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  • C08F214/00—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 a halogen
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  • C09K3/00—Materials not provided for elsewhere
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• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B32—LAYERED PRODUCTS
  • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
  • B32B27/00—Layered products comprising a layer of synthetic resin
  • B32B27/30—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers
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  • C08F214/00—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 a halogen
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  • C08F214/00—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 a halogen
  • C08F214/02—Monomers containing chlorine
  • C08F214/04—Monomers containing two carbon atoms
  • C08F214/08—Vinylidene chloride
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  • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
  • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
  • C08F220/04—Acids; Metal salts or ammonium salts thereof
  • C08F220/06—Acrylic acid; Methacrylic acid; Metal salts or ammonium salts thereof
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  • C09D127/00—Coating compositions based on 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 a halogen; Coating compositions based on derivatives of such polymers
  • C09D127/02—Coating compositions based on 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 a halogen; Coating compositions based on derivatives of such polymers not modified by chemical after-treatment
  • C09D127/04—Coating compositions based on 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 a halogen; Coating compositions based on derivatives of such polymers not modified by chemical after-treatment containing chlorine atoms
  • C09D127/08—Homopolymers or copolymers of vinylidene chloride
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  • C09D133/00—Coating compositions based on 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 only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Coating compositions based on derivatives of such polymers
  • C09D133/04—Homopolymers or copolymers of esters
  • C09D133/14—Homopolymers or copolymers of esters of esters containing halogen, nitrogen, sulfur or oxygen atoms in addition to the carboxy oxygen
  • C09D133/16—Homopolymers or copolymers of esters containing halogen atoms
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  • 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
  • D06M15/21—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
  • D06M15/244—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of halogenated hydrocarbons
  • D06M15/248—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of halogenated hydrocarbons containing chlorine
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  • D06M15/21—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
  • D06M15/244—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of halogenated hydrocarbons
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  • 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
  • D06M15/21—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
  • D06M15/263—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of unsaturated carboxylic acids; Salts or esters thereof
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  • 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
  • D06M15/21—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
  • D06M15/263—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of unsaturated carboxylic acids; Salts or esters thereof
  • D06M15/267—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of unsaturated carboxylic acids; Salts or esters thereof of unsaturated carboxylic esters having amino or quaternary ammonium groups
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  • 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
  • D06M15/21—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
  • D06M15/263—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of unsaturated carboxylic acids; Salts or esters thereof
  • D06M15/273—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of unsaturated carboxylic acids; Salts or esters thereof of unsaturated carboxylic esters having epoxy groups
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  • D06M15/21—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
  • D06M15/263—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of unsaturated carboxylic acids; Salts or esters thereof
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  • 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
  • D06M15/21—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
  • D06M15/285—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of unsaturated carboxylic acid amides or imides
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  • D06M15/21—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
  • D06M15/285—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of unsaturated carboxylic acid amides or imides
  • D06M15/29—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of unsaturated carboxylic acid amides or imides containing a N-methylol group or an etherified N-methylol group; containing a N-aminomethylene group; containing a N-sulfidomethylene group
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  • 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
  • D06M15/21—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
  • D06M15/327—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of unsaturated alcohols or esters thereof
  • D06M15/333—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of unsaturated alcohols or esters thereof of vinyl acetate; Polyvinylalcohol
  • D06M15/3335—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of unsaturated alcohols or esters thereof of vinyl acetate; Polyvinylalcohol fluorinated
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  • D06M15/21—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
  • D06M15/347—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of unsaturated ethers, acetals, hemiacetals, ketones or aldehydes
  • D06M15/353—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of unsaturated ethers, acetals, hemiacetals, ketones or aldehydes containing fluorine
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  • 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
  • D06M15/21—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
  • D06M15/356—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of other unsaturated compounds containing nitrogen, sulfur, silicon or phosphorus atoms
  • D06M15/3562—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of other unsaturated compounds containing nitrogen, sulfur, silicon or phosphorus atoms containing nitrogen
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  • 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
  • D06M15/21—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
  • D06M15/356—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of other unsaturated compounds containing nitrogen, sulfur, silicon or phosphorus atoms
  • D06M15/3568—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of other unsaturated compounds containing nitrogen, sulfur, silicon or phosphorus atoms containing silicon
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  • 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
  • D06M15/564—Polyureas, polyurethanes or other polymers having ureide or urethane links; Precondensation products forming them
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  • D06M23/00—Treatment of fibres, threads, yarns, fabrics or fibrous goods made from such materials, characterised by the process
  • D06M23/10—Processes in which the treating agent is dissolved or dispersed in organic solvents; Processes for the recovery of organic solvents thereof
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L2205/00—Polymer mixtures characterised by other features
  • C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
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  • D06M2200/00—Functionality of the treatment composition and/or properties imparted to the textile material
  • D06M2200/10—Repellency against liquids
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  • D06M2200/10—Repellency against liquids
  • D06M2200/12—Hydrophobic properties
• • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
  • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
  • Y10T428/00—Stock material or miscellaneous articles
  • Y10T428/249921—Web or sheet containing structurally defined element or component
  • Y10T428/249953—Composite having voids in a component [e.g., porous, cellular, etc.]
• • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
  • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
  • Y10T442/00—Fabric [woven, knitted, or nonwoven textile or cloth, etc.]
  • Y10T442/20—Coated or impregnated woven, knit, or nonwoven fabric which is not [a] associated with another preformed layer or fiber layer or, [b] with respect to woven and knit, characterized, respectively, by a particular or differential weave or knit, wherein the coating or impregnation is neither a foamed material nor a free metal or alloy layer
  • Y10T442/2041—Two or more non-extruded coatings or impregnations
  • Y10T442/2098—At least two coatings or impregnations of different chemical composition

Definitions

• the present invention relates to a water / oil repellent composition and an article whose surface is treated with the water / oil repellent composition.
• a monomer having a polyfluoroalkyl group having 8 or more carbon atoms hereinafter, the polyfluoroalkyl group is referred to as Rf group.
• Rf group a monomer having a polyfluoroalkyl group having 8 or more carbon atoms
• perfluoroalkyl group having carbon atoms 7 or more perfluoroalkyl group having carbon atoms (hereinafter, referred perfluoroalkyl group as R F group.)
• R F group 7 or more perfluoroalkyl group having carbon atoms
• the compound having decomposes environment in vivo degradation It has been pointed out that the product may accumulate, that is, the environmental load is high. Therefore, repellent carbon number has a unit based on a monomer having no more than six R F group, with no copolymer units derived from monomers having a C 7 or more R F group
• water / oil repellent compositions There is a need for water / oil repellent compositions.
• the following water / oil repellent compositions (1) and (2) have been proposed.
• a monomer comprising a unit based on the following monomer (a), a copolymer having a unit based on the following monomer (b) and a unit based on the following monomer (c), and a medium
• a water / oil repellent composition having a molar ratio ((b) / (c)) of units based on (b) to units based on monomer (c) of 1 or more
• Monomer (b) Vinyl chloride.
• Monomer (c) Vinyl ether having no R f group and having a functional group capable of crosslinking.
• a water / oil repellent composition comprising a copolymer and a medium (Patent Document 2).
• a textile product comprising a fabric or the like whose surface has been treated with the water / oil repellent composition of (2) has a water repellency (hereinafter referred to as washing durability) after drying without being forcibly heated after washing. It is said that it is good.
• a moisture permeable waterproof membrane may be provided (Patent Document 3).
• a laminating method and a coating method are well known.
• the laminating method is a method in which a porous polyfluoroethylene film or a microporous polyurethane resin film is bonded to the back side of a fabric treated with a water / oil repellent composition via an adhesive component or the like.
• the coating method is a method in which a coating liquid containing a polyurethane resin, an acrylic resin, or the like is applied to the back side of a fabric treated with a water / oil repellent composition.
• the fabric is required that the bonded or applied resin film is not easily peeled off.
• a highly volatile solvent such as methyl ethyl ketone, ethyl acetate, toluene, isopropyl alcohol is used in the case of dry coating in which a resin film is formed by drying after coating.
• a polar organic solvent such as N, N-dimethylformamide (hereinafter referred to as DMF) is used.
• the present invention can provide an article having good water and oil repellency and durability for washing, in which penetration of a coating liquid for forming a moisture permeable waterproof membrane is suppressed, and peeling of the moisture permeable waterproof membrane is suppressed.
• Another object of the present invention is to provide a water / oil repellent composition having a low environmental load and an article having a surface of a porous substrate such as a fabric treated with the water / oil repellent composition.
• the water / oil repellent composition of the present invention comprises a copolymer (A) having 60 to 95% by mass of units based on the following monomer (a1) and 5 to 40% by mass of units based on the following monomer (a2). ), A copolymer (B) having 50 to 95% by mass of units based on the following monomer (b1) and 5 to 50% by mass of units based on the following monomer (b2), and a medium (C) Including The ratio of the copolymer (A) in the total (100% by mass) of the copolymer (A) and the copolymer (B) is 70 to 90% by mass, and the copolymer (B ) Is 10 to 30% by mass.
• Monomer (a1) A compound represented by the following formula (1).
• ZY n X (1).
• Z is a polyfluoroalkyl group having 1 to 6 carbon atoms or a group represented by the following formula (2)
• Y is a divalent organic group having no fluorine atom or a single bond
• X is one of the groups represented by the following formulas (3-1) to (3-5) when n is 1, and when n is 2,
• i is an integer of 1 to 6
• j is an integer of 0 to 10
• X 1 and X 2 are each a fluorine atom or a trifluoromethyl group.
• -CR 2 CH 2 (3-1)
• -C (O) OCR 2 CH 2 (3-2)
• -OC (O) CR 2 CH 2 (3-3)
• -OCH 2 - ⁇ -CR 2 CH 2 (3-4)
• -OCH CH 2 (3-5).
• R 2 is a hydrogen atom, a methyl group or a halogen atom
• phi is a phenylene group.
• R 3 is a hydrogen atom, methyl group or halogen atom, and m is an integer of 0-4.
• Monomer (a2) Vinylidene chloride.
• Monomer (b1) Halogenated olefin.
• Monomer (b2) a monomer having no polyfluoroalkyl group and having a crosslinkable functional group.
• Z is preferably a C 4-6 perfluoroalkyl group. It is preferable that Y is an alkylene group having 2 to 4 carbon atoms, n is 1 and X is a group represented by the formula (3-3).
• the copolymer (A) preferably further has units based on the following monomer (a3), and the crosslinkable functional group in the monomer (a3) includes a hydroxyl group, a blocked isocyanate group, An amino group, an N-hydroxymethylamide group, an epoxy group or a carboxy group is preferred.
• Monomer (a3) a monomer having no polyfluoroalkyl group and having a crosslinkable functional group.
• the copolymer (A) has a unit based on the monomer (a1) of 65 to 89.9% by mass, a unit based on the monomer (a2) of 10 to 34.9% by mass, and the monomer It is preferable to have 0.1 to 25% by mass of units based on the body (a3).
• the monomer (b1) is preferably vinyl chloride.
• the copolymer (B) preferably further has units based on the monomer (b3) which is a monomer other than the monomer (b1) and the monomer (b2).
• the body (b3) is preferably the monomer (a1) or a monomer having an alkyl group having 1 to 22 carbon atoms.
• the proportion of the units based on the monomer (b3) is preferably 2 to 40% by mass among the units (100% by mass) based on all the monomers in the copolymer (B).
• the present invention is also an article having a porous substrate, the porous substrate having a water / oil repellent treated surface treated with the water / oil repellent composition on at least one surface thereof, It has a moisture permeable waterproof membrane on the surface.
• the porous substrate is preferably a fabric.
• the present invention further relates to a method for producing a porous substrate having a water- and oil-repellent treated surface and a moisture-permeable waterproof film, wherein at least one surface of the porous substrate is treated with the water- and oil-repellent composition to repel the surface.
• a water / oil repellent treatment surface is formed, and then a moisture permeable waterproof membrane is formed by applying a coating liquid containing a material of the moisture permeable waterproof membrane to one surface of the porous substrate.
• the water / oil repellent composition of the present invention the water / oil repellency and washing durability are good, the penetration of the coating liquid for forming the moisture permeable waterproof membrane is suppressed, and the moisture permeable waterproof membrane is peeled off. It is possible to obtain a porous substrate such as a fabric in which the above is suppressed.
• the water / oil repellent composition of the present invention has a low environmental load. Articles having a porous substrate subjected to the above-described treatment of the present invention have good water and oil repellency and washing durability, and can prevent the penetration of a coating liquid for forming a moisture permeable waterproof film and the like. Excellent design, moisture-permeable waterproof membrane is difficult to peel off, and environmental impact is low.
• the compound represented by the formula (1) is referred to as “compound (1)”.
• group (2) a group represented by the formula (2).
• Groups represented by other formulas are also described in the same manner.
• (meth) acrylate means acrylate or methacrylate.
• the monomer in the present specification means a compound having a polymerizable unsaturated group.
• the R f group is a group in which some or all of the hydrogen atoms of the alkyl group are substituted with fluorine atoms
• the R F group is a group in which all of the hydrogen atoms of the alkyl group are substituted with fluorine atoms. It is.
• porous substrate among the substrates subjected to water / oil repellent treatment with the water / oil repellent composition, a porous substrate is referred to as a “porous substrate”.
• a typical example of the porous substrate is a sheet-like porous substrate such as a fabric.
• a portion derived from a monomer constituting the polymer in the present specification is referred to as “unit based on monomer” or “monomer unit”.
• a unit based on the monomer may be represented by adding “unit” to the monomer name.
• the ratio of monomer units in the copolymer in the present invention is determined from NMR analysis and elemental analysis. In addition, when it cannot obtain
• the mass average molecular weight (Mw) and number average molecular weight (Mn) of the copolymer are polystyrene-converted molecular weights measured by gel permeation chromatography (GPC), and specifically measured by the following method. .
• Mn number average molecular weight
• Mw mass average molecular weight
• Measurement temperature 37 ° C.
• Injection volume 50 ⁇ L
• Outflow rate 1 mL / min
• the water / oil repellent composition of the present invention contains a specific copolymer (A), a specific copolymer (B), and a medium (C) as essential components, and if necessary, a surfactant. (D) and an additive (E) are included.
• the copolymer (A) has a unit based on the monomer (a1) and a unit based on the monomer (a2).
• the copolymer (A) preferably further has a unit based on the monomer (a3), and may have a unit based on the monomer (a4) described later, if necessary.
• Monomer (a1) Monomer (a) is compound (1). (ZY) n X (1).
• Z is an R f group having 1 to 6 carbon atoms (provided that the R f group may contain an etheric oxygen atom) or a group (2).
• i is an integer of 1 to 6
• j is an integer of 0 to 10
• X 1 and X 2 are each independently a fluorine atom or a trifluoromethyl group.
• the R f group is preferably an R F group.
• the R f group may be linear or branched, and is preferably linear. As the R f group, a linear R F group having 4 to 6 carbon atoms is particularly preferable.
• Examples of Z include the following groups.
• k is an integer of 1 to 6
• h is an integer of 0 to 10.
• Y is a divalent organic group having no fluorine atom or a single bond.
• an alkylene group is preferable.
• the alkylene group may be linear or branched, and preferably has 1 to 6 carbon atoms.
• the divalent organic group is —O—, —NH—, —CO—, —S—, —SO 2 —, —CD 1 ⁇ CD 2 — (wherein D 1 and D 2 are each independently a hydrogen atom Or an organic group having a methyl group.
• Particularly preferred Y is a linear alkylene group having 2 to 4 carbon atoms.
• p is an integer of 2 to 30.
• V is an unbranched contrasting alkylene group, arylene group or aralkylene group, and —C 6 H 12 —, — ⁇ —CH 2 — ⁇ —, — ⁇ — (where ⁇ is a phenylene group). Is preferred.
• W is any of the following groups. —SO 2 N (R 1 ) —C d H 2d —, —CONHC d H 2d —, —C q H 2q —.
• R 1 is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms
• d is an integer of 2 to 8
• q is an integer of 1 to 20.
• n is 1 or 2. n is preferably 1. X is any one of groups (3-1) to (3-5) when n is 1, and when n is 2, X is any of groups (4-1) to (4-4). Either.
• R 2 is a hydrogen atom, a methyl group or a halogen atom
• phi is a phenylene group.
• X is preferably a group (3-3).
• R 3 is a hydrogen atom, methyl group or halogen atom, and m is an integer of 0-4.
• X is preferably a group (4-3).
• (meth) acrylates having 4 to 6 carbon atoms and R F groups are preferred.
• Z is an R F group having 4-6 carbon atoms
• Y is an alkylene group having 1 to 4 carbon atoms
• n is 1
• X is a group (3-3) Compounds are preferred.
• the monomer (a2) is vinylidene chloride.
• the affinity of the copolymer (A) to the substrate and the film-forming property are improved, so that the substrate after being immersed in the water / oil repellent composition is air-dried
• the copolymer (A) penetrates into every part of the fabric where the coating with the copolymer (A) is difficult to form, such as between the fibers, and the copolymer (A) is uniform and ideal. It is thought that a typical film can be formed. As a result, it is considered that sufficient washing durability can be imparted to the article.
• the monomer (a3) does not have an R f group and has a functional group capable of crosslinking. By having the monomer (a3) unit, peeling of the moisture-permeable waterproof membrane is suppressed. Moreover, the washing durability of the article is further improved.
• the functional group capable of crosslinking is preferably a functional group having at least one bond among a covalent bond, an ionic bond and a hydrogen bond, or a functional group capable of forming a crosslinked structure by the interaction of the bonds. Further, it may be a functional group having an active organic group or an element such as hydrogen or halogen in the molecule.
• Examples of the functional group include hydroxyl group, isocyanate group, blocked isocyanate group, alkoxysilyl group, amino group, N-hydroxymethylamide group, N-alkoxymethylamide group, silanol group, ammonium group, amide group, epoxy group, oxazoline Group, carboxy group, alkenyl group, sulfo group and the like are preferable.
• Particularly preferred are a hydroxyl group, a blocked isocyanate group, an amino group, an N-hydroxymethylamide group, an epoxy group, and a carboxy group.
• (meth) acrylates, acrylamides, vinyl ethers, or vinyl esters are preferable.
• the monomer (a3) the following compounds may be mentioned.
• (Meth) acrylates glycidyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, 3-chloro-2-hydroxypropyl (meth) Polycaprolactone ester of acrylate, dimethylaminoethyl (meth) acrylate, diethylaminoethyl (meth) acrylate, dimethylaminopropyl (meth) acrylate, hydroxyethyl (meth) acrylate (FA of trade name “Placcel”, FM series, Daicel Chemical Industries, Ltd.) 2-isocyanatoethyl (meth) acrylate, 3-isocyanatopropyl (meth) acrylate, 4-isocyanatobutyl (meth) acrylate, 2-isocyanatoethyl (meth) 2-butanone oxime adduct of acrylate
• Acrylamides (meth) acrylamide, N-methyl (meth) acrylamide, N-methylol (meth) acrylamide, N-butoxymethyl (meth) acrylamide, methoxymethyl (meth) acrylamide, ethoxymethyl (meth) acrylamide, butoxymethyl ( (Meth) acrylamide, diacetone (meth) acrylamide.
• Vinyl ethers 2-chloroethyl vinyl ether, 2-hydroxyethyl vinyl ether, 3-hydroxypropyl vinyl ether, 2-hydroxypropyl vinyl ether, 2-hydroxyisopropyl vinyl ether, 4-hydroxybutyl vinyl ether, 4-hydroxycyclohexyl vinyl ether, hexamethylene glycol monovinyl ether 1,4-cyclohexanedimethanol monovinyl ether, diethylene glycol monovinyl ether, triethylene glycol monovinyl ether, dipropylene glycol monovinyl ether, glycidyl vinyl ether, 2-aminoethyl vinyl ether, 3-aminopropyl vinyl ether, 2-aminobutyl vinyl ether, allyl vinyl ether .
• (meth) acrylates and acrylamides are preferred, and specific examples thereof include 3,5-dimethylpyrazole adducts of 2-isocyanatoethyl (meth) acrylate and 2-isocyanato.
• Polycaprolactone ester of acrylate (trade name “Placcel” FA, FM series, manufactured by Daicel Chemical Industries, Ltd.) is preferable.
• the monomer (a4) is another monomer excluding the monomer (a1), the monomer (a2), and the monomer (a3).
• the monomer (a4) (meth) acrylates, unsaturated carboxylic acid esters and the like are preferable.
• alkyl (meth) acrylates having an alkyl group having 1 to 22 carbon atoms and cycloalkyl (meth) acrylates having a monocyclic or polycyclic cycloalkyl group having 5 to 16 carbon atoms are preferable.
• unsaturated carboxylic acid esters unsaturated monocarboxylic acid monoalkyl esters and unsaturated dicarboxylic acid dialkyl esters having an alkyl group having 1 to 12 carbon atoms are preferred.
• monomer (a4) including other compounds include the following compounds.
• (Meth) acrylates methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, n-butyl (meth) acrylate, t-butyl (meth) acrylate, i-butyl (meth) acrylate, cyclohexyl ( (Meth) acrylate, 2-ethylhexyl (meth) acrylate, n-hexyl (meth) acrylate, benzyl (meth) acrylate, octyl (meth) acrylate, lauryl (meth) acrylate, cetyl (meth) acrylate, stearyl (meth) acrylate, Behenyl (meth) acrylate, isobornyl (meth) acrylate, dicyclopentanyl (meth) acrylate, dicyclopentenyl (meth) acrylate, (meth) acrylic having repeating structure of
• Unsaturated carboxylic acid ester Crotonic acid alkyl ester, maleic acid alkyl ester such as diethyl maleate, dipropyl maleate, dioctyl maleate, fumaric acid alkyl ester such as diethyl fumarate, dipropyl fumarate, citraconic acid alkyl ester, mesacone Acid alkyl ester, allyl acetate.
• maleic acid alkyl ester such as diethyl maleate, dipropyl maleate, dioctyl maleate
• fumaric acid alkyl ester such as diethyl fumarate, dipropyl fumarate, citraconic acid alkyl ester
• mesacone Acid alkyl ester allyl acetate.
• Other N-vinylcarbazole, maleimide, N-methylmaleimide, vinylpyrrolidone, vinyl chloride.
• the monomer (a1) with an R F group having 4-6 carbon atoms (meth) acrylate units
• the monomer (a2 ) A combination of a vinylidene chloride unit and the monomer (a3) unit of the preferred embodiment described above is preferred.
• the proportion of the monomer (a1) unit is 60 to 95% by mass of all monomer units (100% by mass) in the copolymer (A) from the viewpoint of water / oil repellency and washing durability. 65 to 89.9% by mass is preferable, and 70 to 84.5% by mass is particularly preferable.
• the proportion of the monomer (a2) unit is 5 to 40% by mass of all monomer units (100% by mass) in the copolymer (A) from the viewpoint of water / oil repellency and washing durability. 10 to 34.9% by mass is preferable, and 15 to 29.5% by mass is particularly preferable.
• the proportion of the monomer (a3) unit is preferably 0 to 35% by mass of all the monomer units (100% by mass) in the copolymer (A), and the adhesion to the moisture-permeable waterproof membrane and From the viewpoint of washing durability, 0.1 to 25% by mass is more preferable, and 0.5 to 15% by mass is particularly preferable.
• the proportion of the monomer (a4) unit is preferably 0 to 35% by mass, more preferably 0 to 30% by mass, of all the monomer units (100% by mass) in the copolymer (A). 0 to 15% by mass is particularly preferred.
• the weight average molecular weight (Mw) of the copolymer (A) is preferably 70,000 or more, more preferably 75,000 or more, and particularly preferably 80,000 or more. If it is the said range, the penetration
• the weight average molecular weight (Mw) of the copolymer (A) is preferably 200,000 or less, and particularly preferably 170,000 or less, from the viewpoint of film forming property and storage stability.
• the number average molecular weight (Mn) of the copolymer (A) is preferably 32,000 or more, particularly preferably 35,000 or more.
• the number average molecular weight (Mn) of the copolymer (A) is preferably 100,000 or less, particularly preferably 80,000 or less.
• the copolymer (B) has a unit based on the monomer (b1) and a unit based on the monomer (b2).
• the copolymer (B) may have a unit based on the monomer (b3) as necessary.
• the monomer (b1) is a halogenated olefin.
• the halogenated olefin is preferably a chlorinated olefin or a fluorinated olefin, and specific examples include vinyl chloride, vinylidene chloride, tetrafluoroethylene, and vinylidene fluoride. From the viewpoint of adhesion to the substrate and the moisture-permeable waterproof membrane, vinyl chloride or vinylidene chloride is more preferable, and vinyl chloride is particularly preferable.
• the monomer (b2) is a monomer having no functional group capable of crosslinking without having an R f group. By having the monomer (b2) unit, peeling of the moisture-permeable waterproof membrane is suppressed. Moreover, the washing durability of the article is further improved.
• Examples of the functional group capable of crosslinking include the functional groups exemplified in the monomer (a3), and preferred embodiments are also the same.
• Examples of the monomer (b2) include the compounds exemplified in the monomer (a3), and preferred embodiments are also the same.
• the monomer (b3) is another monomer excluding the monomer (b1) and the monomer (b2).
• a monomer (b3) the compound illustrated by the monomer (a1) mentioned above and the monomer (a4) mentioned above is mentioned.
• the monomer (b3) the monomer (a1) and the monomer (a4) are preferable.
• the copolymer (B) contains a unit based on the monomer (b3) from the viewpoint of compatibility with the copolymer (A), and at least a part of the monomer (b3) is the above-mentioned.
• the copolymer (B) which is the monomer (a1) obtained is preferred.
• the monomer (b1) is a vinyl chloride unit or a vinylidene chloride unit, the monomer (b2) unit of the preferred embodiment described above, and A combination of monomer (b3) units is preferred.
• the proportion of the monomer (b1) unit is 50 to 95% by mass of all the monomer units (100% by mass) in the copolymer (B) from the point that peeling of the moisture-permeable waterproof membrane is suppressed. 55 to 95% by mass is more preferable, and 55 to 90% by mass is particularly preferable.
• the proportion of the monomer (b2) unit is 5 to 50% by mass of all the monomer units (100% by mass) in the copolymer (B) from the point that peeling of the moisture-permeable waterproof membrane is suppressed. 5 to 45 mass% is preferable, 5 to 25 mass% is more preferable, and 10 to 20 mass% is particularly preferable.
• the proportion of the monomer (b3) unit is preferably 0 to 45% by mass, more preferably 2 to 40% by mass, of all the monomer units (100% by mass) in the copolymer (B), 5 to 35% by mass is particularly preferable.
• the weight average molecular weight (Mw) of the copolymer (B) is preferably 10,000 or more, more preferably 20,000 or more, and particularly preferably 30,000 or more. If it is the said range, it is excellent in water and oil repellency and washing durability.
• the mass average molecular weight (Mw) of the copolymer (B) is preferably 1,000,000 or less, particularly preferably 500,000 or less, from the viewpoint of film forming property and storage stability.
• the number average molecular weight (Mn) of the copolymer (B) is preferably 5,000 or more, particularly preferably 10,000 or more.
• the number average molecular weight (Mn) of the copolymer (B) is preferably 300,000 or less, particularly preferably 150,000 or less.
• the copolymer (A) and the copolymer (B) are, for example, a solution of a copolymer obtained by polymerizing a monomer component containing each of the above monomers in a medium in the presence of a polymerization initiator, Manufactured by a method of obtaining a dispersion or emulsion.
• Examples of the polymerization method include solution polymerization method, dispersion polymerization method, emulsion polymerization method, suspension polymerization method and the like, and emulsion polymerization is preferable.
• the polymerization method may be batch polymerization or multistage polymerization.
• a monomer component containing each of the above monomers is emulsion-polymerized in an aqueous medium in the presence of a surfactant and a polymerization initiator.
• a method of obtaining a copolymer emulsion is preferred.
• a mixture comprising a monomer, a surfactant and an aqueous medium is mixed and dispersed with an ultrasonic stirrer, a homomixer or a high-pressure emulsifier.
• Polymerization initiator examples include a thermal polymerization initiator, a photopolymerization initiator, a radiation polymerization initiator, a radical polymerization initiator, an ionic polymerization initiator, and the like, and a water-soluble or oil-soluble radical polymerization initiator is preferable.
• a general-purpose initiator such as an azo polymerization initiator, a peroxide polymerization initiator, or a redox initiator is used depending on the polymerization temperature.
• an azo compound is particularly preferable, and when polymerization is performed in an aqueous medium, a salt of the azo compound is more preferable.
• the polymerization temperature is preferably 20 to 150 ° C.
• the addition amount of the polymerization initiator is preferably 0.1 to 5 parts by mass, and more preferably 0.1 to 3 parts by mass with respect to 100 parts by mass of the monomer component.
• Molecular weight regulator In the polymerization of the monomer component, a molecular weight modifier may be used.
• aromatic compounds, mercapto alcohols or mercaptans are preferable, and alkyl mercaptans are particularly preferable. What is necessary is just to adjust suitably the addition amount of a molecular weight modifier so that Mw and Mn of a copolymer may become said range.
• Examples of the medium include a medium (C) described later, and an aqueous medium is preferable.
• an aqueous medium the thing similar to the aqueous medium mentioned later is mentioned, A preferable aspect is also the same.
• Surfactant (D) mentioned later is mentioned as surfactant, A preferable aspect is also the same.
• the proportion of each monomer in the monomer component is the same as the proportion of each monomer unit in the copolymer because the monomer is polymerized almost 100%, and the preferred embodiment is also the same. .
• the solid content concentration of the emulsion is preferably 20 to 40% by mass in the emulsion (100% by mass) immediately after the production of the copolymer.
• concentration is a density
• the content of the copolymer in the emulsion is preferably 18 to 40% by mass immediately after the production of the copolymer.
• the solid content concentration of the emulsion is calculated from the mass of the emulsion before heating and the mass after drying for 4 hours in a convection dryer at 120 ° C.
• medium (C) water, alcohol (alkanol, alkylene glycol, polyalkylene glycol, etc.), monoalkyl ether of polyhydric alcohol, halogen compound, hydrocarbon, ketone, ester, ether, nitrogen compound, sulfur compound, inorganic solvent And organic acids.
• alcohol an alkanol having 6 or less carbon atoms, a dihydric alcohol having 4 or less carbon atoms (such as alkylene glycol), and a multimer of divalent alcohol having 4 or less carbon atoms (such as dialkylene glycol or trialkylene glycol) are preferable.
• the medium (C) is preferably an aqueous medium from the viewpoint of solubility and ease of handling.
• Examples of the aqueous medium include water or water containing a water-soluble organic solvent.
• water-soluble organic solvents include tert-butanol, 3-methoxymethylbutanol, propylene glycol, dipropylene glycol, dipropylene glycol monomethyl ether, tripropylene glycol, and the like. Dipropylene glycol, tripropylene glycol, dipropylene glycol monomethyl Ether is preferred.
• the content of the water-soluble organic solvent is preferably 1 to 80 parts by mass and more preferably 10 to 60 parts by mass with respect to 100 parts by mass of water.
• surfactant (D) examples include hydrocarbon surfactants and fluorine surfactants, which are anionic surfactants, nonionic surfactants, cationic surfactants, and amphoteric surfactants, respectively. Is mentioned.
• a combination of a nonionic surfactant and an amphoteric surfactant is preferable from the viewpoint of compatibility with the additive, and a nonionic surfactant alone is preferable from the viewpoint of adhesion.
• Use or a combination of a nonionic surfactant and a cationic surfactant is preferred.
• the ratio of the nonionic surfactant to the cationic surfactant is preferably 97/3 to 40/60 (mass ratio).
• the nonionic surfactant is preferably at least one selected from the group consisting of surfactants s 1 to s 6 described in Patent Documents 1 and 2.
• the surfactant (D) comprises a cationic surfactant, examples of the cationic surfactant, preferably a surfactant s 7 described in Patent Documents 1 and 2.
• the surfactant (D) comprises an amphoteric surfactant, the amphoteric surfactant, preferably the surfactant s 8 described in Patent Documents 1 and 2.
• the surfactant (D) it may be used a surfactant s 9 (polymeric surfactant) as described in Patent Documents 1 and 2.
• the preferable aspect of surfactant (D) is the same as the preferable aspect described in patent document 1,2.
• Additives (E) include penetrants, antifoaming agents, water absorbing agents, antistatic agents, antistatic polymers, antifungal agents, texture modifiers, film-forming aids, water-soluble polymers (polyacrylamide, polyvinyl Alcohol), thermosetting agents (melamine resins, urethane resins, triazine ring-containing compounds, isocyanate compounds, etc.), epoxy curing agents (isophthalic acid dihydrazide, adipic acid dihydrazide, sebacic acid dihydrazide, dodecanedioic acid dihydrazide, 1,6- Hexamethylene bis (N, N-dimethylsemicarbazide), 1,1,1 ′, 1′-tetramethyl-4,4 ′-(methylene-di-para-phenylene) disemicarbazide, spiroglycol, etc.), thermosetting catalyst , Crosslinking catalysts (organic acids, ammonium chloride, etc.),
• the water / oil repellent composition of the present invention may be a copolymer other than the copolymer (A) and the copolymer (B) that can exhibit water repellency and / or oil repellency, if necessary (for example, commercially available).
• Examples of the water repellent compound having no fluorine atom include paraffinic compounds, aliphatic amide compounds, alkylethylene urea compounds, silicone compounds, and the like.
• the proportion of the copolymer (A) is 70 to 90% by mass, preferably 75 to 90% by mass, out of the total (100% by mass) of the copolymer (A) and the copolymer (B), and 81 From 90% by weight is particularly preferred.
• the proportion of the copolymer (A) is 70% by mass or more, the water / oil repellency and washing durability are good, and the penetration of the coating liquid for forming the moisture-permeable waterproof film can be suppressed. If the ratio of a copolymer (A) is 90 mass% or less, peeling of a moisture-permeable waterproof film will be suppressed.
• the ratio of the copolymer (B) is 10 to 30% by mass, preferably 10 to 25% by mass, based on the total (100% by mass) of the copolymer (A) and the copolymer (B). ⁇ 19% by weight is particularly preferred. If the ratio of a copolymer (B) is 10 mass% or more, peeling of a moisture-permeable waterproof film will be suppressed. When the ratio of the copolymer (B) is 30% by mass or less, the water / oil repellency and washing durability are good, and the penetration of the coating liquid for forming the moisture-permeable waterproof film is suppressed.
• the amount of the surfactant (D) is preferably 1 to 10 parts by mass, more preferably 1 to 9 parts by mass with respect to the total (100 parts by mass) of the copolymer (A) and the copolymer (B). 1 to 7 parts by mass is particularly preferable.
• the solid content concentration of the water / oil repellent composition of the present invention is preferably 0.2 to 5% by mass in the water / oil repellent composition (100% by mass) when the substrate is treated.
• the solid content concentration of the water / oil repellent composition is calculated from the mass of the water / oil repellent composition before heating and the mass after drying in a convection dryer at 120 ° C. for 4 hours.
• the copolymer is preferably dispersed as particles in an aqueous medium.
• the average particle size of the copolymer is preferably 10 to 1000 nm, more preferably 10 to 300 nm, and particularly preferably 10 to 250 nm. If the average particle size is within this range, it is not necessary to use a large amount of a surfactant or the like, the water repellency is good, no discoloration occurs when a dyed fabric is treated, and it is dispersed in an aqueous medium.
• the particles can exist stably and do not settle.
• the average particle size of the copolymer can be measured by a dynamic light scattering device, an electron microscope or the like.
• the copolymer (A) having 60 to 95% by mass of the monomer (a1) unit and 5 to 40% by mass of the monomer (a2) unit.
• the copolymer (A) having 60 to 95% by mass of the monomer (a1) unit and 5 to 40% by mass of the monomer (a2) unit.
• the copolymer (B) having 50 to 95% by mass of the monomer (b1) unit and 5 to 50% by mass of the monomer (b2) unit. Can be obtained at a specific ratio, and an article in which peeling of the moisture-permeable waterproof membrane is suppressed can be obtained.
• the copolymer (A) and the copolymer (B) do not have a monomer unit having an R F group having 7 or more carbon atoms,
• PFOA perfluorooctanoic acid
• PFOS perfluorooctanesulfonic acid
• the analytical value of LC-MS / MS by the method described in 2009/081822 can be made below the detection limit.
• the water / oil repellent composition of the present invention can be used for treating the surface of a substrate. It is also useful for applications that impart water and oil repellency by mixing and molding with fiber such as polypropylene and nylon.
• Substrates to be treated include fibers (natural fibers, synthetic fibers, blended fibers, etc.), fabrics (woven fabrics, knitted fabrics, nonwoven fabrics, etc.), various textile products (clothing articles (sportswear, coats, blousons, work clothing, uniforms). Etc.), bags, industrial materials, etc.), resin products, paper, leather, metal products, stone products, concrete products, gypsum products, glass products and the like.
• a porous substrate is preferable.
• the porous substrate include fabrics (woven fabrics, knitted fabrics, nonwoven fabrics, etc.), porous fiber products such as clothing articles, porous resin sheets, pumice stones, and wood.
• a fabric is particularly preferable.
• a coating solution containing a water / oil repellent composition is applied to a substrate by a known coating method and then dried, or the substrate is coated with a water / oil repellent composition. And a method of drying after dipping in the substrate.
• antistatic processing, softening processing, antibacterial processing, deodorization processing, waterproofing processing, and the like may be further performed.
• the present invention is an article having a porous substrate having a water / oil repellent treated surface treated with the water / oil repellent composition on one surface and a moisture permeable waterproof film on one surface.
• the fabric has a water- and oil-repellent treated surface on both sides and a water-permeable / oil-repellent treated surface has a moisture permeable waterproof film, or a clothing article obtained using the fabric.
• the moisture permeable waterproof membrane include a microporous polyurethane resin membrane.
• the present invention also provides a water- and oil-repellent treated surface by treating at least one surface of the porous substrate with the water and oil repellent composition.
• a method of forming one surface of a porous substrate with water / oil repellent treatment and then forming a moisture permeable waterproof film on the surface not subjected to water / oil repellent treatment A porous substrate having a water- and oil-repellent treated surface and a moisture-permeable waterproof membrane is produced by a method of forming a moisture-permeable and waterproof membrane on one of the water- and oil-repellent-treated surfaces.
• the porous substrate is preferably a fabric, and the moisture-permeable waterproof membrane is preferably a microporous polyurethane resin membrane.
• the coating liquid contains a moisture permeable waterproof membrane material, a solvent, and the like.
• a material for the moisture permeable waterproof membrane a conventionally known polyurethane resin obtained by reacting a polyisocyanate component and a polyol component can be employed.
• the polyisocyanate component aromatic diisocyanate, aliphatic diisocyanate, alicyclic diisocyanate and the like are used alone or in combination. Specifically, trilene-2,4-diisocyanate, 4,4′-diphenylmethane diisocyanate, 1,6-hexane diisocyanate, 1,4-cyclohexane diisocyanate, etc.
• polyether polyol polyethylene glycol, polypropylene glycol, polytetraethylene glycol or the like is used.
• polyester polyol a reaction product of a diol such as ethylene glycol or propylene glycol and a dibasic acid such as adipic acid or sebacic acid, or a ring-opening polymer such as caprolactone can be used.
• a polymer of the prepolymer can also be used.
• a polar organic solvent is preferably used, and examples thereof include N, N-dimethylformamide (DMF), N, N-dimethylacetamide, dimethyl sulfoxide, N-methylpyrrolidone, hexamethylenephosphonamide and the like.
• An auxiliary agent such as a fluorine-based water repellent or a crosslinking agent may be added to the polyurethane resin solution.
• the moisture permeable waterproof membrane can be formed, for example, by applying a coating liquid to one surface of a porous substrate, then allowing to stand for a predetermined time, then immersing in water for a predetermined time to remove the solvent, and then drying.
• a coating liquid to one surface of a porous substrate
• various coating methods such as knife coating, knife over roll coating, and reverse roll coating can be used.
• the water and oil repellency and washing durability are good, and the penetration of the coating liquid for forming a moisture permeable waterproof film and the like is suppressed.
• Example 1 to 13 are production examples
• Examples 15, 22 to 26, 28 to 30, and 32 to 37 are examples.
• Examples 14, 16 to 21, 27, and 31 are comparative examples.
• washing durability For the test cloth, washing was repeated 20 times or 50 times according to the water washing method of JIS L 0217 Attached Table 103. After washing, the product was air-dried overnight in a room with a room temperature of 25 ° C. and a humidity of 60%, and the water repellency was evaluated.
• Oil repellency The test fabric was evaluated for oil repellency according to the test method of AATCC-TM118-1966. The oil repellency was represented by the grade shown in Table 1. A grade marked with + (-) indicates that each property is slightly better (bad).
• nDoSH n-dodecyl mercaptan
• StSH Stearyl mercaptan
• VA061A 10% by mass aqueous solution of 2,2′-azobis [2- (2-imidazolin-2-yl) propane] acetate
• V-50 10% by mass aqueous solution of 2,2′-azobis (2-methylpropionamidine) ⁇ dihydrochloride.
• KB1000 silicone softener (manufactured by Meisei Chemical Industry Co., Ltd., High Softer KB1000), DP9C: Blocked isocyanate (Trixene DP9C / 214 manufactured by Baxenden), TP-10: Blocked isocyanate (manufactured by Meisei Chemical Co., Ltd., Meikanate TP-10), M-3: Melamine resin (DIC, Beccamine M-3), ACX: Cross-linking catalyst (manufactured by DIC, accelerator ACX).
• the obtained mixed solution was treated at 40 MPa using a high-pressure emulsifier (manufactured by APV Lanier Co., Ltd., Minilab) while maintaining the temperature at 60 ° C. to obtain an emulsion.
• the obtained emulsion was put into a stainless steel reactor and cooled to 40 ° C. or lower. After adding 1.3 g of V-50 and replacing the gas phase with nitrogen, 49 g of VDC was introduced, and the polymerization reaction was carried out at 60 ° C. for 15 hours with stirring to obtain an emulsion of copolymer (A-1). Obtained.
• the solid content was 36.1% by mass.
• Table 2 shows the charged amount of each raw material.
• Table 3 shows the ratio of each monomer unit, the added amount of the molecular weight modifier, and the molecular weight.
• Copolymers (B-1) to (B-3), (B′-4) to (B′ ⁇ ) were prepared in the same manner as in Example 1 except that the amount of each raw material was changed to the amount shown in Table 4. 5), (B-6) to (B-9), and (B′-10) to (B′-12) emulsions were obtained.
• the timing of adding VCM was the same as that of VDC.
• Table 4 shows the amount of each raw material charged.
• Table 5 shows the ratio of each monomer unit and the addition amount of the molecular weight modifier.
• a base fabric nylon high density taffeta
• a water / oil repellent composition After dipping a base fabric (nylon high density taffeta) in a water / oil repellent composition by a padding method, the wet pick-up was squeezed to 52 mass%. This was heated at 110 ° C. for 90 seconds and 170 ° C. for 60 seconds, and adjusted overnight in a room at 25 ° C. and 60% humidity to obtain a test cloth.
• Examples 14 to 17 are examples showing the effect of adding the copolymer (B) to the copolymer (A). From the results of Examples 14 and 15, it can be seen that when the copolymer (B) within the scope of the present invention is added to the copolymer (A), the peel strength of the moisture-permeable waterproof membrane is increased. From the results of Examples 16 and 17, it can be seen that when the copolymer (B ′) outside the scope of the present invention is added to the copolymer (A), the peel strength of the moisture-permeable waterproof membrane is lowered.
• Examples 18 to 26 The emulsion of copolymer (A) and the emulsion of copolymer (B) shown in Table 7 are mixed at the mass ratio shown in Table 7, and then diluted with water to adjust the solid content concentration to 1.2% by mass. After that, the additives shown in Table 7 were added so that the respective concentrations became the concentrations shown in Table 7 to obtain a water / oil repellent composition.
• Example 14 to 17 In the same manner as in Examples 14 to 17, a base fabric (nylon high-density taffeta) was treated with a water / oil repellent composition to obtain a test fabric.
• a base fabric nylon high-density taffeta
• test cloths with a moisture permeable waterproof membrane were obtained in the same manner as in Examples 14 to 17.
• Examples 22 to 26 a test cloth with a moisture permeable waterproof membrane was obtained in the same manner as in Examples 14 to 17, except that the stationary time of the test cloth after coating was changed to 5 minutes. The test fabric was evaluated. The results are shown in Table 7.
• Example 18 is an example in which the copolymer (A) was used alone.
• Examples 19 to 21 are examples in which a known water and oil repellent having a low environmental load is added to the copolymer (A). From the results of Examples 18 to 21, even when the copolymers (B′-10) to (B′-12), which are known water and oil repellents, were added to the copolymer (A), It can be seen that the peel strength is not greatly improved.
• Examples 22 to 26 are examples showing the effect of adding the copolymer (B) to the copolymer (A).
• Examples 27 to 37 The emulsion of copolymer (A) and the emulsion of copolymer (B) shown in Tables 8 to 9 are mixed at a mass ratio shown in Tables 8 to 9, then diluted with water, and the solid content concentration is 1.2. After adjusting to mass%, the additives shown in Tables 8 to 9 were added so that the respective concentrations would be the concentrations shown in Tables 8 to 9 to obtain water and oil repellent compositions.
• a base fabric nylon high-density taffeta
• a water / oil repellent composition to obtain a test fabric.
• a test cloth with a moisture-permeable and waterproof membrane was obtained in the same manner as in Examples 14 to 17 except that the thickness after drying was changed to 10 ⁇ m and the time for which the test cloth was coated was changed to 5 minutes.
• the test fabric was evaluated. The results are shown in Tables 8-9.
• Example 27 is an example in which the copolymer (A) was used alone.
• Examples 28 to 37 are examples in which the mass ratio between the copolymer (A) and the copolymer (B) was changed. From the results of Examples 28 to 37, in the range where the proportion of the copolymer (A) is 70 to 90% by mass and the proportion of the copolymer (B) is 10 to 30% by mass, It can be seen that the balance with the peel strength of the moisture waterproof membrane is good.
• the water / oil repellent composition of the present invention includes fabrics (woven fabrics, knitted fabrics, nonwoven fabrics, etc.), various textile products (clothing articles (sportswear, coats, blousons, work clothing, uniforms, etc.), bags, industrial materials, etc.), etc. It is useful as a water and oil repellent.
• fabrics woven fabrics, knitted fabrics, nonwoven fabrics, etc.
• various textile products clothing articles (sportswear, coats, blousons, work clothing, uniforms, etc.), bags, industrial materials, etc.), etc. It is useful as a water and oil repellent.

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• Chemical & Material Sciences (AREA)
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• Textile Engineering (AREA)
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