CN105765025A - Water-based surface treatment agent - Google Patents

Water-based surface treatment agent Download PDF

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Publication number
CN105765025A
CN105765025A CN201480063525.8A CN201480063525A CN105765025A CN 105765025 A CN105765025 A CN 105765025A CN 201480063525 A CN201480063525 A CN 201480063525A CN 105765025 A CN105765025 A CN 105765025A
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monomer
agent
water
polymer
methyl
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CN105765025B (en
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福森正树
南晋
南晋一
原良辅
川部留美
山本育男
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Daikin Industries Ltd
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Daikin Industries Ltd
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    • 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
    • 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
    • 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
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/62—Polymers of compounds having carbon-to-carbon double bonds
    • C08G18/6275—Polymers of halogen containing compounds having carbon-to-carbon double bonds; halogenated polymers of compounds having carbon-to-carbon double bonds
    • C08G18/6279—Polymers of halogen containing compounds having carbon-to-carbon double bonds; halogenated polymers of compounds having carbon-to-carbon double bonds containing fluorine atoms
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
    • C08G18/72—Polyisocyanates or polyisothiocyanates
    • C08G18/80—Masked polyisocyanates
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J3/00—Processes of treating or compounding macromolecular substances
    • C08J3/02—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques
    • C08J3/03—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques in aqueous media
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    • 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
    • C09D133/14—Homopolymers or copolymers of esters of esters containing halogen, nitrogen, sulfur or oxygen atoms in addition to the carboxy oxygen
    • C09D133/16—Homopolymers or copolymers of esters containing halogen atoms
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    • 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
    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C09D5/02—Emulsion paints including aerosols
    • C09D5/024—Emulsion paints including aerosols characterised by the additives
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    • 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
    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C09D5/16—Antifouling paints; Underwater paints
    • C09D5/1681—Antifouling coatings characterised by surface structure, e.g. for roughness effect giving superhydrophobic coatings or Lotus effect
    • C—CHEMISTRY; METALLURGY
    • C14—SKINS; HIDES; PELTS; LEATHER
    • C14C—CHEMICAL TREATMENT OF HIDES, SKINS OR LEATHER, e.g. TANNING, IMPREGNATING, FINISHING; APPARATUS THEREFOR; COMPOSITIONS FOR TANNING
    • C14C11/00—Surface finishing of leather
    • C14C11/003—Surface finishing of leather using macromolecular compounds
    • C—CHEMISTRY; METALLURGY
    • C14—SKINS; HIDES; PELTS; LEATHER
    • C14C—CHEMICAL TREATMENT OF HIDES, SKINS OR LEATHER, e.g. TANNING, IMPREGNATING, FINISHING; APPARATUS THEREFOR; COMPOSITIONS FOR TANNING
    • C14C9/00—Impregnating leather for preserving, waterproofing, making resistant to heat or similar purposes
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M13/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment
    • D06M13/322—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing nitrogen
    • D06M13/325—Amines
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M13/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment
    • D06M13/322—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing nitrogen
    • D06M13/325—Amines
    • D06M13/332—Di- or polyamines
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M13/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment
    • D06M13/322—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing nitrogen
    • D06M13/402—Amides imides, sulfamic acids
    • 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
    • D06M2200/00—Functionality of the treatment composition and/or properties imparted to the textile material
    • D06M2200/10—Repellency against liquids

Abstract

Provided is a surface treatment agent in which a fluorine-containing monomer, in particular a monomer containing a fluoroalkyl group, is not used. Disclosed is a surface-treatment agent that is a water-based emulsion and includes: (1) a non-fluorine polymer that has a repeat unit derived from a long-chain (meth)acrylate ester monomer represented by the formula (a): CH2=CA11-C(=O)-O-A12 [in the formula, A11 is a hydrogen atom or a methyl group, and A12 is a C18-30 straight-chain or branched aliphatic hydrocarbon group.]; (2) a surfactant that includes both a nonionic surfactant and a cationic surfactant, wherein the quantity of the cationic surfactant relative to the total quantity of the nonionic surfactant and the cationic surfactant is at least 22 wt%; and (3) a liquid medium including water.

Description

Water system surface conditioning agent
Technical field
The present invention relates to water system surface conditioning agent, particularly water extraction oil extracticn agent and anti-fouling agent.
Background technology
It is currently known the fluorine-containing water extraction oil extracticn agent containing fluorochemical.When the base materials such as fibre are processed by this water extraction oil extracticn agent, show good water-repellent oil-repellent.
nullResult [EPA reports " PRELIMINARYRISKASSESSMENTOFTHEDEVELOPMENTALTOXICITYASSOC IATEDWITHEXPOSURETOPERFLUOROOCTANOICACIDANDITSSALTS " (http://www.epa.gov/opptintr/pfoa/pfoara.pdf)] etc. in the light of recent researches，The PFOA (perfluoro caprylic acid: perfluorooctanoicacid) a kind of as long-chain fluorinated alkyl compound is bright and clear gradually to the misgivings of carrying capacity of environment，Issue the strengthening science to PFOA EPA on April 14 in 2003 (Environmental Protection Agency USA) to investigate.
nullOn the other hand，FederalRegister(FRVol.68,No.73/April16,2003[FRL-2303-8],http://www.epa.gov/opptintr/pfoa/pfoafr.pdf)、EPAEnvironmentalNewsFORRELEASE:MONDAYAPRIL14,2003EPAINTENSIFIESSCIENTIFICINVESTIGATIONOFACHEMICALPROC ESSINGAID (http://www.epa.gov/opptintr/pfoa/pfoaprs.pdf) and EPAOPPTFACTSHEETApril14,2003 (http://www.epa.gov/opptintr/pfoa/pfoafacts.pdf) have delivered telomer and have likely generated PFOA (so-called telomer refers to long-chain fluoro-alkyl) by decomposition or metabolism.Further, also delivered telomer to may be used for imparting in the various products such as water-repellent oil-repellent, the fire foam of soil resistance, care article, cleaning article, carpet, textile, paper, leather.Fluorochemical accumulation in the environment is troubling.
It addition, the fluorine-containing water extraction oil extracticn agent containing fluoropolymer, in order to show water-repellent oil-repellent, it is necessary to implement heat treatment with high temperature (such as more than 100 DEG C) after being attached on the base materials such as fibre.Heat treatment under high temperature needs high-energy.
Further, fluoropolymer is expensive.
Therefore, it is desirable to do not use fluoropolymer or reduce the amount of fluoropolymer.
Japanese Unexamined Patent Publication 2006-328624 publication discloses a kind of dryingagent containing non-fluorine based polymer, the carbon number that this non-fluorine based polymer contains ester moiety be (methyl) acrylate of more than 12 as monomeric unit, the composition of (methyl) acrylate is 80～100 mass % relative to constituting the monomeric unit total amount of non-fluorine based polymer.
But, the water-repellent oil-repellent of this dryingagent is poor.
Prior art literature
Patent documentation
Patent documentation 1: Japanese Unexamined Patent Publication 2006-328624 publication
Summary of the invention
The problem that invention to solve
It is an object of the invention to provide a kind of give excellence water-repellent oil-repellent, the surface conditioning agent that preferably do not use fluorochemical monomer, particularly monomer containing fluoro-alkyl.
For solving the means of problem
The present invention relates to a kind of water serial emulsion inorganic agent, it contains:
(1) there is the polymer of the repetitive being derived from long-chain (methyl) acrylate monomer；
(2) surfactant；With
(3) moisture liquid medium.
[1] a kind of surface conditioning agent, it is water serial emulsion, contains:
(1) non-fluorinated polymer, it has and is derived from (a) formula: CH2=CA11-C (=O)-O-A12[in formula, A11For hydrogen atom or methyl, A12The aliphatic alkyl of straight or branched for carbon number 18～30] shown in the repetitive of long-chain (methyl) acrylate monomer；
(2) surfactant, it comprises nonionic surfactant and cationic surface active agent, and the amount of cationic surface active agent relative to the total amount of nonionic surfactant and cationic surface active agent at more than 22 weight %；With
(3) moisture liquid medium.
[2] surface conditioning agent as described in [1], wherein, non-fluorinated polymer (1) is without (methyl) acrylate monomer with cyclic hydrocarbon group.
[3] surface conditioning agent as described in [1] or [2], wherein, nonionic surfactant is at least one in ether, ester, ester ether, alkanolamide, polyhydric alcohol and amine oxide, and cationic surface active agent is at least one in amine, amine salt, quaternary ammonium salt, imidazoline and imidazoline salt.
[4] surface conditioning agent as according to any one of [1]～[3], wherein, surface conditioning agent does not contain fluoropolymer.
[5] surface conditioning agent as according to any one of [1]～[3], wherein, surface conditioning agent contains fluoropolymer.
[6] surface conditioning agent as according to any one of [1]～[5], it is water extraction oil extracticn agent or anti-fouling agent.
[7] a kind of method that fibre is processed, it includes step fibre processed with the surface conditioning agent according to any one of [1]～[6].
Invention effect
The inorganic agent of the present invention does not use the monomer containing fluoro-alkyl, so being absent from the misgivings that fluorochemical is accumulated in the environment.Base material can be given excellent water-repellent oil-repellent by the inorganic agent of the present invention.And, it is not necessary to it is heated processing with high temperature, it is possible to show water-repellent oil-repellent by K cryogenic treatment.
The stability (emulsion intercalation method) of the inorganic agent of the present invention is good.The durability (particularly washing resistance) of the water-repellent oil-repellent (particularly water-repellancy) of the inorganic agent of the present invention is excellent.Further, the feel of base material is good.
Utilize the inorganic agent being only effective ingredient with non-fluorinated polymer, it is possible to obtain with only using contain monomer containing fluoro-alkyl as the fluoropolymer of construction unit be effective ingredient inorganic agent equal or equal more than performance (particularly including the water-repellent oil-repellent of initial water-repellent oil-repellent).
Detailed description of the invention
In the present invention, polymer (being preferably non-fluorinated polymer) has the repetitive being derived from (a) long-chain (methyl) acrylate monomer.
Polymer can be copolymer, it is also possible to have selected from the repetitive being derived from (b) short chain (methyl) acrylate monomer, be derived from the repetitive of (c) non-fluorine cross-linkable monomer and be derived from the repetitive of (d) alkenyl halide monomer in the repetitive of at least one.
Polymer can have fluorine atom, but does not preferably have fluorine atom.That is, polymer is preferably non-fluorinated polymer.
(a) long-chain (methyl) acrylate monomer
Long-chain (methyl) acrylate monomer is formula: CH2=CA11-C (=O)-O-A12[in formula, A11For hydrogen atom or methyl, A12The aliphatic alkyl of straight or branched for carbon number 18～30] shown in compound.
Long-chain (methyl) acrylate monomer does not have fluoro-alkyl.Long-chain (methyl) acrylate monomer can contain fluorine atom, but preferably without fluorine atom.
A11It is particularly preferably methyl.
A12Alkyl for straight-chain or branched.The alkyl of straight-chain or branched can be the alkyl of straight-chain especially.The carbon number of the alkyl of straight-chain or branched is 18～30.The carbon number of the alkyl of straight-chain or branched is 18～28, be particularly preferably 18 or 22, it is usually preferred to saturated aliphatic alkyl, particularly preferably alkyl.
The preferred concrete example of long-chain (methyl) acrylate monomer is stearyl (methyl) acrylate, Shan Yuji (methyl) acrylate.It is particularly preferably stearyl (methyl) acrylate.
By there is long-chain (methyl) acrylate monomer, the water-repellancy that polymer gives and group oiliness improve.
(b) short chain (methyl) acrylate monomer
Polymer can have the repetitive being derived from short chain (methyl) acrylate monomer.
Short chain (methyl) acrylate monomer is preferably formula: CH2=CA21-C (=O)-O-A22[in formula, A21For hydrogen atom or methyl, A22Aliphatic alkyl for the carbon number straight or branched less than 18] shown in compound.
Short chain (methyl) acrylate monomer does not have fluoro-alkyl.Short chain (methyl) acrylate monomer can contain fluorine atom, but preferably without fluorine atom.
A21It is particularly preferably methyl.
A22Alkyl for straight-chain or branched.The alkyl of straight-chain or branched can be the alkyl of straight-chain especially.The carbon number of the alkyl of straight-chain or branched is 1～17.The preferred carbon number 1～14 of alkyl of straight-chain or branched, it is usually preferred to saturated aliphatic alkyl, particularly preferably alkyl.
The concrete example of short chain (methyl) acrylate monomer is methyl (methyl) acrylate, ethyl (methyl) acrylate, isopropyl (methyl) acrylate, the tert-butyl group (methyl) acrylate, lauryl (methyl) acrylate, myristyl (methyl) acrylate, cetyl (methyl) acrylate.The particularly preferred concrete example of short chain (methyl) acrylate monomer is lauryl (methyl) acrylate, cetyl (methyl) acrylate.
By there is short chain (methyl) acrylate monomer, water-repellancy and feel that polymer gives improve.
(c) non-fluorine cross-linkable monomer
Polymer can have the repetitive being derived from non-fluorine cross-linkable monomer, or can not also have.
Non-fluorine cross-linkable monomer is free from the monomer of fluorine atom.Non-fluorine cross-linkable monomer is to have at least 2 reactive groups and/or alkene carbon-to-carbon double bond (being preferably (methyl) acrylate-based) and not fluorine-containing compound.Non-fluorine cross-linkable monomer can be have the compound of at least 2 alkene carbon-to-carbon double bonds (being preferably (methyl) acrylate-based) or for having the compound of at least 1 alkene carbon-to-carbon double bond and at least 1 reactive group.The example of reactive group is hydroxyl, epoxy radicals, chloromethyl, blocked isocyanate base, amino, carboxyl etc..
Non-fluorine cross-linkable monomer can be have list (methyl) acrylate of reactive group, two (methyl) acrylate or single (methyl) acrylamide.Or non-fluorine cross-linkable monomer can also be two (methyl) acrylate.
One example of non-fluorine cross-linkable monomer is have the vinyl monomer of hydroxyl.
As non-fluorine cross-linkable monomer, can illustrate such as: two acetone (methyl) acrylamide, N-methylol (methyl) acrylamide, hydroxymethyl (methyl) acrylate, hydroxyethyl (methyl) acrylate, 3-chlorine-2-hydroxyl propyl group (methyl) acrylate, 2-acetoacetoxyethyl (methyl) acrylate, butadiene, isoprene, chlorobutadiene, monochloro acetic acid vinyl acetate, vinyl methacrylate, glycidyl (methyl) acrylate, 1, 6-hexanediol two (methyl) acrylate, neopentyl glycol two (methyl) acrylate etc., but it is not limited to these.
By there is non-fluorine cross-linkable monomer, the washing resistance that polymer gives improves.
(d) alkenyl halide monomer
Alkenyl halide does not preferably have fluorine atom.
Alkenyl halide is preferably the alkene replacing the carbon number 2～20 having 1～10 chlorine atom, bromine atoms or atomic iodine.Alkenyl halide is preferably the chloroalkene of carbon number 2～20, it is particularly preferred to for having the alkene of the carbon number 2～5 of 1～5 chlorine atom.The preferred concrete example of alkenyl halide is: vinyl halides, for instance vinyl chloride, bromine ethylene, iodoethylene；Vinylidene halide, for instance vinylidene chloride, inclined bromine ethylene, inclined iodoethylene.Preferred vinyl chloride.
By there is alkenyl halide, the washing resistance that polymer gives improves.
(e) other monomers
Other monomers (e) beyond monomer (a)～(d) can also be used, for instance non-fluorine non-crosslinked monomer.
The example of other monomers such as includes: ethylene, vinyl acetate, acrylonitrile, styrene, Polyethylene Glycol (methyl) acrylate, polypropylene glycol (methyl) acrylate, methoxy poly (ethylene glycol) (methyl) acrylate, methoxyl group polypropylene glycol (methyl) acrylate and vinyl alkyl ethers.Other monomers are not limited to these examples.
Non-fluorinated polymer (1) can contain (methyl) acrylate monomer with cyclic hydrocarbon group, but does not preferably contain.
In this manual, " (methyl) acrylate " means acrylate or methacrylate, and " (methyl) acrylamide " means acrylamide or Methacrylamide.
Owing to water-repellent oil-repellent is high, so monomer is respectively preferably acrylate.
Monomer (a)～(e) can be used alone respectively, or can also be mixture of more than two kinds.
The amount of monomer (a) is more than 40 weight % relative to polymer, is preferably more than 50 weight portions.The amount of monomer (a) is below 95 weight portions relative to polymer, such as, is below 80 weight portions or is below 75 weight portions or is below 70 weight portions.
In the polymer, relative to monomer (a) 100 weight portion,
The amount of repetitive (b) can be 0～150 weight portion, be preferably 1～30 weight portion,
The amount of repetitive (c) can be 0～50 weight portion, be preferably 1～10 weight portion,
The amount of repetitive (d) can be 0～100 weight portion, be preferably 1～30 weight portion,
The amount of repetitive (e) can be 0～100 weight portion, be preferably 1～30 weight portion.
The number-average molecular weight (Mn) of polymer is generally 1000～1000000, such as, is 5000～500000, particularly can be 3000～200000.The number-average molecular weight (Mn) of polymer measures usually by GPC (gel permeation chromatography).
Polymer can be a kind of polymer, it is also possible to for the combination of polymer of more than two kinds.
In the present invention, by making monomer polymerization, obtain polymer dispersed or dissolve agent composition in media as well.
The monomer used in the present invention can be as follows:
Monomer (a),
Monomer (a)+(b),
Monomer (a)+(c),
Monomer (a)+(b)+(c),
Monomer (a)+(d),
Monomer (a)+(b)+(d),
Monomer (a)+(c)+(d) or
Monomer (a)+(b)+(c)+(d).
In addition, it is also possible to use monomer (e).
Non-fluorine cross-linkable monomer (c) is preferably used.Monomer is preferably the combination of monomer (a)+non-fluorine cross-linkable monomer (c) or the combination of monomer (a)+non-fluorine cross-linkable monomer (c)+alkenyl halide monomer (d).In this combination, the washing resistance of water-repellancy is high.
(2) surfactant
In the inorganic agent of the present invention, surfactant comprises nonionic surfactant and cationic surface active agent.Surfactant can be only made up of nonionic surfactant and cationic surface active agent, or can also contain (nonionic surfactant and beyond cationic surface active agent) other surfactant.The example of other surfactant is amphoteric surfactant.Surfactant is preferably without anionic surfactant.
(2-1) nonionic surfactant
Example as nonionic surfactant, it is possible to enumerate ether, ester, ester ether, alkanolamide, polyhydric alcohol and amine oxide.
The example of ether is the compound with oxyalkylene (being preferably polyoxyethylene).
The example of ester is the ester of alcohol and fatty acid.The example of alcohol is the alcohol (such as aliphatic alcohol) of the carbon number 1～50 (particularly carbon number 3～30) of 1～6 yuan (particularly 2～5 yuan).The example of fatty acid is the saturated of carbon number 2～50, particularly carbon number 5～30 or undersaturated fatty acid.
The example of ester ether is the compound that addition epoxyalkane (particularly oxirane) obtains in the alcohol ester with fatty acid.The example of alcohol is the alcohol (such as aliphatic alcohol) of the carbon number 1～50 (particularly carbon number 3～30) of 1～6 yuan (particularly 2～5 yuan).The example of fatty acid is the saturated of carbon number 2～50, particularly carbon number 5～30 or undersaturated fatty acid.
The example of alkanolamide is formed by fatty acid and alkanolamine.Alkanolamide can be monoalkylol amide or di alkanolamide.The example of fatty acid is the saturated of carbon number 2～50, particularly carbon number 5～30 or undersaturated fatty acid.Alkanolamine can for have 1～3 amino and the alkanol of the carbon number 2～50 of 1～5 hydroxyl, particularly 5～30.
Polyhydric alcohol can be the alcohol of the carbon number 3～30 of 2～5 yuan.
Amine oxide can be the oxide (such as carbon number 5～50) of amine (secondary amine or preferably tertiary amine).
Nonionic surfactant is preferably the nonionic surfactant with oxyalkylene (preferred polyoxyethylene).In oxyalkylene, the carbon number of alkylidene is preferably 2～10.The quantity of the oxyalkylene in the molecule of nonionic surfactant is preferably generally 2～100.
Nonionic surfactant is selected from ether, ester, ester ether, alkanolamide, polyhydric alcohol and amine oxide, it is however preferred to have the nonionic surfactant of oxyalkylene.
Nonionic surfactant can be the alkylene oxide adducts etc. of aliphatic (the saturated and/or unsaturated) alkylene oxide adducts of group of straight-chain and/or branched, straight-chain and/or the poly alkylene glycol ester of branched fatty acid (saturated and/or unsaturated), polyoxyethylene (POE)/polyoxypropylene (POP) copolymer (random copolymer or block copolymer), acetylenic glycols.Wherein, the structure of preferred epoxyalkane addition part and polyalkylene glycol moiety is the material of polyoxyethylene (POE), polyoxypropylene (POP) or POE/POP copolymer (can be random copolymer, it is also possible to for block copolymer).
It addition, consider from the problem (biological degradability, environmental hormone (environmentalhormone) etc.) of environment aspect, nonionic surfactant preferably structure without aromatic group.
Nonionic surfactant can be formula: R1O-(CH2CH2O)p-(R2O)q-R3Shown compound.
[in formula, R1For the alkyl of carbon number 1～22 or the thiazolinyl of carbon number 2～22 or acyl group, R2Independently, identical or different, for the alkylidene of carbon number more than 3 (such as 3～10), R3For the thiazolinyl of hydrogen atom, the alkyl of carbon number 1～22 or carbon number 2～22, p is the number of more than 2, and q is the number of 0 or more than 1.]
R1Be preferably carbon number 8～20, particularly 10～18.As R1Preferred concrete example, it is possible to enumerate lauryl, tridecyl, oil base.
R2Example be propylidene, butylidene.
In nonionic surfactant, p can be the number (such as 5～200) of more than 3.Q can be the number (such as 5～200) of more than 2.That is ,-(R2O)q-polyoxy alkylidene chain can be formed.
Nonionic surfactant can be central authorities' polyoxyethylene alkylidene alkyl ethers containing hydrophilic polyoxyethylene chain and hydrophobic oxyalkylene chain (particularly polyoxy alkylidene chain).As hydrophobic oxyalkylene chain, it is possible to enumerate oxygen propylene chain, oxygen butylidene chain, styrene chain etc., wherein, it is preferable that oxygen propylene chain.
Preferred nonionic surfactant is formula: R1O-(CH2CH2O)pSurfactant shown in-H.
[in formula, R1With the implication of p ibid.]
The concrete example of nonionic surfactant is:
C10H21O-(CH2CH2O)p-(C3H6O)q-H
C12H25O-(CH2CH2O)p-(C3H6O)q-H
C16H31O-(CH2CH2O)p-(C3H6O)q-H
C16H33O-(CH2CH2O)p-(C3H6O)q-H
C18H35O-(CH2CH2O)p-(C3H6O)q-H
C18H37O-(CH2CH2O)p-(C3H6O)q-H
C12H25O-(CH2CH2O)p-(C3H6O)q-C12H25
C16H31O-(CH2CH2O)p-(C3H6O)q-C16H31
C16H33O-(CH2CH2O)p-(C3H6O)q-C12H25
iso-C13H27O-(CH2CH2O)p-(C3H6O)q-H
C10H21COO-(CH2CH2O)p-(C3H6O)q-H
C16H33COO-(CH2CH2O)p-(C3H6O)q-C12H25Deng.
[in formula, the implication of p and q is ibid.]
The concrete example of nonionic surfactant includes: oxirane and hexylphenol, isooctyl phenol, hexadecanol, oleic acid, alkane (C12-C16) mercaptan, sorbitan mono fatty acid (C7-C19) or alkyl (C12-C18) the condensation product of amine etc..
The ratio of polyoxyethylene block can be 5～80 weight %, such as 30～75 weight %, particularly 40～70 weight % relative to the molecular weight of nonionic surfactant (copolymer).
The mean molecule quantity of nonionic surfactant is generally 300～5,000, such as 500～3,000.
Nonionic surfactant can be used alone or two or more kinds may be used.
Nonionic surfactant is preferably combination of more than two kinds.In combination of more than two kinds, at least one nonionic surfactant can be R1Base (and/or R3Base) for the R of branched alkyl (such as isotridecyl)1O-(CH2CH2O)p-(R2O)q-R3[particularly R1O-(CH2CH2O)p-H] shown in compound.R1Base be the nonionic surfactant of branched alkyl amount relative to nonionic surfactant (B2) add up to 100 weight portions can be 5～100 weight portions, such as be 8～50 weight portions, be in particular 10～40 weight portions.In combination of more than two kinds, remaining nonionic surfactant can be R1Base (and/or R3Base) it is the R of (saturated and/or undersaturated) straight chained alkyl (such as lauryl (positive lauryl))1O-(CH2CH2O)p-(R2O)q-R3[particularly R1O-(CH2CH2O)p-H] shown in compound.
As nonionic surfactant, can enumerate such as: polyoxyethylene ether, polyoxyethylene phenyl ether, polyoxyethylene fatty acid ester, sorbitan fatty acid ester, polyoxy ethylene sorbitol alcohol acid anhydride fatty acid ester, polyoxy ethylene sorbitol alcohol fatty acid ester, fatty acid glyceride, polyoxyethylene fatty acid glyceride, polyglyceryl fatty acid ester, sucrose fatty acid ester, polyoxyethylene amine, polyoxyethylene fatty acid amide, fatty acid alkyl alcohol amide, alkylalkanol amide, acetylenic glycols, the oxygen ethylidene addition product of acetylenic glycols, Polyethylene Glycol polyethylene glycol block copolymer etc..
Owing to the dynamic surface tension of water serial emulsion reduces (namely water-based emulsion easily soaks into base material), so as the oxygen ethylidene addition product of the preferred alkynol of nonionic surfactant (particularly acetylenic glycols) or alkynol (particularly acetylenic glycols).
Preferred nonionic surfactant is the alkylene oxide adducts (this alcohol and this alkylene oxide adducts are called " alkynol compound ") of alcohol or this alcohol with unsaturated three keys.Particularly preferred nonionic surfactant is the alkylene oxide adducts of single methanol or the polyhydric alcohol with unsaturated three keys.
Alkynol compound is the compound containing more than 1 three keys and more than 1 hydroxyl.Alkynol compound can be the compound comprising polyoxyalkylene moieties.Example as polyoxyalkylene moieties, it is possible to enumerate the block addition structure of the random addition structure of polyoxyethylene, polyoxypropylene, polyoxyethylene and polyoxypropylene, polyoxyethylene and polyoxypropylene.
Alkynol compound can be formula:
HO-CR11R12-C ≡ C-CR13R14-OH or
HO-CR15R16Compound shown in-C ≡ C-H.
[in formula, R11、R12、R13、R14、R15、R16Independently, identical or different, for the alkyl of hydrogen atom or carbon number 1～30.]
Alkynol compound can also for the alkylene oxide adducts of the compound shown in this chemical formula.The straight-chain of the preferred carbon number 1～12 of alkyl or the alkyl of branched, it is particularly preferred to the straight-chain of carbon number 6～12 or the alkyl of branched.Such as can enumerate methyl, ethyl, propyl group, butyl, isobutyl group etc..It addition, as epoxyalkane, it is possible to enumerating the epoxyalkane of the carbon number such as oxirane, expoxy propane 1～20 (particularly 2～5), the adduct number of epoxyalkane is preferably 1～50.
Concrete example as alkynol compound, it is possible to enumerate acetylenediol, propilolic alcohol, 2,5-dimethyl-3-hexins-2,5-glycol, 3,6-dimethyl-4-octyne-3,6-glycol, 2,4,7,9-tetramethyl-5-decine-4,7-glycol, 3,5-dimethyl-1-hexin-3-alcohol, 3-methyl isophthalic acid-butine-3-alcohol, methylpentynol, 3-hexin-2,5-glycol, 2-butyne-Isosorbide-5-Nitrae-glycol etc..Polyethoxylate and the ethylene oxide adduct of these concrete example compounds can also be enumerated.
Nonionic surfactant can not have three keys, or can also have three keys.Nonionic surfactant can simply be one of the nonionic surfactant without three keys or the nonionic surfactant with three keys, it is also possible to for do not have three keys nonionic surfactant and with the combination of the nonionic surfactant with three keys.Do not have the nonionic surfactant of three keys with in the combination of nonionic surfactant with three keys, the weight ratio of the nonionic surfactant (such as having the nonionic surfactant of oxyalkylene) without three keys and the nonionic surfactant (such as alkynol compound) with three keys can be 10:90～90:10, for instance for 20:80～80:20.
(2-2) cationic surface active agent
Cationic surface active agent is preferably the compound without amide groups.
Example as cationic surface active agent, it is possible to enumerate amine, amine salt, quaternary ammonium salt, imidazoline and imidazoline salt.
Cationic surface active agent is preferably amine salt, quaternary ammonium salt, oxygen ethylidene add-on type ammonium salt.Concrete example as cationic surface active agent, it does not have be particularly limited to, it is possible to enumerate: the amine salt cationic surfactant of alkylamine salt, amino alcohol fatty acid derivatives, polyamines derivative of fatty acid, imidazoline etc.；The quaternary ammonium salt cationic surfactant etc. of alkyltrimethylammonium salt, dialkyl dimethyl ammonium salt, alkyl dimethyl benzyl ammonium salt, pyridiniujm, alkyl isoquinolinium salt, benzethonium chloride etc..
The example of cationic surface active agent is R21-N+(-R22)(-R23)(-R24)X-Compound.
[in formula, R21、R22、R23And R24Independently, identical or different, for the alkyl of hydrogen atom or carbon number 1～50, X is anionic group.]
Alkyl can have oxygen atom, for instance can be the oxyalkylene (carbon number of alkylidene is such as 2～5) of polyoxy alkyl etc..R21、R22、R23And R24It is preferably the alkyl (such as aliphatic hydrocarbon, aromatic hydrocarbon or aromatic-aliphatic hydrocarbon) of carbon number 1～30.
R21、R22、R23And R24Concrete example be alkyl (such as methyl, butyl, stearyl, palmityl), aryl (such as phenyl), aralkyl (such as benzyl (phenyl methyl), phenethyl (phenylethyl)).
The concrete example of X is halogen (such as chlorine), the acid organic acid such as mineral acid, acetic acid (particularly fatty acid) such as () such as hydrochloric acid.
Cationic surface active agent is particularly preferably monoalkyl front three ammonium salt (carbon number of alkyl is 4～30).
Cationic surface active agent is preferably ammonium salt, is particularly preferably quaternary ammonium salt.Cationic surface active agent can be formula: R31 p-N+R32 qX-Shown ammonium salt.
[in formula, R31Independently, identical or different, for more than C12 (such as C12～C50) straight-chain and/or aliphatic (the saturated and/or unsaturated) group of branched,
R32Independently, identical or different, for the alkyl of H or C1～4, benzyl, polyoxyethylene (oxygen ethylidene numerical example as 1 (be in particular 2, be more particularly 3)～50) (particularly preferably CH3、C2H5),
X is halogen atom (such as chlorine and bromine), C1～C4Fatty acid alkali,
P is 1 or 2, q is 2 or 3, and p+q=4.]
R31Carbon number can be 12～50, such as be 12～30.
The concrete example of cationic surface active agent includes trimethyl ammonium acetate, trimethyl tetradecyl ammonium chloride, cetyl trimethylammonium bromide, trimethyloctadecyl ammonium chloride, (dodecyl methyl benzyl) trimethyl ammonium chloride, benzododecinium ammonium chloride, methyl dodecyl two (hydrogen polyoxyethylene) ammonium chloride, benzyl dodecyl two (hydrogen polyoxyethylene) ammonium chloride.
As amphoteric surfactant, alanine class, imidazolinium betaine class, amide betaine class, acetic acid glycine betaine etc. can be enumerated, specifically can enumerate lauryl betaine, stearyl betaine, lauryl carboxymethyl hydroxyethyl imidazolinium betaine, lauryl dimethyl oxyneurine, fatty amide propyl dimethylaminoethyl acid glycine betaine etc..
Nonionic surfactant, cationic surface active agent and amphoteric surfactant can be the combination of a kind or more than 2 respectively.
Relative to the total amount of nonionic surfactant and cationic surface active agent, the amount of cationic surface active agent is preferably more than 15 weight %, is more preferably more than 20 weight %, is particularly preferably more than 22 weight %, such as be more than 25 weight %, be in particular more than 30 weight %, be more particularly more than 35 weight %.The upper limit of the amount of cationic surface active agent is such as 60 weight %, is in particular 50 weight %, is more particularly 45 weight %.The weight ratio of nonionic surfactant and cationic surface active agent is preferably 85:15～20:80, is more preferably 80:20～40:60.Unless the amount of other the surfactant beyond ionic surfactant and cationic surface active agent, can be below 50 weight % relative to the total amount of surfactant, be such as below 20 weight %, and can be more than 0.1 weight %.
The amount of cationic surface active agent, can be 0.05～10 weight portion relative to polymer 100 weight portion, such as be 0.1～8 weight portion.The total amount of surfactant, can be 0.1～20 weight portion relative to polymer 100 weight portion, such as be 0.2～10 weight portion.
(3) liquid medium
Liquid medium can be individually for water or the mixture for water with (water miscibility) organic solvent.The amount of organic solvent can be below 30 weight % relative to liquid medium, such as be below 10 weight % (are preferably more than 0.1%).Liquid medium is preferably individually for water.
In the water extraction oil extracticn agent compositions of the present invention, as polymer (active component), it is possible to contain only above-mentioned non-fluorinated polymer, it is also possible to except containing above-mentioned non-fluorinated polymer, possibly together with fluoropolymer.Generally, in water extraction oil extracticn agent compositions (particularly water-based emulsion), non-fluorinated polymer the granule and the granule formed by fluoropolymer that are formed are respectively present.Namely, it is preferable that after manufacturing non-fluorinated polymer and fluoropolymer respectively, non-fluorinated polymer and fluoropolymer are mixed.Generally, it is preferred to after the emulsion (particularly water-based emulsion) of the emulsion (particularly water-based emulsion) and fluoropolymer that manufacture non-fluorinated polymer respectively, the emulsion of the emulsion of non-fluorinated polymer and fluoropolymer is mixed.
Fluoropolymer is the polymer with the repetitive being derived from fluorochemical monomer.Fluorochemical monomer is preferably the acrylate shown in following formula (I) or acrylamide.
CH2=C (-X)-C (=O)-Y-Z-Rf (I)
[in formula, X is hydrogen atom, the straight-chain of carbon number 1～21 or the alkyl of branched, fluorine atom, chlorine atom, bromine atoms, atomic iodine, CFX1X2Base (wherein, X1And X2For hydrogen atom, fluorine atom, chlorine atom, bromine atoms or atomic iodine), cyano group, the straight-chain of carbon number 1～21 or the fluoro-alkyl of branched, substituted or non-substituted benzyl, substituted or non-substituted phenyl；
Y is-O-or-NH-；
Z is the aliphatic group of carbon number 1～10, the aromatic group of carbon number 6～18 or cyclic aliphatic group ,-CH2CH2N(R1)SO2-Ji (wherein, R1Alkyl for carbon number 1～4) ,-CH2CH(OZ1)CH2-Ji (wherein, Z1For hydrogen atom or acetyl group) ,-(CH2)m-SO2-(CH2)n-Ji or-(CH2)m-S-(CH2)n-Ji (wherein, m is 1～10, and n is 0～10)；
Rf is the fluoro-alkyl of the straight-chain of carbon number 1～20 or branched.
The carbon number of Rf base is preferably 1～6, is in particular 4～6.
Fluoropolymer can have the repetitive of the non-fluorine monomer of at least one being derived from alkenyl halide monomer, non-fluorine non-crosslinked monomer and non-fluorine cross-linkable monomer.
Alkenyl halide monomer is preferably the alkene replacing the carbon number 2～20 having 1～10 chlorine atom, bromine atoms or atomic iodine.The concrete example of alkenyl halide monomer is: vinyl halides, for instance vinyl chloride, bromine ethylene, iodoethylene；Vinylidene halide, for instance vinylidene chloride, inclined bromine ethylene, inclined iodoethylene.
Preferred non-fluorine non-crosslinked monomer is formula: CH2Compound shown in=CA-T.
[in formula, A is the halogen atom (such as chlorine atom, bromine atoms and atomic iodine) outside hydrogen atom, methyl or fluorine removal atom,
T is hydrogen atom, the chain of carbon number 1～20 or the alkyl of ring-type or has the chain of ester bond or the organic group of the carbon number 1～20 of ring-type.]
The concrete example of non-fluorine non-crosslinked monomer includes: alkyl (methyl) acrylate, ethylene, vinyl acetate, acrylonitrile, styrene, Polyethylene Glycol (methyl) acrylate, polypropylene glycol (methyl) acrylate, methoxy poly (ethylene glycol) (methyl) acrylate, methoxyl group polypropylene glycol (methyl) acrylate and vinyl alkyl ethers.
Non-fluorine cross-linkable monomer can for have the compound of at least 2 carbon-to-carbon double bonds (such as (methyl) acrylic) or to have the compound of at least 1 carbon-to-carbon double bond and at least 1 reactive group.
The weight ratio of the non-fluorinated polymer in water extraction oil extracticn agent compositions and fluoropolymer can be 100:0～10:90, such as 90:10～20:80, preferably 80:20～30:70.
Non-fluorinated polymer and fluoropolymer can be a kind of polymer respectively, it is also possible to for the combination of polymer of more than two kinds.
When using the combination of non-fluorinated polymer and fluoropolymer, it is possible to obtain equal or equal above performance (particularly water-repellent oil-repellent) during with only use fluoropolymer
Polymer (non-fluorinated polymer and fluoropolymer) in the present invention can by any common polymerization manufacture, and the condition of polyreaction can also arbitrarily select.As such polymerization, it is possible to enumerate polymerisation in solution, suspension polymerisation, emulsion polymerization.Preferred emulsion polymerization.
As long as the inorganic agent of the present invention is water serial emulsion, the manufacture method of polymer does not just limit.For example, it is possible to manufacture polymer by polymerisation in solution, carry out the removing of solvent and the interpolation of surfactant and water afterwards, obtain water serial emulsion.
In polymerisation in solution, adopt under the existence of polymerization initiator, make monomer dissolve in organic solvent, after nitrogen displacement, the scope heated and stirred method of 1～10 hour of 30～120 DEG C.As polymerization initiator, for instance, it is possible to enumerate azodiisobutyronitrile, benzoyl peroxide, di-tert-butyl peroxide, lauryl peroxide, cumyl hydroperoxide, tert-Butyl peroxypivalate, di-isopropyl peroxydicarbonate etc..Relative to monomer 100 weight portion, polymerization initiator can use in the scope of the scope of 0.01～20 weight portion, such as 0.01～10 weight portion.
Organic solvent be for monomer torpescence and can by they dissolve solvent, it can be such as ester (the such as ester of carbon number 2～30, be specially ethyl acetate, butyl acetate), ketone (the such as ketone of carbon number 2～30, be specially butanone, diisobutyl ketone), alcohol (such as the alcohol of carbon number 1～30, is specially isopropanol).Concrete example as organic solvent, can enumerate acetone, chloroform, HCHC225, isopropanol, pentane, hexane, heptane, octane, hexamethylene, benzene,toluene,xylene, petroleum ether, oxolane, 1,4-dioxane, butanone, methyl iso-butyl ketone (MIBK), diisobutyl ketone, ethyl acetate, butyl acetate, 1,1,2,2-sym-tetrachloroethane, 1，1，1-trichloroethane, trichloro ethylene, perchloroethylene, tetrachlorodifluoroethane, trichorotrifluoroethane etc..Relative to total 100 weight portion of monomer, organic solvent can use in the scope of the scope of 10～2000 weight portions, such as 50～1000 weight portions.
In emulsion polymerization, adopt under the existence of polymerization initiator and emulsifying agent, make monomer emulsifying in water, after nitrogen displacement, stir the method making it be polymerized in 1～10 hour the scopes of 50～80 DEG C.Polymerization initiator can use benzoyl peroxide, lauroyl peroxide, peroxidized t-butyl perbenzoate, 1-hydroxycyclohexyl hydroperoxide, 3-carboxypropanoyl peroxide, acetyl peroxide, azo diisobutyl amidine-dihydrochloride, azodiisobutyronitrile, sodium peroxide, potassium peroxydisulfate, the water miscible initiator such as Ammonium persulfate. or azodiisobutyronitrile, benzoyl peroxide, di-tert-butyl peroxide, lauryl peroxide, cumyl hydroperoxide, tert-Butyl peroxypivalate, the oil-soluble initiator such as di-isopropyl peroxydicarbonate.Relative to 100 weight parts monomers, polymerization initiator can use in the scope of 0.01～10 weight portion.
The aqueous polymer dispersion excellent in order to obtain shelf-stability, it is preferred to use high-pressure homogenizer or that emulsifier unit that can give powerful crushing energy of ultrasonic homogenizer, makes monomer micronized being polymerized in water.It addition, as emulsifying agent, it is possible to use anionic, cationic or non-ionic various emulsifying agents, relative to 100 weight parts monomers, it is possible to use in the scope of 0.5～20 weight portion.Anionic and/or non-ionic and/or cationic emulsifying agent are preferably used.When monomer not exclusively mixes, it is preferable that add the phase solvation making these monomers fully mix, for instance, add water-miscible organic solvent or low-molecular-weight monomer.By adding phase solvation, it is possible to make emulsibility and copolymerizable be improved.
As water-miscible organic solvent, acetone, butanone, ethyl acetate, propylene glycol, dipropylene glycol methyl ether, dipropylene glycol, tripropylene glycol, ethanol etc. can be enumerated, relative to 100 weight parts waters, it is possible to use in the scope of the scope of 1～50 weight portion, such as 10～40 weight portions.It addition, as low-molecular-weight monomer, it is possible to enumerate methyl methacrylate, glycidyl methacrylate, 2,2,2-trifluoroethyl methacrylate etc., relative to total amount 100 weight portion of monomer, it is possible to use in the scope of 1～50 weight portion, such as 10～40 weight portions.
Polymerization can use chain-transferring agent.The molecular weight that can make polymer corresponds to the consumption that makes of chain-transferring agent to be changed.The example of chain-transferring agent is the inorganic salts etc. such as the compound (particularly (such as carbon number 1～30) alkyl hydrosulfide) containing mercapto such as lauryl mercaptan, thioglycol, thioglycerol, sodium hypophosphite, sodium sulfite.Relative to total amount 100 weight portion of monomer, chain-transferring agent can use in the scope of the scope of 0.01～10 weight portion, such as 0.1～5 weight portion.
Agent composition of the present invention can be solution, emulsion (particularly aqueous liquid dispersion) or aerocolloidal form, it is preferred to aqueous liquid dispersion.Agent composition contains polymer (active component of surface conditioning agent) and medium (particularly liquid medium, such as organic solvent and/or water).The amount of medium can be such as 5～99.9 weight % relative to agent composition, be in particular 10～80 weight %.
In agent composition, the concentration of polymer can be 0.01～95 weight %, such as 5～50 weight %.
The agent composition of the present invention can adopt currently known method to be applied to treated object.Generally, this agent composition is dispersed in organic solvent or water and is diluted by employing, by known methods such as dip coated, spraying coating, foam coatings so that it is the surface being attached to treated object the method being dried.It addition, can apply together with suitable cross-linking agent (such as blocked isocyanate) when needed, carry out solidifying (curing).Insect-proof agent, softening agent, antibacterial, fire retardant, antistatic additive, coating fixative, anti-creasing agent etc. can also be added in the agent composition of the present invention use together.Can be 0.01～10 weight % (particularly during dip coated) with the concentration of the polymer in the treatment fluid of substrate contact, such as be 0.05～10 weight %.
The treated object processed is carried out, it is possible to enumerate fibre, stone material, filter (such as electrostatic filter), anti-dust respirator, the parts (the gentle bulk diffusion supporting mass of such as gas-diffusion electrode) of fuel cell, glass, paper, timber, leather, fur, asbestos, brick, cement, metal and oxide, ceramic, plastics, coated face and Gypsum Fibrosum etc. as the agent composition (such as water extraction oil extracticn agent) utilizing the present invention.Various example can be enumerated as fibre.Such as can enumerate: the of animal or plant nature natural fibers such as cotton, fiber crops, Pilus Caprae seu Ovis, silk, the synthetic fibers such as polyamide, polyester, polyvinyl alcohol, polyacrylonitrile, polrvinyl chloride, polypropylene, the semisynthetic fibres such as artificial silk (rayon), acetate fiber, the inorfils such as glass fibre, carbon fiber, asbestos fibre, or their composite fibre.
Fibre can be any form of fiber, cloth etc..
The agent composition of the present invention can use as internal mold release or external release agent.
Polymer can be applied to fibrous substrate (such as fibre etc.) by known any means fibre processed with liquid.When fibre is cloth, it is possible to cloth is impregnated in the solution, or adhere to cloth or ejection solution.Fibre after treatment, dials oiliness to show, is dried, it is preferable that be such as heated at 100 DEG C～200 DEG C.
Or polymer can be applied to fibre by washing method, for instance fibre can be applied to by washing application or dry cleaning process etc..
The fibre carrying out processing is typically cloth, and this includes textile, knitting and non-woven fabrics, the cloth of dress material product form and blanket but it also may for fiber, line or median fiber goods (such as sliver (sliver) or thick line etc.).Fabric material can be natural fiber (such as cotton or Pilus Caprae seu Ovis etc.), chemical fibre (such as viscose rayon yarn (viscoserayon) or disappearing fibre (lyocell) etc.) or synthetic fibers (such as polyester, polyamide or acrylic fiber etc.), or can also be the mixture (mixture etc. of such as natural fiber and synthetic fibers) of fiber.The manufacture polymer of the present invention is effective especially in making cellulose fibre (such as cotton or artificial silk etc.) present oleophobic property and dial oiliness.Further, the method for invention generally makes fibre possess hydrophobicity and water-repellancy.
Or fibrous substrate can also be leather.In order to make leather present hydrophobicity and oleophobic property, leather processing each stage, such as at leather during moistening processing or during the polish of leather, manufacture polymer is applied to leather by aqueous solution or aqueous emulsifying thing.
Or fibrous substrate can also is that paper.Preformed paper can be applied to by manufacturing polymer, or manufacture polymer can also be applied to the dry period of each stage of papermaking, such as paper.
So-called " process " refers to and by dipping, spraying, coating etc., inorganic agent is applied to treated object.By processing, the polymer as inorganic agent effective ingredient soaks into the inside of treated object and/or is attached to the surface of treated object.
The ZETA current potential of water serial emulsion inorganic agent is preferably more than+30mV.ZETA current potential is measured by laser Doppler method (big Electronics Co., Ltd ELS-8000).
The dynamic surface tension of water serial emulsion inorganic agent is preferably below 55mN/m.Dynamic surface tension is measured by maximum bubble pressure method (consonance Surface Science Co., Ltd. BP-D5).
Embodiment
Below, specifically the present invention will be described to enumerate embodiment and comparative example.But, these explanations can not limit the present invention.
Hereinafter, unless otherwise specified, part, % or ratio represent weight portion, weight % or weight ratio.
The step of test is as described below.
Spray water-repellancy
Spray water-repellancy test is carried out according to JIS-L-1092.Spray water-repellancy test (shown in table described as follows) is represented by water-repellancy No..
Water-repellancy No. State
100 Surface is absent from moistening or water droplet attachment
90 Surface does not moisten, but presents the attachment of little water droplet
80 Surface presents little independent drop-shaped and moistens
70 The half on surface presents moistening, presents the little independent moistening state soaking into cloth
50 Surface entirety presents moistening
0 Surface and back side entirety present moistening
Volume is used to be at least the glass funnel of 250ml and the nozzle of 250ml water can be sprayed at 20 seconds～30 seconds.Test film frame is diameter is the metal frame of 15cm.Prepare 3 test sheet that size is about 20cm × 20cm, sheet material is fixed on test film support, makes sheet material there is no fold.Spraying is centrally located at the center of sheet material.The water (250mL) of room temperature is added glass funnel, sprays to test sheet (times with 25 seconds～30 seconds).Holding frame being taken off from platform, catch one end of holding frame, making forward surface is downside, knocks the end of opposition side gently with hard thing.Make holding frame rotate 180 ° again, repeat same step, make unnecessary water droplet fall.In order to according to water-repellancy from bad to excellent order, wet test film is provided the scoring of 0,50,70,80,90 and 100, contrasts with percentage of wetted soil relatively reference material.Result is obtained according to the meansigma methods that 3 times measure.
The washing resistance of water-repellancy
According to JISL-0217-103 method cyclic washing 5,20 times, water-repellent oil-repellent after evaluation (HL5,20).
Hand valuation
Implemented the sensory evaluation of following 5 grades by 5 detection persons, take its meansigma methods.
5: very soft
4: soft
3: equal with untreated cloth
2: hard
1: stone
Mechanical stability test
Mechanical stability
With tap water, aqueous liquid dispersion is diluted to 1%, it is stirred 3,000rpm × 10 minutes with mixer for well-distribution, by the scum filtering of generation to the cotton of black.
Zero: entirely without scum silica frost
△: slightly scum silica frost
×: scum silica frost is many
Peel strength
The peel strength of synthesis film
With water, the aqueous liquid dispersion of polymer is diluted so that solid component concentration reaches 1 weight %, prepares treatment fluid.Nylon cloth is immersed in treatment fluid, with mangle (mangle) with 4kg/cm2, 4m/ minute extruding.After carrying out 1 minute heat treatment with 170 DEG C, by polyurethane resin system bonding agent (Dainippon Ink Chemicals's system that concentration is 50% being solvent with MEK and ethyl acetate, CRISVON4010FT) one side of nylon cloth it is coated in point-like, after the synthesis film of crimping polyurethane, with 120 DEG C of heat treatments 2 minutes.With the AATCC88B (1) (III) the nylon cloth cyclic washing to obtaining 20 times, afterwards, the stripping state of visual observations synthesis film, with its state of following standard evaluation.
◎: entirely without stripping
Zero: have minute quantity to peel off
×: visible significantly stripping
Manufacture example 1
500mL autoclave adds sterylacrylic acid ester=50g, pure water=145g, tripropylene glycol=15g, sorbitan monooleate=1.5g, polyoxyethylene (EO:18) second alkyl (C12-14) ether=2g, two-octadecyldimethyl ammonium chloride=1.5g, under agitation disperses 15 minutes with ultrasonic emulsification with 60 DEG C.After carrying out nitrogen displacement in autoclave, add double; two (2-amidine propane) 2 hydrochlorates=0.5g of 2,2-azos, react 3 hours with 60 DEG C, obtain the aqueous liquid dispersion of polymer.With pure water, solid component concentration is regulated to 30% again.The monomer composition generating polymer is basically identical with the composition adding monomer.
Manufacture example 2
500mL autoclave adds sterylacrylic acid ester=50g, pure water=145g, tripropylene glycol=15g, acetylenediol polyoxyethylene addition product=1g, polyoxyethylene (EO:18) isotridecyl ether=2g, two-octadecyldimethyl ammonium chloride=2g, under agitation disperses 15 minutes with ultrasonic emulsification with 60 DEG C.After carrying out nitrogen displacement in autoclave, add double; two (2-amidine propane) 2 hydrochlorates=0.5g of 2,2-azos, react 3 hours with 60 DEG C, obtain the aqueous liquid dispersion of polymer.With pure water, solid component concentration is regulated to 30% again.The monomer composition generating polymer is basically identical with the composition adding monomer.
Manufacture example 3
500mL autoclave adds sterylacrylic acid ester=50g, pure water=145g, tripropylene glycol=15g, acetylenediol polyoxyethylene addition product=1g, polyoxyethylene (EO:18) lauryl ether=2.9g, octadecyl trimethyl ammonium chloride=1.1g, under agitation disperses 15 minutes with ultrasonic emulsification with 60 DEG C.After carrying out nitrogen displacement in autoclave, add double; two (2-amidine propane) 2 hydrochlorates=0.5g of 2,2-azos, react 3 hours with 60 DEG C, obtain the aqueous liquid dispersion of polymer.With pure water, solid component concentration is regulated to 30% again.The monomer composition generating polymer is basically identical with the composition adding monomer.
Manufacture example 4
500mL autoclave adds mountain Yu base acrylate=47.5g, glycidyl methacrylate=2.5g, pure water=145g, tripropylene glycol=15g, acetylenediol polyoxyethylene addition product=1g, polyoxyethylene (EO:18) isotridecyl ether=2g, two-octadecyldimethyl ammonium chloride=2g, under agitation disperses 15 minutes with ultrasonic emulsification with 60 DEG C.After carrying out nitrogen displacement in autoclave, add double; two (2-amidine propane) 2 hydrochlorates=0.5g of 2,2-azos, react 3 hours with 60 DEG C, obtain the aqueous liquid dispersion of polymer.With pure water, solid component concentration is regulated to 30% again.The monomer composition generating polymer is basically identical with the composition adding monomer.
Manufacture example 5
500mL autoclave adds sterylacrylic acid ester=47.5g, glycidyl methacrylate=2.5g, pure water=145g, tripropylene glycol=15g, sorbitan monooleate=1.5g, polyoxyethylene (EO:18) second alkyl (C12-14) ether=2g, two-octadecyldimethyl ammonium chloride=1.5g, under agitation disperses 15 minutes with ultrasonic emulsification with 60 DEG C.After carrying out nitrogen displacement in autoclave, add double; two (2-amidine propane) 2 hydrochlorates=0.5g of 2,2-azos, react 3 hours with 60 DEG C, obtain the aqueous liquid dispersion of polymer.With pure water, solid component concentration is regulated to 30% again.The monomer composition generating polymer is basically identical with the composition adding monomer.
Manufacture example 6
500mL autoclave adds sterylacrylic acid ester=20g, mountain Yu base acrylate=15g, mountain Yu methyl acrylate=12.5g, glycidyl methacrylate=2.5g, pure water=145g, tripropylene glycol=15g, acetylenediol polyoxyethylene addition product=1g, polyoxyethylene (EO:18) isotridecyl ether=2g, two-octadecyldimethyl ammonium chloride=2g, under agitation disperses 15 minutes with ultrasonic emulsification with 60 DEG C.After carrying out nitrogen displacement in autoclave, add double; two (2-amidine propane) 2 hydrochlorates=0.5g of 2,2-azos, react 3 hours with 60 DEG C, obtain the aqueous liquid dispersion of polymer.With pure water, solid component concentration is regulated to 30% again.The monomer composition generating polymer is basically identical with the composition adding monomer.
Manufacture example 7
500mL autoclave adds sterylacrylic acid ester=20g, lauryl acrylate=30g, pure water=145g, tripropylene glycol=15g, acetylenediol polyoxyethylene addition product=1g, polyoxyethylene (EO:18) isotridecyl ether=2g, two-octadecyldimethyl ammonium chloride=2g, under agitation disperses 15 minutes with ultrasonic emulsification with 60 DEG C.After carrying out nitrogen displacement in autoclave, add double; two (2-amidine propane) 2 hydrochlorates=0.5g of 2,2-azos, react 3 hours with 60 DEG C, obtain the aqueous liquid dispersion of polymer.With pure water, solid component concentration is regulated to 30% again.The monomer composition generating polymer is basically identical with the composition adding monomer.
Manufacture example 8
500mL autoclave adds mountain Yu base acrylate=20g, lauryl acrylate=27.5g, hydroxyethyl methacrylic acid=2.5g, pure water=145g, tripropylene glycol=15g, acetylenediol polyoxyethylene addition product=1g, polyoxyethylene (EO:18) isotridecyl ether=2g, two-octadecyldimethyl ammonium chloride=2g, under agitation disperses 15 minutes with ultrasonic emulsification with 60 DEG C.After carrying out nitrogen displacement in autoclave, add double; two (2-amidine propane) 2 hydrochlorates=0.5g of 2,2-azos, react 3 hours with 60 DEG C, obtain the aqueous liquid dispersion of polymer.With pure water, solid component concentration is regulated to 30% again.The monomer composition generating polymer is basically identical with the composition adding monomer.
Manufacture example 9
500mL autoclave adds sterylacrylic acid ester=10g, mountain Yu base acrylate=10g, cetyl acrylate=27.5g, hydroxyethyl methacrylic acid=2.5g, pure water=145g, tripropylene glycol=15g, acetylenediol polyoxyethylene addition product=1g, polyoxyethylene (EO:18) lauryl ether=2.9g, octadecyl trimethyl ammonium chloride=1.1g, under agitation disperses 15 minutes with ultrasonic emulsification with 60 DEG C.After carrying out nitrogen displacement in autoclave, add double; two (2-amidine propane) 2 hydrochlorates=0.5g of 2,2-azos, react 3 hours with 60 DEG C, obtain the aqueous liquid dispersion of polymer.With pure water, solid component concentration is regulated to 30% again.The monomer composition generating polymer is basically identical with the composition adding monomer.
Manufacture example 10
500mL autoclave adds sterylacrylic acid ester=35g, glycidyl methacrylate=2.5g, pure water=145g, tripropylene glycol=15g, acetylenediol polyoxyethylene addition product=1g, polyoxyethylene (EO:18) isotridecyl ether=2g, two-octadecyldimethyl ammonium chloride=2g, under agitation disperses 15 minutes with ultrasonic emulsification with 60 DEG C.After carrying out nitrogen displacement in autoclave, add 12.5g vinyl chloride with press mode, and add double; two (2-amidine propane) 2 hydrochlorates=0.5g of 2,2-azos, react 3 hours with 60 DEG C, obtain the aqueous liquid dispersion of polymer.With pure water, solid component concentration is regulated to 30% again.The monomer composition generating polymer is basically identical with the composition adding monomer.
Manufacture example 11
500mL autoclave adds sterylacrylic acid ester=17.5g, mountain Yu base acrylate=17.5g, hydroxyethyl methacrylic acid=5g, pure water=145g, tripropylene glycol=15g, sorbitan monooleate=1.5g, polyoxyethylene (EO:18) second alkyl (C12-14) ether=2g, two-octadecyldimethyl ammonium chloride=1.5g, under agitation disperses 15 minutes with ultrasonic emulsification with 60 DEG C.After carrying out nitrogen displacement in autoclave, in the way of press-in, add 10g vinyl chloride, and add double; two (2-amidine propane) 2 hydrochlorates=0.5g of 2,2-azos, react 3 hours with 60 DEG C, obtain the aqueous liquid dispersion of polymer.With pure water, solid component concentration is regulated to 30% again.The monomer composition generating polymer is basically identical with the composition adding monomer.
Manufacture example 12
500mL autoclave adds sterylacrylic acid ester=30g, lauryl acrylate=10g, glycidyl methacrylate=2.5g, pure water=145g, tripropylene glycol=15g, acetylenediol polyoxyethylene addition product=1g, polyoxyethylene (EO:18) lauryl ether=2.9g, octadecyl trimethyl ammonium chloride=1.1g, under agitation disperses 15 minutes with ultrasonic emulsification with 60 DEG C.After carrying out nitrogen displacement in autoclave, in the way of press-in, add 7.5g vinyl chloride, and add double; two (2-amidine propane) 2 hydrochlorates=0.5g of 2,2-azos, react 3 hours with 60 DEG C, obtain the aqueous liquid dispersion of polymer.With pure water, solid component concentration is regulated to 30% again.The monomer composition generating polymer is basically identical with the composition adding monomer.
Manufacture example 13
500mL autoclave adds sterylacrylic acid ester=35g, glycidyl methacrylate=2.5g, pure water=145g, tripropylene glycol=15g, acetylenediol polyoxyethylene addition product=1g, polyoxyethylene (EO:18) isotridecyl ether=2g, two-octadecyldimethyl ammonium chloride=2g, under agitation disperses 15 minutes with ultrasonic emulsification with 60 DEG C.After carrying out nitrogen displacement in autoclave, in the way of press-in, add 12.5g vinylidene chloride, and add double; two (2-amidine propane) 2 hydrochlorates=0.5g of 2,2-azos, react 3 hours with 60 DEG C, obtain the aqueous liquid dispersion of polymer.With pure water, solid component concentration is regulated to 30% again.The monomer composition generating polymer is basically identical with the composition adding monomer.
Manufacture example 14
500mL autoclave adds sterylacrylic acid ester=20g, lauryl acrylate=17.5g, glycidyl methacrylate=2.5g, pure water=145g, tripropylene glycol=15g, sorbitan monooleate=1.5g, polyoxyethylene (EO:18) second alkyl (C12-14) ether=2g, two-octadecyldimethyl ammonium chloride=1.5g, under agitation disperses 15 minutes with ultrasonic emulsification with 60 DEG C.After carrying out nitrogen displacement in autoclave, in the way of press-in, add 10g vinyl chloride, and add double; two (2-amidine propane) 2 hydrochlorates=0.5g of 2,2-azos, react 3 hours with 60 DEG C, obtain the aqueous liquid dispersion of polymer.With pure water, solid component concentration is regulated to 30% again.The monomer composition generating polymer is basically identical with the composition adding monomer.
Manufacture example 15
500mL autoclave adds mountain Yu base acrylate=20g, lauryl acrylate=17.5g, glycidyl methacrylate=2.5g, pure water=145g, tripropylene glycol=15g, sorbitan monooleate=1.5g, polyoxyethylene (EO:18) second alkyl (C12-14) ether=2g, two-octadecyldimethyl ammonium chloride=1.5g, under agitation disperses 15 minutes with ultrasonic emulsification with 60 DEG C.After carrying out nitrogen displacement in autoclave, in the way of press-in, add 10g vinyl chloride, and add double; two (2-amidine propane) 2 hydrochlorates=0.5g of 2,2-azos, react 3 hours with 60 DEG C, obtain the aqueous liquid dispersion of polymer.With pure water, solid component concentration is regulated to 30% again.The monomer composition generating polymer is basically identical with the composition adding monomer.
Relatively manufacture example 1
500mL autoclave adds lauryl acrylate=50g, pure water=145g, tripropylene glycol=15g, sorbitan monooleate=1.5g, polyoxyethylene (EO:18) second alkyl (C12-14) ether=2g, two-octadecyldimethyl ammonium chloride=1.5g, under agitation disperses 15 minutes with ultrasonic emulsification with 60 DEG C.After carrying out nitrogen displacement in autoclave, add double; two (2-amidine propane) 2 hydrochlorates=0.5g of 2,2-azos, react 3 hours with 60 DEG C, obtain the aqueous liquid dispersion of polymer.With pure water, solid component concentration is regulated to 30% again.The monomer composition generating polymer is basically identical with the composition adding monomer.
Relatively manufacture example 2
500mL autoclave adds cetyl acrylate=50g, pure water=145g, tripropylene glycol=15g, sorbitan monooleate=1.5g, polyoxyethylene (EO:18) second alkyl (C12-14) ether=2g, two-octadecyldimethyl ammonium chloride=1.5g, under agitation disperses 15 minutes with ultrasonic emulsification with 60 DEG C.After carrying out nitrogen displacement in autoclave, add double; two (2-amidine propane) 2 hydrochlorates=0.5g of 2,2-azos, react 3 hours with 60 DEG C, obtain the aqueous liquid dispersion of polymer.With pure water, solid component concentration is regulated to 30% again.The monomer composition generating polymer is basically identical with the composition adding monomer.
Relatively manufacture example 3
500mL autoclave adds sterylacrylic acid ester=15g, lauryl acrylate=35g, pure water=145g, tripropylene glycol=15g, sorbitan monooleate=1.5g, polyoxyethylene (EO:18) second alkyl (C12-14) ether=2g, two-octadecyldimethyl ammonium chloride=1.5g, under agitation disperses 15 minutes with ultrasonic emulsification with 60 DEG C.After carrying out nitrogen displacement in autoclave, add double; two (2-amidine propane) 2 hydrochlorates=0.5g of 2,2-azos, react 3 hours with 60 DEG C, obtain the aqueous liquid dispersion of polymer.With pure water, solid component concentration is regulated to 30% again.The monomer composition generating polymer is basically identical with the composition adding monomer.
Relatively manufacture example 4
500mL autoclave adds sterylacrylic acid ester=50g, pure water=145g, tripropylene glycol=15g, sorbitan monooleate=2g, polyoxyethylene (EO:18) stearyl ether=2g, two-octadecyldimethyl ammonium chloride=1g, under agitation disperses 15 minutes with ultrasonic emulsification with 60 DEG C.After carrying out nitrogen displacement in autoclave, add double; two (2-amidine propane) 2 hydrochlorates=0.5g of 2,2-azos, react 3 hours with 60 DEG C, obtain the aqueous liquid dispersion of polymer.With pure water, solid component concentration is regulated to 30% again.The monomer composition generating polymer is basically identical with the composition adding monomer.
Relatively manufacture example 5
500mL autoclave adds sterylacrylic acid ester=50g, pure water=145g, tripropylene glycol=15g, acetylenediol polyoxyethylene addition product=0.25g, polyoxyethylene (EO:18) lauryl ether=3g, octadecyl trimethyl ammonium chloride=0.75g, under agitation disperses 15 minutes with ultrasonic emulsification with 60 DEG C.After carrying out nitrogen displacement in autoclave, add double; two (2-amidine propane) 2 hydrochlorates=0.5g of 2,2-azos, react 3 hours with 60 DEG C, obtain the aqueous liquid dispersion of polymer.With pure water, solid component concentration is regulated to 30% again.The monomer composition generating polymer is basically identical with the composition adding monomer.
Relatively manufacture example 6
500mL autoclave adds sterylacrylic acid ester=35g, glycidyl methacrylate=2.5g, pure water=145g, tripropylene glycol=15g, sorbitan monooleate=2g, polyoxyethylene (EO:18) stearyl ether=2g, two-octadecyldimethyl ammonium chloride=1g, under agitation disperses 15 minutes with ultrasonic emulsification with 60 DEG C.After carrying out nitrogen displacement in autoclave, in the way of press-in, add 12.5g vinyl chloride, add double; two (2-amidine propane) 2 hydrochlorates=0.5g of 2,2-azos, react 3 hours with 60 DEG C, obtain the aqueous liquid dispersion of polymer.With pure water, solid component concentration is regulated to 30% again.The monomer composition generating polymer is basically identical with the composition adding monomer.
Relatively manufacture example 7
500mL autoclave adds sterylacrylic acid ester=35g, glycidyl methacrylate=2.5g, pure water=145g, tripropylene glycol=15g, acetylenediol polyoxyethylene addition product=0.25g, polyoxyethylene (EO:18) lauryl ether=3g, octadecyl trimethyl ammonium chloride=0.75g, under agitation disperses 15 minutes with ultrasonic emulsification with 60 DEG C.After carrying out nitrogen displacement in autoclave, in the way of press-in, add 12.5g vinyl chloride, add double; two (2-amidine propane) 2 hydrochlorates=0.5g of 2,2-azos, react 3 hours with 60 DEG C, obtain the aqueous liquid dispersion of polymer.With pure water, solid component concentration is regulated to 30% again.The monomer composition generating polymer is basically identical with the composition adding monomer.
Manufacture example and the use raw material compared in manufacture example is shown in table 1.
Reference example 1 manufacture of agent (the fluorine system dial)
500ml reaction flask adds CF3CF2-(CF2CF2)n-CH2CH2OCOC(CH3)=CH2(n=2.0) 14.9g, sterylacrylic acid ester 43,46g, pure water 110g, dipropylene glycol methyl ether 18.62g, VARISOFT TA100 3.08g, stearyl trimethyl ammonium chloride 0.87g, polyoxyethylenelauryl ether (EO:18, EO represents ethylene oxide unit number) 2.1g, polyoxyethylene isotridecyl ether (EO:3) 0.65g, under agitation disperse 15 minutes with ultrasonic emulsification with 60 DEG C.After carrying out nitrogen displacement in reaction flask, add the solution of lauryl mercaptan 0.62g, double; two (2-amidine propane) the 2 hydrochlorate 0.31g and water 9g of 2,2-azos, react 5 hours with 60 DEG C, obtain the aqueous liquid dispersion (agent is dialled by fluorine system) of polymer.The composition of polymer is basically identical with the composition adding monomer.
Embodiment 1
It is diluted manufacturing the waterborne liquid 50g prepared in example 1 with tap water, prepares experimental liquid (1000g).Cloth (510mm × 205mm) is immersed in this experimental liquid, by mangle, processes 2 minutes with 160 DEG C with pin stenter.Cloth uses PET taffeta, nylon taffeta and jean.Various cloth it is divided into unwashed cloth and washs the cloth of 5 times, implementing spray water-repellancy test (washing resistance test).About hand test, mechanical stability test, implement with unwashed cloth.Show the result in table 2.
Embodiment 2～9 and comparative example 1～5
After processing similarly to Example 1, implement spray water-repellancy test (washing resistance test), hand test, mechanical stability test.Show the result in table 2.
Embodiment 10～15 and comparative example 6～7
With tap water, blocked isocyanate (solid component concentration 20%) 10g of waterborne liquid 50g and MDI system prepared in each manufacture example is diluted, prepares experimental liquid (1000g).Process similarly to Example 1 afterwards, carry out spray water-repellancy test (washing resistance test), mechanical stability test, peeling strength test.Show the result in table 2.
Embodiment 16
With tap water, the fluorine system prepared in prepared waterborne liquid 25g in manufacture example 1 and reference example 1 is dialled agent 25g to be diluted, prepare experimental liquid (1000g).Process similarly to Example 1 afterwards, implement spray water-repellancy test (washing resistance test), feel, mechanical stability test.Show the result in table 1.
Embodiment 17
Blocked isocyanate (solid component concentration 20%) 10g fluorine system prepared in waterborne liquid 25g prepared in manufacture example 10, reference example 1 being dialled agent 25g and MDI system with tap water is diluted, and prepares experimental liquid (1000g).Process similarly to Example 1 afterwards, carry out spray water-repellancy test (washing resistance test), mechanical stability test, peeling strength test, washing resistance test.Show the result in table 2.
[table 1]
Note)
Emulsifying agent 1: sorbitan monooleate/polyoxyethylene (EO:18) second alkyl (C12-14) ether/bis--octadecyldimethyl ammonium chloride=3/4/3 (weight ratio)
Emulsifying agent 2: acetylenediol polyoxyethylene addition product/polyoxyethylene (EO:18) isotridecyl ether/bis--octadecyldimethyl ammonium chloride=2/4/4 (weight ratio)
Emulsifying agent 3: acetylenediol polyoxyethylene addition product/polyoxyethylene (EO:18) lauryl ether/octadecyl trimethyl ammonium chloride=2/5.8/2.2 (weight ratio)
Emulsifying agent 4: sorbitan monooleate/polyoxyethylene (EO:18) stearyl ether/bis--octadecyldimethyl ammonium chloride=4/4/2 (weight ratio)
Emulsifying agent 5: acetylenediol polyoxyethylene addition product/polyoxyethylene (EO:18) lauryl ether/octadecyl trimethyl ammonium chloride=0.5/6/1.5 (weight ratio)
[table 2]
Industrial applicability
The inorganic agent of the present invention is suitably applied the base material of fibre and masonry (masonry) etc., gives excellent water-repellent oil-repellent to base material.
Other the mode of the present invention is as described below.
< 1 > water serial emulsion inorganic agent, it contains:
(1) polymer, it has, and to be derived from (a) relative to polymer be more than 40 weight %, formula: CH2=CA11-C (=O)-O-A12The repetitive of shown long-chain (methyl) acrylate monomer,
In formula, A11For hydrogen atom or methyl, A12Aliphatic alkyl for the straight or branched of carbon number 18～30；
(2) surfactant, it contains nonionic surfactant and cationic surface active agent, and the amount of cationic surface active agent is at more than 15 weight %；With
(3) moisture liquid medium.
< 2 > such as water serial emulsion inorganic agent described in < 1 >, wherein, polymer (1) also has and is derived from (b) formula: CH2=CA21-C (=O)-O-A22The repetitive of shown short chain (methyl) acrylate monomer,
In formula, A21For hydrogen atom or methyl, A22Aliphatic alkyl for the carbon number straight or branched less than 18.
< 3 > such as water serial emulsion inorganic agent described in < 1 > or < 2 >, wherein, polymer (1) also has the repetitive being derived from (c) non-fluorine cross-linkable monomer.
< 4 > such as water serial emulsion inorganic agent described in < 3 >, wherein, non-fluorine cross-linkable monomer (c) is have the compound of at least 2 alkene unsaturated double-bonds or for having the compound of at least 1 alkene unsaturated double-bond and at least 1 reactive group.
< 5 > such as water serial emulsion inorganic agent according to any one of < 1 >～< 4 >, wherein, polymer (1) has the repetitive being derived from (d) alkenyl halide monomer.
< 6 > such as water serial emulsion inorganic agent according to any one of < 1 >～< 4 >, wherein, polymer (1) does not have the repetitive being derived from (d) alkenyl halide monomer.
< 7 > such as water serial emulsion inorganic agent described in < 5 > or < 6 >, wherein, alkenyl halide monomer (d) is at least one in vinyl chloride and vinylidene chloride.
< 8 > such as water serial emulsion inorganic agent according to any one of < 1 >～< 7 >, wherein, the polymer (1) homopolymer without monomer has (methyl) acrylate monomer of the glass transition temperature of more than 50 DEG C and has (methyl) acrylate monomer of cyclic hydrocarbon group.
< 9 > such as water serial emulsion inorganic agent according to any one of < 1 >～< 8 >, wherein, polymer (1) is without fluorine atom.
< 10 > such as water serial emulsion inorganic agent according to any one of < 1 >～< 9 >, wherein, in polymer (1), relative to repetitive (a) 100 weight portion, the amount of repetitive (b) be 0～150 weight portion, repetitive (c) amount be 0～50 weight portion, repetitive (d) amount be 0～100 weight portion.
< 11 > such as water serial emulsion inorganic agent according to any one of < 1 >～< 10 >, wherein, nonionic surfactant is formula: R1O-(CH2CH2O)p-(R2O)q-R3Shown compound,
In formula, R1For the alkyl of carbon number 1～22, the thiazolinyl of carbon number 2～22 or acyl group, R2Independently, identical or different, for the alkylidene of carbon number more than 3 (such as 3～10), R3For the thiazolinyl of hydrogen atom, the alkyl of carbon number 1～22 or carbon number 2～22, p is the number of more than 2, and q is the number of 0 or more than 1.
< 12 > such as water serial emulsion inorganic agent according to any one of < 1 >～< 10 >, wherein, nonionic surfactant is the alkynol compound in the oxygen ethylidene addition product of alkynol and alkynol.
< 13 > such as water serial emulsion inorganic agent described in < 12 >, wherein, alkynol compound is formula: HO-CR11R12-C ≡ C-CR13R14-OH or HO-CR15R16Compound shown in-C ≡ C-H,
In formula, R11、R12、R13、R14、R15、R16Independently, identical or different, for the alkyl of hydrogen atom or carbon number 1～30.
< 14 > such as water serial emulsion inorganic agent according to any one of < 1 >～< 13 >, wherein, cationic surface active agent is formula: R21-N+(-R22)(-R23)(-R24)X-Shown compound,
In formula, R21、R22、R23And R24Independently, identical or different, for the alkyl of carbon number 1～30, X is anionic property group.
< 15 > such as water serial emulsion inorganic agent according to any one of < 1 >～< 14 >, wherein, fibre finish is possibly together with fluoropolymer.
< 16 > such as water serial emulsion inorganic agent according to any one of < 1 >～< 15 >, wherein, the ZETA current potential of water serial emulsion is more than+30mV.
< 17 > such as water serial emulsion inorganic agent according to any one of < 1 >～< 16 >, wherein, the dynamic surface tension of water serial emulsion is at below 55mN/m.
< 18 > such as water serial emulsion inorganic agent according to any one of < 1 >～< 17 >, it is fibre finish.
< 19 > such as water serial emulsion inorganic agent according to any one of < 1 >～< 18 >, it is water extraction oil extracticn agent or anti-fouling agent.
< 20 > method that fibre is processed, including step fibre processed with the water serial emulsion inorganic agent according to any one of < 1 >～< 19 >.
The fibre that < 21 > mono-kind processed with the water serial emulsion inorganic agent according to any one of < 1 >～< 19 >.

Claims (8)

1. a surface conditioning agent, it is water serial emulsion, and this surface conditioning agent is characterised by, contains:
(1) non-fluorinated polymer, it has and is derived from (a) formula: CH2=CA11-C (=O)-O-A12The repetitive of shown long-chain (methyl) acrylate monomer,
In formula, A11For hydrogen atom or methyl, A12Aliphatic alkyl for the straight or branched of carbon number 18～30；
(2) surfactant, it contains nonionic surfactant and cationic surface active agent, and the amount of cationic surface active agent relative to the total amount of nonionic surfactant and cationic surface active agent at more than 22 weight %；With
(3) moisture liquid medium.
2. surface conditioning agent as claimed in claim 1, it is characterised in that:
Non-fluorinated polymer (1) is without (methyl) acrylate monomer with cyclic hydrocarbon group.
3. surface conditioning agent as claimed in claim 1 or 2, it is characterised in that:
Nonionic surfactant is at least one in ether, ester, ester ether, alkanolamide, polyhydric alcohol and amine oxide,
Cationic surface active agent is at least one in amine, amine salt, quaternary ammonium salt, imidazoline and imidazoline salt.
4. the surface conditioning agent as according to any one of claims 1 to 3, it is characterised in that:
Surface conditioning agent does not contain fluoropolymer.
5. the surface conditioning agent as according to any one of claims 1 to 3, it is characterised in that:
Surface conditioning agent contains fluoropolymer.
6. the surface conditioning agent as according to any one of Claims 1 to 5, it is characterised in that:
Surface conditioning agent is water extraction oil extracticn agent or anti-fouling agent.
7. the method that fibre is processed, it is characterised in that:
Including step fibre processed with the surface conditioning agent according to any one of claim 1～6.
8. the fibre processed by the surface conditioning agent according to any one of claim 1～6.
CN201480063525.8A 2013-11-22 2014-11-20 Water system surface conditioning agent Active CN105765025B (en)

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JP2013-241991 2013-11-22
JP2013241991 2013-11-22
PCT/JP2014/080816 WO2015076348A1 (en) 2013-11-22 2014-11-20 Water-based surface treatment agent

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