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WO2018110667A1 - Agent hydrofuge - Google Patents

Agent hydrofuge Download PDF

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Publication number
WO2018110667A1
WO2018110667A1 PCT/JP2017/044970 JP2017044970W WO2018110667A1 WO 2018110667 A1 WO2018110667 A1 WO 2018110667A1 JP 2017044970 W JP2017044970 W JP 2017044970W WO 2018110667 A1 WO2018110667 A1 WO 2018110667A1
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WO
WIPO (PCT)
Prior art keywords
monomer
group
water repellent
weight
meth
Prior art date
Application number
PCT/JP2017/044970
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English (en)
Japanese (ja)
Inventor
山本　祐輝
憲正 上杉
福森　正樹
育男 山本
Original Assignee
ダイキン工業株式会社
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Filing date
Publication date
Application filed by ダイキン工業株式会社 filed Critical ダイキン工業株式会社
Priority to KR1020197012508A priority Critical patent/KR102336363B1/ko
Priority to CN201780067693.8A priority patent/CN109923190B/zh
Publication of WO2018110667A1 publication Critical patent/WO2018110667A1/fr

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Classifications

    • 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
    • C08F220/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
    • C08F220/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
    • C08F220/1818—C13or longer chain (meth)acrylate, e.g. stearyl (meth)acrylate
    • 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
    • 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
    • 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
    • C08F290/08—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 side groups
    • C08F290/14—Polymers provided for in subclass C08G
    • C08F290/148—Polysiloxanes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
    • C08G77/04—Polysiloxanes
    • C08G77/20—Polysiloxanes containing silicon bound to unsaturated aliphatic groups
    • 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
    • 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
    • D06M15/356—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of other unsaturated compounds containing nitrogen, sulfur, silicon or phosphorus atoms
    • 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
    • D06M15/356—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of other unsaturated compounds containing nitrogen, sulfur, silicon or phosphorus atoms
    • D06M15/3568—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of other unsaturated compounds containing nitrogen, sulfur, silicon or phosphorus atoms containing silicon
    • 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 containing a silicon-containing polymer having no fluorine atom. Specifically, the present invention can impart excellent water repellency, oil repellency and antifouling properties to the substrate.
  • telomers can produce PFOA by degradation or metabolism (telomers mean long chain fluoroalkyl groups).
  • telomers are used in many products such as foam, water- and oil-repellent and antifouling foams, care products, cleaning products, carpets, textiles, paper and leather. Yes. There is concern about the accumulation of fluorine-containing compounds in the environment.
  • the fluorine-containing water / oil repellent containing the fluorine-containing polymer is subjected to heat treatment at a high temperature (for example, 100 ° C. or more) after being attached to a substrate such as a textile product in order to exhibit water / oil repellency.
  • a high temperature for example, 100 ° C. or more
  • High energy is required for heat treatment at high temperature.
  • the fluoropolymer is expensive.
  • Patent Document 1 discloses a silicone organocopolymer obtained by polymerization of an ethylenically unsaturated organomonomer and a silicone macromer. Patent Document 1 does not describe providing good texture and chalk mark resistance to a textile product.
  • Patent Document 2 discloses a method for producing an aqueous resin dispersion comprising polymerizing a vinyl monomer and a silicone-based macromonomer having a radical polymerizable group. Patent Document 2 does not describe providing a good texture and chalk mark resistance to a textile product.
  • Patent Document 3 discloses a slidable resin composition comprising a thermoplastic resin, a (meth) acrylic acid ester and a radical polymerizable silicone macromonomer. Patent Document 3 does not disclose a water / oil repellent (liquid treatment agent).
  • JP 2010-500498 A Japanese Patent Laid-Open No. 5-9248 Japanese Patent Laid-Open No. 10-182987
  • One object of the present invention is to provide a surface treatment agent (water / oil repellent, especially water repellent) that gives a fiber product excellent water / oil repellency (particularly water repellency), soft texture and good chalk mark resistance. It is to provide.
  • A2 non-fluorine (meth) acrylate ester monomer represented by formula (A2)
  • A2 a repeating unit derived from a silicone macromer having a radically polymerizable group (A2) as an essential component.
  • the water repellent of the present invention imparts excellent water and oil repellency (particularly water repellency), soft texture (good texture) and good chalk mark resistance to a substrate, particularly a textile product.
  • Water repellent (A) a silicon-containing polymer, It comprises (B) a liquid medium, and (C) other components present as necessary, for example additives.
  • the water repellent may consist only of the components (A) to (C). It is preferable that the water repellent does not contain a fluorine-containing polymer.
  • the silicon-containing polymer does not contain a fluorine atom.
  • the silicon-containing polymer does not contain a fluorine-containing monomer, for example, a fluorine-containing monomer having a fluoroalkyl group.
  • the silicon- containing polymer is (A1) a repeating unit derived from a non-fluorine (meth) acrylate ester monomer, (A2) having a repeating unit derived from a silicone macromer, and (A3) a repeating unit derived from another monomer optionally present.
  • non-fluorine (meth) acrylate ester monomers include octyl (meth) acrylate, decyl (meth) acrylate, isodecyl (meth) acrylate, lauryl (meth) acrylate, tridecyl (meth) acrylate, isotridecyl (meth) acrylate , Stearyl (meth) acrylate, isostearyl (meth) acrylate and behenyl (meth) acrylate. Stearyl (meth) acrylate and behenyl (meth) acrylate are preferred.
  • a silicone macromer is a high molecular weight monomer having a silicone as a skeleton. Silicone macromers have radically polymerizable groups at one or both ends. Examples of the radically polymerizable group are (meth) acryloyl group, styryl group, allyl group, vinylbenzyl group, vinyl ether group, vinylalkylsilyl group, vinylketone group and isopropenyl group. (Meth) acryloyl groups, that is, acryloyl groups and methacryloyl groups are preferred. A silicone macromer having a methacryloyl group (that is, a methacryl-modified silicone macromer) is more preferable. A silicone macromer having a methacryloyl group only at one end (a methacryl-modified silicone macromer at one end) is particularly preferable.
  • Silicone macromer has the formula: Wherein R is the same or different and is a hydrocarbon group having 1 to 12 carbon atoms, X is a group having a radical polymerizable functional group, m is a number from 5 to 200. ] It is preferable that it is a compound shown by these. It is preferable that 50 mol% or more of the total R groups are methyl groups.
  • the hydrocarbon group may be substituted.
  • the X group (a group containing a radical polymerizable functional group) is preferably formed by a radical polymerizable functional group and an alkylene group (the alkylene group preferably has 1 to 10 carbon atoms).
  • silicone macromer examples include as follows.
  • m is a number from 5 to 200.
  • the number average molecular weight of the silicone macromer is generally 1,000 to 100,000, for example, 2,000 to 50,000.
  • the number average molecular weight is measured by gel permeation chromatography (polystyrene conversion).
  • Silicone macromer can be produced by a known method.
  • a living polymer is obtained by anionic polymerization of cyclic siloxane using lithium trialkylsilanolate as an initiator, and a silicone macromer is obtained by reacting ⁇ -methacryloxypropyldimethylmonochlorosilane (special feature). No. 59-78236), or a method of obtaining a silicone macromer as a condensate of a terminal silanol group-containing silicone and an organosilicon compound (Japanese Patent Laid-Open No. 58-167606).
  • A3 Other monomers
  • other monomers other than the non-fluorine (meth) acrylate ester monomer (A1) and the silicone macromer (A2) may be used.
  • the other monomer is preferably a non-silicon non-fluorine monomer, that is, a monomer having no silicon atom and no fluorine atom.
  • Examples of other monomers include (I) halogenated olefins, (Ii) a non-crosslinkable monomer, and (iii) a crosslinkable monomer.
  • the halogenated olefin may be a halogenated olefin having 2 to 20 carbon atoms substituted with 1 to 10 chlorine atoms, bromine atoms or iodine atoms.
  • the halogenated olefin is preferably a chlorinated olefin having 2 to 20 carbon atoms, particularly an olefin having 2 to 5 carbon atoms having 1 to 5 chlorine atoms.
  • Preferred examples of halogenated olefins are vinyl halides such as vinyl chloride, vinyl bromide, vinyl iodide, vinylidene halides such as vinylidene chloride, vinylidene bromide, vinylidene iodide. Vinyl chloride and vinylidene chloride, particularly vinyl chloride are preferred.
  • the non-crosslinkable monomer is a monomer other than the monomer (A1).
  • the non-crosslinkable monomer is generally a non-silicon non-fluorine non-crosslinkable monomer that does not contain a silicon atom and a fluorine atom.
  • the non-crosslinkable monomer is preferably a (meth) acrylate ester.
  • a 21 represents a hydrogen atom or a methyl group
  • a 22 is a hydrocarbon group excluding a linear or branched hydrocarbon group.
  • a 22 is a hydrocarbon group having 8 to 30 carbon atoms.
  • a 22 is a hydrocarbon group having 6 to 30 carbon atoms.
  • the hydrocarbon group is preferably a cyclic hydrocarbon group.
  • the hydrocarbon group preferably has 10 to 28 carbon atoms, for example 12 to 26, in particular 14 to 24, in particular 18 or 22.
  • the non-crosslinkable monomer is preferably a (meth) acrylate monomer having a cyclic hydrocarbon group.
  • the (meth) acrylate monomer having a cyclic hydrocarbon group is a compound having a (preferably monovalent) cyclic hydrocarbon group and a monovalent (meth) acrylate group.
  • the monovalent cyclic hydrocarbon group and the monovalent (meth) acrylate group are directly bonded.
  • Examples of the cyclic hydrocarbon group include saturated or unsaturated monocyclic groups, polycyclic groups, and bridged cyclic groups.
  • the cyclic hydrocarbon group is preferably saturated.
  • the cyclic hydrocarbon group preferably has 6 to 30 carbon atoms.
  • Examples of the cyclic hydrocarbon group include a cyclic aliphatic group having 4 to 20 carbon atoms, particularly 5 to 12 carbon atoms, an aromatic group having 6 to 20 carbon atoms, and an araliphatic group having 7 to 20 carbon atoms.
  • the number of carbon atoms of the cyclic hydrocarbon group is particularly preferably 15 or less, for example 10 or less. It is preferred that the carbon atom in the ring of the cyclic hydrocarbon group is directly bonded to the ester group in the (meth) acrylate group.
  • the cyclic hydrocarbon group is preferably a saturated cyclic aliphatic group.
  • cyclic hydrocarbon group examples include a cyclohexyl group, a t-butylcyclohexyl group, an isobornyl group, a dicyclopentanyl group, a dicyclopentenyl group, and an adamantyl group.
  • the acrylate group is preferably an acrylate group or a methacrylate group, but a methacrylate group is particularly preferable.
  • the monomer having a cyclic hydrocarbon group examples include cyclohexyl (meth) acrylate, t-butylcyclohexyl (meth) acrylate, benzyl (meth) acrylate, isobornyl (meth) acrylate, and dicyclopentanyl (meth) acrylate.
  • Dicyclopentenyl (meth) acrylate Dicyclopentenyl (meth) acrylate, dicyclopentanyloxyethyl (meth) acrylate, tricyclopentanyl (meth) acrylate, adamantyl (meth) acrylate, 2-methyl-2-adamantyl (meth) acrylate, 2-ethyl -2-Adamantyl (meth) acrylate and the like.
  • the crosslinkable monomer is generally a non-silicon non-fluorine crosslinkable monomer containing no silicon atom or fluorine atom.
  • the crosslinkable monomer may be a compound having at least two reactive groups and / or ethylenically unsaturated double bonds and not containing fluorine.
  • the crosslinkable monomer may be a compound having at least two ethylenically unsaturated double bonds, or a compound having at least one ethylenically unsaturated double bond and at least one reactive group. Examples of reactive groups are hydroxyl groups, epoxy groups, chloromethyl groups, blocked isocyanate groups, amino groups, carboxyl groups, and the like.
  • crosslinkable monomer examples include diacetone acrylamide, (meth) acrylamide, N-methylol acrylamide, hydroxymethyl (meth) acrylate, hydroxyethyl (meth) acrylate, and 3-chloro-2-hydroxypropyl (meth) acrylate. , 2-acetoacetoxyethyl (meth) acrylate, butadiene, isoprene, chloroprene, glycidyl (meth) acrylate and the like, but are not limited thereto.
  • Each of the monomers (A1) to (A3) may be single or a combination of two or more.
  • the amount of the non-fluorine (meth) acrylate ester monomer (A1) may be 10 to 95% by weight, for example 50 to 90% by weight, particularly 60 to 85% by weight, based on the silicon-containing polymer.
  • the amount of the silicone macromer (A2) is 0.2 to 50 parts by weight, for example 0.5 to 20 parts by weight, particularly 1 to 4 parts by weight based on 100 parts by weight of the non-fluorine (meth) acrylate ester monomer (A1). It may be 15 parts by weight.
  • the amount of the other monomer (A3) may be 200 parts by weight or less, for example, 2 to 50 parts by weight with respect to 100 parts by weight of the non-fluorine (meth) acrylate ester monomer (A1).
  • the amount of halogenated olefin may be 50% by weight or less based on the silicon-containing polymer.
  • the amount of the halogenated olefin may be 10.1% by weight or more based on the silicon-containing polymer.
  • the amount of the halogenated olefin is, for example, from 1 to 40% by weight, particularly from 3 to 30% by weight, preferably from 5 to 28% by weight, more preferably from 10.1 to 26% by weight, particularly preferably based on the silicon-containing polymer. Is 12 to 24% by weight.
  • the amount of the non-crosslinkable monomer may be 50% by weight or less, for example, 1 to 40% by weight, particularly 3 to 30% by weight with respect to the silicon-containing polymer.
  • the amount of the crosslinkable monomer may be 30% by weight or less, for example, 0.1 to 20% by weight, particularly 0.5 to 10% by weight based on the silicon-containing polymer.
  • the number average molecular weight (Mn) of the silicon-containing polymer may generally be from 2000 to 1000000, for example 3000 to 500000, in particular 4000 to 200000.
  • the number average molecular weight (Mn) of the silicon-containing polymer is generally measured by GPC (gel permeation chromatography).
  • the amount of the silicon-containing polymer may be 0.1 to 70% by weight, for example 1 to 50% by weight, in particular 3 to 40% by weight, based on the water repellent.
  • the liquid medium is water and / or an organic solvent.
  • the liquid medium may be only an organic solvent, but is preferably water alone or a mixture of water and a (water-miscible) organic solvent.
  • the amount of the organic solvent may be 30% by weight or less, for example, 10% by weight or less (preferably 0.1% or more) with respect to the liquid medium. More preferably, the liquid medium is water alone.
  • the amount of the liquid medium may be 30 to 99.9% by weight, for example 50 to 99% by weight, in particular 55 to 95% by weight, based on the water repellent.
  • the water repellent may contain an additive as a component other than the silicon-containing polymer and the liquid medium.
  • the additive include a silicon-containing compound and an acrylic emulsion.
  • Other examples of additives include drying rate modifiers, crosslinking agents, film-forming aids, compatibilizers, surfactants, antifreeze agents, viscosity modifiers, UV absorbers, antioxidants, pH adjusters, These include foaming agents, texture modifiers, slipperiness modifiers, antistatic agents, hydrophilizing agents, antibacterial agents, antiseptics, insecticides, fragrances, and flame retardants.
  • the amount of the additive may be 0.1 to 100 parts by weight, for example 1 to 30 parts by weight with respect to 100 parts by weight of the silicon-containing polymer.
  • the silicon-containing polymer in the present invention can be produced by any ordinary polymerization method, and the conditions for the polymerization reaction can be arbitrarily selected.
  • Such polymerization methods include solution polymerization, suspension polymerization, emulsion polymerization and the like.
  • solution polymerization a method in which a monomer is dissolved in an organic solvent in the presence of a polymerization initiator, and after nitrogen substitution, is heated and stirred in the range of 30 to 120 ° C. for 1 to 10 hours.
  • the polymerization initiator include azobisisobutyronitrile, benzoyl peroxide, di-t-butyl peroxide, lauryl peroxide, cumene hydroperoxide, t-butyl peroxypivalate, and diisopropyl peroxydicarbonate. Can be mentioned.
  • the polymerization initiator is used in the range of 0.01 to 20 parts by weight, for example, 0.01 to 10 parts by weight with respect to 100 parts by weight of the monomer.
  • the organic solvent is inert to the monomer and dissolves them.
  • an ester for example, an ester having 2 to 30 carbon atoms, specifically, ethyl acetate or butyl acetate
  • a ketone for example, carbon It may be a ketone having a number of 2 to 30, specifically methyl ethyl ketone or diisobutyl ketone, or an alcohol (for example, an alcohol having 1 to 30 carbon atoms, specifically, isopropyl alcohol).
  • organic solvent examples include acetone, chloroform, HCHC225, isopropyl alcohol, pentane, hexane, heptane, octane, cyclohexane, benzene, toluene, xylene, petroleum ether, tetrahydrofuran, 1,4-dioxane, methyl ethyl ketone, methyl isobutyl ketone, Examples include diisobutyl ketone, ethyl acetate, butyl acetate, 1,1,2,2-tetrachloroethane, 1,1,1-trichloroethane, trichloroethylene, perchloroethylene, tetrachlorodifluoroethane, trichlorotrifluoroethane, and the like.
  • the organic solvent is used in the range of 10 to 2000 parts by weight, for example, 50 to 1000 parts by weight with respect to 100 parts by weight of the total
  • Emulsion polymerization employs a method in which a monomer is emulsified in water in the presence of a polymerization initiator and an emulsifier, and after purging with nitrogen, the mixture is stirred and polymerized in the range of 50 to 80 ° C. for 1 to 10 hours.
  • Polymerization initiators include benzoyl peroxide, lauroyl peroxide, t-butyl perbenzoate, 1-hydroxycyclohexyl hydroperoxide, 3-carboxypropionyl peroxide, acetyl peroxide, azobisisobutylamidine dihydrochloride, azo Water-soluble materials such as bisisobutyronitrile, sodium peroxide, potassium persulfate, ammonium persulfate, azobisisobutyronitrile, benzoyl peroxide, di-t-butyl peroxide, lauryl peroxide, cumene hydroperoxide Oil-soluble ones such as t-butyl peroxypivalate and diisopropyl peroxydicarbonate are used.
  • the polymerization initiator is used in the range of 0.01 to 10 parts by weight with respect to 100 parts by weight of the monomer.
  • the monomer is polymerized by submerging the monomer into water using an emulsifier that can impart strong crushing energy such as a high-pressure homogenizer or an ultrasonic homogenizer. It is desirable.
  • an emulsifier various anionic, cationic or nonionic emulsifiers can be used, and the emulsifier is used in the range of 0.5 to 20 parts by weight with respect to 100 parts by weight of the monomer.
  • the emulsifier may be a nonionic emulsifier.
  • the emulsifier may be a combination of a sorbitan ester and another emulsifier (particularly, another nonionic emulsifier) (weight ratio is, for example, 5:95 to 95: 5).
  • the other emulsifier may be a polyether compound having a polyoxyalkylene group (particularly a polyoxyethylene group).
  • a compatibilizing agent such as a water-soluble organic solvent or a low molecular weight monomer that is sufficiently compatible with these monomers. By adding a compatibilizing agent, it is possible to improve emulsifying properties and copolymerization properties.
  • water-soluble organic solvent examples include acetone, methyl ethyl ketone, ethyl acetate, propylene glycol, dipropylene glycol monomethyl ether, dipropylene glycol, tripropylene glycol, ethanol and the like, and 1 to 50 parts by weight with respect to 100 parts by weight of water.
  • the low molecular weight monomer examples include methyl methacrylate, glycidyl methacrylate, 2,2,2-trifluoroethyl methacrylate, etc., and 1 to 50 parts by weight with respect to 100 parts by weight of the total amount of monomers.
  • it may be used in the range of 10 to 40 parts by weight.
  • a chain transfer agent may be used.
  • the molecular weight of the polymer can be varied.
  • chain transfer agents include mercaptan group-containing compounds such as lauryl mercaptan, thioglycol and thioglycerol (especially alkyl mercaptans (for example, having 1 to 30 carbon atoms)), inorganic salts such as sodium hypophosphite and sodium bisulfite. Etc.
  • the chain transfer agent may be used in an amount of 0.01 to 10 parts by weight, for example, 0.1 to 5 parts by weight with respect to 100 parts by weight of the total amount of monomers.
  • the polymer may be produced by charging monomers at a time.
  • the monomer may be divided and charged.
  • the silicon-containing polymer is, for example, (I) a step of obtaining a first polymer by polymerizing the first monomer, and (II) a second polymer is obtained by polymerizing the second monomer in the presence of the first polymer. It can manufacture by the manufacturing method which has a process.
  • step (II) preferably in both step (I) and step (II)
  • the second polymer is polymerized by polymerizing the second monomer in the presence of the first polymer and the liquid medium. It is preferable to obtain
  • the first monomer is a non-fluorine (meth) acrylate ester monomer (A1) and a silicone macromer (A2)
  • the second monomer is another monomer (A3), particularly a halogenated olefin.
  • the first monomer may contain another monomer (A3), for example, a halogenated olefin, a non-crosslinkable monomer, and a crosslinkable monomer.
  • the halogenated olefin may be either the first monomer or the second monomer, or both the first monomer and the second monomer.
  • the halogenated olefin may be charged after the monomer (ie, other monomer that may contain a halogenated olefin) is polymerized, both when the halogenated olefin is charged at once and when it is charged in portions. . It is particularly preferable to charge 100% of the halogenated olefin. That is, it is particularly preferable that the first monomer does not contain a halogenated olefin and the second monomer consists only of a halogenated olefin.
  • a first polymer is produced by performing a polymerization reaction with a liquid containing a first monomer, and then a second polymer is obtained by performing a polymer reaction with a liquid containing a first polymer and a second monomer.
  • the polymerization of the second polymer may be started during the polymerization of the first polymer, or the polymerization of the second polymer may be started after the completion of the polymerization of the first polymer.
  • This production method is generally a two-stage polymerization having a first polymerization stage which is a first polymerization reaction for polymerizing a first monomer and a second polymerization stage for polymerizing a second monomer.
  • the polymerization reaction of the first polymer (that is, the polymerization reaction of the first monomer) is 10% or more (that is, 10 to 100%), for example, 40% or more (that is, 40 to 100%), particularly 70% or more ( That is, after the completion of 70 to 100%), the polymerization of the second polymer may be started.
  • the polymerization reaction completion rate% (that is, the polymerization reaction progress rate%) means the mol% of the reacted monomer (polymerized monomer). For example, when the polymerization reaction is completed by 10%, the polymerized monomer is 10 mol% and the unreacted (unpolymerized) monomer is 90 mol%.
  • the first monomer is a combination of at least two monomers
  • the mole% of the first monomer is based on the total mole of at least two monomers in the first monomer.
  • the term “during polymerization of the first polymer” means that the polymerization reaction of the first polymer (that is, the polymerization reaction of the first monomer) is not completely completed. For example, polymerization of the first polymer is completed at 10% to less than 40%, 40% to less than 70%, or 70% to less than 100% (especially 80% to 99%, especially 85% to 98%) After that, the polymerization of the second polymer may be started.
  • the term “after completion of polymerization of the first polymer” means that the polymerization reaction of the first polymer (that is, the polymerization reaction of the first monomer) is completed about 100%.
  • the second polymer When the polymerization of the second polymer is initiated during the polymerization of the first polymer, the second polymer has a repeating unit derived from the first monomer and the second monomer. When the polymerization of the second polymer is started after completion of the polymerization of the first polymer, the second polymer has a repeating unit derived from only the second monomer.
  • the amount of the second polymer is 0.1 to 100 parts by weight, 1 to 75 parts by weight, 3 to 60 parts by weight, 6 to 50 parts by weight based on 100 parts by weight of the first polymer and the second polymer. Parts, or 8 to 40 parts by weight.
  • the first monomer may be charged all at once (temporarily) or continuously.
  • the first monomer is preferably charged at a time.
  • the second monomer may be charged all at once or continuously.
  • the continuous charging of the second monomer is preferably performed so that the pressure of the monomer gas (particularly, a halogenated olefin such as vinyl chloride) is constant during the polymerization of the second monomer.
  • the first polymer is chemically bonded or not chemically bonded to the second polymer.
  • substantially no unreacted non-fluorine (meth) acrylate ester monomer that is, a long-chain acrylate ester monomer
  • substantially absent means that the amount of the unreacted long-chain acrylate ester monomer is 10 mol relative to the charged long-chain acrylate ester monomer at the time of starting the polymerization of the second monomer. % Or less, preferably 8 mol% or less, more preferably 5 mol%, especially 3 mol% or less, especially 1 mol% or less. Due to the substantial absence of the long-chain acrylate ester monomer, in the processing of the treating agent containing the copolymer, the performance of preventing roll contamination due to the polymer adhering to the roll is excellent.
  • the treatment agent of the present invention may be in the form of a solution, an emulsion (particularly an aqueous dispersion) or an aerosol, but is preferably an aqueous dispersion.
  • the treatment agent comprises a water / oil repellent polymer (silicon-containing polymer) (active component of the surface treatment agent) and a liquid medium (particularly an aqueous medium such as an organic solvent and / or water).
  • the amount of the liquid medium may be, for example, 5 to 99.9% by weight, particularly 10 to 80% by weight, based on the treatment agent.
  • the concentration of the water / oil repellent polymer may be 0.01 to 95% by weight, for example 5 to 50% by weight.
  • the treatment agent of the present invention can be applied to an object to be treated by a conventionally known method.
  • the treatment agent is dispersed in an organic solvent or water, diluted, attached to the surface of an object to be treated by a known method such as dip coating, spray coating, foam coating, etc., and then dried. .
  • curing may be carried out by applying together with a suitable crosslinking agent (for example, blocked isocyanate).
  • a suitable crosslinking agent for example, blocked isocyanate
  • insecticides, softeners, antibacterial agents, flame retardants, antistatic agents, paint fixing agents, anti-wrinkle agents, and the like can be added to the treatment agent of the present invention.
  • the concentration of the water / oil repellent polymer in the treatment liquid brought into contact with the substrate may be 0.01 to 10% by weight (particularly in the case of dip coating), for example, 0.05 to 10% by weight.
  • Examples of the object to be treated with the treatment agent (for example, water repellent) of the present invention include textile products, stone materials, filters (for example, electrostatic filters), dust masks, fuel cell components (for example, gas diffusion electrodes and Gas diffusion supports), glass, paper, wood, leather, fur, asbestos, brick, cement, metals and oxides, ceramic products, plastics, painted surfaces, plasters and the like.
  • filters for example, electrostatic filters
  • dust masks for example, gas diffusion electrodes and Gas diffusion supports
  • natural animal and vegetable fibers such as cotton, hemp, wool, and silk
  • synthetic fibers such as polyamide, polyester, polyvinyl alcohol, polyacrylonitrile, polyvinyl chloride, and polypropylene
  • semi-synthetic fibers such as rayon and acetate, glass fibers, and carbon fibers
  • Inorganic fibers such as asbestos fibers, or mixed fibers thereof.
  • the fiber product may be in the form of a fiber, cloth or the like.
  • the treatment agent of the present invention can also be used as an internal release agent or an external release agent.
  • the water / oil repellent polymer can be applied to a fibrous substrate (eg, a fiber product, etc.) by any of the known methods for treating a fiber product with a liquid.
  • a fibrous substrate eg, a fiber product, etc.
  • the fabric may be immersed in the solution, or the solution may be attached or sprayed onto the fabric.
  • the treated fiber product is dried and preferably heated at, for example, 100 ° C. to 200 ° C. in order to develop oil repellency.
  • the water / oil repellent polymer may be applied to the textile by a cleaning method, and may be applied to the textile by, for example, a laundry application or a dry cleaning method.
  • the textile products to be treated are typically fabrics, which include woven, knitted and non-woven fabrics, fabrics and carpets in clothing form, but fibers or yarns or intermediate fiber products (eg sliver or It may be a roving yarn).
  • the textile product material may be natural fibers (such as cotton or wool), chemical fibers (such as viscose rayon or rheocell), or synthetic fibers (such as polyester, polyamide or acrylic fibers), or May be a mixture of fibers, such as a mixture of natural and synthetic fibers.
  • the water / oil repellent polymer of the present invention is particularly effective in making cellulosic fibers (eg, cotton or rayon) oleophobic and oil repellent.
  • the method of the present invention also generally makes the textile product hydrophobic and water repellent.
  • the fibrous base material may be leather.
  • Water- and oil-repellent polymers can be used in various stages of leather processing to make the leather hydrophobic and oleophobic, for example, during wet processing of leather or during leather finishing. Or you may apply to leather from aqueous emulsion.
  • the fibrous substrate may be paper.
  • the water and oil repellent polymer may be applied to preformed paper or may be applied at various stages of papermaking, for example during the drying period of the paper.
  • “Processing” means applying a treatment agent to an object to be treated by dipping, spraying, coating, or the like. By the treatment, the polymer which is an active ingredient of the treatment agent penetrates into the treatment object and / or adheres to the surface of the treatment object.
  • the water repellency of the treated fabric was evaluated according to the spray method of JIS-L-1092 (AATCC-22). Furthermore, some treated cloths were obtained by washing 10 times (HL10) or 20 times (HL20) with a washing liquid at 40 ° C. and drying with a tumbler (30 minutes at 60 ° C.) according to JIS L-0217 103. The evaluation results of the water repellency of the test cloth are also shown in Table-4. As described below, the water repellency is as follows. Is represented by The larger the score, the better the water repellency. Intermediate values (95, 85, 75) are assigned depending on the state.
  • Texture test The texture was evaluated in 5 stages according to the hand feeling. Evaluation was performed by five measurers. 1: very hard 2: hard 3: slightly hard 4: soft 5: very soft
  • (Meth) acryl-modified silicone is a high molecular weight monomer having a (meth) acryloyl group at one or both ends of polydimethylsiloxane.
  • Silicone having a methacryloyl group at one end is represented by the following chemical formula.
  • Silicones having methacryloyl groups at both ends are represented by the following chemical formula.
  • Silicones having acryloyl groups at both ends are represented by the following chemical formula. [In the above formula, m is a number giving a predetermined number average molecular weight. ]
  • the emulsified dispersion was transferred to a 500 ml autoclave, purged with nitrogen, and charged with 0.2 g of lauryl mercaptan and 20 g of vinyl chloride. Further, 1 g of 2,2-azobis (2-amidinopropane) dihydrochloride was added, heated to 60 ° C. and reacted for 4 hours to obtain an aqueous dispersion of polymer. This dispersion was further diluted with pure water to prepare an aqueous dispersion 1 having a solid content of 30%.
  • Production Examples 2 to 11 and 23 Polymerization was carried out in the same manner as in Production Example 1 with the formulation shown in Table 1, and diluted with water to obtain aqueous dispersions 2 to 11 having a solid concentration of 30%.
  • the emulsified dispersion was transferred to a 500 ml autoclave, purged with nitrogen, charged with 0.2 g of lauryl mercaptan and 1 g of 2,2-azobis (2-amidinopropane) dihydrochloride, and reacted at 60 ° C. for 1 hour. After reacting for 1 hour, it was confirmed that stearyl acrylate was reacted by 99 mol% or more. Thereafter, 20 g of vinyl chloride was press-fitted and reacted for another 3 hours to obtain an aqueous dispersion of polymer. This dispersion was further diluted with pure water to prepare an aqueous dispersion 12 having a solid concentration of 30%.
  • Production Examples 13 to 22 and 24 Polymerization was carried out in the same manner as in Production Example 12 with the formulation shown in Table 2, and diluted with water to obtain aqueous dispersions 13 to 22 having a solid content concentration of 30%.
  • Comparative Production Examples 1 and 2 Polymerization was carried out in the same manner as in Production Example 1 with the formulation shown in Table 3 and diluted with water to obtain comparative aqueous dispersions 1 and 2 having a solid content concentration of 30%.
  • Comparative production examples 3 to 5 Polymerization was carried out in the same manner as in Production Example 12 with the formulation shown in Table 3, and diluted with water to obtain comparative water dispersions 3 to 5 having a solid content concentration of 30%.
  • Test example 1 The aqueous dispersion 1 having a solid content concentration of 30% prepared in Production Example 1 was further diluted with tap water to prepare a treatment liquid having a solid content concentration of 1.5%. A polyester cloth was dipped in this treatment solution and then squeezed with a mangle. The wet pickup was about 55%. This treated cloth was passed through a pin tenter at 170 ° C. for 1 minute, dried and cured. The fabrics thus treated were tested. The results are shown in Table 4.
  • Test Examples 2 to 11 and 23 The same method as in Test Example 1 was repeated except that the aqueous dispersions 2 to 11 and 23 prepared in Production Examples 2 to 11 and 23 were used. The results are shown in Table 4.
  • Comparative Test Examples 1 and 2 The same method as in Test Example 1 was repeated except that Comparative Aqueous Dispersions 1 and 2 prepared in Comparative Production Examples 1 and 2 were used. The results are shown in Table 4.
  • Test Examples 12 to 22 and 24 The same method as in Test Example 1 was repeated except that the aqueous dispersions 12 to 22 and 24 prepared in Production Examples 12 to 22 and 24 were used. The results are shown in Table 5.
  • Comparative Test Examples 3-5 The same method as in Test Example 1 was repeated except that the comparative aqueous dispersions 3 to 5 prepared in Comparative Production Examples 3 to 5 were used. The results are shown in Table 5.
  • Comparative Test Example 6 27 g of KF-412 (long-chain alkyl-modified silicone) manufactured by Shin-Etsu Chemical Co., Ltd. 2 g of an ethylene oxide 10 mol adduct of a higher alcohol having 18 carbon atoms and 1 g of an ethylene oxide 20 mol adduct of a higher alcohol having 18 carbon atoms In addition, mixing at 60 ° C., 70 g of deionized water at 60 ° C. was gradually added, and emulsified with ultrasonic waves for 10 minutes to obtain an emulsion of KF-412 (solid content concentration 30%).
  • the water repellent of the present invention can be used as a surface treatment agent for various substrates such as textile products (for example, carpets), paper, non-woven fabric, stone, electrostatic filters, dust masks, and fuel cell components. .
  • the water repellent of the present invention can also exhibit the functions of an antifouling agent and a soil release agent.

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Polymers & Plastics (AREA)
  • Medicinal Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Textile Engineering (AREA)
  • Combustion & Propulsion (AREA)
  • Materials Engineering (AREA)
  • Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
  • Macromonomer-Based Addition Polymer (AREA)
  • Materials Applied To Surfaces To Minimize Adherence Of Mist Or Water (AREA)
  • Paints Or Removers (AREA)

Abstract

La présente invention concerne un agent hydrofuge contenant un polymère contenant du silicium qui comprend les constituants suivants en tant que constituants essentiels : (A1) un motif récurrent dérivé d'un monomère de type ester de (méth)acrylate non fluoré représenté par la formule CH2=CA11-C(=O)-O-A12 (dans la formule, A11 représente un atome d'hydrogène ou un groupe méthyle et A12 représente un groupe hydrocarboné linéaire ou ramifié comprenant 8-30 atomes de carbone) ; et (A2) un motif récurrent dérivé d'un macromère de type silicone présentant un groupe polymérisable par voie radicalaire. L'agent hydrofuge permet de conférer d'excellentes propriétés hydrofuges, de texture et de résistance au marquage à la craie sur un produit textile.
PCT/JP2017/044970 2016-12-15 2017-12-14 Agent hydrofuge WO2018110667A1 (fr)

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TW201835290A (zh) 2018-10-01
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