CN116744795A - Antiviral agent composition, antiviral fabric treated with the same, antiviral polyurethane sheet, and antiviral polyvinyl chloride sheet - Google Patents

Antiviral agent composition, antiviral fabric treated with the same, antiviral polyurethane sheet, and antiviral polyvinyl chloride sheet Download PDF

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Publication number
CN116744795A
CN116744795A CN202280011881.XA CN202280011881A CN116744795A CN 116744795 A CN116744795 A CN 116744795A CN 202280011881 A CN202280011881 A CN 202280011881A CN 116744795 A CN116744795 A CN 116744795A
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China
Prior art keywords
antiviral
antiviral agent
sheet
group
agent composition
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CN202280011881.XA
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Chinese (zh)
Inventor
大原弘平
藤田和博
大石贵之
福井龙也
竹田麻希
前田纯一
近藤邦晃
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Nicca Chemical Co Ltd
TB Kawashima Co Ltd
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Nicca Chemical Co Ltd
TB Kawashima Co Ltd
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Publication of CN116744795A publication Critical patent/CN116744795A/en
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    • 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
    • A01N25/10—Macromolecular compounds
    • 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
    • A01N55/00—Biocides, pest repellants or attractants, or plant growth regulators, containing organic compounds containing elements other than carbon, hydrogen, halogen, oxygen, nitrogen and sulfur
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01P—BIOCIDAL, PEST REPELLANT, PEST ATTRACTANT OR PLANT GROWTH REGULATORY ACTIVITY OF CHEMICAL COMPOUNDS OR PREPARATIONS
    • A01P1/00—Disinfectants; Antimicrobial compounds or mixtures thereof
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K31/00—Medicinal preparations containing organic active ingredients
    • A61K31/695—Silicon compounds
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K9/00—Medicinal preparations characterised by special physical form
    • A61K9/08—Solutions
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61P—SPECIFIC THERAPEUTIC ACTIVITY OF CHEMICAL COMPOUNDS OR MEDICINAL PREPARATIONS
    • A61P31/00—Antiinfectives, i.e. antibiotics, antiseptics, chemotherapeutics
    • A61P31/12—Antivirals
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/08—Processes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/54—Silicon-containing compounds
    • C08K5/544—Silicon-containing compounds containing nitrogen
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L1/00—Compositions of cellulose, modified cellulose or cellulose derivatives
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L101/00—Compositions of unspecified macromolecular compounds
    • C08L101/12—Compositions of unspecified macromolecular compounds characterised by physical features, e.g. anisotropy, viscosity or electrical conductivity
    • C08L101/14—Compositions of unspecified macromolecular compounds characterised by physical features, e.g. anisotropy, viscosity or electrical conductivity the macromolecular compounds being water soluble or water swellable, e.g. aqueous gels
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L29/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal or ketal radical; Compositions of hydrolysed polymers of esters of unsaturated alcohols with saturated carboxylic acids; Compositions of derivatives of such polymers
    • C08L29/02—Homopolymers or copolymers of unsaturated alcohols
    • C08L29/04—Polyvinyl alcohol; Partially hydrolysed homopolymers or copolymers of esters of unsaturated alcohols with saturated carboxylic acids
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L3/00—Compositions of starch, amylose or amylopectin or of their derivatives or degradation products
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L71/00—Compositions of polyethers obtained by reactions forming an ether link in the main chain; Compositions of derivatives of such polymers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L75/00—Compositions of polyureas or polyurethanes; Compositions of derivatives of such polymers
    • C08L75/04—Polyurethanes
    • 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
    • D06M13/46—Compounds containing quaternary nitrogen atoms
    • D06M13/463—Compounds containing quaternary nitrogen atoms derived from monoamines

Abstract

The present invention provides an antiviral agent composition which can impart an antiviral agent comprising a methoxysilane quaternary ammonium salt and an aqueous polyurethane resin in a single bath by one-time processing. The present invention also provides an antiviral fabric, a polyurethane sheet, and a polyvinyl chloride sheet each having a layer formed using the antiviral agent composition on the surface. The antiviral agent composition of the present invention is a mixture containing an antiviral agent comprising a methoxysilane quaternary ammonium salt and an aqueous polyurethane resin having a carboxyl group and/or a carboxylate group as a binder, and contains a water-soluble organic polymer (for example, a urethane-modified polyether) as a dispersant.

Description

Antiviral agent composition, antiviral fabric treated with the same, antiviral polyurethane sheet, and antiviral polyvinyl chloride sheet
Technical Field
The present invention relates to an antiviral agent-containing composition, an antiviral fabric treated with the composition, and an antiviral Polyurethane (PU) sheet and an antiviral polyvinyl chloride (PVC) sheet surface-coated with the composition.
Background
In recent years, due to an increase in environmental sanitation consciousness, many antibacterial/antiviral agents and raw materials for imparting antibacterial/antiviral agents have been developed. As the antibacterial/antiviral agent containing silicon, organosilane compounds containing a hydrolyzable group are known. Among these, ethoxysilane quaternary ammonium salts are known as antiviral agents that can be immobilized on the surface of a raw material (patent document 1). The antiviral agent has the following characteristics: an ammonium group having a relatively long chain alkyl group exhibiting antiviral activity and an alkoxysilyl group capable of forming a covalent bond with the surface of a raw material are contained in the molecule, and the alkoxysilyl group reacts with an oxygen-containing functional group such as a hydroxyl group existing on the surface of an inorganic material or the like to form a covalent bond, thereby being firmly fixed to the surface of the material.
On the other hand, when the antiviral agent is fixed to an article having no oxygen-containing functional group on the surface, for example, a synthetic fiber such as a polyester fiber, a resin material such as polypropylene, or the like, a pretreatment step is required. Patent document 1 also discloses that an article is subjected to ozone water treatment before an antiviral agent is applied to the surface of the article in order to apply an oxygen-containing functional group to the article.
Further, patent document 2 discloses that when the antiviral agent is fixed to a synthetic resin article, by performing plasma treatment before fixing the antiviral agent, the antiviral agent can be effectively fixed even when the synthetic resin is a polymethyl methacrylate resin or a polyethylene terephthalate resin. Patent document 3 describes that microwave irradiation is performed in addition to ozone water treatment in order to fix the antiviral agent to the surface of the article. Ozone water treatment and microwave irradiation are both performed to generate-OH groups, -CHO groups (aldehyde groups), or-O-groups on the surface of an article.
Further, patent document 4 discloses that a binder having a carboxyl group is added to synthetic fibers before the fixation treatment of an antiviral agent in order to fix the antiviral agent to the synthetic fibers. According to the invention of patent document 4, an antiviral agent can be appropriately added to synthetic fibers such as polyester fibers.
Patent document 5 discloses a method in which the compatibility of the antiviral agent with a specific acrylic resin component is verified, and the antiviral agent can be treated by a single process.
Prior art literature
Patent literature
Patent document 1: japanese patent laid-open publication No. 2011-98976
Patent document 2: japanese patent laid-open No. 2007-126557
Patent document 3: WO2009/136561
Patent document 4: WO2013/047642
Patent document 5: japanese patent No. 6482099
Disclosure of Invention
Problems to be solved by the invention
As described above, various methods have been proposed for fixing an ethoxysilane quaternary ammonium salt to the surface of an article, but a plasma treatment apparatus is required for performing plasma treatment. In addition, for ozone water treatment and microwave irradiation, an apparatus for supplying ozone water and a dedicated apparatus for generating microwaves are required, respectively.
In patent document 4, it is necessary to perform processing separately two times, namely, first, the application of an adhesive and then the application of an antiviral agent, which is disadvantageous in view of productivity and cost.
Patent document 5 discloses an antiviral agent-containing composition having improved compatibility by using a specific acrylic resin component, but the compatibility is insufficient, leaving room for improvement.
Under these circumstances, an object of the present invention is to provide an antiviral agent composition which comprises a methoxysilane quaternary ammonium salt and has better compatibility with a binder (urethane resin or urethane resin and acrylic resin) than before and can be given in a single bath by one-step processing.
Further, the present invention provides an antiviral agent-immobilized fabric, polyurethane sheet, and polyvinyl chloride sheet.
Means for solving the problems
The inventors studied the above problems and have found that an aqueous urethane resin having a carboxyl group and/or a carboxylic acid ester group or a mixture of the urethane resin and an acrylic resin is used as a binder by using a substance containing a methoxysilane quaternary ammonium salt as an antiviral agent.
Thus, it has been found that when an aqueous urethane resin having a carboxyl group and/or a carboxylate group or a mixture of the urethane resin and an acrylic resin is used as a binder, the addition of a specific water-soluble polymer in advance provides an antiviral agent having good compatibility with the binder, and the antiviral agent can be fixed to a product by one-step processing, and a fabric, a urethane sheet, and a polyvinyl chloride sheet having antibacterial and antiviral properties, which are excellent in durability, can be obtained, and the present invention has been completed.
In the present specification, "having a carboxyl group and/or a carboxylate group" refers to not only the case where a carboxyl group present on the surface of a fabric exists as an undissociated free carboxyl group (-COOH) in the composition, but also the case where a terminal hydrogen atom is detached to form a carboxylate anion, and the case where a carboxylate anion is chemically bonded to an antiviral agent molecule unless otherwise specified.
That is, the present invention has the following configuration.
[1] An antiviral agent composition comprising a mixture of an antiviral agent comprising a methoxysilane quaternary ammonium salt and an aqueous polyurethane resin having a carboxyl group and/or a carboxylate group as a binder,
the antiviral agent composition contains a water-soluble organic polymer as a dispersant.
[2] The antiviral agent composition according to [1], wherein,
the binder is a mixture of the aqueous urethane resin having a carboxyl group and/or a carboxylate group and an acrylic resin.
[3] The antiviral agent composition according to [1] or [2], characterized in that,
the methoxysilane quaternary ammonium salt is a compound having a structure represented by the following formula (1),
[ chemical formula 1]
[4] The antiviral agent composition according to any one of [1] to [3], wherein,
the water-soluble organic polymer is at least one polymer selected from methylcellulose, ethylcellulose, hydroxyethyl cellulose, hydroxypropyl cellulose, carboxymethyl cellulose, starch, carbamate modified polyether, xanthan gum and polyvinyl alcohol.
[5] The antiviral agent composition according to any one of [1] to [4], wherein,
The content of the carboxyl group and/or the carboxylate group in the polyurethane resin is 0.5 to 4.0 mass%.
[6] An antiviral fabric characterized in that an antiviral layer is provided on the surface of a fabric substrate, said layer comprising an antiviral agent comprising a methoxysilane quaternary ammonium salt and an aqueous polyurethane resin binder having a carboxyl group and/or a carboxylate group.
[7] An antiviral polyurethane sheet, characterized in that an antiviral layer containing an antiviral agent containing a methoxysilane quaternary ammonium salt and an aqueous polyurethane resin binder having a carboxyl group and/or a carboxylate group is provided on the surface of a sheet containing polyurethane.
[8] An antiviral polyvinyl chloride sheet, characterized in that an antiviral layer is provided on the surface of a sheet comprising polyvinyl chloride, and the layer comprises an antiviral agent comprising a methoxysilane quaternary ammonium salt and an aqueous polyurethane resin binder having a carboxyl group and/or a carboxylate group.
Effects of the invention
The antiviral agent composition of the present invention contains an antiviral agent comprising a methoxysilane quaternary ammonium salt, a binder and a water-soluble organic polymer, and has excellent compatibility as compared with the conventional composition containing an antiviral agent and a binder, and can be applied to synthetic fibers having no hydroxyl group on the surface thereof by one-time processing. In other words, the pretreatment step is not required before the antiviral agent treatment, and a fabric having antiviral properties can be produced stably and efficiently at low cost without using any special equipment, which is advantageous in terms of production efficiency and cost. The composition of the present invention is excellent in stability, and does not cause resin residues or the like even when diluted with water or the like to prepare a treatment liquid and processed into a fabric.
Further, the fabric and synthetic leather sheet (polyurethane sheet, polyvinyl chloride sheet) having an antiviral layer formed on the surface thereof using the antiviral agent composition of the present invention are excellent in washing durability, and can maintain antiviral effect for a long period of time.
Brief description of the drawings
Fig. 1: to illustrate an example of a process for producing an antiviral fabric using the antiviral agent composition of the present invention.
Fig. 2: (a) The layer structure of the antiviral polyurethane sheet produced using the antiviral agent composition of the present invention is shown in the drawing, and the layer structure of the antiviral polyurethane sheet produced using the antiviral agent composition of the present invention is shown in the drawing.
Fig. 3: (a) The layer structure of the antiviral polyvinyl chloride sheet produced using the antiviral agent composition of the present invention is shown in the drawing, and the layer structure of the antiviral polyvinyl chloride sheet produced using the antiviral agent composition of the present invention is shown in the drawing.
Detailed Description
[ antiviral agent ]
The antiviral agent contained in the antiviral agent composition of the present invention is an antiviral agent comprising a methoxysilane quaternary ammonium salt having an ammonium group having a relatively long chain alkyl group that exhibits antiviral activity and an alkoxysilyl group capable of forming a covalent bond with a binder on the fabric surface. The methoxysilane quaternary ammonium salt is specifically a compound represented by the following general formula (2).
[ chemical formula 2]
(in the formula (2), R 1 Represents an alkyl group having 12 to 24 carbon atoms, R 2 R is R 3 Represents a lower alkyl group having 1 to 6 carbon atoms which may be the same or different, and X represents a halogen ion or an organic carbonyloxy ion (organic carboxylic acid ion). )
Examples of X in the formula (2) include halogen ions such as chloride ions and bromide ions, and organic carbonyloxy ions (organic carboxylate ions) such as methylcarbonyloxy ions (acetate ions), ethylcarbonyloxy ions (propionate ions), phenylcarbonyloxy ions (benzoate ions).
As R in formula (2) 1 Examples of the alkyl group having 12 to 24 carbon atoms include dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl, eicosyl, heneicosyl, docosyl and tricosylA base, tetracosyl, and the like.
R as in formula (2) 2 And R is 3 Examples of the lower alkyl group having 1 to 6 carbon atoms which may be the same or different include methyl, ethyl, propyl, isopropyl, butyl, pentyl, hexyl, cyclohexyl and the like.
Specific examples of the methoxysilane quaternary ammonium salt represented by the above general formula (2) include octadecyl dimethyl (3-trimethoxysilylpropyl) ammonium chloride, dodecyl diisopropyl (3-trimethoxysilylpropyl) ammonium chloride, tetradecyldimethyl (3-trimethoxysilylpropyl) ammonium chloride, tetradecyldiethyl (3-trimethoxysilylpropyl) ammonium chloride, tetradecyldi-n-propyl (3-trimethoxysilylpropyl) ammonium chloride, pentadecyl dimethyl (3-trimethoxysilylpropyl) ammonium chloride, pentadecyl diethyl (3-trimethoxysilylpropyl) ammonium chloride, pentadecyl di-n-propyl (3-trimethoxysilylpropyl) ammonium chloride, hexadecyldimethyl (3-trimethoxysilylpropyl) ammonium chloride, hexadecyldiethyl (3-trimethoxysilylpropyl) ammonium chloride, hexadecyldi-n-propyl (3-trimethoxysilylpropyl) ammonium chloride, octadecyldiethyl (3-trimethoxysilylpropyl) ammonium chloride, octadecyl di-n-propyl (3-trimethoxypropyl) ammonium chloride, and the like, from the viewpoint of further viral resistance, octadecyl dimethyl (3-trimethoxysilylpropyl) ammonium chloride (formula (1) below) is preferred.
[ chemical formula 3]
The antiviral agent contained in the antiviral agent composition of the present invention may be 1 or 2 or more of the aforementioned methoxysilane quaternary ammonium salts, and may be used in combination with other antiviral agents. The methoxysilane quaternary ammonium salt has an antibacterial (bacteriostatic) effect against gram-positive bacteria and gram-negative bacteria, and an antiviral effect against enveloped viruses such as influenza virus and measles virus (hereinafter, antibacterial effect and antiviral effect are sometimes collectively referred to as antiviral effect). Further, it is considered that the composition has an antistatic effect and a deodorizing effect in addition to an antiviral effect.
The concentration of the antiviral agent is not particularly limited as long as the antiviral agent is stably maintained in the composition, and for example, the antiviral agent composition of the present invention may be contained in an undiluted state before dilution with water or the like, and more preferably in an amount of 0.01 to 50% by weight, and even more preferably in an amount of 0.02 to 20% by weight. The concentration of the antiviral agent in the treatment liquid when the fabric is treated is preferably 0.01 to 1.5 wt%, more preferably 0.02 to 0.45 wt%.
[ Water-based polyurethane resin ]
The binder (aqueous polyurethane resin) in the antiviral agent composition of the present invention is obtained by dispersing a neutralized product of an isocyanate-terminated prepolymer in water, and then performing a chain extension reaction in water using an amine-based chain extender, wherein the neutralized product of the isocyanate-terminated prepolymer is obtained by reacting a polyisocyanate compound, a polyol compound, and a diol compound having a carboxyl group and/or a carboxylic acid ester group. Hereinafter, dispersion or emulsification is referred to as emulsified dispersion.
The term "aqueous" as used herein refers to a state in which separation or sedimentation is not observed even when the emulsified dispersion is left to stand at 20℃for 12 hours after the emulsified dispersion (solvent: water) having a concentration of 40 mass% in water in which the aqueous polyurethane resin is prepared.
(polyisocyanate Compound)
The polyisocyanate compound used in the present invention is not particularly limited, and examples thereof include aromatic polyisocyanate compounds, aliphatic polyisocyanate compounds, alicyclic polyisocyanate compounds, and the like. Examples of the aromatic polyisocyanate compound include Toluene Diisocyanate (TDI), xylene Diisocyanate (XDI), diphenylmethane diisocyanate (MDI), naphthalene Diisocyanate (NDI), and tetramethylxylene diisocyanate. Examples of the aliphatic polyisocyanate compound include Hexamethylene Diisocyanate (HDI). Examples of the alicyclic polyisocyanate compound include 1, 3-bis (isocyanatomethyl) cyclohexane, isophorone diisocyanate (IPDI), dicyclohexylmethane diisocyanate (H12 MDI), and norbornane diisocyanate. These polyisocyanate compounds may be used singly or in combination of 2 or more. Among such polyisocyanates, aliphatic polyisocyanates and alicyclic polyisocyanate compounds can be preferably used because they impart no yellowing to fabrics, polyvinyl chloride sheets, and polyurethane sheets, and in particular hexamethylene diisocyanate, isophorone diisocyanate, dicyclohexylmethane diisocyanate, norbornane diisocyanate, and 1, 3-bis (isocyanatomethyl) cyclohexane can be preferably used.
(polyol Compound)
Examples of the polyol compound include polyether polyols, polyester polyols, and polycarbonate polyols. These polyol compounds may be used singly or in combination of 2 or more. Since abrasion resistance of fabric, polyvinyl chloride sheet, and polyurethane sheet can be improved, it is desirable to use a polycarbonate polyol.
Further, the polyol compound preferably has a number average molecular weight of 1,000 to 3,000. When the number average molecular weight is within this range, the appearance quality and abrasion resistance of the fabric, polyvinyl chloride sheet, and polyurethane sheet become good.
Examples of the polyether polyol include polyols which are a single addition polymer or a co-addition polymer (which may be a block copolymer or a random copolymer) of an alkylene oxide having 2 to 4 carbon atoms such as ethylene oxide, propylene oxide and tetrahydrofuran.
Examples of the polycarbonate polyol include those obtained by dealcoholization reaction, dephenolization reaction, etc. of a polyol selected from 1 or 2 or more of ethylene glycol, 1, 2-propylene glycol, 1, 3-propylene glycol, 1, 2-butanediol, 1, 3-butanediol, 1, 4-butanediol, 1, 5-pentanediol, 1, 6-hexanediol, 3-methyl-1, 5-pentanediol, neopentyl glycol, 1, 8-octanediol, 1, 9-nonanediol, diethylene glycol, dipropylene glycol, 1, 4-cyclohexanedimethanol, or ethylene oxide or propylene oxide adducts of bisphenol a; the carbonate is selected from 1 or more than 2 of diethyl carbonate, dimethyl carbonate, diphenyl carbonate and the like. The polycarbonate polyol may be used alone in an amount of 1 or in an amount of 2 or more.
Examples of the polyester polyol include those obtained by polycondensation of a dibasic acid selected from 1 or 2 or more of phthalic acid, isophthalic acid, terephthalic acid, naphthalenedicarboxylic acid, succinic acid, malonic acid, adipic acid, sebacic acid, 1, 4-cyclohexanedicarboxylic acid, maleic acid, fumaric acid, and the like, and a polyhydric alcohol used for synthesis of the above-mentioned polycarbonate polyol. The above polyester polyols may be used singly or in combination of 1 or more than 2.
Examples of the diol compound having a carboxyl group and/or a carboxylate group include 2, 2-dimethylolpropionic acid, 2-dimethylolbutyric acid, and salts thereof. Further, as such a diol compound, a polyester polyol having a pendant carboxyl group obtained by reacting a diol compound having a carboxyl group with an aromatic dicarboxylic acid, an aliphatic dicarboxylic acid or the like can be used. Further, a diol compound having no carboxyl group may be mixed as a diol component with the diol compound having a carboxyl group and reacted. These diol compounds may be used singly or in combination of 1 or more than 2.
In the aqueous polyurethane resin of the present invention, the content of carboxyl groups and/or carboxylate groups in the aqueous polyurethane resin is preferably in the range of 0.5 to 4.0 mass% from the viewpoint of the fixation property of the antiviral agent or the compatibility with the antiviral agent. The content of the carboxyl group and/or the carboxylate group can be obtained by calculating the COO amount per 100g of the polyurethane resin based on the amount of the raw material. When the content of the carboxyl group exceeds 4.0 mass%, the feel of the fabric, the polyvinyl chloride sheet, and the polyurethane sheet becomes hard, and there is a risk that whitening or the like is likely to occur at the time of bending. Meanwhile, when the content is 0.5 mass% or less, the storage stability of the aqueous polyurethane resin is lowered, and therefore there is a risk that stable processing is not possible.
In the present invention, in the preparation of the isocyanate-terminated prepolymer, a low molecular weight polyol such as ethylene glycol, 1, 4-butanediol, hexanediol or the like may be used as the polyol compound.
(chain extender)
Examples of the chain extender include low molecular weight polyamines (polyamine compounds having at least 1 amino group selected from primary and secondary amino groups in the 1 molecule) such as ethylenediamine, propylenediamine, tetramethylenediamine, hexamethylenediamine, hydrazine, 4' -diaminodicyclohexylmethane, piperazine, 2-methylpiperazine, isophoronediamine, norbornadiene diamine, diaminodiphenylmethane, toluenediamine, xylylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, iminodipropylamine, and the like. These chain extenders may be used alone or in combination of 1 or more than 2.
The aqueous polyurethane resin contained in the antiviral agent composition of the present invention may be, for example, a flame retardant-blended polyurethane resin containing a phosphorus compound disclosed in japanese unexamined patent application publication No. 2006-206839 as a flame retardant component.
Next, a method for producing the above aqueous polyurethane resin will be described.
(isocyanate group-terminated prepolymer)
In the present invention, the specific method for producing the isocyanate-terminated prepolymer is not particularly limited, and it can be produced by, for example, a conventionally known one-stage so-called one-shot method, a multistage isocyanate polyaddition method, or the like. The reaction temperature in this case is preferably 40℃to 150 ℃. Meanwhile, an organic solvent which does not react with an isocyanate group may be added during the reaction or after the completion of the reaction. Examples of such organic solvents include acetone, methyl ethyl ketone, toluene, and tetrahydrofuran. In the reaction, if necessary, a reaction catalyst such as dibutyltin dilaurate, stannous octoate, dibutyltin di (2-ethylhexanoate), triethylamine, triethylenediamine, N-methylmorpholine, bismuth tris (2-ethylhexanoate) or a reaction inhibitor such as phosphoric acid, sodium hydrogen phosphate, p-toluenesulfonic acid, adipic acid or benzoyl chloride may be added.
The content of the residual isocyanate groups in the isocyanate group-terminated prepolymer is preferably 0.2 to 4.5 mass%. Within this range, the aqueous polyurethane resin composition obtained by chain extension with a polyamine thereafter becomes excellent in film formation, and the formed film becomes soft and exhibits moderate flexibility.
The residual isocyanate group content can be determined by the following method.
0.3g of the resultant urethane prepolymer was collected in an Erlenmeyer flask, and 10mL of a 0.1N dibutylamine toluene solution was added thereto to dissolve the prepolymer. Then, a few drops of bromophenol blue solution were added and titrated with 0.1N hydrochloric acid methanol solution to determine the content of free isocyanate groups NCO% by the following formula.
NCO％＝(a-b)×0.42×f/x
a: titration of 0.1N methanol hydrochloride in the case of titration of only 10mL of 0.1N dibutylamine toluene solution.
b: titration of the composition during the reaction was performed with 0.1N methanol hydrochloride.
f: factor of 0.1N methanolic hydrochloric acid.
x: sampling amount.
In order to adjust the content of the residual isocyanate groups to be within the above range, the molar ratio of the isocyanate groups/hydroxyl groups of the raw material at the time of producing the prepolymer is preferably adjusted to 100/80 to 100/60. When the molar ratio of isocyanate groups to hydroxyl groups is less than 100/80, the viscosity of the isocyanate group-terminated prepolymer is high, and it is difficult to emulsify and disperse the prepolymer, and when the molar ratio of isocyanate groups to hydroxyl groups exceeds 100/60, the feel of the fabric, polyvinyl chloride sheet or polyurethane sheet becomes hard, and whitening or the like is likely to occur at the time of bending.
(neutralization)
Neutralization of the carboxyl groups of the isocyanate-terminated prepolymer may be carried out before, during or after the preparation of the isocyanate-terminated prepolymer using a suitable known method. The compound used for neutralization of such an isocyanate-terminated prepolymer having a carboxyl group is not particularly limited, and examples thereof include amines such as trimethylamine, triethylamine, tri-N-propylamine, tributylamine, N-methyl-diethanolamine, N-dimethylmonoethanolamine, N-diethylmonoethanolamine, triethanolamine, potassium hydroxide, sodium hydroxide, ammonia, and the like. Among these compounds, tertiary amines such as trimethylamine, triethylamine, tri-n-propylamine and tributylamine are particularly preferable.
(emulsion dispersion)
In the present invention, the emulsifying and dispersing apparatus used in emulsifying and dispersing the neutralized product of the isocyanate group-terminated prepolymer in water is not particularly limited, and examples thereof include a homogenizing mixer, a homogenizer, a disperser and the like. In addition, when the neutralized product of the isocyanate-terminated prepolymer is emulsified and dispersed in water, it is preferable to emulsify and disperse the neutralized product of the isocyanate-terminated prepolymer in water at a temperature ranging from 0 to 40 ℃ to suppress the reaction of the isocyanate groups with water as much as possible. Further, in the case of performing the emulsion dispersion as described above, a reaction inhibitor such as phosphoric acid, sodium dihydrogen phosphate, disodium hydrogen phosphate, p-toluenesulfonic acid, adipic acid, benzoyl chloride and the like may be added as necessary.
(amine extension)
In the present invention, the isocyanate-terminated prepolymer emulsified and dispersed in water is chain-extended using a polyamine compound containing at least 1 amino group selected from the group consisting of primary amino groups and secondary amino groups in 1 molecule.
The reaction of the isocyanate-terminated prepolymer with the polyamine compound is terminated at a reaction temperature of 20℃to 50℃and usually within 30 minutes to 120 minutes.
(desolventizing)
In the case of using the above-mentioned organic solvent in the production of the isocyanate-terminated prepolymer, it is desirable to remove the solvent by distillation at 30 to 80℃under reduced pressure after the chain extension reaction or emulsion dispersion, for example. By such a production method, the polyurethane resin can be obtained as an emulsified dispersion of the polyurethane resin.
The concentration of the resin solid component (nonvolatile component) in the emulsion dispersion of the polyurethane resin is preferably in the range of 20% to 60%. The concentration of the resin solid content can also be adjusted by adding or distilling off water.
[ acrylic resin ]
In the antiviral agent composition of the present invention, an acrylic resin is preferably used in combination with the above aqueous polyurethane resin as a binder. The weight ratio of the aqueous urethane resin to the acrylic resin can be appropriately selected, and is preferably 1:0.1 to 1.
Examples of the monomer of the acrylic resin contained as the binder include (meth) acrylic acid derivatives such as methyl (meth) acrylate, ethyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, lauryl (meth) acrylate, stearyl (meth) acrylate, cyclohexyl (meth) acrylate, isobornyl (meth) acrylate, benzyl (meth) acrylate, acrylic acid, glycidyl (meth) acrylate, dimethylaminoethyl (meth) acrylate, diethylaminoethyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, and 2-hydroxypropyl (meth) acrylate; aromatic vinyl compounds such as styrene, α -methylstyrene and p-methylstyrene; acrylamides such as acrylamide, diacetone acrylamide, methacrylamide, and maleic amide; heterocyclic vinyl compounds such as vinyl pyrrolidone; vinyl compounds such as vinyl chloride, acrylonitrile, vinyl ether, vinyl ketone, and vinyl amide; alpha-olefins such as ethylene and propylene; maleic acid, fumaric acid, itaconic acid, derivatives thereof, and the like. Here, (meth) acrylic acid means acrylic acid or methacrylic acid. Further, 1 kind of such monomer may be used alone, or 2 or more kinds may be used in combination.
[ dispersant ]
In the antiviral agent composition of the present invention, a water-soluble organic polymer is blended as a dispersant for dispersing the above-mentioned antiviral agent and the polyurethane resin in the same liquid, and as such a water-soluble organic polymer, at least one polymer selected from the group consisting of methyl cellulose, ethyl cellulose, hydroxyethyl cellulose, hydroxypropyl cellulose, carboxymethyl cellulose, starch, urethane-modified polyether, xanthan gum and polyvinyl alcohol is preferable, and urethane-modified polyether or xanthan gum is particularly preferable.
In the present invention, water-soluble means becoming transparent when dissolved in water at 20 ℃ at a concentration of 0.1 mass%.
As the urethane-modified polyether, there may be mentioned a urethane-modified polyether having a hydrophobic group at the terminal and a urethane bond in the molecular chain, and examples thereof include those described in japanese patent No. 3972234 and japanese patent No. 4528908:
R1-X-(PEG-X-R2-X)m-PEG-X-R1’
(R1 and R1 'are alkyl groups having 8 to 36 carbon atoms or hydrocarbon groups having an aromatic ring, R1 and R1' may be the same or different, R2 is a diisocyanate residue having 6 to 36 carbon atoms from which NCO groups are removed, X is a urethane bond, PEG is a polyethylene glycol residue having a molecular weight of 1,500 to 33,000, and m is an integer of 0 or more);
R1-Y-R2-(X-PEG-X-R3)m-X-PEG-X-R2-Y-R1’
(R1 and R1 'are hydrocarbon groups having 8 to 36 carbon atoms or aromatic rings, R1 and R1' may be the same or different, R2 and R3 are diisocyanate residues having 6 to 36 carbon atoms from which NCO groups are removed, R2 and R3 may be the same or different, X is a urethane bond, Y is a urethane bond or urea bond, PEG is a polyethylene glycol residue having a molecular weight of 1,500 to 33,000, and m is an integer of 0 or more);
R1-(OA)p-X-R2-(X-PEG-X-R3)m-X-(AO)q-R1’
(R1 and R1 'are hydrocarbon groups having 8 to 36 carbon atoms or aromatic rings, R1 and R1' may be the same or different, R2 and R3 are diisocyanate residues having 6 to 36 carbon atoms from which NCO groups are removed, R2 and R3 may be the same or different, X is a urethane bond, A is a hydrocarbon group having 2 to 4 carbon atoms and is a hydrocarbon residue containing at least ethylene, m is an integer of 0 or more, p and q are integers of 1 to 200, and p and q may be the same or different);
[ chemical formula 4]
(R1, R1': a hydrocarbon group having an alkyl group having 8 to 36 carbon atoms or an aromatic ring, R1' may be the same or different, R4: a polyfunctional polyisocyanate residue excluding NCO groups, A: a hydrocarbon group having 2 to 4 carbon atoms and being a hydrocarbon residue containing at least an ethylene group, X: a urethane bond, an integer of i, j, k:0 or more and (i+j+k) an integer of 3 or more, p, q, R: an integer of 1 to 200, and p, q, R may be the same or different);
[ chemical formula 5]
(R1, R1 ': a hydrocarbon group having an alkyl group having 8 to 36 carbon atoms or an aromatic ring, R1' may be the same or different, R4: a polyfunctional polyisocyanate residue excluding NCO groups, A: a hydrocarbon group having 2 to 4 carbon atoms and being a hydrocarbon residue containing at least an ethylene group, X: a urethane bond, Y: a urethane bond or a urea bond, i, j, k: an integer of 0 or more and (i+j+k) an integer of 3 or more, p, q, R: an integer of 1 to 200, p, q, R may be the same or different);
[ chemical formula 6]
(R1, R1 ': a hydrocarbon group having an alkyl group having 8 to 36 carbon atoms or an aromatic ring, R1' may be the same or different, R5: a polyfunctional polyol or polyamine residue from which active hydrogen is removed, A: a hydrocarbon group having 2 to 4 carbon atoms and being a hydrocarbon residue containing at least an ethylene group, X: a urethane bond, an integer of i, j, k:0 or more and (i+j+k) an integer of 3 or more, p, q, R: an integer of 1 to 200, and p, q, R may be the same or different);
a composition comprising, as essential components, 20% by mass or more and less than 80% by mass of a compound A having a weight average molecular weight of 10,000 or more and less than 40,000 represented by the following general formula (3), and 20% by mass or more and less than 80% by mass of a compound B having a weight average molecular weight of 40,000 or more and less than 140,000 represented by the general formula (4):
[ chemical formula 7]
(wherein X1 and X2 are hydrocarbon groups having 15 to 24 carbon atoms, Y is a 2-valent organic residue derived from a diisocyanate compound, OR' are oxyalkylene groups having 2 to 4 carbon atoms, a, b, d are integers of 1 to 500, and c is an integer of 1 OR more.)
[ chemical formula 8]
(wherein X3 and X4 are hydrocarbon groups having 4 to 24 carbon atoms, Y is a 2-valent organic residue derived from a diisocyanate compound, OR' are oxyalkylene groups having 2 to 4 carbon atoms, a, b, d are integers of 1 to 500, and c is an integer of 1 OR more.)
The antiviral agent composition of the present invention may contain various additives. For example, an emulsifier, a thickener, a preservative, a buffer, a pH adjuster, and the like may be contained as long as the effect of the present invention is not impaired.
[ antiviral cloth ]
The invention also relates to fabrics treated with the above antiviral agent composition. Conventionally, a methoxysilane-based quaternary ammonium salt antiviral agent is difficult to fix to a fabric having no oxygen-containing functional group on the surface, and when fixing is performed, pretreatment is required, but according to the antiviral agent composition of the present invention, a binder and an antiviral agent can be applied to the fabric by one treatment, that is, in the same bath. In addition, according to the antiviral agent composition of the present invention, resin residues and the like are less generated than in the case of conventional one-bath treatment.
The fabric may be any of woven fabric, knitted fabric, and nonwoven fabric, and may be appropriately selected according to the application and purpose. The fabric may be made of natural fibers, chemical fibers, or a combination thereof, and examples of the natural fibers include cotton, wool, silk, and hemp, examples of the chemical fibers include polyester, polyurethane, polyamide, rayon, and acrylic, and the fabric may be selected from the group consisting of these fibers alone and in combination. Further, from the viewpoint of the application and the design, other fibers may be contained, for example, inorganic fibers such as metal fibers and glass fibers. Further, these fabrics may be subjected to various kinds of processing, for example, flame retardant processing, antifouling processing, and the like. For example, in automotive interior applications such as automobile seats, polyester-based fabrics are mainly selected.
The above-mentioned antiviral agent is relatively easy to fix in a fabric, for example, in a fiber having hydroxyl groups on the surface of cotton, wool or the like, but if the antiviral agent composition of the present invention is further used, a fabric excellent in washing durability, which does not come off even after washing the antiviral agent a plurality of times, can be obtained by one-time treatment.
The amount of the antiviral agent and the binder to be added to the fabric is not particularly limited as long as the effect of the present invention is exhibited, and for example, the amount of the antiviral agent to be added may be 0.01g/m 2 ～15g/m 2 More preferably 0.03g/m 2 ～5g/m 2 . If the antiviral agent is less than 0.03g/m 2 It is difficult to obtain a sufficient antiviral effect, if it exceeds 5g/m 2 There is a risk of reduced combustibility. In addition, the adhesive may be attached in an amount of 0.01g/m 2 ～15g/m 2 More preferably 0.06g/m 2 ～5g/m 2 . If the adhesive is less than 0.06g/m 2 There is a risk that the washing durability of the antiviral agent is lowered, if exceeding 5g/m 2 There is a risk that the softness of the raw material is impaired.
The fabric may further contain additives and the like as long as the effect of the present invention is exhibited. Examples of such additives include colorants, antioxidants, light stabilizers, ultraviolet absorbers, flame retardants, softeners, and other thermoplastic resins.
[ method for producing antiviral fabric ]
The aqueous urethane resin having a carboxyl group and/or a carboxylate group as the binder contained in the antiviral agent composition of the present invention can be produced by a conventionally known method, and can be obtained as an aqueous dispersion or emulsion having a solid content of 10 to 50% by weight, for example. The antiviral agent contained in the composition of the present invention can be obtained, for example, as an aqueous dispersion, aqueous/alcoholic solution or emulsion having a solid content of 40 to 80% by weight. These antiviral agents, binders and dispersants may be diluted with alcohol and/or water to a predetermined concentration, and used as a treatment liquid for imparting an antiviral agent to fabric.
When the antiviral agent is to be treated on the fabric, the concentration of the antiviral agent in the treatment liquid may be, for example, 0.01 to 1.5 wt% (the concentration of the active ingredient of the antiviral agent), and is preferably set to 0.02 to 0.45 wt% from the viewpoints of efficiency and cost. The treatment liquid may use water and/or an organic solvent (e.g., ethanol, propanol, acetone, acetonitrile) or a mixture thereof as a solvent. The concentration of the binder in the treatment liquid may be set to, for example, 0.005 to 1 wt% (the concentration of the active ingredient of the binder), and is preferably set to 0.01 to 0.2 wt% from the viewpoints of efficiency and cost. The concentration of the dispersant in the treatment liquid may be set to, for example, 0.01 to 10 wt% (the concentration of the active ingredient of the dispersant), and is preferably set to 0.1 to 5 wt% from the viewpoints of efficiency and cost.
In any case, the above-mentioned antiviral agent, binder and dispersant are first diluted with alcohol and/or water to a predetermined concentration to prepare a treatment solution. Next, the treating liquid is brought into contact with a fabric to produce a fabric having antiviral properties.
Examples of the method of bringing the treatment liquid into contact with the fabric include a Dip-Nip method, an exhaustion method, and a coating method. In the case of performing the treatment by the Dip-Nip method as shown in fig. 1, the fabric is first immersed in a treatment liquid, extruded by a cloth calender or the like, and then heated and dried, whereby the treatment liquid is attached to the fabric. Subsequently, the antiviral agent may be immobilized by heat-drying treatment.
The treatment temperature is not particularly limited, and may be performed in a temperature range including normal temperature. For example, the treatment is carried out at 110℃to 180 ℃. The methoxysilane quaternary ammonium salt is considered to be fixed to the surface of the article in a relatively short period of time, and the treatment time may be set to 30 seconds to 10 minutes, preferably 1 minute to 3 minutes.
In the case of the exhaustion method, the composition (treatment liquid) containing the antiviral agent, the binder and the dispersant may be heated to 80 to 140 ℃, the fabric may be immersed in the liquid, extruded by a fabric calender or the like, and then heated and dried to fix the antiviral agent to the fabric.
When the treatment is carried out by the coating method, the antiviral agent composition of the present invention may be adjusted to have an appropriate viscosity, and the composition (treatment liquid) may be applied to a fabric and dried to fix the antiviral agent. The coating method is not particularly limited, and examples thereof include gravure roll processing, spray processing, roll coater processing, jet printing processing, transfer printing processing, screen printing processing, and the like.
The drying/heat treatment temperature of the fabric to which the treatment liquid containing the binder, antiviral agent and dispersing agent is applied may be set to 100 to 190 ℃, preferably 110 to 160 ℃.
After the fabric is treated with the treatment liquid containing the antiviral agent, the binder and the dispersant, the fabric may be washed, naturally dried, or heated to dry as necessary. In the case of the heat drying, for example, the drying may be performed using a heat drying apparatus such as a blower, a gear oven, a tenter, or the like. In addition, contact between the antiviral agent and the fabric may be performed by spraying or coating.
The drying/heat treatment time may be appropriately selected depending on the material, weight per unit area, and application of the fabric to be produced, and is preferably 1 to 5 minutes. In the drying/heat treatment, a ring dryer, a mesh blower, an oven, a heating device, or the like may be used.
[ antiviral polyurethane sheet and Process for producing the same ]
The antiviral polyurethane sheet of the present invention produced using the above-described antiviral agent composition has a layer structure as shown in fig. 2 (a), and is produced by the process shown in (b).
In the step shown in fig. 2 (b), a skin resin is first applied to the surface of a release paper (or a paper having a concave-convex pattern), and then dried to provide a skin layer, and then an adhesive resin is further applied to the surface of the skin layer, and then dried, and the adhesive resin layer is bonded to a base fabric via the adhesive resin layer, and wound into a roll shape. Then, curing the adhesive resin for 1 day or more in a wound state, peeling off the release paper to obtain a polyurethane sheet, and finally, applying a surface treatment resin liquid containing an antiviral agent to the surface of the skin layer formed of the skin resin, and drying the surface treatment resin liquid to produce the antiviral polyurethane sheet of the present invention.
In the present invention, as in the layer structure of fig. 2 (a), the surface treatment layer is provided by using a treatment liquid having a composition containing no antiviral agent (methoxysilane quaternary ammonium salt) as the surface base treatment layer on the skin layer, and the antiviral surface treatment layer may be further provided by using a treatment liquid having a composition containing an antiviral agent on the surface base treatment layer.
[ antiviral polyvinyl chloride sheet and Process for producing the same ]
The antiviral polyvinyl chloride sheet of the present invention produced using the antiviral agent composition has a layer structure as shown in fig. 3 (a), and is produced by the process shown in (b).
In the step shown in fig. 3 (b), a skin resin is first applied to the surface of a release paper (or a paper having a concave-convex pattern), and then dried to provide a skin layer, and then a foaming resin is further applied to the surface of the skin layer and dried to form a foaming layer, and then an adhesive resin is applied to the surface of the layer, and the release paper is peeled off after the adhesive resin layer is bonded to a base fabric and dried to obtain a polyvinyl chloride artificial leather. Finally, the antiviral polyvinyl chloride sheet of the present invention can be produced by applying a surface-treating resin liquid containing an antiviral agent to the surface of the skin layer formed of a skin resin and drying the resin liquid.
In the present invention, as in the layer structure of fig. 3 (a), a surface base treatment layer is provided on the surface layer by using a treatment liquid having a composition containing an acrylic resin and containing no antiviral agent (methoxysilane quaternary ammonium salt), and a surface treatment layer containing no antiviral agent/an antiviral surface treatment layer or a surface treatment layer containing an antiviral agent (antiviral surface treatment layer) may be further provided on the surface layer for the purpose of improving the adhesion between layers.
Hereinafter, the present invention will be described more specifically based on the present invention and comparative examples, but the present invention is not limited thereto.
Examples
[ Synthesis example of aqueous polyurethane resin contained in antiviral agent composition of the present invention ]
Synthesis example 1
In a four-necked flask equipped with a stirrer, a reflux condenser, a thermometer and a nitrogen-blowing tube, 251.9g of 1, 6-hexanediol polycarbonate polyol (molecular weight: 1,000), 10.3g of DMPA (dimethylolpropionic acid), 3.4g of 1,4-BD (butanediol) and 114.5g of methyl ethyl ketone as a solvent were weighed and uniformly mixed, and 77.0g of HDI (hexamethylene diisocyanate) as a polyisocyanate was added thereto, and reacted at 80.+ -. 5 ℃ for 180 minutes to obtain a methyl ethyl ketone solution of a urethane prepolymer having an isocyanate group at an isocyanate group content of 1.68% by mass. Then 7.3g of triethylamine was added at 60℃to carry out a neutralization reaction. Then, 643.2g of water was slowly added thereto and stirred to emulsify and disperse the urethane prepolymer containing the terminal isocyanate groups. To this emulsified dispersion was added an aqueous polyamine solution obtained by dissolving 9.2g of hydrazine monohydrate and 1.9g of diethylenetriamine in 33.1g of water, followed by stirring at 40.+ -. 5 ℃ for 90 minutes, and then desolvation (demethylethylketone) at 40 ℃ under reduced pressure to give the yield: 1kg, polyurethane non-volatile: 35.0% of an aqueous polyurethane composition A.
Synthesis example 2
In a four-necked flask equipped with a stirrer, a reflux condenser, a thermometer and a nitrogen-blowing tube, 230.0g of 1, 6-hexanediol polycarbonate polyol (molecular weight: 1,000), 10.3g of DMPA (dimethylolpropionic acid), 3.5g of 1,4-BD (butanediol) and 114.0g of methyl ethyl ketone as a solvent were weighed and uniformly mixed, and 96.9g of HDI (hexamethylene diisocyanate) as a polyisocyanate was added thereto, and reacted at 80.+ -. 5 ℃ for 180 minutes to obtain a methyl ethyl ketone solution of a urethane prepolymer having an isocyanate group at an isocyanate group content of 4.26% by mass. Then 7.4g of triethylamine was added at 60℃to carry out a neutralization reaction. Then, 640.2g of water was slowly added thereto and stirred to emulsify and disperse the urethane prepolymer containing the terminal isocyanate groups. To this emulsified dispersion was added an aqueous polyamine solution obtained by dissolving 11.5g of hydrazine monohydrate and 2.4g of diethylenetriamine in 41.7g of water, followed by stirring at 40.+ -. 5 ℃ for 90 minutes, and then desolvation (demethylethylketone) at 40 ℃ under reduced pressure to give the yield: 1kg, polyurethane non-volatile: 35.0% of an aqueous polyurethane composition B.
Synthesis example 3
In a four-necked flask equipped with a stirrer, a reflux condenser, a thermometer and a nitrogen-blowing tube, 263.2g of 1, 6-hexanediol polycarbonate polyol (molecular weight: 1,000), 5.1g of DMPA (dimethylolpropionic acid), 3.4g of 1,4-BD (butanediol) and 114.4g of methyl ethyl ketone as a solvent were weighed and uniformly mixed, and then 71.4g of HDI (hexamethylene diisocyanate) as a polyisocyanate was added thereto, and reacted at 80.+ -. 5 ℃ for 180 minutes to obtain a methyl ethyl ketone solution of a urethane prepolymer having an isocyanate group at an isocyanate group content of 1.56% by mass. Then, 3.7g of triethylamine was added thereto at 60℃to conduct a neutralization reaction. Then, 639.7g of water was slowly added thereto and stirred to emulsify and disperse the urethane prepolymer containing the terminal isocyanate groups. To this emulsified dispersion was added an aqueous polyamine solution prepared by dissolving 8.5g of hydrazine monohydrate and 1.8g of diethylenetriamine in 30.7g of water, stirring at 40.+ -. 5 ℃ for 90 minutes, and then desolvation (demethylethylketone) was carried out at 40 ℃ under reduced pressure to give the yield: 1kg, polyurethane non-volatile: 35.0% of an aqueous polyurethane composition C.
Synthesis example 4
In a four-necked flask equipped with a stirrer, a reflux condenser, a thermometer and a nitrogen-blowing tube, 287.4g of 1, 6-hexanediol polycarbonate polyol (molecular weight: 3,000), 10.2g of DMPA (dimethylolpropionic acid), 3.4g of 1,4-BD (butanediol) and 115.2g of methyl ethyl ketone as a solvent were weighed and uniformly mixed, and then 44.1g of HDI (hexamethylene diisocyanate) as a polyisocyanate was added thereto, and reacted at 80.+ -. 5 ℃ for 180 minutes to obtain a methyl ethyl ketone solution of a urethane prepolymer having an isocyanate group at an isocyanate group content of 0.96% by mass. Then 7.3g of triethylamine was added at 60℃to carry out a neutralization reaction. Then, 647.2g of water was slowly added thereto and stirred to emulsify and disperse the urethane prepolymer containing the terminal isocyanate groups. To this emulsified dispersion was added an aqueous polyamine solution obtained by dissolving 3.8g of ethylenediamine and 1.1g of diethylenetriamine in 14.6g of water, followed by stirring at 40.+ -. 5 ℃ for 90 minutes, and then desolvation (demethylethylketone) at 40 ℃ under reduced pressure to give the yield: 1kg, polyurethane non-volatile: 35.0% of an aqueous polyurethane composition D.
Synthesis example 5
In a four-necked flask equipped with a stirrer, a reflux condenser, a thermometer and a nitrogen-blowing tube, 207.2g of 1, 6-hexanediol polycarbonate polyol (molecular weight: 3,000), 41.6g of DMPA (dimethylolpropionic acid), 3.5g of 1,4-BD (butanediol) and 113.6g of methyl ethyl ketone as a solvent were weighed and uniformly mixed, and 88.0g of HDI (hexamethylene diisocyanate) as a polyisocyanate was added thereto, and reacted at 80.+ -. 5 ℃ for 180 minutes to obtain a methyl ethyl ketone solution of a urethane prepolymer having an isocyanate group at an isocyanate group content of 1.94% by mass. 29.8g of triethylamine was then added at 60℃for neutralization. Then, 664.6g of water was slowly added thereto and stirred to emulsify and disperse the urethane prepolymer containing the terminal isocyanate groups. To this emulsified dispersion was added an aqueous polyamine solution prepared by dissolving 7.6g of ethylenediamine and 2.2g of diethylenetriamine in 29.1g of water, stirring at 40.+ -. 5 ℃ for 90 minutes, and then desolvation (demethylethylketone) was performed at 40 ℃ under reduced pressure to give the yield: 1kg, polyurethane non-volatile: 35.0% of an aqueous polyurethane composition E.
Synthesis example 6
In a four-necked flask equipped with a stirrer, a reflux condenser, a thermometer and a nitrogen-blowing tube, 170.5g of 1, 6-hexanediol polycarbonate polyol (molecular weight: 1,000), 80.6g of 1, 6-hexanediol/terephthalic acid polyester polyol (molecular weight: 1,000), 10.5g of DMPA (dimethylolpropionic acid), 3.5g of 1,4-BD (butanediol) and 114.2g of methyl ethyl ketone as a solvent were weighed and uniformly mixed, and then 77.5g of HDI (hexamethylene diisocyanate) as a polyisocyanate was added and reacted at 80.+ -. 5 ℃ for 180 minutes to obtain a methyl ethyl ketone solution of a urethane prepolymer containing terminal isocyanate groups and having an isocyanate group content of 1.69 mass%. Then 7.5g of triethylamine was added at 60℃to carry out a neutralization reaction. Then, 643.2g of water was slowly added thereto and stirred to emulsify and disperse the urethane prepolymer containing the terminal isocyanate groups. To this emulsified dispersion was added an aqueous polyamine solution obtained by dissolving 9.2g of hydrazine monohydrate and 1.9g of diethylenetriamine in 33.3g of water, followed by stirring at 40.+ -. 5 ℃ for 90 minutes, and then desolvation (demethylethylketone) at 40 ℃ under reduced pressure to give the yield: 1kg, polyurethane non-volatile: 35.0% of an aqueous polyurethane composition F.
Comparative Synthesis example 1
To a four-necked flask equipped with a stirrer, a reflux condenser, a thermometer and a nitrogen inlet tube, 244.2g of 1, 6-hexanediol polycarbonate polyol (molecular weight 1000), 4.7g of trimethylolpropane, 0.099g of dibutyltin dilaurate and 150g of methyl ethyl ketone were added, and after mixing them uniformly, 97.1g of H12MDI (dicyclohexylmethane diisocyanate) was added and reacted at 80℃for 300 minutes to obtain a methyl ethyl ketone solution of a urethane prepolymer having an isocyanate group at an isocyanate group content of 1.26 mass%.
The solution was cooled to 30 ℃ or lower, 0.3g of decyl phosphate and 15.0g of polyoxyethylene tristyrylphenyl ether (hlb=15) were added, and after uniform mixing, 638.7g of water was slowly added using a dispersing blade, and phase inversion emulsification and dispersion were performed to obtain a dispersion. Then, to the above dispersion was added an aqueous polyamine solution obtained by dissolving 4.8g of piperazine hexahydrate and 1.9g of diethylenetriamine in 20.2g of water, followed by chain extension reaction for 90 minutes, and then desolvation was performed at 35 ℃ under reduced pressure to obtain the yield: 1kg of an aqueous polyurethane composition G having a polyurethane nonvolatile content of 35.0% by mass.
The amounts of COO groups, NCO/OH ratios, and types of polyols in the aqueous polyurethane compositions obtained in the above synthesis examples 1 to 6 and comparative synthesis example 1 are summarized in Table 1 below.
PCD in the table represents polycarbonate diol and PED represents polyester diol.
TABLE 1
Synthesis example 1 of acrylic composition
28 parts of ion-exchanged water was weighed into a reaction apparatus equipped with a thermometer, a stirrer, a dropping device, a reflux condenser and a nitrogen inlet tube, and nitrogen was filled therein to raise the internal temperature to 80 ℃. Then, while maintaining the temperature, 2 parts of a 10% strength aqueous ammonium persulfate solution was added, and a separately prepared monomer emulsion prepared as described below was immediately and continuously added dropwise for 4 hours to carry out emulsion polymerization. The monomer emulsion used above was prepared by: to a monomer mixture of 32 parts of acrylic acid, 45 parts of ethyl acrylate, and 23 parts of butyl acrylate, 4 parts of sodium polyoxyethylene alkyl ether sulfate (trade name: LATEMUL E-118B, manufactured by Kao corporation) and 30 parts of ion-exchanged water were mixed and emulsified. In addition, 4 parts of an aqueous 5% ammonium persulfate solution was added dropwise in parallel with the addition of the monomer emulsion. After the completion of the dropwise addition, the mixture was aged at 80℃for 4 hours and then cooled to room temperature. Finally, the aqueous acrylic composition a having a solid content of 60% was obtained by neutralizing with aqueous ammonia and adjusting the solid content with water.
Synthesis example 2 of acrylic composition
An aqueous acrylic composition b was obtained in the same manner as in Synthesis example 1 of the acrylic composition except that 25 parts of methyl methacrylate and 75 parts of butyl acrylate were used as the monomer mixture.
(dispersant Synthesis example 1)
To a 1000mL four-necked flask equipped with a thermometer, a nitrogen inlet pipe and a high-viscosity stirrer, 500 parts of polyethylene glycol 6000 (molecular weight 6000) and 13.5 parts of polyether monol in which 5 mol of ethylene oxide was added to n-dodecanol were added, and dehydration was carried out at 80℃to 90℃under low pressure (500 Pa to 1500 Pa) for 3 hours to thereby obtain a water content of the system of 0.03%. Then, cooling to 70℃and 16.8 parts of hexamethylene diisocyanate were added, the isocyanate content was reacted under a nitrogen stream at 85℃to 90℃to 0% (3 hours), and the urethane-modified polyether c was obtained as a pale yellow viscous solid after cooling at room temperature.
The compositions shown in tables 2 to 4 (examples 1 to 28 and comparative examples 1 to 11) were adjusted to prepare antiviral agent compositions. Among them, the order of addition of the antiviral agent (methoxysilane quaternary ammonium salt) is set to be necessarily performed at the end of the adjustment.
Next, evaluation test results concerning liquid stability, water spot, color development, hand feel, abrasion resistance, and flame retardancy are shown for each of the prepared antiviral agent compositions.
The materials used in the evaluation test are as follows.
1. Antiviral agents: methanol solution of 3- (trimethoxysilyl) propyl dimethyl octadecyl ammonium chloride
2. Additive:
filler: ACEMATT TS-100 (manufactured by Evonik Industries AG. Mu.m, average particle size: 10.)
Defoaming agent: FOAMLEX 747 (manufactured by Rihua chemical Co., ltd.)
Leveling agent: DISPALON AQ-7120 (manufactured by Nanye chemical Co., ltd.)
3. Dispersing agent:
urethane-modified polyether I: NEOSTECKER N (manufactured by Ninhua chemical Co., ltd.)
Urethane-modified polyether II: SN THICKNER 603 (made by Santa Clary Co., ltd.)
Urethane-modified polyether III: ELEMINOL N62 (Sanyo chemical industry Co., ltd.)
Xanthan gum: KELZAN (manufactured by Santa Clara Co., ltd.)
[ liquid stability (compatibility) test ]
The presence or absence of resin residue in the composition after preparation was visually judged for each composition, and the compositions were evaluated based on the evaluation criteria of } (no resin residue was generated), o (little resin residue was generated), Δ (resin residue was generated), and x (much resin residue was generated), and the above criteria were satisfied.
The evaluation results are shown in tables 2 to 4.
[ immobilization treatment of antiviral Agents ]
Regarding the fabric, the fabric had a weight of 390g/m 2 While the polyester raw cloth of (2) was dyed, the composition shown in tables 2 to 4 was dried at 150℃for 2.5 minutes after dip-nip at Pic-up ratio of about 60% by setting the phosphate ester amide as a flame retardant in the bath to 6% owf.
Further, a polyvinyl chloride sheet (trade name: lanchar) was uniformly coated with a polyurethane resin 20g/m as a surface-base treatment layer on the surface of the sheet 2 After drying at 120℃for 2 minutes, each of the compositions shown in tables 2 to 4 was uniformly coated to 20g/m 2 After that, the mixture was dried at 150℃for 2.5 minutes, and an antiviral agent was immobilized.
Further, for a urethane artificial Leather polyurethane sheet (trade name: leather flexed), 20g/m of each composition shown in tables 2 to 4 was uniformly coated on the surface of the sheet 2 After that, the mixture was dried at 150℃for 2.5 minutes, and an antiviral agent was immobilized.
[ evaluation of Water spots ]
1mL of distilled water was dropped onto the surface of the polyurethane sheet, polyvinyl chloride sheet, or fabric subjected to the above-mentioned fixing treatment, and the dried water spots were visually evaluated. The results are shown in tables 2 to 4, and the evaluation criteria are as follows.
In addition, the evaluation of water spots was not performed for the composition that did not have sufficient compatibility in the above-described liquid stability test.
And (3) the following materials: no water spotting was observed at all
And (2) the following steps: almost no water spotting was observed
Delta: water spotting was observed
X: obvious water spots were observed
If the number is equal to or larger than O, the test result is qualified.
[ evaluation of color development ]
In order to detect the antiviral agent attached to the fabric, a cationic color reaction between bromophenol blue and ammonium salt was used. Specifically, a sample piece of 5cm×5cm was cut from a fabric, polyurethane piece or polyvinyl chloride piece after the antiviral agent fixing treatment, a color reaction of bromophenol blue (concentration of a reagent: 0.03% sol, reaction time: 180 seconds) was performed, and after drying, test pieces before and after color development were measured by a spectrophotometer (manufactured by Konikoku Meida Co., ltd.), and ΔE was calculated. The measurement and calculation method is based on JISZ8781 (2012).
○：ΔE≥10
△：5≤ΔE<10
×：ΔE<5
If the number is O, the test result is qualified.
[ evaluation of hand feel ]
3: soft hand feel
2: slightly soft hand
1: rough hand feel
[ evaluation of abrasion resistance ]
The polyurethane sheet and the polyvinyl chloride sheet after the antiviral agent fixing treatment were subjected to abrasion with a cotton canvas (No. 6 of JIS L3102 (1954)) 10,000 times by using a flat abrasion tester with a weight of 0.9kg, and then the state of the test piece was evaluated according to the following criteria.
And (3) the following materials: no damage
O: with slight damage
X: severe damage to
[ evaluation of flame retardancy ]
The burning rate was measured for 10 fabrics according to FMVSS-302 (American Standard for automobile safety) JISD 1201[1973 ]. The average value (arithmetic average value) of the 10 combustion speeds was determined based on the following criteria.
And (3) the following materials: the average burning speed is slower than 50 mm/min, or the burning distance is less than 50mm and the burning time is less than 60 seconds
O: the average value of the combustion speed is 50 mm/min or more and less than 100 mm/min
X: the average value of the combustion speed is 100 mm/min or more
TABLE 2
As shown in table 2 above, the compositions of examples 1 to 8 had compositions containing at least one of 1 water-soluble organic polymer, namely, urethane-modified polyether and xanthan gum, as a dispersant, and in this case, no resin residue was generated, and the liquid stability was excellent, and water spots in the treated fabric were good.
In contrast, the composition of comparative example 1 does not contain any of urethane-modified polyether and xanthan gum as a dispersant, and in this case, the liquid stability is poor and a large amount of resin residue can be observed. In addition, in comparative example 2, the acrylic composition was used instead of the polyurethane composition, and in this case, the resin residue and the color development were also observed to be low, and the combustibility was also deteriorated. Comparative example 3 used polyurethane composition G containing no COOH groups, as a result: no resin residue, good liquid stability, but low color development.
In examples 1 to 5, urethane-modified polyether c, I, II, III and xanthan gum were used, and in this case, the liquid stability, water spotting and color development were all good.
Examples 1, 6 and 7 contained polyurethane compositions A, C, E having COOH% of 0.5%, 1.0% and 4.0%, and in this case, the liquid stability, water spotting and color development were all good.
In example 8, the polyurethane composition F containing the polycarbonate polyol and the polyester polyol in combination was excellent in liquid stability, water spotting and color development.
TABLE 3
TABLE 4
As shown in tables 3 and 4, the compositions of examples 9 to 28 had compositions containing 1 water-soluble organic polymer, that is, at least one of urethane-modified polyether and xanthan gum, as a dispersant, and in this case, no resin residue was generated, and the liquid stability was excellent, and the coated polyurethane sheet or polyvinyl chloride sheet was excellent in water spotting and color development.
In contrast, the compositions of comparative examples 4 and 8 did not contain any of urethane-modified polyether and xanthan gum as a dispersant, and in this case, the liquid stability was poor and a large amount of resin residue was observed. In comparative examples 5 and 9, the urethane composition was replaced with the acrylic composition a having COOH groups, and in this case, the liquid stability was poor, and resin residues were observed, and the color development was also poor. In comparative examples 6 and 10, the acrylic composition b having no COOH group was used, and in this case, the liquid stability was good but the color development was poor. In comparative examples 5, 6, 9 and 10, the polyurethane sheet and the polyvinyl chloride sheet had a hard touch and also had poor abrasion resistance. In comparative examples 7 and 11, polyurethane composition G having no COOH group was used, and in this case, water spotting and color development were poor, and abrasion resistance was also poor as polyurethane sheets or polyvinyl chloride sheets.
In examples 10 to 13 and 20 to 23, urethane-modified polyether c, I, II, III was used, and in this case, the liquid stability, water spotting and color development were all good.
Examples 10, 14 to 17, 20, and 24 to 27 each contained polyurethane compositions A to E having COOH% of 0.5%, 1.0%, 4.0%, or an NCO/OH ratio of 100/80 to 100/60, or a polyol having a molecular weight of 1000 or 3000, and in this case, the liquid stability, water spotting, and color development were all good.
In examples 10, 18, 20 and 28, polyurethane-modified polyether and xanthan gum were used, and in this case, the liquid stability, water spotting and color development were all good, and in examples 10 and 20, polyurethane-modified polyether was used, and in this case, water spotting was even better.
Industrial applicability
The antiviral agent composition of the present invention can be imparted with an antiviral agent by one-time processing even for synthetic fibers having no hydroxyl groups on the surface, and is useful for producing fabrics, polyurethane sheets, and polyvinyl chloride sheets having antibacterial and antiviral properties with excellent durability.

Claims (8)

1. An antiviral agent composition comprising a mixture of an antiviral agent comprising a methoxysilane quaternary ammonium salt and an aqueous polyurethane resin having a carboxyl group and/or a carboxylate group as a binder,
The antiviral agent composition contains a water-soluble organic polymer as a dispersant.
2. The antiviral agent composition of claim 1, wherein,
the binder is a mixture of the aqueous polyurethane resin having a carboxyl group and/or a carboxylate group and an acrylic resin.
3. The antiviral agent composition of claim 1 or 2, wherein,
the methoxysilane quaternary ammonium salt is a compound with a structure shown in the following formula (1),
4. the antiviral agent composition according to any of claim 1 to 3, wherein,
the water-soluble organic polymer is at least one polymer selected from methylcellulose, ethylcellulose, hydroxyethyl cellulose, hydroxypropyl cellulose, carboxymethyl cellulose, starch, carbamate modified polyether, xanthan gum and polyvinyl alcohol.
5. The antiviral agent composition of any of claims 1-4, wherein,
the content of the carboxyl group and/or the carboxylate group in the polyurethane resin is 0.5 to 4.0 mass%.
6. An antiviral fabric characterized in that an antiviral layer is provided on the surface of a fabric substrate, said layer comprising an antiviral agent comprising a methoxysilane quaternary ammonium salt and an aqueous polyurethane resin binder having a carboxyl group and/or a carboxylate group.
7. An antiviral polyurethane sheet, characterized in that an antiviral layer containing an antiviral agent containing a methoxysilane quaternary ammonium salt and an aqueous polyurethane resin binder having a carboxyl group and/or a carboxylate group is provided on the surface of a sheet containing polyurethane.
8. An antiviral polyvinyl chloride sheet, characterized in that an antiviral layer is provided on the surface of a sheet comprising polyvinyl chloride, and the layer comprises an antiviral agent comprising a methoxysilane quaternary ammonium salt and an aqueous polyurethane resin binder having a carboxyl group and/or a carboxylate group.
CN202280011881.XA 2021-02-08 2022-01-17 Antiviral agent composition, antiviral fabric treated with the same, antiviral polyurethane sheet, and antiviral polyvinyl chloride sheet Pending CN116744795A (en)

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JP2011042896A (en) * 2009-08-20 2011-03-03 Nicca Chemical Co Ltd Method for producing leather material, and leather material
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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2006206839A (en) * 2005-01-31 2006-08-10 Nicca Chemical Co Ltd Polyurethane resin water-based dispersion and manufacturing method of flame-retardant polyester fiber using the same
JP2007045866A (en) * 2005-08-08 2007-02-22 Dai Ichi Kogyo Seiyaku Co Ltd Aqueous polyurethane resin composition for nonporous film type moisture-permeable, waterproof finish and method for producing moisture-permeable, waterproof finish fabric
JP2011042896A (en) * 2009-08-20 2011-03-03 Nicca Chemical Co Ltd Method for producing leather material, and leather material
WO2013047642A1 (en) * 2011-09-29 2013-04-04 Ｔｂカワシマ株式会社 Article comprising immobilized antibacterial agent and method for producing same
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