver is less than 0.01 part by weight, antibacterial properties may not be exhibited.
  • the weight ratio of silver exceeds 20 parts by weight, all of the silver may not be supported on the inorganic carrier, and the unsupported silver has very low adhesion to the fiber, and exhibits excellent antibacterial properties and washing durability. There is a risk of not.
  • the silver-based inorganic antibacterial agent include, for example, one in which silver is ion-bonded and supported on zeolite, one in which silver is supported on zirconium phosphate by ion exchange, one in which silver is supported on silica gel, apatite
  • silver is supported by ion exchange, silver is supported on hydrous titanium oxide, silver is supported on montmorillonite, silver is supported on glass powder, silver is supported on potassium titanate whiskers.
  • the antibacterial processing agent for fibers of the present invention contains the compound (A) in order to impart excellent antibacterial properties and washing durability to the fiber material.
  • the compound (A) is a compound represented by the general formula (1).
  • R 1 represents a hydrogen atom, a halogen atom, an alkyl group having 1 to 30 carbon atoms, an aryl group having 6 to 30 carbon atoms, an aralkyl group having 7 to 30 carbon atoms, NR 2 R 3 , OR 4 It is.
  • R 2 , R 3 and R 4 are each independently a hydrogen atom, an alkyl group having 1 to 30 carbon atoms, an aryl group having 6 to 30 carbon atoms or an aralkyl group having 7 to 30 carbon atoms.
  • R 1 having higher hydrophilicity can impart antibacterial properties and washing durability superior as an antibacterial agent. From these points, R 1 is preferably a hydrogen atom, a halogen atom, an alkyl group having 1 to 30 carbon atoms, NR 2 R 3 , or OR 4 , and a hydrogen atom, an alkyl group having 1 to 30 carbon atoms, NR 2 R 3 and OR 4 are more preferable, and a hydrogen atom, NR 2 R 3 and OR 4 are more preferable.
  • halogen atom examples include fluorine, chlorine, bromine and iodine.
  • R 1 is an alkyl group, an aryl group, or an aralkyl group
  • the number of carbon atoms of the alkyl group is preferably 1-20, more preferably 1-14, and still more preferably 1-8.
  • Examples of such alkyl groups include octyl, decyl, lauryl, tridecyl, isotridecyl, cetyl, stearyl, oleyl, and behenyl groups.
  • the number of carbon atoms of the aryl group is preferably 6 to 22, more preferably 6 to 16, and still more preferably 6 to 10.
  • Examples of such an aryl group include a phenyl group, a biphenyl group, a naphthyl group, an anthryl group, and a phenanthryl group.
  • the number of carbon atoms in the aralkyl group is preferably 7 to 22, more preferably 7 to 16, and still more preferably 6 to 10.
  • Examples of such an aralkyl group include a benzyl group, a phenylethyl group, a methylbenzyl group, and a naphthylmethyl group.
  • the aryl group and aralkyl group may have a substituent, and the number of carbon atoms of the substituent is preferably 1 to 30, more preferably 1 to 20, and further preferably 1 to 10.
  • substituents include methyl, ethyl, t-butyl, octyl, nonyl, lauryl, decyl, tridecyl, isotridecyl, cetyl, stearyl, oleyl, behenyl, styryl. Groups and the like.
  • the number of such substituents may be one or plural, and in the case of plural, plural kinds of substituents may be mixed.
  • R 2 , R 3 and R 4 are an alkyl group, an aryl group or an aralkyl group are the same as those for R 1 .
  • M 1 is a hydrogen atom, an alkali metal, an alkaline earth metal, or a group represented by NR a R b R c R d .
  • M 1 is preferably a hydrogen atom, an alkali metal, or a group represented by NR a R b R c R d from the viewpoint that excellent antibacterial properties and washing durability can be imparted, and an alkali metal, NR a R b A group represented by R c R d is more preferable.
  • R a , R b , R c and R d are each independently a hydrogen atom, an alkyl group, an alkanol group or a polyoxyalkylene group.
  • the alkyl group preferably has 1 to 30 carbon atoms, more preferably 1 to 10 carbon atoms. Examples of such an alkyl group include a methyl group, an ethyl group, an n-propyl group, and an isopropyl group.
  • the carbon number of the alkanol group is preferably 1-30, and more preferably 1-10.
  • Examples of such an alkanol group include a methanol group, an ethanol group, an n-propanol group, and an isopropanol group.
  • the polyoxyalkylene group preferably has 2 to 4 carbon atoms. Examples of such a polyoxyalkylene group include a polyoxyethylene group and a polyoxypropylene group.
  • the antibacterial finishing agent for fibers of the present invention includes a surfactant represented by the above general formula (2), a surfactant represented by the above general formula (3), a surfactant represented by the above general formula (4), and the above It is preferable to further contain at least one surfactant (B) selected from surfactants represented by the general formula (5).
  • the surfactant (B) it is possible to improve the dispersibility of the silver-based inorganic antibacterial agent and the temporal stability of the dispersion of the silver-based inorganic antibacterial agent. Sex can be imparted.
  • the surfactant (B) is selected from the surfactant represented by the general formula (3), the surfactant represented by the general formula (4), and the surfactant represented by the general formula (5). It is preferably at least one selected from the group consisting of a surfactant represented by the general formula (3) and a surfactant represented by the general formula (4). More preferably, it is a surfactant represented by (3).
  • R 5 is an alkyl group having 1 to 30 carbon atoms, an aryl group having 6 to 30 carbon atoms, or an aralkyl group having 7 to 30 carbon atoms. is there. Preferred ranges and examples of the alkyl group, aryl group and aralkyl group are the same as those described for R 1 . Among these, from the viewpoint of improving the dispersibility of the silver-based inorganic antibacterial agent and the stability over time, R 1 is preferably an alkyl group or an aralkyl group, and more preferably an alkyl group.
  • a 1 O is an oxyalkylene group having 2 to 4 carbon atoms.
  • the number of carbon atoms is preferably 2 to 3, and more preferably 2.
  • a 1 O may be one type or two or more types, and in the case of two or more types, A 1 O may constitute any of a block adduct, an alternating adduct, or a random adduct.
  • a 1 O preferably contains an oxyethylene group essentially from the viewpoint of improving the dispersibility of the silver-based inorganic antibacterial agent and the stability over time.
  • the proportion of the oxyethylene group in the entire oxyalkylene group is preferably 40 mol% or more, more preferably 50 mol%, still more preferably 60 mol% or more, and particularly preferably 80 mol% or more.
  • n is an integer of 0 to 50. From the viewpoint of improving the dispersibility and stability over time of the silver-based inorganic antibacterial agent, n is preferably 1 to 45, more preferably 2 to 40, and particularly preferably 3 to 35. m is an integer of 1 to 3, and preferably 1 or 2.
  • M 2 is a hydrogen atom, an alkali metal, an alkaline earth metal, or a group represented by NR a R b R c R d .
  • R a , R b , R c and R d are each independently a hydrogen atom, an alkyl group, an alkanol group or a polyoxyalkylene group.
  • the group represented by alkali metal, alkaline earth metal, or NR a R b R c R d is the same as that described for compound (A).
  • M 2 is preferably an alkali metal, a group represented by NR a R b R c R d , and more preferably an alkali metal. preferable.
  • the phosphoric acid ester compound which is the surfactant represented by the general formula (2) may be any of phosphoric acid triester, phosphoric acid diester, and phosphoric acid monoester, or a mixture thereof.
  • the production method of the phosphate ester compound is not particularly limited, and a known method can be adopted.
  • a method for producing a phosphoric acid ester compound a method is generally known in which a phosphorylation reaction is performed with raw alcohol and phosphoric anhydride, and then, in some cases, the phosphoric acid ester compound is obtained by neutralization. Yes.
  • diesters and monoesters can be roughly prepared separately by changing the charged molar ratio of the raw material alcohol and phosphoric anhydride.
  • phosphoric anhydride 1: 1 (molar ratio)
  • a 2 O is an oxyalkylene group having 2 to 4 carbon atoms.
  • the number of carbon atoms is preferably 2 to 3, and more preferably 2.
  • a 2 O may be one type or two or more types, and in the case of two or more types, A 2 O may constitute any of a block adduct, an alternating adduct, or a random adduct.
  • a 2 O preferably contains an oxyethylene group essentially from the viewpoint of improving the dispersibility of the silver-based inorganic antibacterial agent and the stability over time.
  • the proportion of the oxyethylene group in the entire oxyalkylene group is preferably 40 mol% or more, more preferably 50 mol%, still more preferably 60 mol% or more, and particularly preferably 80 mol% or more.
  • q is 1 to 3, and 2 to 3 is preferable from the viewpoint of improving the dispersibility and stability over time of the silver-based inorganic antibacterial agent.
  • k is an integer of 2 to 70. From the viewpoint of improving the dispersibility and stability over time of the silver-based inorganic antibacterial agent, k is preferably 3 to 60, more preferably 4 to 50, and even more preferably 5 to 40.
  • a 3 O is an oxyalkylene group having 2 to 4 carbon atoms.
  • the number of carbon atoms is preferably 2 to 3, and more preferably 2.
  • a 3 O may be one type or two or more types, and in the case of two or more types, A 3 O may constitute any of a block adduct, an alternating adduct, or a random adduct.
  • a 3 O preferably contains an oxyethylene group essential from the viewpoint of improving the dispersibility of the silver-based inorganic antibacterial agent and the stability over time.
  • the proportion of the oxyethylene group in the entire oxyalkylene group is preferably 40 mol% or more, more preferably 50 mol%, still more preferably 60 mol% or more, and particularly preferably 80 mol% or more.
  • r is 1 to 3, and 2 to 3 is preferable from the viewpoint of improving the dispersibility and stability over time of the silver-based inorganic antibacterial agent.
  • j is an integer of 2 to 70. From the viewpoint of improving the dispersibility and stability over time of the silver-based inorganic antibacterial agent, j is preferably from 3 to 60, more preferably from 4 to 50, and even more preferably from 5 to 40.
  • M 3 is a hydrogen atom, an alkali metal, an alkaline earth metal or a group represented by NR a R b R c R d .
  • R a , R b , R c and R d are each independently a hydrogen atom, an alkyl group, an alkanol group or a polyoxyalkylene group.
  • M 3 is preferably an alkali metal, a group represented by NR a R b R c R d , and more preferably an alkali metal. preferable.
  • a 4 O is an oxyalkylene group having 2 to 4 carbon atoms.
  • the number of carbon atoms is preferably 2 to 3, and more preferably 2.
  • a 4 O may be one type or two or more types, and in the case of two or more types, A 4 O may constitute any of a block adduct, an alternating adduct, or a random adduct.
  • a 4 O preferably contains an oxyethylene group essential from the viewpoint of improving the dispersibility of the silver-based inorganic antibacterial agent and the stability over time.
  • the proportion of the oxyethylene group in the entire oxyalkylene group is preferably 40 mol% or more, more preferably 50 mol%, still more preferably 60 mol% or more, and particularly preferably 80 mol% or more.
  • s is an integer of 1 to 3, and preferably 2 to 3 from the viewpoint of improving the dispersibility and stability over time of the silver-based inorganic antibacterial agent.
  • t is an integer of 1 or 2
  • 2 is preferable from the viewpoint of improving the dispersibility of the silver-based inorganic antibacterial agent and the stability over time.
  • h is an integer of 2 to 70. From the viewpoint of improving the dispersibility and stability over time of the silver-based inorganic antibacterial agent, h is preferably 3 to 60, more preferably 4 to 50, and even more preferably 5 to 40.
  • M 4 is a hydrogen atom, an alkali metal, an alkaline earth metal, or a group represented by NR a R b R c R d .
  • R a , R b , R c and R d are each independently a hydrogen atom, an alkyl group, an alkanol group or a polyoxyalkylene group.
  • the group represented by alkali metal, alkaline earth metal, or NR a R b R c R d is the same as that described for compound (A).
  • M 4 is preferably an alkali metal, a group represented by NR a R b R c R d , and more preferably an alkali metal. preferable.
  • the antibacterial finishing agent for fibers of the present invention is used for imparting antibacterial properties to fiber materials. That is, it is an antibacterial processing agent to be applied to the fiber material in post-processing.
  • the antibacterial processing agent of the present invention is obtained by dispersing the silver-based inorganic antibacterial agent having an average particle size of 0.01 to 3 ⁇ m in the presence of the compound (A) and water. With such a configuration, it is possible to impart excellent antibacterial properties to the fiber material, and even when the processed fiber material is washed, it is possible to prevent a decrease in antibacterial properties and to have excellent washing durability. It has the effect. Although it is not clear about this effect
  • the compound (X) represented by the following general formula (6) is generated by the silver-based inorganic antibacterial agent and the compound (A) exchange-reacting silver atoms.
  • Compound (X) is produced in a larger amount by wet-grinding the silver-based inorganic antibacterial agent in the presence of compound (A) and water and dispersing it to a predetermined average particle size as described later. It is presumed that The produced compound (X) is more organic than silver-based inorganic antibacterial agents, so it has good adhesion to the fiber material, and also holds silver ions, so it has antibacterial properties and washing durability. It is thought that there is.
  • the antibacterial processing agent of the present invention has an excellent effect that even if the agent is applied to the fiber material, yellowing (coloring) of the fiber material due to silver ions can be prevented.
  • R 1 represents a hydrogen atom, a halogen atom, an alkyl group having 1 to 30 carbon atoms, an aryl group having 6 to 30 carbon atoms, an aralkyl group having 7 to 30 carbon atoms, NR 2 R 3 or OR 4 It is.
  • R 2 , R 3 and R 4 are each independently a hydrogen atom, an alkyl group having 1 to 30 carbon atoms, an aryl group having 6 to 30 carbon atoms or an aralkyl group having 7 to 30 carbon atoms.
  • R 1 , R 2 , R 3 and R 4 are the same as those described for the compound (A).
  • the average particle size of the silver-based inorganic antibacterial agent is 0.01 to 3 ⁇ m, preferably 0.03 to 2 ⁇ m, more preferably 0.05 to 1.5 ⁇ m, still more preferably 0.1 to 1 ⁇ m, and 0.1 ⁇ 1 ⁇ m is particularly preferred.
  • the average particle size used in the present invention is a value obtained by measuring the volume-based median particle size using a laser diffraction / scattering particle size distribution measuring apparatus LA-910 (manufactured by Horiba, Ltd.).
  • the compounding ratio of the compound (A) is preferably 0.1 to 10000 parts by weight, more preferably 0.5 to 5000 parts by weight, with respect to 100 parts by weight of the silver-based inorganic antibacterial agent. Part by weight is more preferable, and 2 to 100 parts by weight is particularly preferable.
  • the blending ratio of the surfactant (B) is preferably 0.01 to 200 parts by weight, more preferably 0.1 to 100 parts by weight, with respect to 100 parts by weight of the silver-based inorganic antibacterial agent. 5 to 70 parts by weight is more preferable, and 1 to 50 parts by weight is particularly preferable.
  • the antibacterial processing agent of the present invention essentially contains water.
  • the water used in the present invention may be any of pure water, distilled water, purified water, soft water, ion exchange water, tap water and the like.
  • Other components other than the above components may be included as long as the effects of the present invention are not impaired.
  • Other components include antibacterial agents, fungicides, insecticides, acaricides, deodorants, antistatic agents, water and oil repellents, UV absorbers, flame retardants, antifouling agents, deep colorants, and smoothing agents.
  • post-processing agents for fibers such as softeners or water-absorbing agents, oil agents, surfactants, inorganic substances, preservatives, pH adjusters, antifoaming agents, solvents, fatty acids (salts) and the like.
  • the antibacterial processing agent of the present invention may contain a binder resin as long as the effects of the present invention are not impaired.
  • the texture of the fiber material may be reduced.
  • the blending ratio of the binder resin is preferably 20 parts by weight or less, more preferably 10 parts by weight or less, and more preferably 5 parts by weight or less with respect to 100 parts by weight of the silver-based inorganic antibacterial agent. More preferred is 0 part by weight.
  • binder resin polyvinyl acetate, polyglycerin, polyvinyl alcohol, polysaccharide compounds, melamine compounds, glyoxal compounds, urethane compounds, blocked isocyanate compounds, silicon compounds, acrylic resins, polyester resins Examples thereof include resins and acrylic resins containing silicon.
  • polysaccharide compounds include starch and carboxymethyl cellulose.
  • melamine compounds include synthetic resins obtained by polymerizing melamine and formaldehyde.
  • Examples of the glyoxal compound include glyoxal.
  • Examples of the urethane compound include a compound obtained by reacting a compound having two or more active hydrogens reactive with an isocyanate group and a polyisocyanate.
  • examples of the compound having two or more active hydrogens include polyhydric alcohols, compounds having a carboxyl group and two hydroxyl groups, and polyamines.
  • examples of the polyisocyanate include aliphatic diisocyanate, alicyclic diisocyanate, and aromatic diisocyanate.
  • the compound which blocked a part of the isocyanate group with sodium bisulfite, methyl ethyl ketoxime, etc. can also be used.
  • blocked isocyanate compounds sodium bisulfite, acetylacetone, ethyl acetoacetate, diethylmalonate, etc. are reacted with isocyanate groups to form temporarily stable compounds, which are then dissociated by heat treatment to regenerate isocyanate groups. Obtained by reacting at least one compound containing at least one blocked isocyanate group in the molecule with a (meth) acrylic compound, a silicon-modified (meth) acrylic compound or a fluorine-modified (meth) acrylic compound And the like.
  • the silicon compound include condensation-crosslinking resins classified into silicone resins or silicone varnishes. This condensation-crosslinking resin can be obtained by polycondensing one or two or more silane compounds selected from silane compounds such as tetraethoxysilane and methyltrimethoxysilane.
  • acrylic resin examples include one or two or more types of (meth) acrylic monomers such as (meth) acrylate monomers such as acrylic acid, methacrylic acid, methyl (meth) acrylate, and n-butyl (meth) acrylate. Examples thereof include a polymer and a copolymer with another vinyl monomer copolymerizable with these (meth) acrylic monomers.
  • the polyester resin examples include polyethylene terephthalate, polybutylene terephthalate, polyethylene isophthalate / terephthalate copolycondensate, and the like.
  • acrylic resin containing silicon examples include a polycondensate of a (meth) acrylic acid ester monomer and an organopolysiloxane compound.
  • the concentration of the nonvolatile content of the antibacterial processing agent of the present invention is preferably 0.0001 to 90% by weight, more preferably 0.0005 to 70% by weight, and further preferably 0.001 to 50% by weight.
  • medical agent of this invention contains not only the chemical
  • the non-volatile content in the present invention refers to an absolutely dry component when a sample is heat treated at 105 ° C. to remove the solvent and the like and reach a constant weight.
  • the method for producing an antibacterial processing agent for fibers according to the present invention includes a step of wet-grinding the silver-based inorganic antibacterial agent in the presence of the compound (A) and water.
  • the wet pulverization method is not particularly limited, and a known method can be adopted.
  • a slurry solution is prepared by mixing and stirring the compound (A), water, and an unground silver-based inorganic antibacterial agent.
  • the compounding ratio of the compound (A) is preferably 0.1 to 10000 parts by weight, more preferably 0.5 to 5000 parts by weight, with respect to 100 parts by weight of the silver-based inorganic antibacterial agent. Part by weight is more preferable, and 2 to 100 parts by weight is particularly preferable.
  • the compounding ratio of the compound (A) is less than 0.1 parts by weight, it is estimated that the compound (X) is also produced in a small amount, and it may be difficult to develop the durability to washing. Furthermore, yellowing (coloring) due to silver ions may not be prevented.
  • the weight ratio of the nonvolatile content of the slurry is preferably 1 to 90% by weight, more preferably 3 to 70% by weight, and further preferably 5 to 50% by weight. If it is less than 1% by weight, the antibacterial component in the antibacterial processing agent may be small, and the treated fiber may not exhibit antibacterial properties. If it exceeds 90% by weight, aggregation of the silver-based inorganic antibacterial agent may occur over time, and it may be difficult to exhibit excellent antibacterial properties and washing durability.
  • the slurry liquid prepared is passed through a wet pulverizer such as a bead mill, a sand grinder, an attritor, or a ball mill, and finely divided until the average particle size becomes 0.1 to 3 ⁇ m.
  • a wet pulverizer such as a bead mill, a sand grinder, an attritor, or a ball mill.
  • the preferred range of the average particle size of the finely divided silver-based inorganic antibacterial agent and the method for measuring the average particle size are the same as those described for the antibacterial processing agent.
  • the wet pulverization process include a continuous process such as a pass system or a tank internal circulation system, and a batch process.
  • the step is a step of wet-grinding the silver-based inorganic antibacterial agent in the presence of the surfactant (B) in addition to the compound (A) and water.
  • the surfactant (B) in addition to the compound (A) and water.
  • it is a step of preparing a slurry liquid by mixing and stirring the compound (A), the surfactant (B), water and unmilled silver-based inorganic antibacterial agent, and finely pulverizing the slurry liquid with a wet pulverizer. Is preferred.
  • the surfactant (B) is at least one selected from a surfactant represented by the general formula (3), a surfactant represented by the general formula (4), and a surfactant represented by the general formula (5). It is preferable that it is at least one selected from a surfactant represented by the general formula (3) and a surfactant represented by the general formula (4), and is represented by the general formula (3). More preferably, it is a surfactant.
  • the blending ratio of the surfactant (B) is preferably 0.01 to 200 parts by weight, more preferably 0.1 to 100 parts by weight, with respect to 100 parts by weight of the silver-based inorganic antibacterial agent. 5 to 70 parts by weight is more preferable, and 1 to 50 parts by weight is particularly preferable.
  • the antibacterial processing agent thus obtained is presumed to produce more compound (X) as described above. And by attaching the antibacterial processing agent containing the finely divided silver-based inorganic antibacterial agent, compound (A) and compound (X) to the fiber material, excellent antibacterial properties can be imparted and washing durability It is presumed that there is an effect that it is excellent. Furthermore, the antibacterial finishing agent obtained by the production method of the present invention has an excellent effect that even if the agent is applied to the fiber material, yellowing (coloring) of the fiber material due to silver ions can be prevented. Yes.
  • the method for producing an antibacterial fiber of the present invention includes a step of applying to the fiber material an antibacterial processing agent of the present invention and / or an antibacterial processing agent obtained by the production method of the present invention. That is, the manufacturing method of the antibacterial fiber of this invention includes the process of providing an antibacterial processing chemical
  • the fiber material may be either natural fiber or chemical fiber.
  • natural fibers include plant fibers such as cotton, cannabis, flax, palm, and rush; animal fibers such as wool, goat wool, mohair, cashmere, camel, and silk; and mineral fibers such as asbestos.
  • Examples of the chemical fiber include inorganic fibers such as rock fiber, metal fiber, graphite, silica, and titanate; regenerated cellulosic fibers such as rayon, cupra, viscose, polynosic, and purified cellulose fiber; melt-spun cellulose fiber; Protein fibers such as milk protein and soybean protein; Regenerated and semi-synthetic fibers such as regenerated silk and alginate fiber; Polyamide fiber, Polyester fiber, Cationic dyeable polyester fiber, Polyvinyl fiber, Polyacrylic alcohol fiber, Polyurethane fiber, Acrylic fiber, Examples thereof include synthetic fibers such as polyethylene fibers, polyvinylidene fibers, and polystyrene fibers.
  • inorganic fibers such as rock fiber, metal fiber, graphite, silica, and titanate
  • regenerated cellulosic fibers such as rayon, cupra, viscose, polynosic, and purified cellulose fiber
  • melt-spun cellulose fiber Protein fibers such as milk protein and soybean protein
  • a water-absorbing fiber is preferably a plant fiber, an animal fiber, a regenerated cellulose fiber, a melt-spun cellulose fiber, or a fiber in which these are combined from the viewpoint of easily exhibiting antibacterial properties.
  • Examples of the form of the fiber material include forms such as a woven fabric, a knitted fabric, a fabric, a thread shape, and a non-woven fabric.
  • Examples of the use of the fiber material include objects that impart antibacterial properties, water absorption, and washing resistance, such as underwear, sports clothing, bedding, and covers.
  • the method for applying the antibacterial agent to the fiber material is not particularly limited, and a known method can be employed. Among these, at least one method selected from the exhaust method, the pad dry method, the spray method, and the coating method is preferable, and the pad dry method is more preferable because the antibacterial processing agent is securely fixed to the fiber material.
  • the exhaust method is a method in which a diluted solution of a drug is used, conditions such as temperature, immersion time, number of times of liquid circulation, etc. are set, and the drug is selectively adsorbed on a fiber to be exhausted and adhered. Thereafter, washing is usually carried out, followed by centrifugal dehydration and drying.
  • the pad dry method is a method in which fibers are immersed in a drug solution for a short time and immediately attached by squeezing with a dehydrated mangle or the like. Then, drying is performed and curing is performed as necessary.
  • the spray method is a method in which fibers are placed on a conveyor at a constant speed and adhered by spraying a predetermined amount of a solution of the drug from the fiber. Then, drying is performed and curing is performed as necessary.
  • the coating method is a method in which a drug solution is usually applied by applying from one side with a mangle. Then, the excess drug is scraped off with a doctor, dried, and cured if necessary.
  • the weight ratio of the non-volatile content of the antibacterial processing agent (processing solution) when applied to the fiber material is preferably 0.0001 to 10% by weight, more preferably 0.0005 to 7% by weight, and 0.001 to 5% by weight. % Is more preferable.
  • the predetermined weight ratio can be prepared by diluting with water or the like.
  • the temperature at which the antibacterial processing agent of the present invention is applied to the fiber material is preferably 5 to 40 ° C. If the application temperature is lower than 5 ° C., it may be difficult to maintain the constant temperature, and thus it may not be possible to apply the constant to the fiber material. On the other hand, when the application temperature is higher than 40 ° C., the elution of dyes contained in the fiber material may increase.
  • the fiber material to which the antibacterial processing agent has been applied is dried by a method such as tensionless or applying tension, whereby the antibacterial fiber of the present invention can be obtained.
  • the tensionless drying method include a non-touch dryer, a short loop dryer, a tensionless roller type, and a cylinder dryer.
  • the method of applying a tension and drying include a pin tenter and a clip tenter.
  • the drying temperature is not particularly limited, but is preferably 100 ° C. or higher and more preferably 110 to 200 ° C. in order to fix the antibacterial processing agent to the fiber material. When the drying temperature is lower than 100 ° C., the antibacterial processing agent may not adhere to the fiber material.
  • the amount of the non-volatile component of the antibacterial processing agent applied to the fiber material is not particularly limited, but is preferably 0.01 to 20% by weight, more preferably 0.03 to 15% by weight, more preferably 0.05 to the fiber material. More preferred is ⁇ 10% by weight. If the amount is less than 0.01% by weight, the antibacterial component in the antibacterial processing agent may be a small amount, and the treated fiber may not exhibit antibacterial properties. If it exceeds 20% by weight, no further improvement in antibacterial properties and washing durability is observed, which may be economically disadvantageous.
  • Processes that can be processed at the same time include insecticides, fungicides, mites, deodorants, antistatic agents, water and oil repellents, UV absorbers, flame retardants, antifouling agents, deep colorants, smoothing agents
  • insecticides insecticides
  • fungicides mites, deodorants, antistatic agents, water and oil repellents
  • UV absorbers flame retardants
  • antifouling agents deep colorants
  • smoothing agents etc. which provide a softener or a water absorbing agent.
  • Example 1 As shown in the mixing ratio of Table 1, 200 parts by weight of silver-based inorganic antibacterial agent 1 in which an antibacterial metal containing silver is ion-bonded to zeolite, 20 parts by weight of benzotriazole, and 780 parts by weight of soft water are added to the stirrer. A slurry liquid was prepared by stirring and dispersing. The silver-based inorganic antibacterial agent 1 contains 2.4% by weight of silver element and 5.2% by weight of zinc with respect to the whole antibacterial agent.
  • the slurry liquid was made into fine particles for 4 hours using Starmill ZRS (manufactured by Ashizawa Finetech Co., Ltd.) to obtain an antibacterial agent for fibers having an average particle diameter of the silver-based inorganic antibacterial agent of 0.4 ⁇ m.
  • the average particle size was measured by the following method.
  • medical agent stability was evaluated by the following method. The results are shown in Table 1.
  • water was added to the antibacterial processing agent to prepare a processing solution having a nonvolatile content of 1% by weight. Cotton broad (100% cotton plain weave) was immersed in this processing solution and squeezed with mangle. At this time, the adhesion amount of the processing solution to the fiber was 80% by weight.
  • the adhesion amount with respect to the fiber was calculated by the following formula.
  • Amount of adhesion to fiber (% by weight) (weight of cotton broad including processing solution ⁇ weight of raw cotton broad) / weight of raw cotton broad ⁇ 100
  • the cotton broad band containing this aqueous solution was dried with a pin tenter at 110 ° C. for 3 minutes to obtain a target sample (antibacterial fiber).
  • the antibacterial properties, washing durability, texture and yellowing of the obtained samples were evaluated by the following methods. The results are shown in Table 1.
  • the antibacterial processing agent is diluted with distilled water so that the weight ratio of the non-volatile content is 3% by weight, and this diluted solution is volume-based using a laser diffraction / scattering particle size distribution measuring apparatus LA-910 (manufactured by Horiba). The median particle size was measured.
  • ⁇ 10% or more and less than 20% of the aqueous dispersion is precipitated.
  • X 20% or more of the aqueous dispersion is precipitated.
  • Antibacterial property was measured according to the SEK unification test method (JIS L1902, bacteria absorption method).
  • JIS L1902 bacteria absorption method
  • Staphylococcus aureus was used as a test bacterium, and the growth value at that time was 2.1, which satisfied the test establishment condition.
  • the SEK unified test method in order to have antibacterial properties, the following conditions must be satisfied.
  • Antibacterial criteria Bactericidal activity value ⁇ 0
  • Antibacterial deodorization standard bacteriostatic activity value ⁇ 2.2
  • JIS L 0217 103 using a JAFET standard detergent at a rate of 3 g / L, washing with water at 40 ° C. for 5 minutes at a bath ratio of 1:30, then rinsing twice at 40 ° C. for 2 minutes, and centrifugal dehydration After that, the work of drying in the shade was defined as one cycle, and this was performed for 10 cycles.
  • ⁇ Texture> The texture of the obtained sample was evaluated by touch. In addition, the evaluation of the texture was determined by classifying into the following four stages based on the following criteria.
  • ⁇ Yellowing> The sample was left in an incubator adjusted to a temperature of 70 ° C. and a humidity of 90% for 4 days to evaluate yellowing. Evaluation of yellowing was performed using a spectrocolorimeter (CM-3600d, manufactured by Konica Minolta) and measuring ⁇ YI with reference to an unprocessed cotton broad cloth. If the evaluation criterion was ⁇ YI ⁇ 5, it was regarded as not yellowing.
  • CM-3600d manufactured by Konica Minolta
  • Example 2 to 5, 8 to 11, 14 to 36 Examples 2 to 5, 8 to 11, and 14 to 36 were the same as Example 1 except that slurry liquids were prepared by changing the slurry liquid of Example 1 to the components and blending ratios shown in Tables 1 to 3. And evaluated. The results are shown in Tables 1 to 3.
  • Silver-based inorganic antibacterial agent 2 is a silver-based inorganic antibacterial agent in which an antibacterial metal containing silver is ion-bonded to zeolite, and 1.2% by weight of silver element and 2. It contains 6% by weight.
  • Silver-based inorganic antibacterial agent 3 is a silver-based inorganic antibacterial agent in which an antibacterial metal containing silver is ion-bonded to zeolite, and 0.5% by weight of silver element and 1.1% of zinc with respect to the whole antibacterial agent % Content.
  • the silver-based inorganic antibacterial agent 4 is a silver-based inorganic antibacterial agent in which an antibacterial metal containing silver is ion-bonded to zirconium phosphate. 0.5% by weight of silver element and 1. It contains 1% by weight.
  • Example 6 and 7 are antibacterial processing agents in which the slurry liquid of Example 1 is finely divided by a star mill ZRS for 2 hours and 3 hours, respectively, and the average particle diameter of the silver-based inorganic antibacterial agent 1 is 1.3 ⁇ m and 2.6 ⁇ m. Evaluation was carried out in the same manner as in Example 1 except that the above was obtained. The results are shown in Table 1.
  • Example 12 and 13 water was added to the antibacterial processing agent for fibers of Example 1, and a processing solution was prepared in which the weight ratios of nonvolatile components were 0.1% by weight and 0.001% by weight, respectively. Evaluation was performed in the same manner as in Example 1. The results are shown in Table 1.
  • Comparative Examples 1 to 4 were evaluated in the same manner as in Example 1 except that the antibacterial processing agent of Example 1 was changed to the following antibacterial processing agent. The results are shown in Table 4.
  • Antibacterial finishing agents of Comparative Examples 1 to 4 Each component was added to a stirrer in the blending ratio shown in Table 4, and sufficiently stirred and dispersed to prepare antibacterial finishing agents of Comparative Examples 1 to 4, respectively.
  • the average particle diameters of the antibacterial processing agents of Comparative Examples 1 to 4 were 4.1 ⁇ m, 4.2 ⁇ m, 4.1 ⁇ m, and 4.1 ⁇ m, respectively.
  • Examples 1A, 8A, 14A, 15A, 16A, 27A, 32A are the antibacterial agents used for evaluating the stability of Examples 1, 8, 14, 15, 16, 27, and 32 (temperature 70 ° C, left for 1 week). Antibacterial properties were measured in the same manner as in Example 1 except that the performed drug was used. The results are shown in Table 5.
  • the fiber material to which the antibacterial agent for fibers of the present invention has been applied has excellent antibacterial properties and maintains its antibacterial properties even after washing (has washing durability). I understand). In addition, the texture does not decrease. Furthermore, it is excellent also about yellowing.
  • the use of the surfactant (B) is effective in improving the dispersibility of the silver-based inorganic antibacterial agent and improving the temporal stability of the dispersion of the silver-based inorganic antibacterial agent. . Furthermore, it can be seen from Table 5 that more excellent antibacterial properties and washing durability can be imparted.
  • the antibacterial processing agent of the present invention can be suitably used for imparting antibacterial properties to fiber materials.

Abstract

Disclosed is an antibacterial fiber treatment agent which wash-durable and capable of imparting excellent antibacterial properties to a fiber material; also disclosed are a manufacturing method of said antibacterial treatment agent, and a method of manufacturing antibacterial fiber treated with said antibacterial treatment agent. The disclosed antibacterial fiber treatment agent necessarily contains a silver-based inorganic antibacterial agent in which a silver-containing antibacterial metal is carried on an inorganic carrier, a compound (A) represented by general formula (1), and water, and is in a state in which said silver-based inorganic antibacterial agent is dispersed in water with an average particle diameter of 0.01-3μm.

Description

繊維用抗菌加工薬剤とその製造方法及び抗菌性繊維の製造方法Antibacterial finishing agent for fibers, method for producing the same and method for producing antibacterial fibers
　本発明は、繊維材料に抗菌性を付与するために用いられる繊維用抗菌加工薬剤と該抗菌加工薬剤の製造方法、及び該抗菌加工薬剤を繊維材料に付与する抗菌性繊維の製造方法に関する。 The present invention relates to an antibacterial processing agent for fibers used for imparting antibacterial properties to a fiber material, a method for producing the antibacterial processing agent, and a method for producing an antibacterial fiber for imparting the antibacterial processing agent to a fiber material.
　近年、快適性や衛生面が重視され、そのニーズを担う機能の一つに抗菌機能・防臭機能がある。今や抗菌機能は一般に根強く浸透し、商品素材に抗菌性を付与していることが当然のようになってきている。抗菌性を付与する素材の中でも、特に衣類や寝具・リビング品などに使われている繊維材料への抗菌加工が注目されている。 In recent years, emphasis has been placed on comfort and hygiene, and antibacterial and deodorizing functions are one of the functions that bear that need. Nowadays, antibacterial functions have generally permeated deeply, and it has become natural that product materials are given antibacterial properties. Among the materials that impart antibacterial properties, antibacterial processing is especially attracting attention for textile materials used in clothing, bedding and living items.
　繊維材料に抗菌性を付与する抗菌剤としては、従来から、第４級アンモニウム系化合物やピリチオン系の有機抗菌剤、抗菌性を有する金属や金属酸化物、更にこれらをゼオライト等の担体に担持させてなる無機抗菌剤が用いられている。このような抗菌剤の中でも、無機抗菌剤は繊維材料の抗菌加工に広く用いられている。特に銀系無機抗菌剤は、抗菌効果が高く、広い抗菌スペクトルを有し、かつ人体または環境への安全性が高いとの理由から、現在使用されている無機抗菌剤の主流となっている。 As antibacterial agents for imparting antibacterial properties to fiber materials, conventionally, quaternary ammonium compounds, pyrithione organic antibacterial agents, antibacterial metals and metal oxides, and further, these are supported on a carrier such as zeolite. An inorganic antibacterial agent is used. Among such antibacterial agents, inorganic antibacterial agents are widely used for antibacterial processing of fiber materials. In particular, silver-based inorganic antibacterial agents are the mainstream of inorganic antibacterial agents currently used because they have a high antibacterial effect, a broad antibacterial spectrum, and high safety to the human body or the environment.
　繊維材料に抗菌性を付与する方法としては、繊維材料の製造段階における紡糸原液に抗菌剤を予め練り込む方法、抗菌剤を後加工にて繊維材料に付与する方法等が知られている。 As a method for imparting antibacterial properties to a fiber material, a method in which an antibacterial agent is kneaded in advance into a spinning dope in the production stage of the fiber material, a method in which the antibacterial agent is imparted to the fiber material by post-processing, etc. are known.
　紡糸原液に抗菌剤を予め練り込む方法では、樹脂内部に入った抗菌剤は全く効果が出ないばかりでなく、樹脂表面近傍の抗菌剤の多くは樹脂被覆により充分な抗菌効果を発揮できないこと、溶融紡糸段階で糸切れを起こすことがある。抗菌効果を高める目的で抗菌剤を多く添加したときは、繊維の物理的性質が損なわれたり、繊維が不透明になったりしやすい。逆に抗菌剤の添加量が少ないときは、抗菌効果が充分に発揮されない。このように、紡糸原液に抗菌剤を予め練り込む方法には、多くの問題点がある。 In the method in which the antibacterial agent is kneaded in advance in the spinning dope, not only the antibacterial agent inside the resin is ineffective, but many of the antibacterial agents in the vicinity of the resin surface cannot exhibit a sufficient antibacterial effect by the resin coating Thread breakage may occur at the melt spinning stage. When a large amount of an antibacterial agent is added for the purpose of enhancing the antibacterial effect, the physical properties of the fiber are easily lost or the fiber is likely to become opaque. Conversely, when the amount of the antibacterial agent added is small, the antibacterial effect is not sufficiently exhibited. As described above, there are many problems in the method of kneading the antibacterial agent into the spinning dope in advance.
　このような理由から、優れた抗菌性を付与するためには、抗菌剤を後加工にて繊維材料に付与する方法が望ましいが、繊維材料に対する抗菌剤の固着力が不足し、洗濯耐久性が劣るという問題点があった。この問題を解決するために、例えば、特許文献１の抗菌性繊維の製造法が提案されているが、加工条件により洗濯耐久性を得ているものであり、使用されている抗菌加工薬剤自体は、優れた洗濯耐久性を有するものではなかった。さらに、この方法は複雑な工程・条件を必要とし、現実的ではなかった。 For these reasons, in order to impart excellent antibacterial properties, it is desirable to apply an antibacterial agent to the fiber material by post-processing, but the antibacterial agent has insufficient adhesive strength to the fiber material, and the washing durability is low. There was a problem of being inferior. In order to solve this problem, for example, the method for producing an antibacterial fiber of Patent Document 1 has been proposed. However, the antibacterial processing agent itself is used because it has obtained washing durability depending on processing conditions. It did not have excellent washing durability. Furthermore, this method requires complicated processes and conditions and is not practical.
日本国特開平７－２４３１８０号公報Japanese Unexamined Patent Publication No. 7-243180
　本発明は、かかる従来の繊維材料の抗菌加工における問題を解決するためになされたものであり、後加工にて繊維材料に付与する加工薬剤であり、繊維材料に対して優れた抗菌性を付与することができ、さらに洗濯耐久性にも優れている繊維用抗菌加工薬剤、該抗菌加工薬剤の製造方法、及び該抗菌加工薬剤が付与された抗菌性繊維の製造方法を提供することを目的とする。 The present invention has been made in order to solve the problems in the antibacterial processing of such conventional fiber materials, and is a processing agent applied to the fiber material in post-processing, and imparts excellent antibacterial properties to the fiber material. It is an object of the present invention to provide an antibacterial finishing agent for fibers that can be used and has excellent washing durability, a method for producing the antibacterial finishing agent, and a method for producing an antibacterial fiber to which the antibacterial finishing agent is applied. To do.
　本発明者らは、上記の課題を解決するために鋭意検討した結果、特定の化合物（Ａ）及び水の存在下、銀系無機抗菌剤が分散されてなる繊維用抗菌加工薬剤であれば、繊維材料に対して、優れた抗菌性を付与することができ、さらに洗濯耐久性にも優れていることを見出した。 As a result of intensive studies to solve the above problems, the present inventors have obtained an antibacterial processing agent for fibers in which a silver-based inorganic antibacterial agent is dispersed in the presence of a specific compound (A) and water. It has been found that excellent antibacterial properties can be imparted to the fiber material and that it is also excellent in washing durability.
　すなわち、本発明の繊維用抗菌加工薬剤（以下、「抗菌加工薬剤」ということがある）は、無機担体に銀を含有する抗菌性金属を担持させてなる銀系無機抗菌剤、下記一般式（１）で示される化合物（Ａ）及び水を必須に含み、該銀系無機抗菌剤が水に分散された状態であり、かつその平均粒子径が０．０１～３μｍである。
Figure JPOXMLDOC01-appb-C000011
 （式中、Ｒ１は、水素原子、ハロゲン原子、炭素数１～３０のアルキル基、炭素数６～３０のアリール基、炭素数７～３０のアラルキル基、ＮＲ２Ｒ３又はＯＲ４である。Ｒ２、Ｒ３及びＲ４は、それぞれ独立して、水素原子、炭素数１～３０のアルキル基、炭素数６～３０のアリール基または炭素数７～３０のアラルキル基である。Ｍ１は、水素原子、アルカリ金属又はＮＲａＲｂＲｃＲｄで示される基である。Ｒａ、Ｒｂ、Ｒｃ及びＲｄは、それぞれ独立して、水素原子、アルキル基、アルカノール基又はポリオキシアルキレン基である。） That is, the antibacterial finishing agent for fibers of the present invention (hereinafter sometimes referred to as “antibacterial finishing agent”) is a silver-based inorganic antibacterial agent obtained by supporting an antibacterial metal containing silver on an inorganic carrier, The compound (A) represented by 1) and water are essential, the silver-based inorganic antibacterial agent is dispersed in water, and the average particle size is 0.01 to 3 μm.
Figure JPOXMLDOC01-appb-C000011
 (Wherein R 1 is a hydrogen atom, a halogen atom, an alkyl group having 1 to 30 carbon atoms, an aryl group having 6 to 30 carbon atoms, an aralkyl group having 7 to 30 carbon atoms, NR 2 R 3 or OR 4 . .R 2, R 3 and R 4 are each independently hydrogen atom, an alkyl group having 1 to 30 carbon atoms, an aryl group or an aralkyl group having 7 to 30 carbon atoms of 6 to 30 carbon atoms .M 1 Is a hydrogen atom, an alkali metal or a group represented by NR a R b R c R d , R a , R b , R c and R d are each independently a hydrogen atom, an alkyl group, an alkanol group or It is a polyoxyalkylene group.)
　前記無機担体は、ゼオライト、リン酸ジルコニウム、シリカゲル、アパタイト、含水酸化チタン、モンモリロナイト、ガラス粉末及びチタン酸カリウムウインスカーから選ばれる少なくとも１種であることが好ましい。 The inorganic carrier is preferably at least one selected from zeolite, zirconium phosphate, silica gel, apatite, hydrous titanium oxide, montmorillonite, glass powder and potassium titanate winker.
　本発明の抗菌加工薬剤は、さらに、下記一般式（２）で示される界面活性剤、下記一般式（３）で示される界面活性剤、下記一般式（４）で示される界面活性剤及び下記一般式（５）で示される界面活性剤から選ばれる少なくとも１種の界面活性剤（Ｂ）を含むことが好ましい。 The antibacterial processing agent of the present invention further includes a surfactant represented by the following general formula (2), a surfactant represented by the following general formula (3), a surfactant represented by the following general formula (4), and the following: It is preferable to include at least one surfactant (B) selected from surfactants represented by the general formula (5).
Figure JPOXMLDOC01-appb-C000012
 （式中、Ｒ５は、炭素数１～３０のアルキル基、炭素数６～３０のアリール基又は炭素数７～３０のアラルキル基である。Ａ１Ｏは炭素数２～４のオキシアルキレン基である。ｎは０～５０の整数である。ｍは１～３の整数である。Ｍ２は、水素原子、アルカリ金属、アルカリ土類金属又はＮＲａＲｂＲｃＲｄで示される基である。Ｒａ、Ｒｂ、Ｒｃ及びＲｄは、それぞれ独立して、水素原子、アルキル基、アルカノール基又はポリオキシアルキレン基である。）
Figure JPOXMLDOC01-appb-C000012
 (Wherein R 5 is an alkyl group having 1 to 30 carbon atoms, an aryl group having 6 to 30 carbon atoms, or an aralkyl group having 7 to 30 carbon atoms. A 1 O is an oxyalkylene group having 2 to 4 carbon atoms. N is an integer of 0 to 50. m is an integer of 1 to 3. M 2 is a hydrogen atom, an alkali metal, an alkaline earth metal, or a group represented by NR a R b R c R d R a , R b , R c and R d are each independently a hydrogen atom, an alkyl group, an alkanol group or a polyoxyalkylene group.)
Figure JPOXMLDOC01-appb-C000013
 （式中、Ａ２Ｏは、炭素数２～４のオキシアルキレン基であり、ｋは２～７０の整数であり、ｑは１～３の整数である。）
Figure JPOXMLDOC01-appb-C000013
 (Wherein A 2 O is an oxyalkylene group having 2 to 4 carbon atoms, k is an integer of 2 to 70, and q is an integer of 1 to 3)
Figure JPOXMLDOC01-appb-C000014
 （式中、Ａ３Ｏは、炭素数２～４のオキシアルキレン基であり、ｊは２～７０の整数であり、ｒは１～３の整数である。Ｍ３は、水素原子、アルカリ金属、アルカリ土類金属又はＮＲａＲｂＲｃＲｄで示される基である。Ｒａ、Ｒｂ、Ｒｃ及びＲｄは、それぞれ独立して、水素原子、アルキル基、アルカノール基又はポリオキシアルキレン基である。）
Figure JPOXMLDOC01-appb-C000014
 (Wherein A 3 O is an oxyalkylene group having 2 to 4 carbon atoms, j is an integer of 2 to 70, and r is an integer of 1 to 3. M 3 is a hydrogen atom, an alkali metal , Alkaline earth metal or a group represented by NR a R b R c R d R a , R b , R c and R d are each independently a hydrogen atom, an alkyl group, an alkanol group or a polyoxy group. An alkylene group.)
Figure JPOXMLDOC01-appb-C000015
 （式中、Ａ４Ｏは、炭素数２～４のオキシアルキレン基であり、ｈは２～７０の整数であり、ｓは１～３の整数であり、ｔは１又は２の整数である。Ｍ４は、水素原子、アルカリ金属、アルカリ土類金属又はＮＲａＲｂＲｃＲｄで示される基である。Ｒａ、Ｒｂ、Ｒｃ及びＲｄは、それぞれ独立して、水素原子、アルキル基、アルカノール基又はポリオキシアルキレン基である。）
Figure JPOXMLDOC01-appb-C000015
 (In the formula, A 4 O is an oxyalkylene group having 2 to 4 carbon atoms, h is an integer of 2 to 70, s is an integer of 1 to 3, and t is an integer of 1 or 2) M 4 is a hydrogen atom, an alkali metal, an alkaline earth metal or a group represented by NR a R b R c R d R a , R b , R c and R d are each independently hydrogen An atom, an alkyl group, an alkanol group or a polyoxyalkylene group.)
　前記界面活性剤（Ｂ）は、前記一般式（３）で示される界面活性剤、前記一般式（４）で示される界面活性剤及び前記一般式（５）で示される界面活性剤から選ばれる少なくとも１種であるであることが好ましい。 The surfactant (B) is selected from the surfactant represented by the general formula (3), the surfactant represented by the general formula (4), and the surfactant represented by the general formula (5). It is preferable that there is at least one kind.
　本発明の抗菌加工薬剤の製造方法は、前記化合物（Ａ）及び水の存在下、無機担体に銀を含有する抗菌性金属を担持させてなる銀系無機抗菌剤を湿式粉砕する工程を含み、湿式粉砕された銀系無機抗菌剤の平均粒子径が０．０１～３μｍである。 The method for producing an antibacterial processing agent of the present invention includes a step of wet-grinding a silver-based inorganic antibacterial agent in which an antibacterial metal containing silver is supported on an inorganic carrier in the presence of the compound (A) and water, The average particle size of the wet-ground silver-based inorganic antibacterial agent is 0.01 to 3 μm.
　本発明の抗菌加工薬剤の製造方法において、前記無機担体は、ゼオライト、リン酸ジルコニウム、シリカゲル、アパタイト、含水酸化チタン、モンモリロナイト、ガラス粉末及びチタン酸カリウムウインスカーから選ばれる少なくとも１種であることが好ましい。 In the method for producing an antibacterial processing agent of the present invention, the inorganic carrier is at least one selected from zeolite, zirconium phosphate, silica gel, apatite, hydrous titanium oxide, montmorillonite, glass powder, and potassium titanate winker. preferable.
　前記湿式粉砕する工程は、前記化合物（Ａ）及び水に加え、前記界面活性剤（Ｂ）の存在下、前記銀系無機抗菌剤を湿式粉砕する工程であることが好ましい。前記界面活性剤（Ｂ）は、前記一般式（３）で示される界面活性剤、前記一般式（４）で示される界面活性剤及び前記一般式（５）で示される界面活性剤から選ばれる少なくとも１種であるであることが好ましい。 The wet pulverization step is preferably a step of wet pulverizing the silver-based inorganic antibacterial agent in the presence of the surfactant (B) in addition to the compound (A) and water. The surfactant (B) is selected from the surfactant represented by the general formula (3), the surfactant represented by the general formula (4), and the surfactant represented by the general formula (5). It is preferable that there is at least one kind.
　本発明の抗菌性繊維の製造方法は、前記の抗菌加工薬剤及び／又は前記の製造方法で得られる抗菌加工薬剤を繊維材料に付与する工程を含むものである。 The method for producing an antibacterial fiber of the present invention includes a step of imparting to the fiber material the antibacterial processing agent and / or the antibacterial processing agent obtained by the production method.
　本発明の繊維用抗菌加工薬剤は、繊維材料に対して優れた抗菌性を付与することができ、洗濯耐久性にも優れている。
　本発明の繊維用抗菌加工薬剤の製造方法は、繊維材料に対して優れた抗菌性を付与することができ、洗濯耐久性にも優れている繊維用抗菌加工薬剤を得ることができる。
　また、本発明の抗菌性繊維の製造方法は、抗菌性が優れ、洗濯耐久性にも優れた抗菌性繊維を得ることができる。 The antibacterial finishing agent for fibers of the present invention can impart excellent antibacterial properties to fiber materials and is excellent in washing durability.
The method for producing an antibacterial processing agent for fibers of the present invention can provide an antibacterial agent for fibers that can impart excellent antibacterial properties to fiber materials and is also excellent in washing durability.
In addition, the method for producing an antibacterial fiber of the present invention can provide an antibacterial fiber that is excellent in antibacterial properties and excellent in washing durability.
　本発明の繊維用抗菌加工薬剤は、無機担体に銀を含有する抗菌性金属を担持させてなる銀系無機抗菌剤、上記一般式（１）で示される化合物（Ａ）及び水を必須に含み、該銀系無機抗菌剤が水に分散されてなるものである。以下に、詳細に説明する。 The antibacterial processing agent for fibers of the present invention essentially contains a silver-based inorganic antibacterial agent obtained by supporting an antibacterial metal containing silver on an inorganic carrier, the compound (A) represented by the above general formula (1), and water. The silver-based inorganic antibacterial agent is dispersed in water. This will be described in detail below.
［銀系無機抗菌剤］
　銀系無機抗菌剤は、無機担体に銀を含有する抗菌性金属を担持させてなるものである。
　無機担体としては、粉末状のものが用いられ、これらは市販されている。無機担体としては、例えば、ゼオライト、リン酸ジルコニウム、シリカゲル、アパタイト、含水酸化チタン、モンモリロナイト、ガラス粉末、チタン酸カリウムウイスカー等を挙げることができるが、これらに限定されるものではない。無機担体は１種でもよく、２種以上を併用してもよい。これら無機担体の中でも、ゼオライト、リン酸ジルコニウム、シリカゲル、アパタイト、モンモリロナイト、ガラス粉末、チタン酸カリウムウイスカーが好ましく、ゼオライト、リン酸ジルコニウム、アパタイト、チタン酸カリウムウイスカーがさらに好ましい。 [Silver inorganic antibacterial agent]
The silver-based inorganic antibacterial agent is formed by supporting an antibacterial metal containing silver on an inorganic carrier.
As the inorganic carrier, powdery ones are used, and these are commercially available. Examples of the inorganic carrier include zeolite, zirconium phosphate, silica gel, apatite, hydrous titanium oxide, montmorillonite, glass powder, and potassium titanate whisker, but are not limited thereto. One inorganic carrier may be used, or two or more inorganic carriers may be used in combination. Among these inorganic carriers, zeolite, zirconium phosphate, silica gel, apatite, montmorillonite, glass powder and potassium titanate whisker are preferable, and zeolite, zirconium phosphate, apatite and potassium titanate whisker are more preferable.
　無機担体に担持させる抗菌性金属は、銀を必須に含有するものである。抗菌性金属としては、銀単独を担持させてもよく、銀と銀以外の抗菌性金属を併用して担持させてもよい。銀以外の抗菌性金属としては、例えば、銅、亜鉛、水銀、鉛、ビスマス、カドミウム、クロム、コバルト、ニッケル等を挙げることができ、１種でもよく、２種以上を併用してもよい。銀以外の抗菌性金属を併用する場合、銅、亜鉛、鉛、ビスマス、コバルト、ニッケルが好ましい。 The antibacterial metal carried on the inorganic carrier contains silver essential. As an antibacterial metal, silver alone may be supported, or an antibacterial metal other than silver and silver may be supported in combination. Examples of the antibacterial metal other than silver include copper, zinc, mercury, lead, bismuth, cadmium, chromium, cobalt, nickel and the like, and one kind may be used or two or more kinds may be used in combination. When using an antibacterial metal other than silver, copper, zinc, lead, bismuth, cobalt, and nickel are preferable.
　無機担体に銀を含有する抗菌性金属を担持させる方法は、特に限定はなく、公知の方法を採用できる。例えば、物理吸着又は化学吸着により抗菌性金属を担持させる方法、イオン交換反応により抗菌性金属を担持させる方法、結合剤により抗菌性金属を担持させる方法、抗菌性金属を無機化合物に打ち込むことにより担持させる方法、蒸着、溶解析出反応、スパッタ等により無機担体の表面に抗菌性金属の薄膜を形成して担持させる方法等が挙げられる。これらの中でも、物理吸着又は化学吸着により抗菌性金属を担持させる方法、イオン交換反応により抗菌性金属を担持させる方法が好ましい。 The method for supporting an antibacterial metal containing silver on an inorganic carrier is not particularly limited, and a known method can be adopted. For example, a method of supporting an antibacterial metal by physical adsorption or chemical adsorption, a method of supporting an antibacterial metal by an ion exchange reaction, a method of supporting an antibacterial metal by a binder, or a method of supporting an antibacterial metal by implanting it into an inorganic compound And a method of forming an antibacterial metal thin film on the surface of an inorganic carrier by vapor deposition, dissolution precipitation reaction, sputtering, or the like. Among these, a method for supporting an antibacterial metal by physical adsorption or chemical adsorption and a method for supporting an antibacterial metal by ion exchange reaction are preferable.
　無機担体に担持させる銀の重量割合は、無機担体１００重量部に対して、０．０１～２０重量部が好ましく、０．０３～１０重量部がより好ましく、０．０５～７重量部がさらに好ましい。銀の重量割合が０．０１重量部未満の場合、抗菌性を発現しない可能性がある。銀の重量割合が２０重量部超の場合、銀全てが無機担体に担持しない可能性があり、担持していない銀は繊維への固着が非常に低く、優れた抗菌性及び洗濯耐久性が発揮しないおそれがある。 The weight ratio of silver supported on the inorganic carrier is preferably 0.01 to 20 parts by weight, more preferably 0.03 to 10 parts by weight, and further 0.05 to 7 parts by weight with respect to 100 parts by weight of the inorganic carrier. preferable. When the weight ratio of silver is less than 0.01 part by weight, antibacterial properties may not be exhibited. When the weight ratio of silver exceeds 20 parts by weight, all of the silver may not be supported on the inorganic carrier, and the unsupported silver has very low adhesion to the fiber, and exhibits excellent antibacterial properties and washing durability. There is a risk of not.
　銀系無機抗菌剤の好ましい具体例として、例えば、ゼオライトに銀をイオン結合させて担持させたもの、リン酸ジルコニウムにイオン交換によって銀を担持させたもの、シリカゲルに銀を担持させたもの、アパタイトにイオン交換によって銀を担持させたもの、含水酸化チタンに銀を担持させたもの、モンモリロナイトに銀を担持させたもの、ガラス粉末に銀を担持させたもの、チタン酸カリウムウィスカーに銀を担持させたもの等を挙げることができる。 Preferable specific examples of the silver-based inorganic antibacterial agent include, for example, one in which silver is ion-bonded and supported on zeolite, one in which silver is supported on zirconium phosphate by ion exchange, one in which silver is supported on silica gel, apatite In this case, silver is supported by ion exchange, silver is supported on hydrous titanium oxide, silver is supported on montmorillonite, silver is supported on glass powder, silver is supported on potassium titanate whiskers. Can be mentioned.
［化合物（Ａ）］
　本発明の繊維用抗菌加工薬剤は、繊維材料に優れた抗菌性及び洗濯耐久性を付与するために、化合物（Ａ）を必須に含むものである。化合物（Ａ）は、上記一般式（１）で示される化合物である。式（１）中、Ｒ１は、水素原子、ハロゲン原子、炭素数１～３０のアルキル基、炭素数６～３０のアリール基、炭素数７～３０のアラルキル基、ＮＲ２Ｒ３、ＯＲ４である。Ｒ２、Ｒ３及びＲ４は、それぞれ独立して、水素原子、炭素数１～３０のアルキル基、炭素数６～３０のアリール基又は炭素数７～３０のアラルキル基である。
　Ｒ１は、親水性が高くなる方が、抗菌加工薬剤として優れた抗菌性及び洗濯耐久性を付与できる。このような点から、Ｒ１としては、水素原子、ハロゲン原子、炭素数１～３０のアルキル基、ＮＲ２Ｒ３、ＯＲ４が好ましく、水素原子、炭素数１～３０のアルキル基、ＮＲ２Ｒ３、ＯＲ４がより好ましく、水素原子、ＮＲ２Ｒ３、ＯＲ４がさらに好ましい。 [Compound (A)]
The antibacterial processing agent for fibers of the present invention contains the compound (A) in order to impart excellent antibacterial properties and washing durability to the fiber material. The compound (A) is a compound represented by the general formula (1). In formula (1), R 1 represents a hydrogen atom, a halogen atom, an alkyl group having 1 to 30 carbon atoms, an aryl group having 6 to 30 carbon atoms, an aralkyl group having 7 to 30 carbon atoms, NR 2 R 3 , OR 4 It is. R 2 , R 3 and R 4 are each independently a hydrogen atom, an alkyl group having 1 to 30 carbon atoms, an aryl group having 6 to 30 carbon atoms or an aralkyl group having 7 to 30 carbon atoms.
R 1 having higher hydrophilicity can impart antibacterial properties and washing durability superior as an antibacterial agent. From these points, R 1 is preferably a hydrogen atom, a halogen atom, an alkyl group having 1 to 30 carbon atoms, NR 2 R 3 , or OR 4 , and a hydrogen atom, an alkyl group having 1 to 30 carbon atoms, NR 2 R 3 and OR 4 are more preferable, and a hydrogen atom, NR 2 R 3 and OR 4 are more preferable.
　ハロゲン原子としては、フッ素、塩素、臭素、よう素等が挙げられる。 Examples of the halogen atom include fluorine, chlorine, bromine and iodine.
　Ｒ１がアルキル基、アリール基、アラルキル基の場合、優れた抗菌性及び洗濯耐久性を付与できる点から、それぞれの基の炭素数としては、次の範囲が好ましい。
　アルキル基の炭素数としては、１～２０が好ましく、１～１４がより好ましく、１～８がさらに好ましい。このようなアルキル基としては、たとえば、オクチル基、デシル基、ラウリル基、トリデシル基、イソトリデシル基、セチル基、ステアリル基、オレイル基、ベヘニル基等を挙げることができる。
　アリール基の炭素数としては、６～２２が好ましく、６～１６がより好ましく、６～１０がさらに好ましい。このようなアリール基としては、たとえば、フェニル基、ビフェニル基、ナフチル基、アントリル基、フェナントリル基等を挙げることができる。
　アラルキル基の炭素数としては、７～２２が好ましく、７～１６がより好ましく、６～１０がさらに好ましい。このようなアラルキル基としては、たとえば、ベンジル基、フェニルエチル基、メチルベンジル基、ナフチルメチル基等を挙げることができる。 When R 1 is an alkyl group, an aryl group, or an aralkyl group, the following ranges are preferable as the carbon number of each group from the viewpoint that excellent antibacterial properties and washing durability can be imparted.
The number of carbon atoms of the alkyl group is preferably 1-20, more preferably 1-14, and still more preferably 1-8. Examples of such alkyl groups include octyl, decyl, lauryl, tridecyl, isotridecyl, cetyl, stearyl, oleyl, and behenyl groups.
The number of carbon atoms of the aryl group is preferably 6 to 22, more preferably 6 to 16, and still more preferably 6 to 10. Examples of such an aryl group include a phenyl group, a biphenyl group, a naphthyl group, an anthryl group, and a phenanthryl group.
The number of carbon atoms in the aralkyl group is preferably 7 to 22, more preferably 7 to 16, and still more preferably 6 to 10. Examples of such an aralkyl group include a benzyl group, a phenylethyl group, a methylbenzyl group, and a naphthylmethyl group.
　なお、上記アリール基及びアラルキル基は、置換基を有していてもよく、置換基の炭素数は、１～３０が好ましく、１～２０がより好ましく、１～１０がさらに好ましい。このような置換基としては、メチル基、エチル基、ｔ－ブチル基、オクチル基、ノニル基、ラウリル基、デシル基、トリデシル基、イソトリデシル基、セチル基、ステアリル基、オレイル基、ベヘニル基、スチリル基等が挙げられる。このような置換基の数は１つであっても複数であってもよく、複数の場合に複数種の置換基が混在していてもよい。 The aryl group and aralkyl group may have a substituent, and the number of carbon atoms of the substituent is preferably 1 to 30, more preferably 1 to 20, and further preferably 1 to 10. Such substituents include methyl, ethyl, t-butyl, octyl, nonyl, lauryl, decyl, tridecyl, isotridecyl, cetyl, stearyl, oleyl, behenyl, styryl. Groups and the like. The number of such substituents may be one or plural, and in the case of plural, plural kinds of substituents may be mixed.
　Ｒ２、Ｒ３及びＲ４がアルキル基、アリール基、アラルキル基である場合の例示や好ましい炭素数は、Ｒ１と同様である。 Examples and preferred carbon numbers when R 2 , R 3 and R 4 are an alkyl group, an aryl group or an aralkyl group are the same as those for R 1 .
　式（１）中、Ｍ１は、水素原子、アルカリ金属、アルカリ土類金属又はＮＲａＲｂＲｃＲｄで示される基である。これらの中でも、優れた抗菌性及び洗濯耐久性を付与できる点から、Ｍ１は、水素原子、アルカリ金属、ＮＲａＲｂＲｃＲｄで示される基が好ましく、アルカリ金属、ＮＲａＲｂＲｃＲｄで示される基がさらに好ましい。 In Formula (1), M 1 is a hydrogen atom, an alkali metal, an alkaline earth metal, or a group represented by NR a R b R c R d . Among these, M 1 is preferably a hydrogen atom, an alkali metal, or a group represented by NR a R b R c R d from the viewpoint that excellent antibacterial properties and washing durability can be imparted, and an alkali metal, NR a R b A group represented by R c R d is more preferable.
　アルカリ金属としては、たとえば、リチウム、ナトリウム、カリウム等を挙げることができる。アルカリ土類金属としては、たとえば、マグネシウム、カルシウム、バリウム等を挙げることができる。
　Ｒａ、Ｒｂ、Ｒｃ及びＲｄは、それぞれ独立して、水素原子、アルキル基、アルカノール基またはポリオキシアルキレン基である。アルキル基の炭素数は、１～３０が好ましく、１～１０がさらに好ましい。このようなアルキル基としては、たとえば、メチル基、エチル基、ｎ－プロピル基、イソプロピル基等が挙げられる。アルカノール基の炭素数は、１～３０が好ましく、１～１０がさらに好ましい。このようなアルカノール基としては、たとえば、メタノール基、エタノール基、ｎ－プロパノール基、イソプロパノール基等が挙げられる。ポリオキシアルキレン基の炭素数は、２～４が好ましい。このようなポリオキシアルキレン基としては、たとえば、ポリオキシエチレン基、ポリオキシプロピレン基等が挙げられる。 Examples of the alkali metal include lithium, sodium, and potassium. Examples of the alkaline earth metal include magnesium, calcium, barium and the like.
R a , R b , R c and R d are each independently a hydrogen atom, an alkyl group, an alkanol group or a polyoxyalkylene group. The alkyl group preferably has 1 to 30 carbon atoms, more preferably 1 to 10 carbon atoms. Examples of such an alkyl group include a methyl group, an ethyl group, an n-propyl group, and an isopropyl group. The carbon number of the alkanol group is preferably 1-30, and more preferably 1-10. Examples of such an alkanol group include a methanol group, an ethanol group, an n-propanol group, and an isopropanol group. The polyoxyalkylene group preferably has 2 to 4 carbon atoms. Examples of such a polyoxyalkylene group include a polyoxyethylene group and a polyoxypropylene group.
［界面活性剤（Ｂ）］
　本発明の繊維用抗菌加工薬剤は、上記一般式（２）で示される界面活性剤、上記一般式（３）で示される界面活性剤、上記一般式（４）で示される界面活性剤及び上記一般式（５）で示される界面活性剤から選ばれる少なくとも１種の界面活性剤（Ｂ）をさらに含有することが好ましい。界面活性剤（Ｂ）を用いることにより、銀系無機抗菌剤の分散性や、銀系無機抗菌剤の分散体の経時的な安定性を向上させることができ、一層優れた抗菌性及び洗濯耐久性を付与することができる。界面活性剤（Ｂ）は、上記の観点から、一般式（３）で示される界面活性剤、一般式（４）で示される界面活性剤及び一般式（５）で示される界面活性剤から選ばれる少なくとも１種であるであることが好ましく、一般式（３）で示される界面活性剤及び一般式（４）で示される界面活性剤から選ばれる少なくとも１種であることがより好ましく、一般式（３）で示される界面活性剤であることがさらに好ましい。 [Surfactant (B)]
The antibacterial finishing agent for fibers of the present invention includes a surfactant represented by the above general formula (2), a surfactant represented by the above general formula (3), a surfactant represented by the above general formula (4), and the above It is preferable to further contain at least one surfactant (B) selected from surfactants represented by the general formula (5). By using the surfactant (B), it is possible to improve the dispersibility of the silver-based inorganic antibacterial agent and the temporal stability of the dispersion of the silver-based inorganic antibacterial agent. Sex can be imparted. From the above viewpoint, the surfactant (B) is selected from the surfactant represented by the general formula (3), the surfactant represented by the general formula (4), and the surfactant represented by the general formula (5). It is preferably at least one selected from the group consisting of a surfactant represented by the general formula (3) and a surfactant represented by the general formula (4). More preferably, it is a surfactant represented by (3).
　一般式（２）で示される界面活性剤について、式（２）中、Ｒ５は、炭素数１～３０のアルキル基、炭素数６～３０のアリール基又は炭素数７～３０のアラルキル基である。アルキル基、アリール基、アラルキル基の好ましい範囲や例示は、Ｒ１で記載したものと同様である。これらの中でも、銀系無機抗菌剤の分散性及び経時的な安定性を向上させる点から、Ｒ１としては、アルキル基、アラルキル基が好ましく、アルキル基がさらに好ましい。 Regarding the surfactant represented by the general formula (2), in the formula (2), R 5 is an alkyl group having 1 to 30 carbon atoms, an aryl group having 6 to 30 carbon atoms, or an aralkyl group having 7 to 30 carbon atoms. is there. Preferred ranges and examples of the alkyl group, aryl group and aralkyl group are the same as those described for R 1 . Among these, from the viewpoint of improving the dispersibility of the silver-based inorganic antibacterial agent and the stability over time, R 1 is preferably an alkyl group or an aralkyl group, and more preferably an alkyl group.
　Ａ１Ｏは炭素数２～４のオキシアルキレン基である。炭素数は２～３が好ましく、２がさらに好ましい。Ａ１Ｏは、１種または２種以上であってもよく、２種以上の場合、ブロック付加体、交互付加体、またはランダム付加体のいずれを構成してもよい。Ａ１Ｏは、銀系無機抗菌剤の分散性及び経時的な安定性を向上させる点から、オキシエチレン基を必須に含有することが好ましい。オキシアルキレン基全体に占めるオキシエチレン基の割合は、４０モル％以上が好ましく、５０モル％がより好ましく、６０モル％以上がさらに好ましく、８０モル％以上が特に好ましい。
　ｎは０～５０の整数である。銀系無機抗菌剤の分散性及び経時的な安定性を向上させる点から、ｎは１～４５が好ましく、２～４０がより好ましく、３～３５が特に好ましい。
　ｍは１～３の整数であり、１～２が好ましい。 A 1 O is an oxyalkylene group having 2 to 4 carbon atoms. The number of carbon atoms is preferably 2 to 3, and more preferably 2. A 1 O may be one type or two or more types, and in the case of two or more types, A 1 O may constitute any of a block adduct, an alternating adduct, or a random adduct. A 1 O preferably contains an oxyethylene group essentially from the viewpoint of improving the dispersibility of the silver-based inorganic antibacterial agent and the stability over time. The proportion of the oxyethylene group in the entire oxyalkylene group is preferably 40 mol% or more, more preferably 50 mol%, still more preferably 60 mol% or more, and particularly preferably 80 mol% or more.
n is an integer of 0 to 50. From the viewpoint of improving the dispersibility and stability over time of the silver-based inorganic antibacterial agent, n is preferably 1 to 45, more preferably 2 to 40, and particularly preferably 3 to 35.
m is an integer of 1 to 3, and preferably 1 or 2.
　Ｍ２は、水素原子、アルカリ金属、アルカリ土類金属又はＮＲａＲｂＲｃＲｄで示される基である。Ｒａ、Ｒｂ、Ｒｃ及びＲｄは、それぞれ独立して、水素原子、アルキル基、アルカノール基又はポリオキシアルキレン基である。アルカリ金属、アルカリ土類金属又はＮＲａＲｂＲｃＲｄで示される基については、化合物（Ａ）のところで記載したものと同様である。
　これらの中でも、銀系無機抗菌剤の分散性及び経時的な安定性を向上させる点から、Ｍ２は、アルカリ金属、ＮＲａＲｂＲｃＲｄで示される基が好ましく、アルカリ金属がさらに好ましい。 M 2 is a hydrogen atom, an alkali metal, an alkaline earth metal, or a group represented by NR a R b R c R d . R a , R b , R c and R d are each independently a hydrogen atom, an alkyl group, an alkanol group or a polyoxyalkylene group. The group represented by alkali metal, alkaline earth metal, or NR a R b R c R d is the same as that described for compound (A).
Among these, from the viewpoint of improving the dispersibility of the silver-based inorganic antibacterial agent and the stability over time, M 2 is preferably an alkali metal, a group represented by NR a R b R c R d , and more preferably an alkali metal. preferable.
　一般式（２）で示される界面活性剤であるリン酸エステル化合物は、リン酸トリエステル、リン酸ジエステル、リン酸モノエステルのいずれでもよく、これらの混合物であってもよい。 The phosphoric acid ester compound which is the surfactant represented by the general formula (2) may be any of phosphoric acid triester, phosphoric acid diester, and phosphoric acid monoester, or a mixture thereof.
　リン酸エステル化合物の製造方法としては、特に限定はなく、公知の方法を採用できる。例えば、リン酸エステル化合物の製造方法としては、原料アルコールと無水リン酸によるリン酸化反応を行い、その後、場合によっては、中和することでリン酸エステル化合物を得る方法が一般的に知られている。ここで、原料アルコールと無水リン酸との仕込みモル比を変化させることで、ジエステルおよびモノエステルを大まかに作り分けることができる。たとえば、原料アルコール：無水リン酸＝１：１（モル比）の場合は、モノエステル（一般式（２）でｍ＝１）が主に得られる。原料アルコール：無水リン酸＝２：１（モル比）の場合は、ジエステル（一般式（２）でｍ＝２）が主に得られる。 The production method of the phosphate ester compound is not particularly limited, and a known method can be adopted. For example, as a method for producing a phosphoric acid ester compound, a method is generally known in which a phosphorylation reaction is performed with raw alcohol and phosphoric anhydride, and then, in some cases, the phosphoric acid ester compound is obtained by neutralization. Yes. Here, diesters and monoesters can be roughly prepared separately by changing the charged molar ratio of the raw material alcohol and phosphoric anhydride. For example, in the case of raw material alcohol: phosphoric anhydride = 1: 1 (molar ratio), monoester (m = 1 in the general formula (2)) is mainly obtained. In the case of raw material alcohol: phosphoric anhydride = 2: 1 (molar ratio), a diester (m = 2 in the general formula (2)) is mainly obtained.
　一般式（３）で示される界面活性剤について、式（３）中、Ａ２Ｏは、炭素数２～４のオキシアルキレン基である。炭素数は２～３が好ましく、２がさらに好ましい。Ａ２Ｏは、１種または２種以上であってもよく、２種以上の場合、ブロック付加体、交互付加体、またはランダム付加体のいずれを構成してもよい。Ａ２Ｏは、銀系無機抗菌剤の分散性及び経時的な安定性を向上させる点から、オキシエチレン基を必須に含有することが好ましい。オキシアルキレン基全体に占めるオキシエチレン基の割合は、４０モル％以上が好ましく、５０モル％がより好ましく、６０モル％以上がさらに好ましく、８０モル％以上が特に好ましい。 Regarding the surfactant represented by the general formula (3), in the formula (3), A 2 O is an oxyalkylene group having 2 to 4 carbon atoms. The number of carbon atoms is preferably 2 to 3, and more preferably 2. A 2 O may be one type or two or more types, and in the case of two or more types, A 2 O may constitute any of a block adduct, an alternating adduct, or a random adduct. A 2 O preferably contains an oxyethylene group essentially from the viewpoint of improving the dispersibility of the silver-based inorganic antibacterial agent and the stability over time. The proportion of the oxyethylene group in the entire oxyalkylene group is preferably 40 mol% or more, more preferably 50 mol%, still more preferably 60 mol% or more, and particularly preferably 80 mol% or more.
　ｑは１～３であり、銀系無機抗菌剤の分散性及び経時的な安定性を向上させる点から、２～３が好ましい。
　ｋは２～７０の整数である。銀系無機抗菌剤の分散性及び経時的な安定性を向上させる点から、ｋは３～６０が好ましく、４～５０がより好ましく、５～４０がさらに好ましい。 q is 1 to 3, and 2 to 3 is preferable from the viewpoint of improving the dispersibility and stability over time of the silver-based inorganic antibacterial agent.
k is an integer of 2 to 70. From the viewpoint of improving the dispersibility and stability over time of the silver-based inorganic antibacterial agent, k is preferably 3 to 60, more preferably 4 to 50, and even more preferably 5 to 40.
　一般式（４）で示される界面活性剤について、式（４）中、Ａ３Ｏは、炭素数２～４のオキシアルキレン基である。炭素数は２～３が好ましく、２がさらに好ましい。Ａ３Ｏは、１種または２種以上であってもよく、２種以上の場合、ブロック付加体、交互付加体、またはランダム付加体のいずれを構成してもよい。Ａ３Ｏは、銀系無機抗菌剤の分散性及び経時的な安定性を向上させる点から、オキシエチレン基を必須に含有することが好ましい。オキシアルキレン基全体に占めるオキシエチレン基の割合は、４０モル％以上が好ましく、５０モル％がより好ましく、６０モル％以上がさらに好ましく、８０モル％以上が特に好ましい。 Regarding the surfactant represented by the general formula (4), in the formula (4), A 3 O is an oxyalkylene group having 2 to 4 carbon atoms. The number of carbon atoms is preferably 2 to 3, and more preferably 2. A 3 O may be one type or two or more types, and in the case of two or more types, A 3 O may constitute any of a block adduct, an alternating adduct, or a random adduct. A 3 O preferably contains an oxyethylene group essential from the viewpoint of improving the dispersibility of the silver-based inorganic antibacterial agent and the stability over time. The proportion of the oxyethylene group in the entire oxyalkylene group is preferably 40 mol% or more, more preferably 50 mol%, still more preferably 60 mol% or more, and particularly preferably 80 mol% or more.
　ｒは１～３であり、銀系無機抗菌剤の分散性及び経時的な安定性を向上させる点から、２～３が好ましい。
　ｊは２～７０の整数である。銀系無機抗菌剤の分散性及び経時的な安定性を向上させる点から、ｊは３～６０が好ましく、４～５０がより好ましく、５～４０がさらに好ましい。
　Ｍ３は、水素原子、アルカリ金属、アルカリ土類金属又はＮＲａＲｂＲｃＲｄで示される基である。Ｒａ、Ｒｂ、Ｒｃ及びＲｄは、それぞれ独立して、水素原子、アルキル基、アルカノール基又はポリオキシアルキレン基である。アルカリ金属、アルカリ土類金属又はＮＲａＲｂＲｃＲｄで示される基については、化合物（Ａ）のところで記載したものと同様である。
　これらの中でも、銀系無機抗菌剤の分散性及び経時的な安定性を向上させる点から、Ｍ３は、アルカリ金属、ＮＲａＲｂＲｃＲｄで示される基が好ましく、アルカリ金属がさらに好ましい。 r is 1 to 3, and 2 to 3 is preferable from the viewpoint of improving the dispersibility and stability over time of the silver-based inorganic antibacterial agent.
j is an integer of 2 to 70. From the viewpoint of improving the dispersibility and stability over time of the silver-based inorganic antibacterial agent, j is preferably from 3 to 60, more preferably from 4 to 50, and even more preferably from 5 to 40.
M 3 is a hydrogen atom, an alkali metal, an alkaline earth metal or a group represented by NR a R b R c R d . R a , R b , R c and R d are each independently a hydrogen atom, an alkyl group, an alkanol group or a polyoxyalkylene group. The group represented by alkali metal, alkaline earth metal, or NR a R b R c R d is the same as that described for compound (A).
Among these, from the viewpoint of improving the dispersibility of the silver-based inorganic antibacterial agent and the stability over time, M 3 is preferably an alkali metal, a group represented by NR a R b R c R d , and more preferably an alkali metal. preferable.
　一般式（５）で示される界面活性剤について、式（５）中、Ａ４Ｏは、炭素数２～４のオキシアルキレン基である。炭素数は２～３が好ましく、２がさらに好ましい。Ａ４Ｏは、１種または２種以上であってもよく、２種以上の場合、ブロック付加体、交互付加体、またはランダム付加体のいずれを構成してもよい。Ａ４Ｏは、銀系無機抗菌剤の分散性及び経時的な安定性を向上させる点から、オキシエチレン基を必須に含有することが好ましい。オキシアルキレン基全体に占めるオキシエチレン基の割合は、４０モル％以上が好ましく、５０モル％がより好ましく、６０モル％以上がさらに好ましく、８０モル％以上が特に好ましい。 Regarding the surfactant represented by the general formula (5), in the formula (5), A 4 O is an oxyalkylene group having 2 to 4 carbon atoms. The number of carbon atoms is preferably 2 to 3, and more preferably 2. A 4 O may be one type or two or more types, and in the case of two or more types, A 4 O may constitute any of a block adduct, an alternating adduct, or a random adduct. A 4 O preferably contains an oxyethylene group essential from the viewpoint of improving the dispersibility of the silver-based inorganic antibacterial agent and the stability over time. The proportion of the oxyethylene group in the entire oxyalkylene group is preferably 40 mol% or more, more preferably 50 mol%, still more preferably 60 mol% or more, and particularly preferably 80 mol% or more.
　ｓは１～３の整数であり、銀系無機抗菌剤の分散性及び経時的な安定性を向上させる点から、２～３が好ましい。
　ｔは１又は２の整数であり、銀系無機抗菌剤の分散性及び経時的な安定性を向上させる点から、２が好ましい。
　ｈは２～７０の整数である。銀系無機抗菌剤の分散性及び経時的な安定性を向上させる点から、ｈは３～６０が好ましく、４～５０がより好ましく、５～４０がさらに好ましい。
　Ｍ４は、水素原子、アルカリ金属、アルカリ土類金属又はＮＲａＲｂＲｃＲｄで示される基である。Ｒａ、Ｒｂ、Ｒｃ及びＲｄは、それぞれ独立して、水素原子、アルキル基、アルカノール基又はポリオキシアルキレン基である。アルカリ金属、アルカリ土類金属又はＮＲａＲｂＲｃＲｄで示される基については、化合物（Ａ）のところで記載したものと同様である。
　これらの中でも、銀系無機抗菌剤の分散性及び経時的な安定性を向上させる点から、Ｍ４は、アルカリ金属、ＮＲａＲｂＲｃＲｄで示される基が好ましく、アルカリ金属がさらに好ましい。 s is an integer of 1 to 3, and preferably 2 to 3 from the viewpoint of improving the dispersibility and stability over time of the silver-based inorganic antibacterial agent.
t is an integer of 1 or 2, and 2 is preferable from the viewpoint of improving the dispersibility of the silver-based inorganic antibacterial agent and the stability over time.
h is an integer of 2 to 70. From the viewpoint of improving the dispersibility and stability over time of the silver-based inorganic antibacterial agent, h is preferably 3 to 60, more preferably 4 to 50, and even more preferably 5 to 40.
M 4 is a hydrogen atom, an alkali metal, an alkaline earth metal, or a group represented by NR a R b R c R d . R a , R b , R c and R d are each independently a hydrogen atom, an alkyl group, an alkanol group or a polyoxyalkylene group. The group represented by alkali metal, alkaline earth metal, or NR a R b R c R d is the same as that described for compound (A).
Among these, from the viewpoint of improving the dispersibility of the silver-based inorganic antibacterial agent and the stability over time, M 4 is preferably an alkali metal, a group represented by NR a R b R c R d , and more preferably an alkali metal. preferable.
［繊維用抗菌加工薬剤］
　本発明の繊維用抗菌加工薬剤は、繊維材料に抗菌性を付与するために用いられるものである。すなわち、後加工にて繊維材料に付与する抗菌加工薬剤である。
　本発明の抗菌加工薬剤は、化合物（Ａ）及び水の存在下、平均粒子径が０．０１～３μｍの前記銀系無機抗菌剤が分散されてなるものである。このような構成により、繊維材料に対して優れた抗菌性を付与することができるとともに、加工された繊維材料を洗濯した場合においても抗菌性の低下を防ぐことができ、洗濯耐久性にも優れるという効果を有する。この作用について、明確ではないが、次のように推測される。 [Antimicrobial finishing agent for textiles]
The antibacterial finishing agent for fibers of the present invention is used for imparting antibacterial properties to fiber materials. That is, it is an antibacterial processing agent to be applied to the fiber material in post-processing.
The antibacterial processing agent of the present invention is obtained by dispersing the silver-based inorganic antibacterial agent having an average particle size of 0.01 to 3 μm in the presence of the compound (A) and water. With such a configuration, it is possible to impart excellent antibacterial properties to the fiber material, and even when the processed fiber material is washed, it is possible to prevent a decrease in antibacterial properties and to have excellent washing durability. It has the effect. Although it is not clear about this effect | action, it estimates as follows.
　抗菌加工薬剤において、銀系無機抗菌剤と化合物（Ａ）が銀原子を交換反応することにより、下記一般式（６）で示される化合物（Ｘ）が生成するものと推測される。化合物（Ｘ）の生成は、化合物（Ａ）及び水の存在下、後述のように銀系無機抗菌剤を湿式粉砕して、所定の平均粒子径となるよう分散することにより、より多く生成されているものと推測される。生成された化合物（Ｘ）は、銀系無機抗菌剤よりも有機性を持つため、繊維材料との接着がよく、さらに銀イオンを保持しているため、抗菌性と洗濯耐久性を有しているものと考えられる。微粒子化された銀系無機抗菌剤及び化合物（Ａ）と共にこのような化合物（Ｘ）を含有する抗菌加工薬剤を繊維材料に付着することによって、優れた抗菌性を付与することができるとともに、洗濯耐久性にも優れるという効果を奏するものと推測される。
　さらに、本発明の抗菌加工薬剤は、繊維材料に該薬剤を付与しても、銀イオンによる繊維材料の黄変（着色）を防止できるという優れた効果をも有している。 In the antibacterial processing agent, it is presumed that the compound (X) represented by the following general formula (6) is generated by the silver-based inorganic antibacterial agent and the compound (A) exchange-reacting silver atoms. Compound (X) is produced in a larger amount by wet-grinding the silver-based inorganic antibacterial agent in the presence of compound (A) and water and dispersing it to a predetermined average particle size as described later. It is presumed that The produced compound (X) is more organic than silver-based inorganic antibacterial agents, so it has good adhesion to the fiber material, and also holds silver ions, so it has antibacterial properties and washing durability. It is thought that there is. By attaching an antibacterial processing agent containing such a compound (X) together with the finely divided silver-based inorganic antibacterial agent and the compound (A) to the fiber material, excellent antibacterial properties can be imparted and washing It is presumed that the durability is also excellent.
Furthermore, the antibacterial processing agent of the present invention has an excellent effect that even if the agent is applied to the fiber material, yellowing (coloring) of the fiber material due to silver ions can be prevented.
Figure JPOXMLDOC01-appb-C000016
Figure JPOXMLDOC01-appb-C000016
　式（６）中、Ｒ１は、水素原子、ハロゲン原子、炭素数１～３０のアルキル基、炭素数６～３０のアリール基、炭素数７～３０のアラルキル基、ＮＲ２Ｒ３又はＯＲ４である。Ｒ２、Ｒ３及びＲ４は、それぞれ独立して、水素原子、炭素数１～３０のアルキル基、炭素数６～３０のアリール基または炭素数７～３０のアラルキル基である。Ｒ１、Ｒ２、Ｒ３及びＲ４は、化合物（Ａ）のところで記載したものと同様である。 In the formula (6), R 1 represents a hydrogen atom, a halogen atom, an alkyl group having 1 to 30 carbon atoms, an aryl group having 6 to 30 carbon atoms, an aralkyl group having 7 to 30 carbon atoms, NR 2 R 3 or OR 4 It is. R 2 , R 3 and R 4 are each independently a hydrogen atom, an alkyl group having 1 to 30 carbon atoms, an aryl group having 6 to 30 carbon atoms or an aralkyl group having 7 to 30 carbon atoms. R 1 , R 2 , R 3 and R 4 are the same as those described for the compound (A).
　銀系無機抗菌剤の平均粒子径は、０．０１～３μｍであり、０．０３～２μｍが好ましく、０．０５～１．５μｍがより好ましく、０．１～１μｍがさらに好ましく、０．１～１μｍが特に好ましい。平均粒子径が０．０１μｍ未満の場合、銀系無機抗菌剤が繊維材料の内部に入り込み過ぎ、抗菌性が発現し難くとなる。一方、平均粒子径が３μｍ超の場合、繊維表面に付着し難く固着率が低くなり、抗菌性が発現し難くなる。なお、本発明で用いる平均粒子径とは、レーザー回折・散乱式粒子径分布測定装置ＬＡ－９１０（堀場製作所製）を用いて、体積基準とするメジアン粒径を測定したものをいう。 The average particle size of the silver-based inorganic antibacterial agent is 0.01 to 3 μm, preferably 0.03 to 2 μm, more preferably 0.05 to 1.5 μm, still more preferably 0.1 to 1 μm, and 0.1 ˜1 μm is particularly preferred. When the average particle diameter is less than 0.01 μm, the silver-based inorganic antibacterial agent enters the inside of the fiber material too much, and the antibacterial property is hardly exhibited. On the other hand, when the average particle diameter is more than 3 μm, it is difficult to adhere to the fiber surface, the fixing rate is lowered, and antibacterial properties are hardly exhibited. The average particle size used in the present invention is a value obtained by measuring the volume-based median particle size using a laser diffraction / scattering particle size distribution measuring apparatus LA-910 (manufactured by Horiba, Ltd.).
　前記化合物（Ａ）の配合割合は、前記銀系無機抗菌剤１００重量部に対して、０．１～１００００重量部であることが好ましく、０．５～５０００重量部がより好ましく、１～１０００重量部がさらに好ましく、２～１００重量部が特に好ましい。 The compounding ratio of the compound (A) is preferably 0.1 to 10000 parts by weight, more preferably 0.5 to 5000 parts by weight, with respect to 100 parts by weight of the silver-based inorganic antibacterial agent. Part by weight is more preferable, and 2 to 100 parts by weight is particularly preferable.
　前記界面活性剤（Ｂ）の配合割合は、前記銀系無機抗菌剤１００重量部に対して、０．０１～２００重量部であることが好ましく、０．１～１００重量部がより好ましく、０．５～７０重量部がさらに好ましく、１～５０重量部が特に好ましい。 The blending ratio of the surfactant (B) is preferably 0.01 to 200 parts by weight, more preferably 0.1 to 100 parts by weight, with respect to 100 parts by weight of the silver-based inorganic antibacterial agent. 5 to 70 parts by weight is more preferable, and 1 to 50 parts by weight is particularly preferable.
　本発明の抗菌加工薬剤は水を必須に含有する。本発明に使用する水としては、純水、蒸留水、精製水、軟水、イオン交換水、水道水等のいずれであってもよい。
　本発明の効果を損なわない範囲で上記成分以外のその他成分を含んでもよい。その他成分としては、抗菌剤、防黴剤、防虫剤、防ダニ剤、消臭剤、帯電防止剤、撥水撥油剤、紫外線吸収剤、難燃剤、防汚剤、深色化剤、平滑剤、柔軟剤または吸水剤等の繊維の後加工剤、油剤、界面活性剤、無機物、防腐剤、ｐＨ調整剤、消泡剤、溶剤、脂肪酸（塩）等が挙げられる。 The antibacterial processing agent of the present invention essentially contains water. The water used in the present invention may be any of pure water, distilled water, purified water, soft water, ion exchange water, tap water and the like.
Other components other than the above components may be included as long as the effects of the present invention are not impaired. Other components include antibacterial agents, fungicides, insecticides, acaricides, deodorants, antistatic agents, water and oil repellents, UV absorbers, flame retardants, antifouling agents, deep colorants, and smoothing agents. And post-processing agents for fibers such as softeners or water-absorbing agents, oil agents, surfactants, inorganic substances, preservatives, pH adjusters, antifoaming agents, solvents, fatty acids (salts) and the like.
　本発明の抗菌加工薬剤は、本発明の効果を損なわない範囲でバインダー樹脂を含んでもよい。しかし、抗菌加工薬剤がバインダー樹脂を含有する場合に、繊維材料の風合いを低下させるおそれがある。風合いの低下を防止する観点からは、バインダー樹脂の配合割合は、前記銀系無機抗菌剤１００重量部に対して、２０重量部以下が好ましく、１０重量部以下がより好ましく、５重量部以下がさらに好ましく、０重量部が特に好ましい。 The antibacterial processing agent of the present invention may contain a binder resin as long as the effects of the present invention are not impaired. However, when the antibacterial agent contains a binder resin, the texture of the fiber material may be reduced. From the viewpoint of preventing the deterioration of the texture, the blending ratio of the binder resin is preferably 20 parts by weight or less, more preferably 10 parts by weight or less, and more preferably 5 parts by weight or less with respect to 100 parts by weight of the silver-based inorganic antibacterial agent. More preferred is 0 part by weight.
　ここでバインダー樹脂としては、ポリ酢酸ビニル、ポリグリセリン、ポリビニルアルコール、多糖類系化合物、メラミン系化合物、グリオキサール系化合物、ウレタン系化合物、ブロック化イソシアネート系化合物、シリコン系化合物、アクリル系樹脂、ポリエステル系樹脂、シリコンを含有するアクリル系樹脂等を挙げられる。 Here, as a binder resin, polyvinyl acetate, polyglycerin, polyvinyl alcohol, polysaccharide compounds, melamine compounds, glyoxal compounds, urethane compounds, blocked isocyanate compounds, silicon compounds, acrylic resins, polyester resins Examples thereof include resins and acrylic resins containing silicon.
　多糖類系化合物としては、でんぷん、カルボキシメチルセルロース等が挙げられる。
　メラミン系化合物としては、例えば、メラミンとホルムアルデヒドを重合して得られる合成樹脂等が挙げられる。 Examples of polysaccharide compounds include starch and carboxymethyl cellulose.
Examples of melamine compounds include synthetic resins obtained by polymerizing melamine and formaldehyde.
　グリオキサール系化合物としては、グリオキサール等が挙げられる。
　ウレタン系化合物としては、例えば、イソシアネート基に対して反応性のある活性水素を２個以上有する化合物と、ポリイソシアネートとを反応させた化合物等が挙げられる。このうち、活性水素を２個以上有する化合物としては、多価アルコール、カルボキシル基と２個のヒドロキシル基を有する化合物、ポリアミン等が挙げられる。また、ポリイソシアネートとしては、脂肪族ジイソシアネート、脂環式ジイソシアネート、芳香族ジイソシアネート等が挙げられる。また、このウレタン系化合物の末端にイソシアネート基を有する場合は、そのイソシアネート基の一部を重亜硫酸ナトリウムやメチルエチルケトオキシム等によりブロック化した化合物を使用することもできる。 Examples of the glyoxal compound include glyoxal.
Examples of the urethane compound include a compound obtained by reacting a compound having two or more active hydrogens reactive with an isocyanate group and a polyisocyanate. Among these, examples of the compound having two or more active hydrogens include polyhydric alcohols, compounds having a carboxyl group and two hydroxyl groups, and polyamines. Examples of the polyisocyanate include aliphatic diisocyanate, alicyclic diisocyanate, and aromatic diisocyanate. Moreover, when it has an isocyanate group in the terminal of this urethane type compound, the compound which blocked a part of the isocyanate group with sodium bisulfite, methyl ethyl ketoxime, etc. can also be used.
　ブロック化イソシアネート系化合物としては、重亜硫酸ナトリウム、アセチルアセトン、アセト酢酸エチル、ジエチルマロネート等をイソシアネート基と反応させて一時的に安定な化合物を作り、後から熱処理することにより解離しイソシアネート基を再生するブロック化イソシアネート基を分子中に少なくとも１個以上含有する化合物の少なくとも１種を、（メタ）アクリル化合物、シリコン変性（メタ）アクリル系化合物又はフッ素変性（メタ）アクリル系化合物と反応させて得られた化合物等が挙げられる。
　シリコン系化合物としては、シリコーンレジン又はシリコーンワニスに分類される縮合架橋型樹脂等が挙げられる。この縮合架橋型樹脂は、テトラエトキシシランやメチルトリメトキシシランなどのシラン化合物から選ばれる一種又は二種以上のシラン化合物を重縮合することによって得ることができる。 As blocked isocyanate compounds, sodium bisulfite, acetylacetone, ethyl acetoacetate, diethylmalonate, etc. are reacted with isocyanate groups to form temporarily stable compounds, which are then dissociated by heat treatment to regenerate isocyanate groups. Obtained by reacting at least one compound containing at least one blocked isocyanate group in the molecule with a (meth) acrylic compound, a silicon-modified (meth) acrylic compound or a fluorine-modified (meth) acrylic compound And the like.
Examples of the silicon compound include condensation-crosslinking resins classified into silicone resins or silicone varnishes. This condensation-crosslinking resin can be obtained by polycondensing one or two or more silane compounds selected from silane compounds such as tetraethoxysilane and methyltrimethoxysilane.
　アクリル系樹脂としては、アクリル酸、メタクリル酸、メチル（メタ）アクリレート、ｎ－ブチル（メタ）アクリレートなど、（メタ）アクリレート系モノマー等の（メタ）アクリル系モノマーの一種又は二種以上のモノマーの重合体、またはこれら（メタ）アクリル系モノマーと共重合可能な他のビニル系モノマーとの共重合体が挙げられる。
　ポリエステル系樹脂としては、ポリエチレンテレフタレート、ポリブチレンテレフタレート、ポリエチレンイソフタレート／　テレフタレート共重縮合体等が挙げられる。
　シリコンを含有するアクリル系樹脂としては、（メタ）アクリル酸エステルモノマーとオルガノポリシロキサン化合物の重縮合物等が挙げられる。 Examples of the acrylic resin include one or two or more types of (meth) acrylic monomers such as (meth) acrylate monomers such as acrylic acid, methacrylic acid, methyl (meth) acrylate, and n-butyl (meth) acrylate. Examples thereof include a polymer and a copolymer with another vinyl monomer copolymerizable with these (meth) acrylic monomers.
Examples of the polyester resin include polyethylene terephthalate, polybutylene terephthalate, polyethylene isophthalate / terephthalate copolycondensate, and the like.
Examples of the acrylic resin containing silicon include a polycondensate of a (meth) acrylic acid ester monomer and an organopolysiloxane compound.
　本発明の抗菌加工薬剤の不揮発分の濃度は、０．０００１～９０重量％が好ましく、０．０００５～７０重量％がより好ましく、０．００１～５０重量％がさらに好ましい。なお、本発明の抗菌加工薬剤とは、後述する製造方法で製造された薬剤のみならず、繊維材料に付与する際に該薬剤を水等により希釈した加工処理液を含むものである。本発明における不揮発分とは、試料を１０５℃で熱処理して溶媒等を除去し、恒量に達した時の絶乾成分をいう。 The concentration of the nonvolatile content of the antibacterial processing agent of the present invention is preferably 0.0001 to 90% by weight, more preferably 0.0005 to 70% by weight, and further preferably 0.001 to 50% by weight. In addition, the antibacterial processing chemical | medical agent of this invention contains not only the chemical | medical agent manufactured with the manufacturing method mentioned later but the processing liquid which diluted this chemical | medical agent with water etc., when providing to a fiber material. The non-volatile content in the present invention refers to an absolutely dry component when a sample is heat treated at 105 ° C. to remove the solvent and the like and reach a constant weight.
［繊維用抗菌加工薬剤の製造方法］
　本発明の繊維用抗菌加工薬剤の製造方法は、前記化合物（Ａ）及び水の存在下、前記銀系無機抗菌剤を湿式粉砕する工程を含ものである。湿式粉砕する方法としては、特に限定はなく、公知の方法を採用できる。 [Manufacturing method of antibacterial agents for textiles]
The method for producing an antibacterial processing agent for fibers according to the present invention includes a step of wet-grinding the silver-based inorganic antibacterial agent in the presence of the compound (A) and water. The wet pulverization method is not particularly limited, and a known method can be adopted.
　詳細には、まず化合物（Ａ）、水及び未粉砕の銀系無機抗菌剤を混合撹拌してスラリー液を調製する。前記化合物（Ａ）の配合割合は、前記銀系無機抗菌剤１００重量部に対して、０．１～１００００重量部であることが好ましく、０．５～５０００重量部がより好ましく、１～１０００重量部がさらに好ましく、２～１００重量部が特に好ましい。化合物（Ａ）の配合割合が０．１重量部よりも小さいと、前記化合物（Ｘ）の生成も少量になるものと推測され、洗濯耐久性が発現し難くとなることがある。さらに、銀イオンによる黄変（着色）を防止できないことがある。１００００重量部よりも大きいと、洗濯耐久性がこれ以上の向上は見られず、経済的に不利となることがある。
　また、このスラリー液の不揮発分の重量割合は、１～９０重量％が好ましく、３～７０重量％がより好ましく、５～５０重量％がさらに好ましい。１重量％未満の場合、抗菌加工薬剤中の抗菌成分が少量で、処理した繊維が抗菌性を示さなくなることがある。９０重量％超の場合、経時的に銀系無機抗菌剤の凝集が起こり、優れた抗菌性及び洗濯耐久性が発揮し難いことがある。 Specifically, first, a slurry solution is prepared by mixing and stirring the compound (A), water, and an unground silver-based inorganic antibacterial agent. The compounding ratio of the compound (A) is preferably 0.1 to 10000 parts by weight, more preferably 0.5 to 5000 parts by weight, with respect to 100 parts by weight of the silver-based inorganic antibacterial agent. Part by weight is more preferable, and 2 to 100 parts by weight is particularly preferable. When the compounding ratio of the compound (A) is less than 0.1 parts by weight, it is estimated that the compound (X) is also produced in a small amount, and it may be difficult to develop the durability to washing. Furthermore, yellowing (coloring) due to silver ions may not be prevented. When it is larger than 10,000 parts by weight, the washing durability is not improved any more, which may be economically disadvantageous.
Further, the weight ratio of the nonvolatile content of the slurry is preferably 1 to 90% by weight, more preferably 3 to 70% by weight, and further preferably 5 to 50% by weight. If it is less than 1% by weight, the antibacterial component in the antibacterial processing agent may be small, and the treated fiber may not exhibit antibacterial properties. If it exceeds 90% by weight, aggregation of the silver-based inorganic antibacterial agent may occur over time, and it may be difficult to exhibit excellent antibacterial properties and washing durability.
　次いで、ビーズミル、サンドグラインダ－、アトライター、ボールミル等の湿式粉砕機に調製したスラリー液を通過させて、平均粒子径が０．１～３μｍとなるまで微粒子化を行う。微粒子化された銀系無機抗菌剤の平均粒子径の好ましい範囲や平均粒子径の測定方法については、抗菌加工薬剤で記載したものと同様である。湿式粉砕する工程としては、例えば、パス方式又は槽内部循環方式等の連続工程やバッチ工程が挙げられる。 Next, the slurry liquid prepared is passed through a wet pulverizer such as a bead mill, a sand grinder, an attritor, or a ball mill, and finely divided until the average particle size becomes 0.1 to 3 μm. The preferred range of the average particle size of the finely divided silver-based inorganic antibacterial agent and the method for measuring the average particle size are the same as those described for the antibacterial processing agent. Examples of the wet pulverization process include a continuous process such as a pass system or a tank internal circulation system, and a batch process.
　本発明の抗菌加工薬剤の製造方法は、前記工程が、前記化合物（Ａ）及び水に加え、前記界面活性剤（Ｂ）の存在下、前記銀系無機抗菌剤を湿式粉砕する工程であることが好ましい。すなわち、化合物（Ａ）、界面活性剤（Ｂ）、水及び未粉砕の銀系無機抗菌剤を混合撹拌してスラリー液を調製し、このスラリー液を湿式粉砕機により微粒子化する工程であることが好ましい。このような工程により、銀系無機抗菌剤の分散性や、銀系無機抗菌剤の分散体の経時的な安定性を向上させることができ、一層優れた抗菌性及び洗濯耐久性を付与することができる。界面活性剤（Ｂ）は、一般式（３）で示される界面活性剤、一般式（４）で示される界面活性剤及び一般式（５）で示される界面活性剤から選ばれる少なくとも１種であるであることが好ましく、一般式（３）で示される界面活性剤及び一般式（４）で示される界面活性剤から選ばれる少なくとも１種であることがより好ましく、一般式（３）で示される界面活性剤であることがさらに好ましい。
　界面活性剤（Ｂ）の配合割合は、前記銀系無機抗菌剤１００重量部に対して、０．０１～２００重量部であることが好ましく、０．１～１００重量部がより好ましく、０．５～７０重量部がさらに好ましく、１～５０重量部が特に好ましい。 In the method for producing an antibacterial processing agent of the present invention, the step is a step of wet-grinding the silver-based inorganic antibacterial agent in the presence of the surfactant (B) in addition to the compound (A) and water. Is preferred. That is, it is a step of preparing a slurry liquid by mixing and stirring the compound (A), the surfactant (B), water and unmilled silver-based inorganic antibacterial agent, and finely pulverizing the slurry liquid with a wet pulverizer. Is preferred. By such a process, the dispersibility of the silver-based inorganic antibacterial agent and the stability over time of the dispersion of the silver-based inorganic antibacterial agent can be improved, and further excellent antibacterial properties and washing durability can be imparted. Can do. The surfactant (B) is at least one selected from a surfactant represented by the general formula (3), a surfactant represented by the general formula (4), and a surfactant represented by the general formula (5). It is preferable that it is at least one selected from a surfactant represented by the general formula (3) and a surfactant represented by the general formula (4), and is represented by the general formula (3). More preferably, it is a surfactant.
The blending ratio of the surfactant (B) is preferably 0.01 to 200 parts by weight, more preferably 0.1 to 100 parts by weight, with respect to 100 parts by weight of the silver-based inorganic antibacterial agent. 5 to 70 parts by weight is more preferable, and 1 to 50 parts by weight is particularly preferable.
　このようにして得られた抗菌加工薬剤は、前述したように、前記化合物（Ｘ）がより多く生成されているものと推測される。そして、微粒子化された銀系無機抗菌剤、化合物（Ａ）及び化合物（Ｘ）を含む抗菌加工薬剤を繊維材料に付着することによって、優れた抗菌性を付与することができるとともに、洗濯耐久性にも優れるという効果を奏するものと推測される。さらに、本発明の製造方法で得られた抗菌加工薬剤は、繊維材料に該薬剤を付与しても、銀イオンよる繊維材料の黄変（着色）を防止できるという優れた効果をも有している。 The antibacterial processing agent thus obtained is presumed to produce more compound (X) as described above. And by attaching the antibacterial processing agent containing the finely divided silver-based inorganic antibacterial agent, compound (A) and compound (X) to the fiber material, excellent antibacterial properties can be imparted and washing durability It is presumed that there is an effect that it is excellent. Furthermore, the antibacterial finishing agent obtained by the production method of the present invention has an excellent effect that even if the agent is applied to the fiber material, yellowing (coloring) of the fiber material due to silver ions can be prevented. Yes.
［抗菌性繊維の製造方法］
　本発明の抗菌性繊維の製造方法は、本発明の抗菌加工薬剤及び／又は本発明の製造方法で得られる抗菌加工薬剤を繊維材料に付与する工程を含むものである。すなわち、本発明の抗菌繊維の製造方法は、抗菌加工薬剤を後加工にて繊維材料に付与する工程を含むものである。後加工とは、繊維材料が製造された後に加工することを意味する。本製造方法によれば、抗菌性が優れ、洗濯耐久性にも優れた抗菌性繊維を得ることができる。さらに、銀イオンよる繊維材料の黄変（着色）を防止できる抗菌性繊維を得ることができる。 [Method for producing antibacterial fibers]
The method for producing an antibacterial fiber of the present invention includes a step of applying to the fiber material an antibacterial processing agent of the present invention and / or an antibacterial processing agent obtained by the production method of the present invention. That is, the manufacturing method of the antibacterial fiber of this invention includes the process of providing an antibacterial processing chemical | medical agent to a fiber material by post-processing. Post-processing means processing after the fiber material is manufactured. According to this production method, antibacterial fibers having excellent antibacterial properties and excellent washing durability can be obtained. Furthermore, the antibacterial fiber which can prevent yellowing (coloring) of the fiber material by silver ion can be obtained.
　繊維材料としては、天然繊維、化学繊維のいずれであってもよい。天然繊維としては、例えば、綿、***、亜麻、ヤシ、いぐさ等の植物繊維；羊毛、山羊毛、モヘア、カシミア、ラクダ、絹等の動物繊維；石綿等の鉱物繊維等を挙げることができる。化学繊維としては、例えば、ロックファィバ－、金属繊維、グラファイト、シリカ、チタン酸塩等の無機繊維；レーヨン、キュプラ、ビスコ－ス、ポリノジック、精製セルロース繊維等の再生セルロース系繊維；溶融紡糸セルロース繊維；牛乳タンパク、大豆タンパク等のタンパク質系繊維；再生絹、アルギン酸繊維等の再生・半合成繊維；ポリアミド繊維、ポリエステル繊維、カチオン可染ポリエステル繊維、ポリビニル繊維、ポリアクリルアルコール繊維、ポリウレタン繊維、アクリル繊維、ポリエチレン繊維、ポリビニリデン繊維、ポリスチレン繊維等の合成繊維を挙げることができる。また、これら繊維を２種以上複合（混紡、混繊、交織、交編等）されていてもよい。
　これらの中でも、吸水性の繊維の方が抗菌性を発揮し易い点から、植物繊維、動物繊維、再生セルロース系繊維、溶融紡糸セルロース繊維、又はこれらが複合された繊維が好ましい。 The fiber material may be either natural fiber or chemical fiber. Examples of natural fibers include plant fibers such as cotton, cannabis, flax, palm, and rush; animal fibers such as wool, goat wool, mohair, cashmere, camel, and silk; and mineral fibers such as asbestos. Examples of the chemical fiber include inorganic fibers such as rock fiber, metal fiber, graphite, silica, and titanate; regenerated cellulosic fibers such as rayon, cupra, viscose, polynosic, and purified cellulose fiber; melt-spun cellulose fiber; Protein fibers such as milk protein and soybean protein; Regenerated and semi-synthetic fibers such as regenerated silk and alginate fiber; Polyamide fiber, Polyester fiber, Cationic dyeable polyester fiber, Polyvinyl fiber, Polyacrylic alcohol fiber, Polyurethane fiber, Acrylic fiber, Examples thereof include synthetic fibers such as polyethylene fibers, polyvinylidene fibers, and polystyrene fibers. Two or more of these fibers may be combined (mixed spinning, mixed fiber, union, union, etc.).
Among these, a water-absorbing fiber is preferably a plant fiber, an animal fiber, a regenerated cellulose fiber, a melt-spun cellulose fiber, or a fiber in which these are combined from the viewpoint of easily exhibiting antibacterial properties.
　繊維材料の形態としては、例えば、織物、編物、布帛、糸状、不織布等の形態を挙げることができる。繊維材料の用途としては、抗菌性、吸水性、耐洗濯性を付与する対象物、例えば、アンダーウェア、スポーツ衣料、寝具類、カバー類等を挙げることができる。 Examples of the form of the fiber material include forms such as a woven fabric, a knitted fabric, a fabric, a thread shape, and a non-woven fabric. Examples of the use of the fiber material include objects that impart antibacterial properties, water absorption, and washing resistance, such as underwear, sports clothing, bedding, and covers.
　抗菌加工薬剤を繊維材料に付与する方法としては、特に限定はなく、公知の方法を採用できる。これらの中でも、抗菌加工薬剤を繊維材料に確実に固着させる理由から、吸尽法、パッドドライ法、スプレー法及びコーティング法から選ばれる少なくとも１種の方法が好ましく、パッドドライ法がさらに好ましい。 The method for applying the antibacterial agent to the fiber material is not particularly limited, and a known method can be employed. Among these, at least one method selected from the exhaust method, the pad dry method, the spray method, and the coating method is preferable, and the pad dry method is more preferable because the antibacterial processing agent is securely fixed to the fiber material.
　吸尽法、パッドドライ法、スプレー法、コーティング法としては、公知の方法を採用できる。吸尽法とは、薬剤の希薄溶液を用い、温度、浸せき時間、液循環回数等の条件を設定して、薬剤を繊維に選択吸着させることで吸尽付着させる方法である。その後、通常、水洗を行い、遠心脱水、乾燥を行う。パッドドライ法とは、薬剤の溶液中に繊維を短時間浸漬し、直ちに脱水マングル等で絞ることで付着させる方法である。その後乾燥を行い、必要に応じて、キュアリングを行う。スプレー法とは、一定速度のコンベアー上に繊維を乗せ、その上から、薬剤の溶液を一定量スプレーする事で付着させる方法である。その後乾燥を行い、必要に応じて、キュアリングを行う。コーティング法とは、通常マングルで薬剤の溶液を片面より塗布することで付着させる方法である。その後、余分の薬剤はドクターでかき落とし、乾燥を行い、必要に応じて、キュアリングを行う。 As the exhaust method, pad dry method, spray method, and coating method, known methods can be employed. The exhaust method is a method in which a diluted solution of a drug is used, conditions such as temperature, immersion time, number of times of liquid circulation, etc. are set, and the drug is selectively adsorbed on a fiber to be exhausted and adhered. Thereafter, washing is usually carried out, followed by centrifugal dehydration and drying. The pad dry method is a method in which fibers are immersed in a drug solution for a short time and immediately attached by squeezing with a dehydrated mangle or the like. Then, drying is performed and curing is performed as necessary. The spray method is a method in which fibers are placed on a conveyor at a constant speed and adhered by spraying a predetermined amount of a solution of the drug from the fiber. Then, drying is performed and curing is performed as necessary. The coating method is a method in which a drug solution is usually applied by applying from one side with a mangle. Then, the excess drug is scraped off with a doctor, dried, and cured if necessary.
　繊維材料に付与する際の抗菌加工薬剤（加工処理液）の不揮発分の重量割合は、０．０００１～１０重量％が好ましく、０．０００５～７重量％がより好ましく、０．００１～５重量％がさらに好ましい。なお、所定の重量割合は、水等で希釈することにより調製することができる。 The weight ratio of the non-volatile content of the antibacterial processing agent (processing solution) when applied to the fiber material is preferably 0.0001 to 10% by weight, more preferably 0.0005 to 7% by weight, and 0.001 to 5% by weight. % Is more preferable. The predetermined weight ratio can be prepared by diluting with water or the like.
　本発明の抗菌加工薬剤を繊維材料に付与する際の温度は、５～４０℃が好適である。付与温度が５℃より低いと、一定温度保持が難しいために繊維材料への一定付与ができなくなることがある。一方、付与温度が４０℃より高いと、繊維材料に含まれる染料等の溶出が多くなることがある。 The temperature at which the antibacterial processing agent of the present invention is applied to the fiber material is preferably 5 to 40 ° C. If the application temperature is lower than 5 ° C., it may be difficult to maintain the constant temperature, and thus it may not be possible to apply the constant to the fiber material. On the other hand, when the application temperature is higher than 40 ° C., the elution of dyes contained in the fiber material may increase.
　抗菌加工薬剤が付与された繊維材料は、テンションレス、あるいはテンションを加える等の方法によって乾燥され、本発明の抗菌性繊維を得ることができる。テンションレスで乾燥する方法としては、ノンタッチ乾燥機、ショートループ乾燥機、テンションレスローラ型、シリンダー乾燥機等が挙げられ、テンションを加え乾燥する方法としては、ピンテンター、クリップテンター等が挙げられる。
　乾燥温度については、特に限定はないが、抗菌加工薬剤を繊維材料に固着させるためには、１００℃以上が好ましく、１１０～２００℃がさらに好ましい。乾燥温度が１００℃より低いと、抗菌加工薬剤が繊維材料に固着しないことがある。 The fiber material to which the antibacterial processing agent has been applied is dried by a method such as tensionless or applying tension, whereby the antibacterial fiber of the present invention can be obtained. Examples of the tensionless drying method include a non-touch dryer, a short loop dryer, a tensionless roller type, and a cylinder dryer. Examples of the method of applying a tension and drying include a pin tenter and a clip tenter.
The drying temperature is not particularly limited, but is preferably 100 ° C. or higher and more preferably 110 to 200 ° C. in order to fix the antibacterial processing agent to the fiber material. When the drying temperature is lower than 100 ° C., the antibacterial processing agent may not adhere to the fiber material.
　繊維材料に対する抗菌加工薬剤の不揮発分の付与量については、特に限定はないが、繊維材料に対して０．０１～２０重量％が好ましく、０．０３～１５重量％がより好ましく、０．０５～１０重量％がさらに好ましい。０．０１重量％未満の場合、抗菌加工薬剤中の抗菌成分が少量で、処理した繊維が抗菌性を示さなくなることがある。２０重量％超の場合、抗菌性及び洗濯耐久性のこれ以上の向上は見られず、経済的に不利となることがある。 The amount of the non-volatile component of the antibacterial processing agent applied to the fiber material is not particularly limited, but is preferably 0.01 to 20% by weight, more preferably 0.03 to 15% by weight, more preferably 0.05 to the fiber material. More preferred is ˜10% by weight. If the amount is less than 0.01% by weight, the antibacterial component in the antibacterial processing agent may be a small amount, and the treated fiber may not exhibit antibacterial properties. If it exceeds 20% by weight, no further improvement in antibacterial properties and washing durability is observed, which may be economically disadvantageous.
　同時に加工可能な工程としては、防虫剤、防黴剤、防ダニ剤、消臭剤、帯電防止剤、撥水撥油剤、紫外線吸収剤、難燃剤、防汚剤、深色化剤、平滑剤、柔軟剤又は吸水剤を付与する工程等が挙げられる。これら工程は、複数同時に行うことも可能である。各剤については、公知のものを採用できる。 Processes that can be processed at the same time include insecticides, fungicides, mites, deodorants, antistatic agents, water and oil repellents, UV absorbers, flame retardants, antifouling agents, deep colorants, smoothing agents The process etc. which provide a softener or a water absorbing agent are mentioned. A plurality of these steps can be performed simultaneously. About each agent, a well-known thing can be employ | adopted.
　以下、本発明の実施例を示し、本発明をさらに詳細に説明するが、本発明はこれらの実施例に限定されるものではない。なお、例中の「部」および「％」とあるのは、それぞれ「重量部」および「重量％」を表す。 Hereinafter, examples of the present invention will be shown and the present invention will be described in more detail. However, the present invention is not limited to these examples. In the examples, “part” and “%” represent “part by weight” and “% by weight”, respectively.
（実施例１）
　表１の配合割合にあるように、ゼオライトに銀を含む抗菌性金属をイオン結合させた銀系無機抗菌剤１　２００重量部、ベンゾトリアゾール　２０重量部、軟水　７８０重量部を攪拌機に加え、十分に攪拌および分散させて、スラリー液を調製した。なお、銀系無機抗菌剤１は、抗菌剤全体に対して銀元素を２．４重量％、亜鉛を５．２重量％含有するものである。次いで、このスラリー液をスターミルＺＲＳ（アシザワファインテック（株）製）を用いて４時間微粒子化し、銀系無機抗菌剤の平均粒子径が０．４μｍである繊維用抗菌加工薬剤を得た。平均粒子径については、下記方法により測定した。得られた抗菌加工薬剤について、下記方法により安定性を評価した。その結果を表１に示す。
　次に、この抗菌加工薬剤に水を投入し、不揮発分の重量割合が１重量％となる加工処理液を調製した。綿ブロード（綿１００％平織り）をこの加工処理液に浸漬させ、マングルで絞った。この際、加工処理液の繊維に対する付着量は８０重量％であった。なお、繊維に対する付着量は次式により計算した。
　繊維に対する付着量（重量％）＝（加工処理液が含まれる綿ブロードの重量－未加工綿ブロードの重量）／未加工綿ブロードの重量×１００
　次に、この水溶液が含まれる綿ブロードをピンテンターで１１０℃、３分間乾燥させ、目的の試料（抗菌性繊維）を得た。得られた試料の抗菌性、洗濯耐久性、風合い及び黄変性について、下記方法により評価した。その結果を表１に示す。 Example 1
As shown in the mixing ratio of Table 1, 200 parts by weight of silver-based inorganic antibacterial agent 1 in which an antibacterial metal containing silver is ion-bonded to zeolite, 20 parts by weight of benzotriazole, and 780 parts by weight of soft water are added to the stirrer. A slurry liquid was prepared by stirring and dispersing. The silver-based inorganic antibacterial agent 1 contains 2.4% by weight of silver element and 5.2% by weight of zinc with respect to the whole antibacterial agent. Next, the slurry liquid was made into fine particles for 4 hours using Starmill ZRS (manufactured by Ashizawa Finetech Co., Ltd.) to obtain an antibacterial agent for fibers having an average particle diameter of the silver-based inorganic antibacterial agent of 0.4 μm. The average particle size was measured by the following method. About the obtained antibacterial processing chemical | medical agent, stability was evaluated by the following method. The results are shown in Table 1.
Next, water was added to the antibacterial processing agent to prepare a processing solution having a nonvolatile content of 1% by weight. Cotton broad (100% cotton plain weave) was immersed in this processing solution and squeezed with mangle. At this time, the adhesion amount of the processing solution to the fiber was 80% by weight. In addition, the adhesion amount with respect to the fiber was calculated by the following formula.
Amount of adhesion to fiber (% by weight) = (weight of cotton broad including processing solution−weight of raw cotton broad) / weight of raw cotton broad × 100
Next, the cotton broad band containing this aqueous solution was dried with a pin tenter at 110 ° C. for 3 minutes to obtain a target sample (antibacterial fiber). The antibacterial properties, washing durability, texture and yellowing of the obtained samples were evaluated by the following methods. The results are shown in Table 1.
＜平均粒子径＞
　抗菌加工薬剤を不揮発分の重量割合が３重量％となるよう蒸留水で希釈し、この希釈液についてレーザー回折・散乱式粒子径分布測定装置ＬＡ－９１０（堀場製作所製）を用いて、体積基準とするメジアン粒径を測定した。 <Average particle size>
The antibacterial processing agent is diluted with distilled water so that the weight ratio of the non-volatile content is 3% by weight, and this diluted solution is volume-based using a laser diffraction / scattering particle size distribution measuring apparatus LA-910 (manufactured by Horiba). The median particle size was measured.
＜繊維用抗菌加工薬剤の安定性＞
　抗菌加工薬剤１００ｍＬをスクリュー管に投入し、密閉した。これを温度７０℃に調節したインキュベーターに１週間放置し、安定性を以下の４段階に分類して判定した。
　　◎：水分散体の５％未満しか沈殿しない。
　　○：水分散体の５％以上、１０％未満が沈殿する。
　　△：水分散体の１０％以上、２０％未満が沈殿する。
　　×：水分散体の２０％以上が沈殿する。 <Stability of antibacterial agents for textiles>
100 mL of the antibacterial processing agent was put into a screw tube and sealed. This was left in an incubator adjusted to a temperature of 70 ° C. for 1 week, and the stability was determined by classifying into the following four stages.
A: Only less than 5% of the aqueous dispersion is precipitated.
○: 5% or more and less than 10% of the aqueous dispersion is precipitated.
Δ: 10% or more and less than 20% of the aqueous dispersion is precipitated.
X: 20% or more of the aqueous dispersion is precipitated.
＜抗菌性（加工仕上がり）＞
　得られた試料について、ＳＥＫ統一試験法（ＪＩＳ　Ｌ　１９０２、菌吸収法）に準じて、抗菌性を測定した。試験には、試験菌として黄色ぶどう球菌を用い、その際の増殖値は２．１と試験成立条件を満たしていた。ＳＥＫ統一試験法によれば、抗菌性を有するためには、下記を満たす必要がある。
　制菌基準　　：殺菌活性値≧０
　抗菌防臭基準：静菌活性値≧２．２ <Antimicrobial (finished)>
About the obtained sample, antibacterial property was measured according to the SEK unification test method (JIS L1902, bacteria absorption method). In the test, Staphylococcus aureus was used as a test bacterium, and the growth value at that time was 2.1, which satisfied the test establishment condition. According to the SEK unified test method, in order to have antibacterial properties, the following conditions must be satisfied.
Antibacterial criteria: Bactericidal activity value ≧ 0
Antibacterial deodorization standard: bacteriostatic activity value ≧ 2.2
＜抗菌性（洗濯後）＞
　得られた試料を下記の条件で洗濯したものについて、上記の抗菌性（加工仕上がり）の試験方法と同じ方法により抗菌性を測定して、洗濯耐久性の評価を行った。
　ＪＩＳ　Ｌ　０２１７　１０３号に従って、ＪＡＦＥＴ標準洗剤を３ｇ／Ｌの割合で用い、浴比１：３０として、４０℃で５分間水洗擢した後、４０℃で２分間のすすぎを２回行い、遠心脱水を行い、その後、陰干しする作業を１サイクルとし、これを１０サイクル行った。 <Antimicrobial (after washing)>
About what wash | cleaned the obtained sample on the following conditions, antibacterial property was measured by the same method as the test method of said antibacterial property (processed finish), and washing durability was evaluated.
In accordance with JIS L 0217 103, using a JAFET standard detergent at a rate of 3 g / L, washing with water at 40 ° C. for 5 minutes at a bath ratio of 1:30, then rinsing twice at 40 ° C. for 2 minutes, and centrifugal dehydration After that, the work of drying in the shade was defined as one cycle, and this was performed for 10 cycles.
＜風合い＞
　得られた試料について、風合を、触感にて評価した。なお、風合の評価は以下の基準に基づき、以下の４段階に分類して判定した。
　　◎：　柔軟である。
　　○：　やや柔軟である（未加工の綿ブロード布と同等）。
　　△：　やや粗硬である。
　　×：　粗硬である。 <Texture>
The texture of the obtained sample was evaluated by touch. In addition, the evaluation of the texture was determined by classifying into the following four stages based on the following criteria.
A: Flexible.
○: Slightly flexible (equivalent to raw cotton broad cloth)
Δ: Slightly coarse and hard
X: It is coarse and hard.
＜黄変性＞
　試料を温度７０℃、湿度９０％に調節したインキュベーターに４日間放置し、黄変性を評価した。黄変性の評価は、分光測色計（ＣＭ－３６００ｄ、コニカミノルタ製）を使用し、未加工の綿ブロード布を基準にΔＹＩを測定し、行った。
　評価基準はΔＹＩ＜５ならば、黄変していないと見なした。 <Yellowing>
The sample was left in an incubator adjusted to a temperature of 70 ° C. and a humidity of 90% for 4 days to evaluate yellowing. Evaluation of yellowing was performed using a spectrocolorimeter (CM-3600d, manufactured by Konica Minolta) and measuring ΔYI with reference to an unprocessed cotton broad cloth.
If the evaluation criterion was ΔYI <5, it was regarded as not yellowing.
（実施例２～５、８～１１、１４～３６）
　実施例２～５、８～１１、１４～３６は、実施例１のスラリー液を表１～３に示す成分及び配合割合に変更したスラリー液を調製した以外は、実施例１と同様にして、評価をした。その結果を表１～３に示す。
　なお、銀系無機抗菌剤２は、ゼオライトに銀を含む抗菌性金属をイオン結合させた銀系無機抗菌剤であり、抗菌剤全体に対して銀元素を１．２重量％、亜鉛を２．６重量％含有するものである。銀系無機抗菌剤３は、ゼオライトに銀を含む抗菌性金属をイオン結合させた銀系無機抗菌剤であり、抗菌剤全体に対して銀元素を０．５重量％、亜鉛を１．１重量％含有するものである。銀系無機抗菌剤４は、リン酸ジルコニウムに銀を含む抗菌性金属をイオン結合させた銀系無機抗菌剤であり、抗菌剤全体に対して銀元素を０．５重量％、亜鉛を１．１重量％含有するものである。 (Examples 2 to 5, 8 to 11, 14 to 36)
Examples 2 to 5, 8 to 11, and 14 to 36 were the same as Example 1 except that slurry liquids were prepared by changing the slurry liquid of Example 1 to the components and blending ratios shown in Tables 1 to 3. And evaluated. The results are shown in Tables 1 to 3.
Silver-based inorganic antibacterial agent 2 is a silver-based inorganic antibacterial agent in which an antibacterial metal containing silver is ion-bonded to zeolite, and 1.2% by weight of silver element and 2. It contains 6% by weight. Silver-based inorganic antibacterial agent 3 is a silver-based inorganic antibacterial agent in which an antibacterial metal containing silver is ion-bonded to zeolite, and 0.5% by weight of silver element and 1.1% of zinc with respect to the whole antibacterial agent % Content. The silver-based inorganic antibacterial agent 4 is a silver-based inorganic antibacterial agent in which an antibacterial metal containing silver is ion-bonded to zirconium phosphate. 0.5% by weight of silver element and 1. It contains 1% by weight.
（実施例６、７）
　実施例６、７は、実施例１のスラリー液をスターミルＺＲＳにより、それぞれ２時間、３時間微粒子化し、銀系無機抗菌剤１の平均粒子径が１．３μｍ、２．６μｍである抗菌加工薬剤を得た以外は、実施例１と同様にして、評価をした。その結果を表１に示す。 (Examples 6 and 7)
Examples 6 and 7 are antibacterial processing agents in which the slurry liquid of Example 1 is finely divided by a star mill ZRS for 2 hours and 3 hours, respectively, and the average particle diameter of the silver-based inorganic antibacterial agent 1 is 1.3 μm and 2.6 μm. Evaluation was carried out in the same manner as in Example 1 except that the above was obtained. The results are shown in Table 1.
（実施例１２、１３）
　実施例１２、１３は、実施例１の繊維用抗菌加工薬剤に水を投入し、不揮発分の重量割合がそれぞれ０．１重量％、０．００１重量％となる加工処理液を調製した以外は実施例１と同様にして、評価をした。その結果を表１に示す。 (Examples 12 and 13)
In Examples 12 and 13, water was added to the antibacterial processing agent for fibers of Example 1, and a processing solution was prepared in which the weight ratios of nonvolatile components were 0.1% by weight and 0.001% by weight, respectively. Evaluation was performed in the same manner as in Example 1. The results are shown in Table 1.
（比較例１～４）
　比較例１～４は、実施例１の抗菌加工薬剤を次の抗菌加工薬剤に変更する以外は、実施例１と同様にして、評価をした。その結果を表４に示す。
　比較例１～４の抗菌加工薬剤：表４に示す配合割合で各成分を攪拌機に加え、十分に攪拌および分散させ、比較例１～４の抗菌加工薬剤をそれぞれ調製した。比較例１～４の抗菌加工薬剤の平均粒子径は、それぞれ、４．１μｍ、４．２μｍ、４．１μｍ、４．１μｍであった。 (Comparative Examples 1 to 4)
Comparative Examples 1 to 4 were evaluated in the same manner as in Example 1 except that the antibacterial processing agent of Example 1 was changed to the following antibacterial processing agent. The results are shown in Table 4.
Antibacterial finishing agents of Comparative Examples 1 to 4: Each component was added to a stirrer in the blending ratio shown in Table 4, and sufficiently stirred and dispersed to prepare antibacterial finishing agents of Comparative Examples 1 to 4, respectively. The average particle diameters of the antibacterial processing agents of Comparative Examples 1 to 4 were 4.1 μm, 4.2 μm, 4.1 μm, and 4.1 μm, respectively.
（比較例５）
　ブランク（ＢＬ）として、未加工の綿ブロードについて、実施例１と同様に評価した。その結果を表３に示す。 (Comparative Example 5)
As blank (BL), raw cotton broad was evaluated in the same manner as in Example 1. The results are shown in Table 3.
（実施例１Ａ、８Ａ、１４Ａ、１５Ａ、１６Ａ、２７Ａ、３２Ａ）
　実施例１Ａ、８Ａ、１４Ａ、１５Ａ、１６Ａ、２７Ａ、３２Ａは、抗菌加工薬剤として実施例１、８、１４、１５、１６、２７、３２の安定性評価（温度７０℃、１週間放置）を行った薬剤を用いる以外は実施例１と同様にして、抗菌性を測定した。その結果を表５に示す。 (Examples 1A, 8A, 14A, 15A, 16A, 27A, 32A)
Examples 1A, 8A, 14A, 15A, 16A, 27A, and 32A are the antibacterial agents used for evaluating the stability of Examples 1, 8, 14, 15, 16, 27, and 32 (temperature 70 ° C, left for 1 week). Antibacterial properties were measured in the same manner as in Example 1 except that the performed drug was used. The results are shown in Table 5.
Figure JPOXMLDOC01-appb-T000017
Figure JPOXMLDOC01-appb-T000017
Figure JPOXMLDOC01-appb-T000018
Figure JPOXMLDOC01-appb-T000018
Figure JPOXMLDOC01-appb-T000019
Figure JPOXMLDOC01-appb-T000019
Figure JPOXMLDOC01-appb-T000020
Figure JPOXMLDOC01-appb-T000020
Figure JPOXMLDOC01-appb-T000021
Figure JPOXMLDOC01-appb-T000021
　表１～５より、本発明の繊維用抗菌加工薬剤を付与した繊維材料は、優れた抗菌性を有しており、また洗濯後もその抗菌性を維持している（洗濯耐久性を有している）ことがわかる。また、風合いについても低下することはない。さらに、黄変性についても優れている。
　加えて、界面活性剤（Ｂ）を用いると、銀系無機抗菌剤の分散性を向上させ、銀系無機抗菌剤の分散体の経時的な安定性を向上させるのに有効であることがわかる。さらに、表５から、一層優れた抗菌性及び洗濯耐久性を付与できることがわかる。 From Tables 1 to 5, the fiber material to which the antibacterial agent for fibers of the present invention has been applied has excellent antibacterial properties and maintains its antibacterial properties even after washing (has washing durability). I understand). In addition, the texture does not decrease. Furthermore, it is excellent also about yellowing.
In addition, it can be seen that the use of the surfactant (B) is effective in improving the dispersibility of the silver-based inorganic antibacterial agent and improving the temporal stability of the dispersion of the silver-based inorganic antibacterial agent. . Furthermore, it can be seen from Table 5 that more excellent antibacterial properties and washing durability can be imparted.
　本発明の抗菌加工薬剤は、繊維材料に抗菌性を付与するときに好適に使用できる。 The antibacterial processing agent of the present invention can be suitably used for imparting antibacterial properties to fiber materials.

Claims (9)

  1. 　無機担体に銀を含有する抗菌性金属を担持させてなる銀系無機抗菌剤、下記一般式（１）で示される化合物（Ａ）及び水を必須に含み、
    　該銀系無機抗菌剤が水に分散された状態であり、かつその平均粒子径が０．０１～３μｍである、繊維用抗菌加工薬剤。
    Figure JPOXMLDOC01-appb-C000001
     （式中、Ｒ１は、水素原子、ハロゲン原子、炭素数１～３０のアルキル基、炭素数６～３０のアリール基、炭素数７～３０のアラルキル基、ＮＲ２Ｒ３又はＯＲ４ある。Ｒ２、Ｒ３及びＲ４は、それぞれ独立して、水素原子、炭素数１～３０のアルキル基、炭素数６～３０のアリール基または炭素数７～３０のアラルキル基である。Ｍ１は、水素原子、アルカリ金属、アルカリ土類金属又はＮＲａＲｂＲｃＲｄで示される基である。Ｒａ、Ｒｂ、Ｒｃ及びＲｄは、それぞれ独立して、水素原子、アルキル基、アルカノール基又はポリオキシアルキレン基である。）     A silver-based inorganic antibacterial agent obtained by supporting an antibacterial metal containing silver on an inorganic carrier, a compound (A) represented by the following general formula (1), and water are essential.
    An antibacterial processing agent for fibers, wherein the silver-based inorganic antibacterial agent is dispersed in water and has an average particle size of 0.01 to 3 μm.
    Figure JPOXMLDOC01-appb-C000001
     (Wherein R 1 is a hydrogen atom, a halogen atom, an alkyl group having 1 to 30 carbon atoms, an aryl group having 6 to 30 carbon atoms, an aralkyl group having 7 to 30 carbon atoms, NR 2 R 3 or OR 4 . R 2, R 3 and R 4 are each independently a hydrogen atom, an alkyl group having 1 to 30 carbon atoms, .M 1 is an aryl group or an aralkyl group having 7 to 30 carbon atoms of 6 to 30 carbon atoms is , A hydrogen atom, an alkali metal, an alkaline earth metal or a group represented by NR a R b R c R d R a , R b , R c and R d are each independently a hydrogen atom, an alkyl group, , An alkanol group or a polyoxyalkylene group.)
  2. 　前記無機担体が、ゼオライト、リン酸ジルコニウム、シリカゲル、アパタイト、含水酸化チタン、モンモリロナイト、ガラス粉末及びチタン酸カリウムウインスカーから選ばれる少なくとも１種である、請求項１に記載の抗菌加工薬剤。 The antibacterial processing agent according to claim 1, wherein the inorganic carrier is at least one selected from zeolite, zirconium phosphate, silica gel, apatite, hydrous titanium oxide, montmorillonite, glass powder and potassium titanate winker.
  3. 　さらに、下記一般式（２）で示される界面活性剤、下記一般式（３）で示される界面活性剤、下記一般式（４）で示される界面活性剤及び下記一般式（５）で示される界面活性剤から選ばれる少なくとも１種の界面活性剤（Ｂ）を含む、請求項１又は２に記載の抗菌加工薬剤。
    Figure JPOXMLDOC01-appb-C000002
     （式中、Ｒ５は、炭素数１～３０のアルキル基、炭素数６～３０のアリール基又は炭素数７～３０のアラルキル基である。Ａ１Ｏは炭素数２～４のオキシアルキレン基である。ｎは０～５０の整数である。ｍは１～３の整数である。Ｍ２は、水素原子、アルカリ金属、アルカリ土類金属又はＮＲａＲｂＲｃＲｄで示される基である。Ｒａ、Ｒｂ、Ｒｃ及びＲｄは、それぞれ独立して、水素原子、アルキル基、アルカノール基又はポリオキシアルキレン基である。）
    Figure JPOXMLDOC01-appb-C000003
     （式中、Ａ２Ｏは、炭素数２～４のオキシアルキレン基であり、ｋは２～７０の整数であり、ｑは１～３の整数である。）
    Figure JPOXMLDOC01-appb-C000004
     （式中、Ａ３Ｏは、炭素数２～４のオキシアルキレン基であり、ｊは２～７０の整数であり、ｒは１～３の整数である。Ｍ３は、水素原子、アルカリ金属、アルカリ土類金属又はＮＲａＲｂＲｃＲｄで示される基である。Ｒａ、Ｒｂ、Ｒｃ及びＲｄは、それぞれ独立して、水素原子、アルキル基、アルカノール基又はポリオキシアルキレン基である。）
    Figure JPOXMLDOC01-appb-C000005
     （式中、Ａ４Ｏは、炭素数２～４のオキシアルキレン基であり、ｈは２～７０の整数であり、ｓは１～３の整数であり、ｔは１又は２の整数である。Ｍ４は、水素原子、アルカリ金属、アルカリ土類金属又はＮＲａＲｂＲｃＲｄで示される基である。Ｒａ、Ｒｂ、Ｒｃ及びＲｄは、それぞれ独立して、水素原子、アルキル基、アルカノール基又はポリオキシアルキレン基である。）     Furthermore, the surfactant represented by the following general formula (2), the surfactant represented by the following general formula (3), the surfactant represented by the following general formula (4), and the following general formula (5) The antibacterial processing agent according to claim 1 or 2, comprising at least one surfactant (B) selected from surfactants.
    Figure JPOXMLDOC01-appb-C000002
     (Wherein R 5 is an alkyl group having 1 to 30 carbon atoms, an aryl group having 6 to 30 carbon atoms, or an aralkyl group having 7 to 30 carbon atoms. A 1 O is an oxyalkylene group having 2 to 4 carbon atoms. N is an integer of 0 to 50. m is an integer of 1 to 3. M 2 is a hydrogen atom, an alkali metal, an alkaline earth metal, or a group represented by NR a R b R c R d R a , R b , R c and R d are each independently a hydrogen atom, an alkyl group, an alkanol group or a polyoxyalkylene group.)
    Figure JPOXMLDOC01-appb-C000003
     (Wherein A 2 O is an oxyalkylene group having 2 to 4 carbon atoms, k is an integer of 2 to 70, and q is an integer of 1 to 3)
    Figure JPOXMLDOC01-appb-C000004
     (Wherein A 3 O is an oxyalkylene group having 2 to 4 carbon atoms, j is an integer of 2 to 70, and r is an integer of 1 to 3. M 3 is a hydrogen atom, an alkali metal , Alkaline earth metal or a group represented by NR a R b R c R d R a , R b , R c and R d are each independently a hydrogen atom, an alkyl group, an alkanol group or a polyoxy group. An alkylene group.)
    Figure JPOXMLDOC01-appb-C000005
     (In the formula, A 4 O is an oxyalkylene group having 2 to 4 carbon atoms, h is an integer of 2 to 70, s is an integer of 1 to 3, and t is an integer of 1 or 2) M 4 is a hydrogen atom, an alkali metal, an alkaline earth metal or a group represented by NR a R b R c R d R a , R b , R c and R d are each independently hydrogen An atom, an alkyl group, an alkanol group or a polyoxyalkylene group.)
  4. 　前記界面活性剤（Ｂ）が、前記一般式（３）で示される界面活性剤、前記一般式（４）で示される界面活性剤及び前記一般式（５）で示される界面活性剤から選ばれる少なくとも１種である、請求項１～３のいずれかに記載の抗菌加工薬剤。 The surfactant (B) is selected from the surfactant represented by the general formula (3), the surfactant represented by the general formula (4), and the surfactant represented by the general formula (5). The antibacterial processing agent according to any one of claims 1 to 3, which is at least one kind.
  5. 　下記一般式（１）で示される化合物（Ａ）及び水の存在下、無機担体に銀を含有する抗菌性金属を担持させてなる銀系無機抗菌剤を湿式粉砕する工程を含み、
    　湿式粉砕された銀系無機抗菌剤の平均粒子径が０．０１～３μｍである、繊維用抗菌加工薬剤の製造方法。
    Figure JPOXMLDOC01-appb-C000006
     （式中、Ｒ１は、水素原子、ハロゲン原子、炭素数１～３０のアルキル基、炭素数６～３０のアリール基、炭素数７～３０のアラルキル基、ＮＲ２Ｒ３又はＯＲ４である。Ｒ２、Ｒ３及びＲ４は、それぞれ独立して、水素原子、炭素数１～３０のアルキル基、炭素数６～３０のアリール基または炭素数７～３０のアラルキル基である。Ｍ１は、水素原子、アルカリ金属又はＮＲａＲｂＲｃＲｄで示される基である。Ｒａ、Ｒｂ、Ｒｃ及びＲｄは、それぞれ独立して、水素原子、アルキル基、アルカノール基又はポリオキシアルキレン基である。）     Including a step of wet-grinding a silver-based inorganic antibacterial agent in which an antibacterial metal containing silver is supported on an inorganic carrier in the presence of the compound (A) represented by the following general formula (1) and water,
    A method for producing an antibacterial agent for fibers, wherein the wet-pulverized silver-based inorganic antibacterial agent has an average particle size of 0.01 to 3 μm.
    Figure JPOXMLDOC01-appb-C000006
     (Wherein R 1 is a hydrogen atom, a halogen atom, an alkyl group having 1 to 30 carbon atoms, an aryl group having 6 to 30 carbon atoms, an aralkyl group having 7 to 30 carbon atoms, NR 2 R 3 or OR 4 . .R 2, R 3 and R 4 are each independently hydrogen atom, an alkyl group having 1 to 30 carbon atoms, an aryl group or an aralkyl group having 7 to 30 carbon atoms of 6 to 30 carbon atoms .M 1 Is a hydrogen atom, an alkali metal or a group represented by NR a R b R c R d , R a , R b , R c and R d are each independently a hydrogen atom, an alkyl group, an alkanol group or It is a polyoxyalkylene group.)
  6. 　前記無機担体が、ゼオライト、リン酸ジルコニウム、シリカゲル、アパタイト、含水酸化チタン、モンモリロナイト、ガラス粉末及びチタン酸カリウムウインスカーから選ばれる少なくとも１種である、請求項５に記載の抗菌加工薬剤の製造方法。 The method for producing an antibacterial processing agent according to claim 5, wherein the inorganic carrier is at least one selected from zeolite, zirconium phosphate, silica gel, apatite, hydrous titanium oxide, montmorillonite, glass powder and potassium titanate winker. .
  7. 　前記工程が、前記化合物（Ａ）及び水に加え、界面活性剤（Ｂ）の存在下、前記銀系無機抗菌剤を湿式粉砕する工程であり、
    　前記界面活性剤（Ｂ）が、下記一般式（２）で示される界面活性剤、下記一般式（３）で示される界面活性剤、下記一般式（４）で示される界面活性剤及び下記一般式（５）で示される界面活性剤から選ばれる少なくとも１種である、請求項５又は６に記載の抗菌加工薬剤の製造方法。
    Figure JPOXMLDOC01-appb-C000007
     （式中、Ｒ５は、炭素数１～３０のアルキル基、炭素数６～３０のアリール基または炭素数７～３０のアラルキル基である。Ａ１Ｏは炭素数２～４のオキシアルキレン基である。ｎは０～５０の整数である。ｍは１～３の整数である。Ｍ２は、水素原子、アルカリ金属、アルカリ土類金属又はＮＲａＲｂＲｃＲｄで示される基である。Ｒａ、Ｒｂ、Ｒｃ及びＲｄは、それぞれ独立して、水素原子、アルキル基、アルカノール基又はポリオキシアルキレン基である。）
    Figure JPOXMLDOC01-appb-C000008
     （式中、Ａ２Ｏは、炭素数２～４のオキシアルキレン基であり、ｋは２～７０の整数であり、ｑは１～３の整数である。）
    Figure JPOXMLDOC01-appb-C000009
     （式中、Ａ３Ｏは、炭素数２～４のオキシアルキレン基であり、ｊは２～７０の整数であり、ｒは１～３の整数である。Ｍ３は、水素原子、アルカリ金属、アルカリ土類金属又はＮＲａＲｂＲｃＲｄで示される基である。Ｒａ、Ｒｂ、Ｒｃ及びＲｄは、それぞれ独立して、水素原子、アルキル基、アルカノール基又はポリオキシアルキレン基である。）
    Figure JPOXMLDOC01-appb-C000010
     （式中、Ａ４Ｏは、炭素数２～４のオキシアルキレン基であり、ｈは２～７０の整数であり、ｓは１～３の整数であり、ｔは１または２の整数である。Ｍ４は、水素原子、アルカリ金属、アルカリ土類金属又はＮＲａＲｂＲｃＲｄで示される基である。Ｒａ、Ｒｂ、Ｒｃ及びＲｄは、それぞれ独立して、水素原子、アルキル基、アルカノール基又はポリオキシアルキレン基である。）     The step is a step of wet-grinding the silver-based inorganic antibacterial agent in the presence of the surfactant (B) in addition to the compound (A) and water,
    The surfactant (B) is a surfactant represented by the following general formula (2), a surfactant represented by the following general formula (3), a surfactant represented by the following general formula (4), and the following general formula The method for producing an antibacterial processing agent according to claim 5 or 6, which is at least one selected from surfactants represented by formula (5).
    Figure JPOXMLDOC01-appb-C000007
     (Wherein R 5 is an alkyl group having 1 to 30 carbon atoms, an aryl group having 6 to 30 carbon atoms, or an aralkyl group having 7 to 30 carbon atoms. A 1 O is an oxyalkylene group having 2 to 4 carbon atoms. N is an integer of 0 to 50. m is an integer of 1 to 3. M 2 is a hydrogen atom, an alkali metal, an alkaline earth metal, or a group represented by NR a R b R c R d R a , R b , R c and R d are each independently a hydrogen atom, an alkyl group, an alkanol group or a polyoxyalkylene group.)
    Figure JPOXMLDOC01-appb-C000008
     (Wherein A 2 O is an oxyalkylene group having 2 to 4 carbon atoms, k is an integer of 2 to 70, and q is an integer of 1 to 3)
    Figure JPOXMLDOC01-appb-C000009
     (Wherein A 3 O is an oxyalkylene group having 2 to 4 carbon atoms, j is an integer of 2 to 70, and r is an integer of 1 to 3. M 3 is a hydrogen atom, an alkali metal , Alkaline earth metal or a group represented by NR a R b R c R d R a , R b , R c and R d are each independently a hydrogen atom, an alkyl group, an alkanol group or a polyoxy group. An alkylene group.)
    Figure JPOXMLDOC01-appb-C000010
     (Wherein A 4 O is an oxyalkylene group having 2 to 4 carbon atoms, h is an integer of 2 to 70, s is an integer of 1 to 3, and t is an integer of 1 or 2) M 4 is a hydrogen atom, an alkali metal, an alkaline earth metal or a group represented by NR a R b R c R d R a , R b , R c and R d are each independently hydrogen An atom, an alkyl group, an alkanol group or a polyoxyalkylene group.)
  8. 　前記界面活性剤（Ｂ）が、前記一般式（３）で示される界面活性剤、前記一般式（４）で示される界面活性剤及び前記一般式（５）で示される界面活性剤から選ばれる少なくとも１種である、請求項５～７のいずれかに記載の抗菌加工薬剤の製造方法。 The surfactant (B) is selected from the surfactant represented by the general formula (3), the surfactant represented by the general formula (4), and the surfactant represented by the general formula (5). The method for producing an antibacterial processing agent according to any one of claims 5 to 7, wherein there is at least one kind.
  9. 　請求項１～４のいずれかに記載の抗菌加工薬剤及び／又は請求項５～８のいずれかに記載の製造方法で得られる抗菌加工薬剤を繊維材料に付与する工程を含む、抗菌性繊維の製造方法。 An antibacterial fiber comprising a step of applying to the fiber material an antibacterial processing agent according to any one of claims 1 to 4 and / or an antibacterial processing agent obtained by the production method according to any one of claims 5 to 8. Production method.
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CN102899893A (en) * 2012-09-17 2013-01-30 南通市田园装饰布有限公司 Insect-protected, antistatic and antibacterial sofa cloth
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