WO2024111616A1 - 撥水剤組成物、非フッ素重合体の製造方法、処理方法及び物品 - Google Patents

撥水剤組成物、非フッ素重合体の製造方法、処理方法及び物品 Download PDF

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Publication number
WO2024111616A1
WO2024111616A1 PCT/JP2023/041935 JP2023041935W WO2024111616A1 WO 2024111616 A1 WO2024111616 A1 WO 2024111616A1 JP 2023041935 W JP2023041935 W JP 2023041935W WO 2024111616 A1 WO2024111616 A1 WO 2024111616A1
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Prior art keywords
monomer
mass
meth
water repellent
acrylate monomer
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PCT/JP2023/041935
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English (en)
French (fr)
Japanese (ja)
Inventor
俊輔 大西
由紀子 塩田
柚香 上條
龍二郎 山▲崎▼
和典 杉山
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AGC Inc
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Asahi Glass Co Ltd
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Application filed by Asahi Glass Co Ltd filed Critical Asahi Glass Co Ltd
Priority to CN202380079965.1A priority Critical patent/CN120225630A/zh
Priority to KR1020257015855A priority patent/KR20250110823A/ko
Priority to EP23894620.6A priority patent/EP4624549A1/en
Priority to JP2024560181A priority patent/JPWO2024111616A1/ja
Publication of WO2024111616A1 publication Critical patent/WO2024111616A1/ja
Priority to US19/212,906 priority patent/US20250277336A1/en
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • 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
    • D06M15/643—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds containing silicon in the main chain
    • D06M15/6433—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds containing silicon in the main chain containing carboxylic groups
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K3/00—Materials not provided for elsewhere
    • C09K3/18—Materials not provided for elsewhere for application to surfaces to minimize adherence of ice, mist or water thereto; Thawing or antifreeze materials for application to surfaces
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • 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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • 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
    • C08F214/06—Vinyl chloride
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • 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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • 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
    • C08F220/10—Esters
    • C08F220/12—Esters of monohydric alcohols or phenols
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F290/00—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups
    • C08F290/02—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups on to polymers modified by introduction of unsaturated end groups
    • C08F290/06—Polymers provided for in subclass C08G
    • C08F290/068—Polysiloxanes
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • 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
    • C09D133/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, the oxygen atom being present only as part of the carboxyl radical
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D151/00—Coating compositions based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Coating compositions based on derivatives of such polymers
    • C09D151/08—Coating compositions based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Coating compositions based on derivatives of such polymers grafted on to macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
    • D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
    • D06M15/21—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
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
    • D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
    • D06M15/21—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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2810/00—Chemical modification of a polymer
    • C08F2810/20—Chemical modification of a polymer leading to a crosslinking, either explicitly or inherently
    • 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
    • D06M2101/00—Chemical constitution of the fibres, threads, yarns, fabrics or fibrous goods made from such materials, to be treated
    • D06M2101/16—Synthetic fibres, other than mineral fibres
    • D06M2101/30—Synthetic polymers consisting of macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • D06M2101/34—Polyamides
    • 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
    • D06M2200/00—Functionality of the treatment composition and/or properties imparted to the textile material
    • D06M2200/10—Repellency against liquids
    • D06M2200/12—Hydrophobic properties

Definitions

  • the present invention relates to a water repellent composition, a method for producing a non-fluorinated polymer, a treatment method, and an article.
  • a method of treating an article such as a textile product with a water repellent composition containing a fluoropolymer is known as a method of imparting water repellency to the surface of the article.
  • the fluoropolymer used in this method is of concern due to its high environmental impact. Therefore, there is a demand for a water repellent composition containing a non-fluoropolymer that can impart sufficient water repellency to the surface of the article and has a low environmental impact.
  • Patent Document 1 discloses a water repellent composition containing a non-fluorinated polymer, which has constituent units based on a (meth)acrylate monomer (A) that does not have a polyfluoroalkyl group and has an alkyl group with 20 to 30 carbon atoms, and constituent units based on a halogenated olefin monomer (B), in which the proportion of the constituent units based on the monomer (A) is 5 to 95 mass% of all constituent units (100 mass%), the proportion of the constituent units based on the monomer (B) is 5 to 60 mass% of all constituent units (100 mass%), and the total content of the constituent units based on the monomer (A) and the constituent units based on the monomer (B) is 65 mass% or more of all constituent units (100 mass%).
  • a non-fluorinated polymer which has constituent units based on a (meth)acrylate monomer (A) that does not have a polyfluoroalkyl group and has an alky
  • the content of the non-fluorinated polymer in the water repellent composition is low, good water repellency may not be achieved. Furthermore, when an article that has been subjected to a water repellent treatment is used for a long period of time, a durability problem may occur in which the water repellency decreases. In the water repellent composition described in Patent Document 1, if the content of the non-fluorinated polymer is low, the water repellency and durability are insufficient. Therefore, there is a demand for a water repellent composition containing a non-fluorinated copolymer that can provide sufficient water repellency and durability even when the content of the non-fluorinated polymer in the water repellent composition is low.
  • the present invention aims to provide a water repellent composition that can provide articles with superior water repellency, a method for producing a non-fluoropolymer, a treatment method using the water repellent composition, and articles with superior water repellency that have been treated with the water repellent composition.
  • a water repellent composition comprising a non-fluorinated polymer having structural units based on a long-chain alkyl (meth)acrylate monomer, structural units based on a halogenated vinyl monomer, and structural units based on a (meth)acrylate monomer having a polysiloxane structure, wherein the molecular weight of the (meth)acrylate monomer having a polysiloxane structure is 1000 to 3600, 1200 to 3500, or 1500 to 3300, and the proportion of the structural units based on the halogenated vinyl monomer relative to the total amount of the structural units of the non-fluorinated polymer is 1 to 12 mass%, 2 to 11 mass%, or 3 to 10 mass%.
  • R 5 represents H, CH 3 , or a chlorine atom, preferably H or CH 3 , and more preferably CH 3 ;
  • R 6 represents a divalent hydrocarbon group having 1 to 6, 1 to 4, or 1 to 3 carbon atoms;
  • R 7 represents H or CH 3 , and preferably CH 3 ;
  • n represents an integer of 8 to 55, an integer of 10 to 45, an integer of 12 to 43, or an integer of 16 to 40;
  • a plurality of R 5s may be the same or different, and are preferably the same;
  • a plurality of R 6s may be the same or different, and are preferably the same; and
  • a plurality of R 7s may be the same or different, and are preferably the same.
  • the water repellent composition according to [5], wherein the constitutional unit based on the long-chain alkyl (meth)acrylate monomer includes a constitutional unit based on a long-chain alkyl (meth)acrylate monomer in which the carbon number of R 9 in the formula (3) is 12 to 18, 16 to 18, or 18, and a constitutional unit based on a long-chain alkyl (meth)acrylate monomer in which the carbon number of R 9 in the formula (3) is 19 to 30, 20 to 28, or 20 to 24.
  • a method for producing a non-fluorinated polymer comprising polymerizing a mixture containing a long-chain alkyl (meth)acrylate monomer, a halogenated vinyl monomer, and a (meth)acrylate monomer having a polysiloxane structure in the presence of a surfactant and a polymerization initiator, wherein the ratio of the long-chain alkyl (meth)acrylate monomer to the total mass of all monomers constituting the non-fluorinated polymer is 73 to 95 mass%, 74 to 92 mass%, or 75 to 90 mass%, the ratio of the halogenated vinyl monomer is 1 to 12 mass%, 2 to 11 mass%, or 3 to 10 mass%, and the ratio of the (meth)acrylate monomer having a polysiloxane structure is 0.5 to 15 mass%, 0.8 to 14 mass%, or 1 to 13 mass%.
  • the present invention provides a water repellent composition that can provide articles with superior water repellency, a method for producing a non-fluoropolymer, a treatment method using the water repellent composition, and articles with superior water repellency that have been treated with the water repellent composition.
  • non-fluorinated polymer is a general term for polymers having a fluorine atom content of 0.1% by mass or less relative to the total mass of the polymer.
  • the fluorine atom content relative to the total mass of the polymer can be measured by combustion ion chromatography or the like.
  • structural unit based on a monomer is a general term for an atomic group formed directly by polymerizing one monomer molecule, and an atomic group obtained by chemically converting a part of the above-mentioned atomic group.
  • (Meth)acrylate is a general term for acrylate, methacrylate, and a compound in which the methyl group in the methacryloyl group of the methacrylate is replaced with a chlorine atom.
  • (meth)acryloyl group is a general term for an acryloyl group, a methacryloyl group, and a group in which the methyl group in the methacryloyl group is replaced with a chlorine atom.
  • “Long chain alkyl” means an alkyl group having 12 or more carbon atoms.
  • a "vinyl halide” is a compound in which at least one hydrogen atom in ethylene has been replaced with a halogen atom.
  • Having a polysiloxane structure means that the polymer has a repeating unit represented by "-(Si(R) 2 O) x1 -", where R represents H or CH 3 , and x1 is an integer of 5 or more. Multiple R's may be the same or different.
  • the molecular weight of the (meth)acrylate monomer having a polysiloxane structure can be calculated from the measurement result of the (meth)acryloyl group equivalent (the number of methacryloyl group molecules per unit mass). When the structure of the (meth)acrylate monomer having a polysiloxane structure is known, it is the formula weight.
  • the number average molecular weight (hereinafter also referred to as "Mn”) and weight average molecular weight (hereinafter also referred to as "Mw”) of the polymer are polystyrene-equivalent molecular weights obtained by measuring by gel permeation chromatography (hereinafter also referred to as "GPC") using a calibration curve prepared using standard polystyrene samples.
  • the solid content concentration is calculated by (solid content mass/sample mass) ⁇ 100, where the mass of the sample before heating is the sample mass and the mass of the sample after drying for 4 hours in a convection dryer at 120° C. is the solid content mass.
  • the numerical range indicated by “to” means that the numerical range includes the numerical values before and after it as the lower and upper limits.
  • the water repellent composition of the present embodiment contains a specific polymer (hereinafter also referred to as “polymer (A)").
  • the polymer (A) is a non-fluorine polymer having a constitutional unit based on a long-chain alkyl (meth)acrylate monomer (hereinafter also referred to as “monomer (a)”), a constitutional unit based on a halogenated vinyl monomer (hereinafter also referred to as “monomer (b)”), and a constitutional unit based on a (meth)acrylate monomer having a polysiloxane structure having a molecular weight of 1000 to 3600 (hereinafter also referred to as “monomer (c)").
  • the proportion of the constitutional unit based on monomer (b) to the total amount of the constitutional units of the polymer (A) is 1 to 12 mass%.
  • the polymer (A) may contain either one or both of a constitutional unit based on monomer (d) and a constitutional unit based on monomer (e) described later.
  • the composition may comprise a polymer (A) and a medium.
  • the present composition may contain one or more members selected from the group consisting of a surfactant, a molecular weight regulator, and a polymerization initiator.
  • the composition may optionally contain other ingredients.
  • the present composition is preferably a non-fluoropolymer solution containing the polymer (A).
  • the non-fluoropolymer solution includes a dispersion obtained by the production method described below, and a dispersion further diluted in an optional medium for treating an article.
  • the present composition may be a non-fluorinated polymer solution containing the polymer (A) and an organic solvent as a medium, and not containing a surfactant.
  • Polymer (A) has units based on monomer (a) (hereinafter also referred to as “units (a)”), units based on monomer (b) (hereinafter also referred to as “units (b)”), and units based on monomer (c) (hereinafter also referred to as “units (c)”).
  • the polymer (A) may further have, as necessary, either one or both of units based on a monomer (d) (hereinafter also referred to as “units (d)”) and units based on a monomer (e) (hereinafter also referred to as “units (e)”).
  • Monomer (a) is a long-chain alkyl (meth)acrylate monomer.
  • the long-chain alkyl (meth)acrylate is a monomer having an alkyl group having 12 or more carbon atoms and one (meth)acryloyl group in one molecule.
  • a long-chain alkyl (meth)acrylate monomer represented by the following formula (3) is preferable.
  • R 8 represents H, CH 3 or a chlorine atom
  • R 9 represents an alkyl group having 12 to 30 carbon atoms.
  • R8 is preferably H or CH3 , more preferably H.
  • the long chain alkyl group may be straight chain or branched chain, and is preferably straight chain.
  • the carbon number of R9 is preferably 12 to 30, more preferably 14 to 28, and even more preferably 16 to 24. When the carbon number is equal to or more than the lower limit, the water repellency is excellent. When the carbon number is equal to or less than the upper limit, the availability and handling are excellent.
  • lauryl (meth)acrylate cetyl (meth)acrylate, stearyl (meth)acrylate, and behenyl (meth)acrylate are preferred.
  • the monomer (a) may be used in combination of two or more kinds.
  • the monomer (a) it is particularly preferable to use in combination a long-chain alkyl (meth)acrylate monomer in which R 9 in the formula (3) has 12 to 18 carbon atoms (hereinafter also referred to as "monomer (a1)”) and a long-chain alkyl (meth)acrylate monomer in which R 9 in the formula (3) has 19 to 30 carbon atoms (hereinafter also referred to as "monomer (a2)").
  • the monomer (a1) may be a mixture of two or more long-chain alkyl (meth)acrylate monomers in which R 9 in the formula (3) has a carbon number of 12 to 18.
  • the monomer (a2) may be a mixture of two or more long-chain alkyl (meth)acrylate monomers in which R 9 in the formula (3) has a carbon number of 19 to 30.
  • the number of carbon atoms in the alkyl group of monomer (a1) is 12 to 18, preferably 16 to 18, and more preferably 18.
  • the number of carbon atoms is equal to or greater than the lower limit, the water repellency is excellent.
  • the number of carbon atoms is equal to or less than the upper limit, the availability and handling are excellent.
  • the number of carbon atoms in the alkyl group of monomer (a2) is 19 to 30, preferably 20 to 28, and more preferably 20 to 24.
  • the number of carbon atoms is equal to or greater than the lower limit, the water repellency is excellent.
  • the number of carbon atoms is equal to or less than the upper limit, the availability and handling are excellent.
  • the ratio of the constituent units based on monomer (a1) to the total amount of constituent units based on monomer (a) is preferably 1 to 50 mass%, more preferably 5 to 40 mass%, and even more preferably 10 to 38 mass%.
  • the ratio is equal to or greater than the lower limit, the initial water repellency is better.
  • the ratio is equal to or less than the upper limit, the water repellency after washing is better.
  • the ratio of the constituent units based on monomer (a2) to the total amount of constituent units based on monomer (a) is preferably 50 to 99 mass%, more preferably 60 to 95 mass%, and even more preferably 62 to 90 mass%.
  • the ratio is equal to or greater than the lower limit, the initial water repellency is better.
  • the ratio is equal to or less than the upper limit, the water repellency after washing is better.
  • the ratio of the constituent units based on monomer (a1) and the constituent units based on monomer (a2) to the total amount of constituent units based on monomer (a) is preferably 70% by mass or more, more preferably 72% by mass or more, even more preferably 75% by mass or more, particularly preferably 85% by mass or more, and may be 100% by mass.
  • the ratio is equal to or more than the lower limit, the initial water repellency is good.
  • the ratio is equal to or less than the upper limit, the water repellency after washing is better.
  • the mass ratio of the structural unit based on monomer (a1) to the total amount of the structural unit based on monomer (a1) and the structural unit based on monomer (a2) is preferably 1/99 to 50/50, more preferably 5/95 to 40/60, and even more preferably 10/90 to 38/62.
  • the mass ratio is equal to or greater than the lower limit, the treated article is likely to have good water repellency.
  • the mass ratio is equal to or less than the upper limit, the treated article is likely to have good washing durability.
  • the monomer (b) is a vinyl halide.
  • a vinyl halide having one or two halogen atoms is preferable, and a vinylidene halide having two halogen atoms is more preferable.
  • the halogen atom of the vinyl halide is preferably a chlorine atom, a bromine atom, or an iodine atom, more preferably a chlorine atom or a bromine atom, and further preferably a chlorine atom.
  • the multiple halogen atoms may be the same or different.
  • the monomer (b) vinyl chloride or vinylidene chloride is preferred.
  • the monomer (b) may be used in combination of two or more kinds.
  • the polymer (A) By containing the unit (b), the polymer (A) has improved adhesion to the article being treated, improving durability. Furthermore, a dense water-repellent film is easily formed on the surface of the article, improving water repellency.
  • the monomer (c) is a (meth)acrylate monomer having a polysiloxane structure with a molecular weight of 1000 to 3600.
  • the polymer (A) has the unit (c), which improves the water slippage of the water-repellent film formed on the surface of the article to be treated, thereby improving the water repellency.
  • the molecular weight of the monomer (c) is 1000 to 3600, preferably 1200 to 3500, and more preferably 1500 to 3300. When the molecular weight is equal to or greater than the lower limit of the above range, the unit (c) is easily exposed on the surface of the water-repellent film, thereby improving the water repellency. When the molecular weight is equal to or less than the upper limit of the above range, the viscosity of the water repellent composition does not become too high, and the water slippage of the water-repellent film is improved, thereby improving the water repellency.
  • the monomer (c) has at least one (meth)acryloyl group, preferably 1 to 4, and more preferably 1 or 2.
  • the monomer (c) may have a crosslinkable functional group as described below.
  • the monomer (c) is preferably a (meth)acrylate monomer having a polysiloxane structure represented by the following formula (1) or (2):
  • R 1 represents a monovalent hydrocarbon group having 1 to 12 carbon atoms
  • R 2 represents H or CH 3
  • R 3 represents a divalent hydrocarbon group having 1 to 6 carbon atoms
  • R 4 represents H, CH 3 or a chlorine atom
  • m represents an integer of 8 to 55
  • multiple R 2s may be the same or different.
  • R 5 represents H, CH 3 or a chlorine atom
  • R 6 represents a divalent hydrocarbon group having 1 to 6 carbon atoms
  • R 7 represents H or CH 3
  • n represents an integer of 8 to 55
  • a plurality of R 5s may be the same or different
  • a plurality of R 6s may be the same or different
  • a plurality of R 7s may be the same or different.
  • R 1 preferably has 1 to 10 carbon atoms, more preferably has 1 to 8 carbon atoms, and further preferably has 1 to 6 carbon atoms.
  • Examples of the monovalent hydrocarbon group of R1 include a monovalent saturated hydrocarbon group and a monovalent unsaturated hydrocarbon group.
  • Examples of the monovalent unsaturated hydrocarbon group include a monovalent saturated hydrocarbon group in which one or more carbon-carbon single bonds are replaced with a carbon-carbon double bond or triple bond.
  • R1 is linear, branched, or cyclic, and is preferably linear.
  • R1 is preferably a methyl group, an ethyl group, a propyl group, a butyl group, a hexyl group, or an octyl group.
  • R2 is preferably CH3 .
  • a plurality of R2 are preferably the same, and all of the plurality of R2 are preferably CH3 .
  • R3 preferably has 1 to 6 carbon atoms, more preferably has 1 to 4 carbon atoms, and further preferably has 1 to 3 carbon atoms.
  • Examples of the divalent hydrocarbon group of R3 include a divalent saturated hydrocarbon group and a divalent unsaturated hydrocarbon group.
  • Examples of the divalent unsaturated hydrocarbon group include a divalent saturated hydrocarbon group in which one or more carbon-carbon single bonds are replaced with a carbon-carbon double bond or triple bond.
  • R3 is a straight chain or branched chain, and is preferably a straight chain.
  • R3 is preferably a methylene group, an ethylene group, a propylene group, a trimethylene group, or a hexylene group.
  • R4 is preferably H or CH3 , more preferably CH3 .
  • m is preferably 10 to 45, more preferably 12 to 43, and even more preferably 16 to 40.
  • R5 is preferably H or CH3 , more preferably CH3 .
  • a plurality of R5 are preferably the same, and both of the plurality of R5 are preferably CH3 .
  • R 6 preferably has 1 to 6 carbon atoms, more preferably has 1 to 4 carbon atoms, and further preferably has 1 to 3 carbon atoms.
  • Examples of the divalent hydrocarbon group of R6 include a divalent saturated hydrocarbon group and a divalent unsaturated hydrocarbon group.
  • Examples of the divalent unsaturated hydrocarbon group include a divalent saturated hydrocarbon group in which one or more carbon-carbon single bonds are replaced with a carbon-carbon double bond or triple bond.
  • R6 is linear or branched, and is preferably linear.
  • R 6 is preferably a methylene group, an ethylene group, a propylene group, a trimethylene group, or a hexylene group. It is preferable that a plurality of R 6 in the formula (2) are the same.
  • R 7 is preferably CH 3.
  • a plurality of R 7's are preferably the same, and all of the plurality of R 7 's are preferably CH 3 .
  • n is preferably 10 to 45, more preferably 12 to 43, and even more preferably 16 to 40.
  • the monomer (c) As the monomer (c), a commercially available product can be used.
  • An example of the monomer (c) represented by the formula (1) is a compound in which R1 is a butyl group, all R2 are CH3 , R3 are trimethylene groups, R4 are CH3 , m is 27, and the molecular weight is 2300 (manufactured by Shin-Etsu Silicones, X-22-174BX).
  • An example of the monomer (c) represented by the formula (2) is a compound in which R5 is CH3 , all R6 are trimethylene groups, all R7 are CH3 , n is 27, and the molecular weight is 2370 (manufactured by Shin-Etsu Silicones, X-22-164C).
  • monomer (c) can also be synthesized by the method described in JP-A-59-78263. Specifically, a living polymer is obtained by anionically polymerizing a cyclic siloxane using lithium trialkylsilanolate as an initiator, and then reacting it with ⁇ -methacryloxypropyldimethylmonochlorosilane to obtain monomer (c) represented by the above formula (2).
  • the monomer (d) is a crosslinkable monomer.
  • the crosslinkable monomer is a monomer having a crosslinkable functional group and one group polymerizable with a (meth)acryloyl group, or a monomer having two or more groups polymerizable with a (meth)acryloyl group.
  • the monomer (d) does not have a polysiloxane structure.
  • the polymer (A) contains a structural unit based on the monomer (d), the washing and friction durability are further improved.
  • groups polymerizable with a (meth)acryloyl group include groups having a carbon-carbon double bond at the molecular end, and preferred examples include a (meth)acryloyl group, a vinyl group, and an allyl group.
  • the crosslinkable functional group is preferably a functional group having at least one of 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 above bonds.
  • the functional group is preferably an isocyanate group, a blocked isocyanate group, an alkoxysilyl group, a primary amino group, an alkoxymethylamide group, a silanol group, a primary amide group, an epoxy group, a hydroxyl group, an oxazoline group, a carboxyl group, a sulfonic acid group, or the like, and more preferably a hydroxyl group, a blocked isocyanate group, a primary amino group, or an epoxy group.
  • (meth)acrylates having a crosslinkable functional group acrylamides, vinyl ethers having a crosslinkable functional group, or vinyl esters having a crosslinkable functional group are preferred.
  • Examples of the monomer (d) include the following compounds.
  • Methoxymethyl (meth)acrylamide ethoxymethyl (meth)acrylamide, butoxymethyl (meth)acrylamide, diacetone acrylamide, gamma-methacryloyloxypropyltrimethoxysilane, trimethoxyvinylsilane, vinyltrimethoxysilane.
  • Tri(meth)allyl isocyanurate (T(M)AIC, manufactured by Nippon Kasei Chemical Industry Co., Ltd.), triallyl cyanurate (TAC, manufactured by Nippon Kasei Chemical Industry Co., Ltd.), 3-(methylethylketoxime)isocyanatomethyl-3,5,5-trimethylcyclohexyl(2-hydroxyethyl methacrylate) cyanate (Techcoat HE-6P, manufactured by Kyokin Chemical Industry Co., Ltd.). Polycaprolactone ester of hydroxyethyl (meth)acrylate (Placcel FA, FM series, manufactured by Daicel Chemical Industries, Ltd.).
  • Preferred monomers (d) are N-methylol (meth)acrylamide, 2-hydroxyethyl (meth)acrylate, glycidyl (meth)acrylate, 3-chloro-2-hydroxypropyl methacrylate or polycaprolactone ester of hydroxyethyl (meth)acrylate (Placcel FA, FM series, manufactured by Daicel Chemical Industries, Ltd.), and 3,5-dimethylpyrazole adduct of 2-isocyanatoethyl (meth)acrylate.
  • the monomer (e) is a monomer other than the monomers (a), (b), (c), and (d).
  • Examples of the monomer (e) include the following compounds. Methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, butyl (meth)methacrylate, cyclohexyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, n-hexyl (meth)acrylate, benzyl (meth)acrylate, octyl (meth)acrylate, decyl methacrylate, cyclododecyl acrylate, 3-ethoxypropyl acrylate, methoxy-butyl acrylate, 2-ethylbutyl acrylate, 1,3-dimethylbutyl acrylate, 2-methylpentyl acrylate.
  • Vinyl alkyl ethers halogenated alkyl vinyl ethers, vinyl alkyl ketones, aziridinyl ethyl (meth)acrylate, 2-ethylhexyl polyoxyalkylene (meth)acrylate, polyoxyalkylene di(meth)acrylate.
  • the total proportion of the units (a), (b) and (c) to all units constituting the polymer (A) is preferably 80% by mass or more, more preferably 80 to 99% by mass, and even more preferably 82 to 98% by mass.
  • the water repellency of the article treated with the composition is superior.
  • the total proportion of the units (a), the units (b) and the units (c) to all the units constituting the polymer (A) is preferably 80% by mass or more, more preferably 85% by mass or more, even more preferably 90% by mass or more, and particularly preferably 95% by mass or more.
  • the ratio of units (a) to all units constituting polymer (A) is preferably 73 to 95% by mass, more preferably 74 to 92% by mass, and even more preferably 75 to 90% by mass.
  • the ratio of units (a) to the total amount of units (a), units (b), and units (c) is preferably 73 to 95% by mass, more preferably 75 to 95% by mass, and even more preferably 78 to 94% by mass. If the ratio of units (a) is equal to or greater than the lower limit, the water repellency of an article treated with this composition is superior. If the ratio of units (a) is equal to or less than the upper limit, units (b), units (c), and other units can be sufficiently contained, and the water repellency of an article treated with this composition is superior.
  • the proportion of unit (b) relative to all units constituting polymer (A) is 1 to 12 mass%, preferably 2 to 11 mass%, and more preferably 3 to 10 mass%.
  • the proportion of unit (b) relative to the total amount of unit (a), unit (b), and unit (c) is preferably 1 to 12 mass%, more preferably 2 to 11 mass%, and even more preferably 3 to 10 mass%. If the proportion of unit (b) is equal to or greater than the lower limit, the water repellency of an article treated with this composition is superior. If the proportion of unit (b) is equal to or less than the upper limit, the unit (a), unit (c), and other units can be sufficiently contained, and the water repellency of an article treated with this composition is superior.
  • the ratio of units (c) to all units constituting polymer (A) is preferably 0.5 to 15 mass%, more preferably 0.8 to 14 mass%, and even more preferably 1 to 13 mass%.
  • the ratio of units (c) to the total amount of units (a), units (b), and units (c) is preferably 1 to 15 mass%, more preferably 1 to 14 mass%, and even more preferably 1 to 10 mass%. If the ratio of units (c) is equal to or greater than the lower limit, the water repellency of an article treated with this composition is superior. If the ratio of units (c) is equal to or less than the upper limit, units (a), units (b), and other units can be sufficiently contained, and the water repellency of an article treated with this composition is superior.
  • the total proportion of units (a) and units (b) to all units constituting polymer (A) is preferably 70% by mass or more, more preferably 75 to 98% by mass, and even more preferably 80 to 97% by mass. If the total proportion of units (a) and units (b) is equal to or greater than the lower limit above, the water repellency of an article treated with this composition is superior. If the proportion of units (a) and units (b) is equal to or less than the upper limit above, units (c) and other units can be sufficiently contained, and the water repellency of an article treated with this composition is superior.
  • the total proportion of units (b) and units (c) relative to all units constituting polymer (A) is preferably 4 to 30% by mass, more preferably 5 to 25% by mass, and even more preferably 6 to 22% by mass. If the total proportion of units (b) and units (c) is equal to or greater than the lower limit above, the water repellency of an article treated with this composition is superior. If the proportion of units (b) and units (c) is equal to or less than the upper limit above, units (a) and other units can be sufficiently contained, and the water repellency of an article treated with this composition is superior.
  • the total proportion of units (c) and units (a) relative to all units constituting polymer (A) is preferably 50.1 to 95% by mass, more preferably 55 to 90% by mass, and even more preferably 60 to 90% by mass. If the total proportion of units (c) and units (a) is equal to or greater than the lower limit above, the water repellency of an article treated with this composition is superior. If the proportion of units (c) and units (a) is equal to or less than the upper limit above, units (b) and other units can be sufficiently contained, and the water repellency of an article treated with this composition is superior.
  • the mass ratio of unit (a)/unit (b) is preferably 1.5 to 25, more preferably 2.0 to 24, and even more preferably 3.0 to 23. If the mass ratio of unit (a)/unit (b) is equal to or greater than the above lower limit, the water repellency of the article treated with the composition is superior. If the mass ratio of unit (a)/unit (b) is equal to or less than the above upper limit, polymerization of the monomer components is more likely to proceed during the production of polymer (A).
  • the mass ratio of units (b)/units (c) is preferably 0.6 to 15, more preferably 0.7 to 13, and even more preferably 0.8 to 12. If the mass ratio of units (b)/units (c) is equal to or greater than the above lower limit, the water repellency of the article treated with the composition is superior. If the mass ratio of units (b)/units (c) is equal to or less than the above upper limit, polymerization of the monomer components is more likely to proceed during the production of polymer (A).
  • the mass ratio of unit (c)/unit (a) is preferably 0.001 to 0.4, more preferably 0.005 to 0.27, and even more preferably 0.010 to 0.17. If the mass ratio of unit (c)/unit (a) is equal to or greater than the above lower limit, the water repellency of the article treated with this composition is superior. If the mass ratio of unit (c)/unit (a) is equal to or less than the above upper limit, polymerization of the monomer components is more likely to proceed during the production of polymer (A).
  • the mass ratio of ⁇ unit (a) + unit (b) ⁇ /unit (c) is preferably 1.0 to 120, more preferably 1.5 to 110, and even more preferably 2.0 to 100. If the mass ratio of ⁇ unit (a) + unit (b) ⁇ /unit (c) is equal to or greater than the above lower limit, the water repellency of the article treated with the composition is superior. If the mass ratio of ⁇ unit (a) + unit (b) ⁇ /unit (c) is equal to or less than the above upper limit, polymerization of the monomer components is more likely to proceed during the production of polymer (A).
  • the ratio of unit (d) to all units constituting polymer (A) is preferably 0.1 to 15 mass%, more preferably 0.2 to 10 mass%, and even more preferably 0.5 to 6 mass%. If the ratio of unit (d) is equal to or greater than the lower limit, the water repellency of an article treated with the composition is superior. If the ratio of unit (d) is equal to or less than the upper limit, the composition can contain sufficient units (a), (b), (c) and other units, and the water repellency of an article treated with the composition is superior.
  • the ratio of unit (e) to all units constituting polymer (A) is preferably 0.1 to 15 mass%, more preferably 0.2 to 10 mass%, and even more preferably 0.5 to 6 mass%. If the ratio of unit (e) is equal to or greater than the above lower limit, the water repellency of an article treated with this composition is superior. If the ratio of unit (e) is equal to or less than the above upper limit, the unit (a), unit (b), unit (c) and other units can be sufficiently contained, and the water repellency of an article treated with this composition is superior.
  • the total ratio of unit (d) and unit (e) to all units constituting polymer (A) is preferably 0.2 to 30 mass%, more preferably 0.4 to 20 mass%, and even more preferably 1 to 12 mass%. If the ratio of unit (d) and unit (e) is equal to or greater than the lower limit, the water repellency of an article treated with this composition is superior. If the ratio of unit (d) and unit (e) is equal to or less than the upper limit, units (a), (b), and (c) can be sufficiently contained, and the water repellency of an article treated with this composition is superior.
  • the proportion of each unit can be calculated from the reaction rate of each monomer component by 1H -NMR, gas chromatography, and high performance liquid chromatography.
  • the proportion of each unit may be calculated based on the amount of the monomer components charged.
  • the Mn of polymer (A) is preferably 5,000 to 200,000, more preferably 10,000 to 150,000, and even more preferably 20,000 to 120,000. If the Mn of polymer (A) is equal to or greater than the lower limit above, the water repellency of an article treated with this composition is superior. If the Mn of polymer (A) is equal to or less than the upper limit above, the water dispersibility of polymer (A) is superior.
  • the Mw of polymer (A) is preferably 8,000 to 600,000, more preferably 16,000 to 400,000, and even more preferably 32,000 to 350,000. If the Mw of polymer (A) is equal to or greater than the lower limit, the water repellency of an article treated with the composition is superior. If the Mw of polymer (A) is equal to or less than the upper limit, the water dispersibility of polymer (A) is superior.
  • Examples of the medium include water, alcohol, glycol, glycol ether, halogen compounds, hydrocarbons, ketones, esters, ethers, nitrogen compounds, sulfur compounds, inorganic solvents, organic acids, etc.
  • the medium include water, alcohol, glycol, glycol ether, halogen compounds, hydrocarbons, ketones, esters, ethers, nitrogen compounds, sulfur compounds, inorganic solvents, organic acids, etc.
  • one or more types of medium selected from the group consisting of water, alcohol, glycol, glycol ether, and glycol ester are preferred.
  • alcohol examples include methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 2-butanol, 2-methylpropanol, 1,1-dimethylethanol, 1-pentanol, 2-pentanol, 3-pentanol, 2-methyl-1-butanol, 3-methyl-1-butanol, 1,1-dimethylpropanol, 3-methyl-2-butanol, 1,2-dimethylpropanol, 1-hexanol, 2-methyl-1-pentanol, 4-methyl-2-pentanol, 2-ethyl-1-butanol, 1-heptanol, 2-heptanol, and 3-heptanol.
  • glycols or glycol ethers examples include ethylene glycol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol monobutyl ether acetate, propylene glycol, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol dimethyl ether, dipropylene glycol, dipropylene glycol monomethyl ether, dipropylene glycol dimethyl ether, dipropylene glycol monoethyl ether, tripropylene glycol, tripropylene glycol monomethyl ether, polypropylene glycol, hexylene glycol, etc.
  • Halogenated compounds include halogenated hydrocarbons, halogenated ethers, etc. It is preferable that the halogenated compounds do not contain fluorine.
  • Halogenated hydrocarbons include hydrochlorocarbons, hydrobromocarbons, etc.
  • hydrocarbon examples include aliphatic hydrocarbons, alicyclic hydrocarbons, and aromatic hydrocarbons.
  • aliphatic hydrocarbons include pentane, 2-methylbutane, 3-methylpentane, hexane, 2,2-dimethylbutane, 2,3-dimethylbutane, heptane, octane, 2,2,4-trimethylpentane, 2,2,3-trimethylhexane, decane, undecane, dodecane, 2,2,4,6,6-pentamethylheptane, tridecane, tetradecane, and hexadecane.
  • Examples of the alicyclic hydrocarbon include cyclopentane, methylcyclopentane, cyclohexane, methylcyclohexane, and ethylcyclohexane.
  • Examples of aromatic hydrocarbons include benzene, toluene, and xylene.
  • Examples of the ketone include acetone, methyl ethyl ketone, 2-pentanone, 3-pentanone, 2-hexanone, and methyl isobutyl ketone.
  • Examples of the ester include methyl acetate, ethyl acetate, butyl acetate, methyl propionate, methyl lactate, ethyl lactate, and pentyl lactate.
  • Examples of the ether include diisopropyl ether, dioxane, and tetrahydrofuran.
  • Examples of the nitrogen compound include pyridine, N,N-dimethylformamide, N,N-dimethylacetamide, and N-methylpyrrolidone.
  • Examples of the sulfur compound include dimethyl sulfoxide and sulfolane.
  • Inorganic solvents include liquid carbon dioxide.
  • Examples of the organic acid include acetic acid, propionic acid, malic acid, and lactic acid.
  • the medium may be used alone or in a mixture of two or more. When two or more types of media are used in a mixture, it is preferable to use the medium in a mixture with water. By using a mixed medium, it is easy to control the solubility and dispersibility of the polymer, and it is easy to control the permeability, wettability, solvent drying speed, etc. of the article during processing.
  • the content of the organic solvent is preferably 1 to 40 parts by mass, more preferably 2 to 30 parts by mass, and even more preferably 3 to 25 parts by mass, per 100 parts by mass of water.
  • the surfactant may be a hydrocarbon surfactant, such as an anionic surfactant, a nonionic surfactant, a cationic surfactant, or an amphoteric surfactant.
  • a hydrocarbon surfactant such as an anionic surfactant, a nonionic surfactant, a cationic surfactant, or an amphoteric surfactant.
  • a combination of a nonionic surfactant and a cationic surfactant or an amphoteric surfactant, or an anionic surfactant alone is preferred, and a combination of a nonionic surfactant and a cationic surfactant is preferred.
  • the mass ratio of the cationic surfactant to the nonionic surfactant is preferably from 97/3 to 40/60.
  • the total amount relative to the polymer (A) (100 mass%) can be made 5 mass% or less, thereby reducing adverse effects on the water repellency of an article.
  • nonionic surfactant one or more types selected from the group consisting of surfactants s 1 to s 6 are preferred.
  • Surfactant s1 is a polyoxyalkylene monoalkyl ether, a polyoxyalkylene monoalkenyl ether, or a polyoxyalkylene monoalkapopolyenyl ether.
  • the surfactant s1 is preferably a polyoxyalkylene monoalkyl ether or a polyoxyalkylene monoalkenyl ether.
  • the surfactant s1 may be used alone or in combination of two or more kinds.
  • the alkyl group, alkenyl group, or alkapolyenyl group (hereinafter, alkyl group, alkenyl group, and alkapolyenyl group will be collectively referred to as Rs group) is preferably a group having 4 to 26 carbon atoms.
  • the Rs group may be a straight chain or a branched chain.
  • the branched chain Rs group is preferably a secondary alkyl group, a secondary alkenyl group, or a secondary alkapolyenyl group.
  • R s groups include octyl, dodecyl, tetradecyl, hexadecyl, stearyl (octadecyl), behenyl (docosyl), and oleyl (9-octadecenyl).
  • the polyoxyalkylene (hereinafter referred to as POA) chain is preferably a chain consisting of two or more linked chains of either or both of polyoxyethylene (hereinafter referred to as POE) chains and polyoxypropylene (hereinafter referred to as POP) chains.
  • the POA chain may be a chain consisting of one type of POA chain, or a chain consisting of two or more types of POA chains. When consisting of two or more types of POA chains, it is preferable that the POA chains are linked in a block shape.
  • the compound ( s11 ) is more preferable.
  • R 10 O[CH 2 CH(CH 3 )O] s -(CH 2 CH 2 O) r H ...(s 11 ).
  • R 10 is an alkyl group having 8 or more carbon atoms or an alkenyl group having 8 or more carbon atoms
  • r is an integer of 5 to 50
  • s is an integer of 0 to 20.
  • the water repellent composition When r is 5 or more, the water repellent composition is soluble in water and dissolves uniformly in an aqueous medium, and therefore the water repellent composition has good permeability into articles. When r is 50 or less, hydrophilicity is suppressed and water repellency is good. When s is 20 or less, the water repellent composition is soluble in water and dissolves uniformly in an aqueous medium, so that the water repellent composition has good permeability into articles.
  • R 10 is preferably a straight chain or a branched chain.
  • r is preferably an integer of 10 to 30.
  • s is preferably an integer of 0 to 10.
  • Examples of the compound (s 11 ) include the following compounds, in which the POE chain and the POP chain are linked in a block form.
  • the surfactant s2 is a compound having one or more carbon-carbon triple bonds and one or more hydroxyl groups in the molecule.
  • the surfactant s2 may have a POA chain in the molecule. Examples of the POA chain include a POE chain, a POP chain, a chain in which POE chains and POP chains are randomly linked, and a chain in which POE chains and POP chains are linked in blocks.
  • the compounds ( s21 ) to ( s24 ) are preferred. HO-C(R 11 )(R 12 )-C ⁇ C-C(R 13 )(R 14 )-OH ... (s 21 ), HO-(A 1 O) u -C(R 11 )(R 12 )-C ⁇ C-C(R 13 )(R 14 )-(OA 2 ) v -OH ... (s 22 ), HO-C(R 15 )(R 16 )-C ⁇ C-H ... (s 23 ), HO-(A 3 O) w -C(R 15 )(R 16 )-C ⁇ C-H...(s 24 ).
  • a 1 to A 3 each represent an alkylene group.
  • Each of u and v is an integer of 0 or more, and (u+v) is an integer of 1 or more.
  • w is an integer of 1 or greater. When u, v and w are each 2 or more, A 1 to A 3 may be the same or different.
  • the POA chain is preferably a POE chain, a POP chain, or a chain containing a POE chain and a POP chain.
  • the number of repeating units of the POA chain is preferably 1 to 50.
  • R 11 to R 16 each represent a hydrogen atom or an alkyl group.
  • the alkyl group is preferably an alkyl group having a carbon number of 1 to 12, and more preferably an alkyl group having a carbon number of 1 to 4.
  • Examples of the alkyl group include a methyl group, an ethyl group, a propyl group, a butyl group, and an isobutyl group.
  • the compound (s 22 ) is preferable.
  • x and y are each an integer of 0 to 100.
  • the compound (s 25 ) may be used alone or in combination of two or more kinds.
  • a compound in which x and y are 0, a compound in which the sum of x and y is 1 to 4 on average, or a compound in which the sum of x and y is 10 to 30 on average is preferred.
  • the surfactant s3 is a compound in which a POE chain is linked to a POA chain in which two or more oxyalkylene units each having three or more carbon atoms are linked in succession, and both ends are terminated with hydroxyl groups.
  • a POE chain is linked to a POA chain in which two or more oxyalkylene units each having three or more carbon atoms are linked in succession, and both ends are terminated with hydroxyl groups.
  • POT polyoxytetramethylene
  • POP chains are preferred.
  • the compound ( s31 ) or the compound ( s32 ) is preferable. HO(CH 2 CH 2 O) g1 (C 3 H 6 O) t (CH 2 CH 2 O) g2 H ... (s 31 ), HO( CH2CH2O ) g1 ( CH2CH2CH2CH2O ) t ( CH2CH2O ) g2 H ... (s 32 ).
  • g1 is an integer from 0 to 200.
  • t is an integer from 2 to 100.
  • g2 is an integer from 0 to 200.
  • g1 is 0, g2 is an integer equal to or greater than 2.
  • g1 is an integer equal to or greater than 2.
  • --C 3 H 6 -- may be --CH(CH 3 )CH 2 --, --CH 2 CH(CH 3 )--, or a mixture of --CH(CH 3 )CH 2 -- and --CH 2 CH(CH 3 )--.
  • the POA chain is in blocks.
  • Examples of the surfactant s3 include the following compounds. HO- ( CH2CH2O ) 15- ( C3H6O ) 35- ( CH2CH2O ) 15H , HO- ( CH2CH2O ) 8- ( C3H6O ) 35- ( CH2CH2O ) 8H , HO- ( CH2CH2O ) 45- ( C3H6O ) 17- ( CH2CH2O ) 45H , HO -- ( CH2CH2O ) 34 -- ( CH2CH2CH2CH2O ) 28 -- ( CH2CH2O ) 34H .
  • Surfactant s4 is a compound having an amine oxide moiety in the molecule.
  • the compound ( s41 ) is preferable.
  • R 17 to R 19 are each a monovalent hydrocarbon group.
  • surfactants having an amine oxide (N ⁇ O) are considered to be nonionic surfactants.
  • the compound (s 41 ) may be used alone or in combination of two or more kinds.
  • the compound (s 41 ) is preferable from the viewpoint of the dispersion stability of the polymer.
  • R 20 is an alkyl group having 6 to 22 carbon atoms, an alkenyl group having 6 to 22 carbon atoms, a phenyl group bonded to an alkyl group having 6 to 22 carbon atoms, or a phenyl group bonded to an alkenyl group having 6 to 22 carbon atoms.
  • R 20 is preferably an alkyl group having 8 to 22 carbon atoms, or an alkenyl group having 8 to 22 carbon atoms.
  • Examples of the compound (s 42 ) include the following compounds. [H( CH2 ) 12 ]( CH3 ) 2N ( ⁇ O), [H( CH2 ) 14 ]( CH3 ) 2N ( ⁇ O), [H( CH2 ) 16 ]( CH3 ) 2N ( ⁇ O), [H( CH2 ) 18 ]( CH3 ) 2N ( ⁇ O).
  • Surfactant s5 is a condensate of polyoxyethylene mono(substituted phenyl) ether or a polyoxyethylene mono(substituted phenyl) ether.
  • a substituted phenyl group a phenyl group substituted with a monovalent hydrocarbon group is preferable, and a phenyl group substituted with an alkyl group, an alkenyl group or a styryl group is more preferable.
  • a condensation product of polyoxyethylene mono(alkylphenyl) ether a condensation product of polyoxyethylene mono(alkenylphenyl) ether, a polyoxyethylene mono(alkylphenyl) ether, a polyoxyethylene mono(alkenylphenyl) ether, or a polyoxyethylene mono[(alkyl)(styryl)phenyl] ether is preferred.
  • polyoxyethylene mono(substituted phenyl) ether condensates or polyoxyethylene mono(substituted phenyl) ethers include formaldehyde condensates of polyoxyethylene mono(nonylphenyl) ether, polyoxyethylene mono(octylphenyl) ether, polyoxyethylene mono(oleylphenyl) ether, polyoxyethylene mono[(nonyl)(styryl)phenyl] ether, polyoxyethylene mono[(oleyl)(styryl)phenyl] ether, etc.
  • Surfactant s6 is a fatty acid ester of a polyol.
  • the polyol represents glycerin, sorbitan, sorbit, polyglycerin, polyethylene glycol, polyoxyethylene glyceryl ether, polyoxyethylene sorbitan ether or polyoxyethylene sorbit ether.
  • surfactant s6 examples include a 1:1 (molar ratio) ester of stearic acid and polyethylene glycol, a 1:4 (molar ratio) ester of an ether of sorbitol and polyethylene glycol and oleic acid, a 1:1 (molar ratio) ester of an ether of polyoxyethylene glycol and sorbitan and stearic acid, a 1:1 (molar ratio) ester of an ether of polyethylene glycol and sorbitan and oleic acid, a 1:1 (molar ratio) ester of dodecanoic acid and sorbitan, a 1:1 or 2:1 (molar ratio) ester of oleic acid and decaglycerin, and a 1:1 or 2:1 (molar ratio) ester of stearic acid and decaglycerin.
  • Surfactant s7 When the surfactant comprises a cationic surfactant, the cationic surfactant is preferably surfactant s7 . Surfactant s7 is a substituted ammonium salt.
  • the surfactant s7 is preferably an ammonium salt in which one or more hydrogen atoms bonded to the nitrogen atom are substituted with an alkyl group, an alkenyl group, or a POA chain terminated with a hydroxyl group, and more preferably the compound ( s71 ). [(R 21 ) 4 N + ] ⁇ X ⁇ . . . (s 71 ).
  • R 21 is a hydrogen atom, an alkyl group having 1 to 22 carbon atoms, an alkenyl group having 2 to 22 carbon atoms, or a POA chain having a hydroxyl group at the end.
  • the four R 21 may be the same or different, but all four R 21 are not hydrogen atoms at the same time.
  • R 21 is preferably a long-chain alkyl group having 6 to 22 carbon atoms, or a long-chain alkenyl group having 6 to 22 carbon atoms.
  • R 21 is an alkyl group other than a long-chain alkyl group, R 21 is preferably a methyl group or an ethyl group.
  • R 21 is a POA chain having a hydroxyl group at the end, the POA chain is preferably a POE chain.
  • X ⁇ is a counter ion.
  • X ⁇ is preferably a chloride ion, an ethyl sulfate ion, or an acetate ion.
  • Examples of the compound (s 71 ) include monostearyl trimethyl ammonium chloride, monostearyl dimethyl monoethyl ammonium ethyl sulfate, mono(stearyl) monomethyl di(polyethylene glycol) ammonium chloride, monofluorohexyl trimethyl ammonium chloride, di(tallow alkyl) dimethyl ammonium chloride, and dimethyl monococonut amine acetate.
  • Surfactant s8 When the surfactant comprises an amphoteric surfactant, the amphoteric surfactant is preferably surfactant s8 .
  • Surfactants s8 are alanines, imidazolinium betaines, amido betaines or acetate betaine.
  • the hydrophobic group contained in the surfactant s8 is preferably a long-chain alkyl group having 6 to 22 carbon atoms, or a long-chain alkenyl group having 6 to 22 carbon atoms.
  • Examples of surfactant s8 include dodecyl betaine, stearyl betaine, dodecyl carboxymethyl hydroxyethyl imidazolinium betaine, dodecyl dimethyl amino acetic acid betaine, and fatty acid amidopropyl dimethyl amino acetic acid betaine.
  • Surfactant s9 As the surfactant, surfactant s9 may be used. Surfactant s9 is a polymer surfactant consisting of a block copolymer, a random copolymer, or a hydrophobic modified product of a hydrophilic copolymer, of a hydrophilic monomer and a hydrocarbon-based hydrophobic monomer.
  • surfactant s9 examples include block or random copolymers of polyethylene glycol (meth)acrylate and long-chain alkyl acrylate, block or random copolymers of vinyl acetate and long-chain alkyl vinyl ether, block or random copolymers of vinyl acetate and long-chain alkyl vinyl ester, polymers of styrene and maleic anhydride, condensates of polyvinyl alcohol and stearic acid, condensates of polyvinyl alcohol and stearyl mercaptan, condensates of polyallylamine and stearic acid, condensates of polyethyleneimine and stearyl alcohol, methylcellulose, hydroxypropylmethylcellulose, and hydroxyethylmethylcellulose.
  • surfactants s9 include MP Polymer (product numbers: MP-103, MP-203) from Kuraray Co., Ltd., SMA Resin from Elf Atochem Co., Ltd., Metrose from Shin-Etsu Chemical Co., Ltd., and Epomin RP from Nippon Shokubai Co., Ltd.
  • a combination of surfactants s1 , s2 and s7 is preferred, and the above combination in which surfactant s7 is compound ( s71 ) is more preferred.
  • the total amount of the surfactants is preferably 1 to 10 parts by mass, more preferably 1 to 7 parts by mass, based on the polymer (100 parts by mass).
  • molecular weight regulator examples include aromatic compounds, mercaptoalcohols, mercaptocarboxylic acids, and alkyl mercaptans, and more preferably mercaptocarboxylic acids or alkyl mercaptans.
  • the molecular weight regulator examples include mercaptoethanol, mercaptopropionic acid, n-octyl mercaptan, n-dodecyl mercaptan, tert-dodecyl mercaptan, stearyl mercaptan, and ⁇ -methylstyrene dimer (CH 2 ⁇ C(Ph)CH 2 C(CH 3 ) 2 Ph, where Ph is a phenyl group), and particularly preferably n-dodecyl mercaptan, tert-dodecyl mercaptan, and stearyl mercaptan.
  • Polymerization initiator examples include a thermal polymerization initiator, a photopolymerization initiator, a radiation polymerization initiator, a radical polymerization initiator, and an ionic polymerization initiator, and a radical polymerization initiator is preferred.
  • examples of the radical polymerization initiator include an azo-based polymerization initiator, a peroxide-based polymerization initiator, and a redox-based initiator, depending on the polymerization temperature.
  • examples of the radical polymerization initiator include an azo-based compound, and more preferably a salt of an azo-based compound.
  • the initiator examples include an acetate salt of 2,2'-azobis[2-(2-imidazolin-2-yl)propane] (VA-061, manufactured by Wako Pure Chemical Industries, Ltd.) and 2,2'-azobis(2-aminodinopropane) (NC-32, manufactured by Nippoh Chemical Industries, Ltd.).
  • VA-061 2,2'-azobis[2-(2-imidazolin-2-yl)propane]
  • NC-32 2,2'-azobis(2-aminodinopropane)
  • the water repellent composition of the present embodiment may contain other components as necessary.
  • other components include crosslinking agents, penetrating agents, defoamers, water absorbents, antistatic agents, antistatic polymers, anti-wrinkling agents, texture adjusters, film-forming assistants, water-soluble polymers (polyacrylamide, polyvinyl alcohol, etc.), heat curing 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-hexamethylenebis(N,N-dimethylsemicarbazide), 1,1,1',1,'-tetramethyl-4,4'-(methylene-di-para-phenylene) disemicarbazide, spiroglycol, etc.), heat curing
  • the water repellent composition of this embodiment may contain, as necessary, a polymer capable of exhibiting water repellency other than the polymer (A) of this embodiment, a commercially available water repellent, a water repellent compound that does not have a fluorine atom, etc.
  • water repellent compounds that do not have a fluorine atom include paraffin-based compounds, aliphatic amide-based compounds, alkylethylene urea compounds, and silicon-based compounds.
  • the adhesion to a substrate is likely to be improved.
  • a crosslinking agent an isocyanate-based crosslinking agent, a methylol-based crosslinking agent, a carbodiimide-based crosslinking agent, and an oxazoline-based crosslinking agent are preferable.
  • the isocyanate crosslinking agent is preferably an isocyanate crosslinking agent having two or more isocyanate groups.
  • examples of the isocyanate crosslinking agent include an aromatic block type isocyanate crosslinking agent, an aliphatic block type isocyanate crosslinking agent, an aromatic non-block type isocyanate crosslinking agent, and an aliphatic non-block type isocyanate crosslinking agent.
  • the isocyanate crosslinking agent is preferably a water-dispersed type emulsified with a surfactant, or a self-water-dispersed type having a hydrophilic group.
  • methylol-based crosslinking agents include condensates or precondensates of urea or melamine with formaldehyde, methylol-dihydroxyethylene-urea and its derivatives, methylol-ethylene-urea, methylol-propylene-urea, methylol-triazone, dicyandiamide-formaldehyde condensates, methylol-carbamate, methylol-(meth)acrylamide, and polymers of these.
  • the carbodiimide crosslinking agent is a polymer having a carbodiimide group in the molecule, and is a crosslinking agent that exhibits excellent reactivity with carboxy groups, amino groups, and active hydrogen groups of articles and the like.
  • the oxazoline-based crosslinking agent is a polymer having an oxazoline group in the molecule, and is a crosslinking agent that exhibits excellent reactivity with carboxy groups of articles and the like.
  • crosslinking agents include, for example, divinyl sulfone, polyamides and their cationic derivatives, polyamines and their cationic derivatives, epoxy derivatives such as diglycidyl glycerol, halide derivatives such as (epoxy-2,3-propyl)trimethylammonium chloride and N-methyl-N-(epoxy-2,3-propyl)morpholinium chloride, pyridinium salts of chloromethyl ether of ethylene glycol, polyamine-polyamide-epichlorohydrin resins, polyvinyl alcohol or its derivatives, polyacrylamide or its derivatives, and glyoxal resin-based wrinkle inhibitors.
  • divinyl sulfone polyamides and their cationic derivatives
  • polyamines and their cationic derivatives epoxy derivatives such as diglycidyl glycerol
  • halide derivatives such as (epoxy-2,3-propyl)trimethylammonium chloride and N-methyl
  • catalysts include, for example, inorganic amine salts and organic amine salts.
  • inorganic amine salts include ammonium chloride.
  • organic amine salts include amino alcohol hydrochloride and semicarbazide hydrochloride.
  • amino alcohol hydrochloride include monoethanolamine hydrochloride, diethanolamine hydrochloride, triethanol hydrochloride, and 2-amino-2-methylpropanol hydrochloride.
  • the content of the medium can be appropriately selected depending on the desired solids concentration of the present composition.
  • the solids concentration of the present composition immediately after production of the present composition is preferably from 5 to 60% by mass, more preferably from 10 to 50% by mass, and even more preferably from 15 to 45% by mass.
  • the solids concentration of the present composition is preferably from 0.03 to 1.2 mass %, more preferably from 0.05 to 1.0 mass %, and even more preferably from 0.08 to 0.9 mass %.
  • the solid content concentration is the total content of the polymer (A) and the surfactant in the composition.
  • the proportion of the polymer (A) relative to the total mass of the present composition is preferably from 0.03 to 60 mass %, more preferably from 0.05 to 50 mass %, and even more preferably from 0.08 to 45 mass %.
  • the content of the surfactant in the composition is preferably 1 to 10 parts by mass, more preferably 1 to 8 parts by mass, and even more preferably 2 to 7 parts by mass, per 100 parts by mass of polymer (A).
  • the content of the molecular weight regulator in the composition is preferably 0.1 to 10 parts by mass, more preferably 0.5 to 9 parts by mass, and even more preferably 1 to 8 parts by mass, per 100 parts by mass of polymer (A).
  • the content of the polymerization initiator in the present composition is preferably 0.01 to 5 parts by mass, more preferably 0.05 to 4 parts by mass, and even more preferably 0.1 to 3 parts by mass, per 100 parts by mass of the polymer (A).
  • the content of fluorine atoms relative to the total mass of the present composition is preferably 0.1 mass% or less, more preferably 0 mass%.
  • the content of fluorine atoms relative to the total mass of the present composition can be measured by combustion ion chromatography or the like.
  • the method for producing a non-fluorinated polymer of this embodiment is a method for polymerizing a mixture containing monomer components including monomer (a), monomer (b) and monomer (c) in the presence of a surfactant and a polymerization initiator.
  • a water repellent composition is also produced at the same time.
  • the proportion of monomer (a) is 73 to 95 mass%
  • the proportion of monomer (b) is 1 to 12 mass%
  • the proportion of monomer (c) is 0.5 to 15 mass%, relative to the total mass of all monomers constituting the non-fluorinated polymer.
  • the monomer component may further contain either or both of a monomer (d) and a monomer (e).
  • the monomers (a), (b), (c), (d) and (e) may be produced by known production methods. Commercially available monomers may be used.
  • the total proportion of the monomers (a), (b) and (c) contained in the mixture relative to the total mass of the monomers constituting the non-fluorinated polymer is preferably 80% by mass or more, more preferably 80 to 99% by mass, and even more preferably 82 to 98% by mass.
  • the total proportion of the monomers (a), (b) and (c) is equal to or more than the above lower limit, the water repellency and washing durability of the article treated with the composition are excellent.
  • the total proportion of the monomer (a), the monomer (b) and the monomer (c) contained in the mixture relative to the total mass of the monomers constituting the non-fluorinated polymer is preferably 80 mass% or more, more preferably 85 mass% or more, even more preferably 90 mass% or more, and particularly preferably 95 mass% or more.
  • the ratio of monomer (a) contained in the mixture to the total mass of monomers constituting the non-fluorinated polymer is 73 to 95 mass%, preferably 74 to 92 mass%, and more preferably 75 to 90 mass%.
  • the ratio of monomer (a) to the total mass of monomer (a), monomer (b), and monomer (c) contained in the mixture is preferably 73 to 95 mass%, more preferably 75 to 95 mass%, and even more preferably 78 to 94 mass%. If the ratio of monomer (a) is equal to or greater than the lower limit, the water repellency of the article treated with the composition is superior. If the ratio of monomer (a) is equal to or less than the upper limit, monomer (b) and monomer (c) can be sufficiently contained, and the water repellency of the article treated with the composition is superior.
  • the ratio of monomer (b) contained in the mixture to the total mass of monomers constituting the non-fluorinated polymer is 1 to 12 mass%, preferably 2 to 11 mass%, and more preferably 3 to 10 mass%.
  • the ratio of monomer (b) to the total mass of monomer (a), monomer (b), and monomer (c) contained in the mixture is preferably 1 to 12 mass%, more preferably 2 to 11 mass%, and even more preferably 3 to 10 mass%. If the ratio of monomer (b) is equal to or greater than the lower limit, the water repellency of the article treated with the composition is superior. If the ratio of monomer (b) is equal to or less than the upper limit, the monomer (c) and monomer (a) can be sufficiently contained, and the water repellency of the article treated with the composition is superior.
  • the ratio of monomer (c) contained in the mixture to the total mass of monomers constituting the non-fluorinated polymer is 0.5 to 15 mass%, preferably 0.8 to 14 mass%, and more preferably 1 to 13 mass%.
  • the ratio of monomer (c) to the total mass of monomer (a), monomer (b), and monomer (c) contained in the mixture is preferably 1 to 15 mass%, more preferably 1 to 14 mass%, and even more preferably 1 to 10 mass%. If the ratio of monomer (c) is equal to or greater than the lower limit, the water repellency of the article treated with the composition is superior. If the ratio of monomer (c) is equal to or less than the upper limit, the monomer (a) and monomer (b) can be sufficiently contained, and the water repellency of the article treated with the composition is superior.
  • the total proportion of monomer (a) and monomer (b) contained in the mixture relative to the total mass of the monomers constituting the non-fluorinated polymer is preferably 70% by mass or more, more preferably 75 to 98% by mass, and even more preferably 80 to 97% by mass. If the total proportion of monomer (a) and monomer (b) is equal to or greater than the above lower limit, the water repellency of the article treated with this composition is superior. If the total proportion of monomer (a) and monomer (b) is equal to or less than the above upper limit, monomer (c) can be sufficiently contained, and the water repellency of the article treated with this composition is superior.
  • the total proportion of monomer (b) and monomer (c) contained in the mixture relative to the total mass of the monomers constituting the non-fluorinated polymer is preferably 4 to 30 mass%, more preferably 5 to 25 mass%, and even more preferably 6 to 22 mass%. If the total proportion of monomer (b) and monomer (c) is equal to or greater than the above lower limit, the water repellency of the article treated with this composition is superior. If the total proportion of monomer (b) and monomer (c) is equal to or less than the above upper limit, monomer (a) can be contained sufficiently, and the water repellency of the article treated with this composition is superior.
  • the total proportion of monomer (c) and monomer (a) contained in the mixture relative to the total mass of the monomers constituting the non-fluorinated polymer is preferably 50.1 to 95 mass%, more preferably 55 to 90 mass%, and even more preferably 60 to 90 mass%. If the total proportion of monomer (c) and monomer (a) is equal to or greater than the above lower limit, the water repellency of the article treated with this composition is superior. If the total proportion of monomer (c) and monomer (a) is equal to or less than the above upper limit, monomer (b) can be contained sufficiently, and the water repellency of the article treated with this composition is superior.
  • the mass ratio of monomer (a)/monomer (b) contained in the mixture is preferably 1.5 to 25, more preferably 2.0 to 24, and even more preferably 3.0 to 23. If the mass ratio of monomer (a)/monomer (b) is equal to or greater than the above lower limit, the water repellency of the article treated with the composition is superior. If the mass ratio of monomer (a)/monomer (b) is equal to or less than the above upper limit, polymerization of the monomer components is more likely to proceed during the production of polymer (A).
  • the mass ratio of monomer (b)/monomer (c) contained in the mixture is preferably 0.6 to 15, more preferably 0.7 to 13, and even more preferably 0.8 to 12. If the mass ratio of monomer (b)/monomer (c) is equal to or greater than the above lower limit, the water repellency of the article treated with the composition is superior. If the mass ratio of monomer (b)/monomer (c) is equal to or less than the above upper limit, polymerization of the monomer components is more likely to proceed during the production of polymer (A).
  • the mass ratio of monomer (c)/monomer (a) contained in the mixture is preferably 0.001 to 0.4, more preferably 0.005 to 0.27, and even more preferably 0.010 to 0.17. If the mass ratio of monomer (c)/monomer (a) is equal to or greater than the above lower limit, the water repellency of the article treated with the composition is superior. If the mass ratio of monomer (c)/monomer (a) is equal to or less than the above upper limit, polymerization of the monomer components is more likely to proceed during the production of polymer (A).
  • the mass ratio of ⁇ monomer (a) + monomer (b) ⁇ /monomer (c) contained in the mixture is preferably 1.0 to 120, more preferably 1.5 to 110, and even more preferably 2.0 to 100. If the mass ratio of ⁇ monomer (a) + monomer (b) ⁇ /monomer (c) is equal to or greater than the above lower limit, the water repellency of the article treated with the composition is superior. If the mass ratio of ⁇ monomer (a) + monomer (b) ⁇ /monomer (c) is equal to or less than the above upper limit, polymerization of the monomer components is more likely to proceed during the production of polymer (A).
  • the ratio of monomer (d) to the total mass of the monomer components contained in the mixture relative to the total mass of the monomers constituting the non-fluorinated polymer is preferably 0.1 to 15 mass%, more preferably 0.2 to 10 mass%, and even more preferably 0.5 to 6 mass%.
  • the ratio of monomer (e) to the total mass of the monomer components contained in the mixture relative to the total mass of the monomers constituting the non-fluorinated polymer is preferably 0.1 to 15 mass%, more preferably 0.2 to 10 mass%, and even more preferably 0.5 to 6 mass%.
  • the ratio of the total of monomer (d) and monomer (e) contained in the mixture to the total mass of the monomers constituting the non-fluorinated polymer is preferably 0.2 to 30 mass%, more preferably 0.4 to 20 mass%, and even more preferably 1 to 12 mass%.
  • Methods for polymerizing the monomer components include emulsion polymerization, solution polymerization, suspension polymerization, bulk polymerization, etc. Among these, emulsion polymerization is preferred.
  • the molecular weight (Mn, Mw) of the polymer (A) can be increased.
  • the monomer components are polymerized in an emulsion containing a medium, a monomer component, a surfactant, and a polymerization initiator.
  • the emulsion may contain a molecular weight modifier as necessary.
  • the medium, surfactant, polymerization initiator, and molecular weight regulator may be the same as those described above.
  • the proportion of the molecular weight modifier relative to 100 parts by mass of all monomers constituting the non-fluorinated polymer is preferably from 0.1 to 20 parts by mass, more preferably from 0.1 to 10 parts by mass, and even more preferably from 0.1 to 5 parts by mass.
  • the emulsion can be prepared by mixing the medium, the monomer component, and optionally a surfactant, dispersing the mixture using a homogenizer, a high-pressure emulsifier, etc., and then adding a polymerization initiator.
  • the monomer component is a gas, it can be added to the reaction system after the dispersion.
  • the concentration of the monomer component in the emulsion is preferably 5 to 60% by mass, more preferably 10 to 50% by mass. When the concentration of the monomer component in the emulsion is within the above range, the molecular weight of the polymer (A) can be sufficiently increased.
  • the content of the surfactant in the emulsion is preferably 0.1 to 10 parts by mass per 100 parts by mass of the monomer component. If the content of the surfactant is equal to or greater than the lower limit, the dispersion stability of the emulsion is excellent. If the content of the surfactant is equal to or less than the upper limit, the adverse effect of the surfactant on the water repellency of an article treated with a composition containing polymer (A) can be reduced.
  • the content of the polymerization initiator in the emulsion is preferably 0.01 to 5 parts by mass per 100 parts by mass of the monomer component. If the content of the polymerization initiator is equal to or greater than the lower limit, the reaction rate is likely to be high and the polymerization yield is likely to be improved. If the content of the polymerization initiator is equal to or less than the upper limit, a polymer with a molecular weight in the desired range is likely to be obtained.
  • the polymer (A) By polymerizing the monomer components in the emulsion, a dispersion of the polymer (A) is obtained.
  • the polymer (A) is dispersed in the aqueous medium as emulsified particles.
  • the average particle size of the emulsion particles of polymer (A) is preferably 10 to 1000 nm, more preferably 30 to 600 nm, and even more preferably 50 to 300 nm. When the average particle size is equal to or less than the upper limit, the water repellency of the article treated with the emulsion particles of polymer (A) and the dispersibility of the emulsion particles of polymer (A) are superior.
  • the emulsion particles of polymer (A) are more stable against mechanical shearing force.
  • the average particle size of the emulsion particles of polymer (A) is calculated by cumulant method analysis from the autocorrelation function obtained by dynamic light scattering of a sample prepared by diluting a dispersion of polymer (A) with water to a solid content concentration of 1% by mass.
  • the dispersion of polymer (A) obtained by polymerizing the monomer components in the emulsion may be used as the present composition as is, or may be used as the present composition after diluting with an aqueous medium to adjust the solids concentration. Other components may also be added to the present composition.
  • the treatment method of the present embodiment is a treatment method using the present composition. Any method can be used as long as the present composition can be attached to the article to be treated.
  • the method includes a method in which the article is treated with the present dispersion by a known method such as coating, impregnation, immersion, spraying, brushing, padding, size press, roller, etc., and then dried.
  • the amount of solids in the water repellent composition to be applied to the article to be treated is not particularly limited, but in the case of a fiber fabric, for example, the amount is preferably 0.1 to 5 g, more preferably 0.1 to 3 g, and even more preferably 0.1 to 1 g per 100 g of fiber fabric.
  • the amount of the polymer (A) in the water repellent composition to be applied to the article to be treated is not particularly limited.
  • the amount is preferably 0.01 to 5 g, more preferably 0.02 to 3 g, and even more preferably 0.03 to 1 g per 100 g of the fiber fabric.
  • the drying may be performed at room temperature or with heating, and is preferably performed with heating. When heating is performed, the heating temperature is preferably 90 to 200° C.
  • the water repellent composition contains a crosslinking agent, it is preferable to cure the composition by heating to a crosslinking temperature of the crosslinking agent or higher, if necessary.
  • the article of this embodiment is an article that has been treated with the present composition.
  • the articles to be treated with the composition include fibers, fiber fabrics (woven fiber fabrics, knitted fiber fabrics, nonwoven fabrics, raised fabrics, etc.), fiber products with fiber fabrics (ski wear, rain wear, coats, blousons, windbreakers, down jackets, sportswear, work clothes, uniforms, protective clothing, backpacks, bags, tents, etc.), glass, paper, wood, leather, artificial leather, stone, concrete, ceramics, metals, metal oxides, ceramic products, resin molded products, and porous resins.
  • Porous resins are used, for example, as filters. Examples of materials for porous resins include polypropylene, polyethylene terephthalate, and polytetrafluoroethylene.
  • the article to be treated is preferably a fiber, a fiber fabric, or a fiber product having a fiber fabric.
  • the type of fiber is not particularly limited, but includes natural fibers such as cotton, wool, silk, or cellulose, chemical fibers such as polyester, polyamide, acrylic, aramid, rayon, or lyocell, and fibers obtained by using a plurality of these fibers.
  • the fiber substrate is a nonwoven fabric
  • the fiber includes polyethylene, polypropylene, polyolefin, polyethylene terephthalate, polytetrafluoroethylene, glass, and rayon.
  • the thickness of the fiber fabric is not particularly limited, but is in the range of 10 ⁇ m to 5 cm.
  • the article treated with the present composition has excellent water repellency and durability.
  • the durability is improved by the polymer (A) containing the unit (b), as a result of which the adhesion to the article to be treated is improved.
  • a dense water repellent film is easily formed on the surface of the article, and the water repellency is also improved.
  • the proportion of the unit (b) is 12 mass% or less, the water repellent film is unlikely to become hydrophilic, and the water repellency is improved.
  • the polymer (A) contains the unit (c), and the water slippage of the water repellent film is improved, and the water repellency is improved.
  • the molecular weight of the monomer (c) is 1000 or more, as a result of which the unit (c) is easily exposed on the surface of the water repellent film, and the water repellency is improved.
  • the viscosity of the polysiloxane portion of the unit (c) that exhibits water sliding property by being exposed to the surface of the water-repellent film does not become too high because the molecular weight of the monomer (c) is 3600 or less, and as a result, the viscosity of the polymer (A) does not become too high, and the water sliding property of the water-repellent film is improved, and the water repellency is improved.
  • Examples 1 to 13 are examples, and Examples 14 to 41 are comparative examples.
  • composition of the polymer (the ratio of each monomer unit to the total units constituting the polymer) was calculated based on the amount of the monomer component charged.
  • ⁇ Water repellent treatment for fabrics low concentration>
  • the emulsion obtained in the examples described below was diluted with distilled water to adjust the solid content concentration to 0.2% by mass, and then a crosslinking agent, blocked isocyanate (Meisei Chemical Industry Co., Ltd.'s Meikanate TP-10), was added as a co-agent to a concentration of 1.5% by mass to prepare a water repellent composition.
  • a dyed nylon fabric was immersed in this water repellent composition and squeezed so that the content of the water repellent composition relative to the total mass of the water repellent composition and the dyed nylon fabric was 60% by mass. This was dried at 110°C for 90 seconds and then further heat-treated at 170°C for 60 seconds to obtain a test cloth (low concentration).
  • ⁇ Water-repellent treatment for fabrics high concentration>
  • the emulsion obtained in the examples described below was diluted with distilled water to adjust the solid content concentration to 1.5% by mass, and then a crosslinking agent, blocked isocyanate (Meisei Chemical Industry Co., Ltd.'s Meikanate TP-10), was added as a co-agent to a concentration of 1.5% by mass to prepare a water repellent composition.
  • a dyed nylon fabric was immersed in this water repellent composition and squeezed so that the content of the water repellent composition relative to the total mass of the water repellent composition and the dyed nylon fabric was 60% by mass. This was dried at 110°C for 90 seconds and then further heat-treated at 170°C for 60 seconds to obtain a test cloth (high concentration).
  • E420 Polyoxyethylene oleyl ether (Emulgen (Kao Corporation product name) 420, approximately 13 moles of ethylene oxide adduct)
  • P204 10% by mass aqueous solution of ethylene oxide propylene oxide polymer (product name of NOF Corporation, Pronon 204, ethylene oxide ratio is 40% by mass)
  • AQ-18-63 63% stearyltrimethylammonium chloride, 32% isopropanol, 5% water solution (manufactured by Lion Specialty Chemicals)
  • SmOA Sorbitan monooleate
  • PELE Polyoxyethylene lauryl ether
  • PEtDE Polyoxyethylene tridecyl ether dODACl: Dioctadecyl ammonium chloride
  • LSH lauryl mercaptan
  • StSH stearyl mercaptan
  • VA-061A Acetate of 2,2'-azobis[2-(2-imidazolin-2-yl)
  • Example 1 ⁇ Preparation of polymer emulsion> In a glass beaker, 29.8 g of StA, 58.7 g of BeA, 2.0 g of MOI-BP, 2 g of DMAA, 3.0 g of silicone monomer 1, 1.0 g of StSH, 2.5 g of E420, 0.5 g of P-204, 0.5 g of AQ-18-63, 30 g of DPG, and 155 g of water were placed, heated at 60 ° C. for 30 minutes, and then mixed using a homomixer (manufactured by Nippon Seiki Seisakusho Co., Ltd., Biomixer) to obtain a mixed liquid.
  • a homomixer manufactured by Nippon Seiki Seisakusho Co., Ltd., Biomixer
  • the above mixed liquid 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.
  • This emulsion was placed in a stainless steel reactor and cooled to 40 ° C. or less.
  • 4.5 g of VdCl and 0.5 g of VA-061A were added, and the gas phase was replaced with nitrogen, after which a polymerization reaction was carried out at 60° C. for 15 hours with stirring to obtain a polymer emulsion.
  • the obtained emulsion was used to perform the above-mentioned water repellency evaluation (initial) and water repellency evaluation (after washing). The results are shown in Table 1.
  • Examples 2, 4, 6-17, 19, 21-24, 26-34, 36, 37 Polymer emulsions were obtained in the same manner as in Example 1, except that the monomers (a) to (e), surfactants, molecular weight modifiers, polymerization initiators, and media shown in Tables 1 to 3 were used and the charging ratios were changed to those shown in Tables 1 to 3.
  • the charging ratios in Tables 1 to 3 refer to parts by mass.
  • the obtained emulsions were used to perform the above-mentioned water repellency evaluation (initial) and water repellency evaluation (after washing). The results are shown in Tables 1 to 3.
  • Example 3 A glass beaker was charged with 29.8 g of StA, 58.7 g of BeA, 2.0 g of MOI-BP, 2 g of DMAA, 3.0 g of silicone monomer 1, 1.0 g of StSH, 2.5 g of E420, 0.5 g of P-204, 0.5 g of AQ-18-63, 30 g of DPG, and 155 g of water, and the mixture was heated at 60° C. for 30 minutes and then mixed using a homomixer (manufactured by Nippon Seiki Seisakusho, Ltd., Biomixer) to obtain a mixed liquid.
  • a homomixer manufactured by Nippon Seiki Seisakusho, Ltd., Biomixer
  • the above mixture was treated at 40 MPa using a high-pressure emulsifier (Minilab, manufactured by APV Lanier) while maintaining the temperature at 60°C to obtain an emulsion.
  • This emulsion was placed in a stainless steel reactor and cooled to 40°C or lower.
  • 0.5 g of VA-061A was added and the gas phase was replaced with nitrogen, after which 9.6 g of VCM was introduced and a polymerization reaction was carried out at 60°C for 15 hours with stirring to obtain a polymer emulsion.
  • the obtained emulsion was used to perform the above-mentioned water repellency evaluation (initial) and water repellency evaluation (after washing). The results are shown in Table 1.
  • Examples 5, 18, 20, 25, 35, 38 to 41 Polymer emulsions were obtained in the same manner as in Example 3, except that the monomers (a) to (e), surfactants, molecular weight modifiers, polymerization initiators, and media shown in Tables 1 to 3 were used and the charging ratios were changed to those shown in Tables 1 to 3.
  • the above-mentioned water repellency evaluation (initial) and water repellency evaluation (after washing) were performed using the obtained emulsions. The results are shown in Tables 1 to 3.
  • Examples 1 to 13 which used monomers (a), (b), and (c) and in which the proportion of the constituent units based on monomer (b) relative to the total amount of the constituent units of the non-fluoropolymer was 1 to 12% by mass, showed good water repellency and durability even when the content of the non-fluoropolymer in the water repellent composition was low (low concentration).
  • Example 14 which did not use monomer (b), and Examples 36 and 37, which did not use monomer (b) and monomer (c), showed low water repellency and durability when the content of the non-fluoropolymer in the water repellent composition was low (low concentration).
  • Example 40 in which the proportion of the constituent units based on monomer (b) relative to the total amount of the constituent units of the non-fluoropolymer was more than 12% by mass and monomer (c) was not used, showed low water repellency and durability when the content of the non-fluoropolymer in the water repellent composition was low (low concentration).
  • Examples 15 to 20, 30 to 32, 34, 39, and 41 which do not use monomer (b) or in which the proportion of structural units based on monomer (b) to the total amount of structural units of the non-fluoropolymer is more than 12 mass%, had low water repellency and durability when the content of the non-fluoropolymer in the water repellent composition was low (low concentration).

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Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5978263A (ja) 1982-10-27 1984-05-07 Toshiba Corp 入力装置
JPS60163908A (ja) * 1984-02-07 1985-08-26 Shin Etsu Chem Co Ltd 複合化塩化ビニル系樹脂材料
WO2009113589A1 (ja) 2008-03-12 2009-09-17 旭硝子株式会社 共重合体およびその製造方法
JP2018095879A (ja) * 2016-12-15 2018-06-21 ダイキン工業株式会社 撥水剤
JP2019026747A (ja) * 2017-07-31 2019-02-21 ダイキン工業株式会社 撥水剤組成物
JP2022186729A (ja) 2019-03-07 2022-12-15 日本電気株式会社 撮影装置、撮影方法、プログラム

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5978263A (ja) 1982-10-27 1984-05-07 Toshiba Corp 入力装置
JPS60163908A (ja) * 1984-02-07 1985-08-26 Shin Etsu Chem Co Ltd 複合化塩化ビニル系樹脂材料
WO2009113589A1 (ja) 2008-03-12 2009-09-17 旭硝子株式会社 共重合体およびその製造方法
JP2018095879A (ja) * 2016-12-15 2018-06-21 ダイキン工業株式会社 撥水剤
JP2019026747A (ja) * 2017-07-31 2019-02-21 ダイキン工業株式会社 撥水剤組成物
JP2022186729A (ja) 2019-03-07 2022-12-15 日本電気株式会社 撮影装置、撮影方法、プログラム

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
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