CN107683317B - Surface treatment agent composition - Google Patents

Surface treatment agent composition Download PDF

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CN107683317B
CN107683317B CN201680037178.0A CN201680037178A CN107683317B CN 107683317 B CN107683317 B CN 107683317B CN 201680037178 A CN201680037178 A CN 201680037178A CN 107683317 B CN107683317 B CN 107683317B
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monomer
fluorine
carbon atoms
agent composition
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CN107683317A (en
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南晋一
福森正树
宫原正弘
井置正人
山本育男
榎本孝司
陈涛
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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
    • 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
    • C09D127/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Coating compositions based on derivatives of such polymers
    • C09D127/02—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Coating compositions based on derivatives of such polymers not modified by chemical after-treatment
    • C09D127/12—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Coating compositions based on derivatives of such polymers not modified by chemical after-treatment containing fluorine atoms
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D127/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Coating compositions based on derivatives of such polymers
    • C09D127/02—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Coating compositions based on derivatives of such polymers not modified by chemical after-treatment
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D133/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Coating compositions based on derivatives of such polymers
    • C09D133/04—Homopolymers or copolymers of esters
    • C09D133/14—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
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • 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
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • 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
    • 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

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Organic Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Wood Science & Technology (AREA)
  • Dispersion Chemistry (AREA)
  • Combustion & Propulsion (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
  • Materials Applied To Surfaces To Minimize Adherence Of Mist Or Water (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)

Abstract

The present invention provides a surface treatment agent composition, which contains: (I) a 1 st fluoropolymer having repeating units derived from a fluoromonomer (a) and repeating units derived from a halogenated olefin (b); (II) a 2 nd fluoropolymer having repeating units derived from the fluoromonomer (a) and not having repeating units derived from a halogenated olefin; and (III) a liquid medium.

Description

Surface treatment agent composition
Technical Field
The present invention relates to a treatment agent, and particularly to a surface treatment agent composition such as a water and oil repellent composition containing a fluoropolymer mixture. More specifically, the present invention relates to a water-and oil-repellent composition which is excellent in water repellency, oil repellency, and stain resistance to fiber products (e.g., carpets), paper, nonwoven fabrics, stone materials, electrostatic filters, dust masks, and fuel cell parts, and which is excellent in high processing durability particularly in continuous water-and oil-repellent processing of fibers.
Background
Various fluorine-containing compounds have been proposed. The fluorine-containing compound has an advantage of excellent properties such as heat resistance, oxidation resistance and weather resistance. Fluorine-containing compounds are used, for example, as water-and oil-repellent agents and antifouling agents, taking advantage of their low free energy, i.e., their poor adhesion.
Examples of the fluorine-containing compound that can be used as a water-and oil-repellent agent include a fluorine-containing polymer having a (meth) acrylate having a fluoroalkyl group as a constituent monomer. In practical treatment of fibers with a surface treatment agent, it has been revealed from various research results so far that not a static contact angle but a dynamic contact angle, particularly a receding contact angle is important as the surface characteristics. That is, the advancing contact angle of water is not dependent on the number of carbon atoms of the side chain of the fluoroalkyl group, but the receding contact angle of water shows that the receding contact angle is significantly smaller in the case where the number of carbon atoms is 7 or less than in the case where the number of carbon atoms of the side chain is 8 or more. In contrast, the X-ray analysis showed that crystallization of the side chain occurred when the number of carbon atoms in the side chain was 7 or more. It is known that practical water repellency has a correlation with crystallinity of a side chain, and that mobility of a surface treatment agent molecule is an important cause of exhibiting practical performance (for example, proChuanlong Mao, FINE CHEMICAL (ファインケミカル), Vol23, No.6, P12 (1994)). For the above reasons, there is a problem that a (meth) acrylate polymer having a fluoroalkyl group having a side chain with a carbon number of 7 or less (particularly 6 or less) has low crystallinity of the side chain, and therefore, practical performance cannot be directly satisfied. In addition, continuous processing is generally performed in water-repellent oil-repellent processing, and a water-repellent oil-repellent agent having high processing durability is demanded from the viewpoint of drainage and productivity.
Japanese patent application laid-open No. 2001-98257 discloses a composition containing, as essential components, a polymer (A) containing polymerized units of a polymerizable monomer having a polyfluoroalkyl group, a surfactant (B) having a specific Dellavian wetting time, and an aqueous medium (C). Jp 2004-262970 a discloses a water-and oil-repellent aqueous composition containing a fluorine-based water-and oil-repellent agent (a), an emulsion (B) containing paraffin and carboxyl group-containing polyethylene, and an organic acid (C).
In these patents, the process continuity is not described.
Documents of the prior art
Patent document
Patent document 1: japanese patent laid-open publication No. 2001-98257
Patent document 2: japanese patent laid-open publication No. 2004-262970
Disclosure of Invention
Problems to be solved by the invention
One object of the present invention is: provided is a surface treatment agent composition which is excellent in the processing continuity of water-repellent oil-repellent processing of fibers and the like.
Means for solving the problems
The present invention relates to a surface treatment agent composition containing:
(I) a 1 st fluoropolymer having repeating units derived from a fluoromonomer (a) and repeating units derived from a halogenated olefin (b);
(II) a 2 nd fluoropolymer having repeating units derived from the fluoromonomer (a) and not having repeating units derived from a halogenated olefin; and
(III) a liquid medium.
Effects of the invention
The surface treatment agent composition of the present invention is excellent in the processing durability in water-repellent and oil-repellent processing.
According to the present invention, excellent water repellency, oil repellency, stain resistance and stain release properties, for example, excellent durability of water and oil repellency can be obtained.
The surface treatment agent composition of the present invention can be used as a water-and oil-repellent agent composition, an antifouling agent composition and/or a soil release agent composition.
Detailed Description
(1) Fluorine-containing polymer
In the present invention, the fluoropolymer is a combination of the 1 st fluoropolymer and the 2 nd fluoropolymer.
As the monomers constituting the repeating units of the fluorine-containing polymer, a fluorine-containing monomer (a), a halogenated olefin monomer (b), and a monomer (c) other than the monomers (a) and (b) are used.
In the present invention, the 1 st fluoropolymer and the 2 nd fluoropolymer function as active ingredients of a water-and oil-repellent agent, an antifouling agent and a soil release agent.
(a) Fluorine-containing monomer
The fluorine-containing monomer is generally a polymerizable compound having a perfluoroalkyl group or a perfluoroalkenyl group and an acrylic group or a methacrylic group or an α -substituted acrylic group.
The fluoromonomer (a) may be, for example, of the general formula: CH (CH)2A compound represented by ═ C (-X) -C (═ O) -Y-Z-rf (i).
[ wherein X is a hydrogen atom, a monovalent organic group or a halogen atom,
y is-O-or-NH-,
z is a direct bond or a divalent organic group,
rf is a C1-20 fluoroalkyl group. ]
The fluoromonomer (a) is preferably of the formula: CH (CH)2A compound represented by ═ C (-X) -C (═ O) -Y-Z-rf (i).
[ wherein X represents a hydrogen atom, a linear or branched alkyl group having 1 to 21 carbon atoms, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, CFX1X2Group (wherein, X)1And X2Is a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom or an iodine atom. ) A cyano group, a straight-chain or branched fluoroalkyl group having 1 to 21 carbon atoms, a substituted or unsubstituted benzyl group, a substituted or unsubstituted phenyl group,
y is-O-or-NH-,
z is direct bonding; or
A linear or branched aliphatic group (particularly an alkylene group) having 1 to 20 carbon atoms, for example, a group represented by the formula- (CH)2)x- (in which x is 1)10) a group shown in (a); or
An aromatic group or cyclic aliphatic group having 6 to 30 carbon atoms; or
formula-R2(R1)N-SO2Or formula-R2(R1) A group represented by N-CO- (wherein R is1Is an alkyl group having 1 to 10 carbon atoms, R2Is a linear or branched alkylene group having 1 to 10 carbon atoms. ) (ii) a Or
formula-CH2CH(OR3)CH2-(Ar-O)p- (in the formula, R3Represents a hydrogen atom or an acyl group having 1 to 10 carbon atoms (for example, a formyl group, an acetyl group or the like), Ar represents an arylene group having a substituent as required, and p represents 0 or 1. ) A group shown; or
formula-CH2-Ar-(O)q- (wherein Ar is an arylene group which may have a substituent, and q is 0 or 1.); or
-(CH2)m-SO2-(CH2)n-radical or- (CH)2)m-S-(CH2)nA group (wherein m is 1 to 10 and n is 0 to 10.),
rf is a linear or branched fluoroalkyl group having 1 to 20 carbon atoms. ]
Representative examples of X are Cl, Br, I, F, CN, CF3Preferably Cl., particularly when the α -position is a chlorine atom, the practical water repellency (particularly shower water repellency) of the surface treatment agent composition is excellent.
In the fluorine-containing monomer, the Rf group is preferably a perfluoroalkyl group. The Rf group preferably has 1 to 12 carbon atoms, for example, 1 to 6 carbon atoms, particularly preferably 4 to 6 carbon atoms, and more preferably 6 carbon atoms. Examples of Rf groups are-CF3、-CF2CF3、-CF2CF2CF3、-CF(CF3)2、-CF2CF2CF2CF3、-CF2CF(CF3)2、-C(CF3)3、-(CF2)4CF3、-(CF2)2CF(CF3)2、-CF2C(CF3)3、-CF(CF3)CF2CF2CF3、-(CF2)5CF3、-(CF2)3CF(CF3)2、-(CF2)4CF(CF3)2、-C8F17And the like.
Z is preferably an aliphatic group having 1 to 10 carbon atoms, an aromatic group having 6 to 18 carbon atoms or a cycloaliphatic group, -CH2CH2N(R1)SO2-radical (wherein, R1Is an alkyl group having 1 to 4 carbon atoms. ) -CH2CH(OZ1)CH2-(Ph-O)pA radical (wherein, Z1Is a hydrogen atom or acetyl group, Ph is phenylene, and p is 0 or 1. ) - (CH)2)n-Ph-O-group (wherein Ph is phenylene and n is 0 to 10.), - (CH)2)m-SO2-(CH2)n-radical or- (CH)2)m-S-(CH2)nA group (wherein m is 1 to 10 and n is 0 to 10). The aliphatic group is preferably an alkylene group (particularly, having 1 to 4 carbon atoms, for example, 1 or 2). The aromatic group or the cycloaliphatic group may be substituted or unsubstituted. S radical or SO2The group may be directly bonded to the Rf group.
Specific examples of the fluorine-containing monomer (a) include, but are not limited to, the following.
CH2＝C(－H)－C(＝O)－O－(CH2)2－Rf
CH2＝C(－H)－C(＝O)－O－C6H4－Rf
CH2＝C(－Cl)－C(＝O)－O－(CH2)2－Rf
CH2＝C(－H)－C(＝O)－O－(CH2)2N(－CH3)SO2－Rf
CH2＝C(－H)－C(＝O)－O－(CH2)2N(－C2H5)SO2－Rf
CH2＝C(－H)－C(＝O)－O－CH2CH(－OH)CH2－Rf
CH2＝C(－H)－C(＝O)－O－CH2CH(－OCOCH3)CH2－Rf
CH2＝C(－H)－C(＝O)－O－(CH2)2－S－Rf
CH2＝C(－H)－C(＝O)－O－(CH2)2－S－(CH2)2－Rf
CH2＝C(－H)－C(＝O)－O－(CH2)3－SO2－Rf
CH2＝C(－H)－C(＝O)－O－(CH2)2－SO2－(CH2)2－Rf
CH2＝C(－H)－C(＝O)－NH－(CH2)2－Rf
CH2＝C(－CH3)－C(＝O)－O－(CH2)2－S－Rf
CH2＝C(－CH3)－C(＝O)－O－(CH2)2－S－(CH2)2－Rf
CH2＝C(－CH3)－C(＝O)－O－(CH2)3－SO2－Rf
CH2＝C(－CH3)－C(＝O)－O－(CH2)2－SO2－(CH2)2－Rf
CH2＝C(－CH3)－C(＝O)－NH－(CH2)2－Rf
CH2＝C(－F)－C(＝O)－O－(CH2)2－S－Rf
CH2＝C(－F)－C(＝O)－O－(CH2)2－S－(CH2)2－Rf
CH2＝C(－F)－C(＝O)－O－(CH2)2－SO2－Rf
CH2＝C(－F)－C(＝O)－O－(CH2)2－SO2－(CH2)2－Rf
CH2＝C(－F)－C(＝O)－NH－(CH2)2－Rf
CH2＝C(－Cl)－C(＝O)－O－(CH2)2－S－Rf
CH2＝C(－Cl)－C(＝O)－O－(CH2)2－S－(CH2)2－Rf
CH2＝C(－Cl)－C(＝O)－O－(CH2)2－SO2－Rf
CH2＝C(－Cl)－C(＝O)－O－(CH2)2－SO2－(CH2)2－Rf
CH2＝C(－Cl)－C(＝O)－NH－(CH2)2－Rf
CH2＝C(－CF3)－C(＝O)－O－(CH2)2－S－Rf
CH2＝C(－CF3)－C(＝O)－O－(CH2)2－S－(CH2)2－Rf
CH2＝C(－CF3)－C(＝O)－O－(CH2)2－SO2－Rf
CH2＝C(－CF3)－C(＝O)－O－(CH2)2－SO2－(CH2)2－Rf
CH2＝C(－CF3)－C(＝O)－NH－(CH2)2－Rf
CH2＝C(－CF2H)－C(＝O)－O－(CH2)2－S－Rf
CH2＝C(－CF2H)－C(＝O)－O－(CH2)2－S－(CH2)2－Rf
CH2＝C(－CF2H)－C(＝O)－O－(CH2)2－SO2－Rf
CH2＝C(－CF2H)－C(＝O)－O－(CH2)2－SO2－(CH2)2－Rf
CH2＝C(－CF2H)－C(＝O)－NH－(CH2)2－Rf
CH2＝C(－CN)－C(＝O)－O－(CH2)2－S－Rf
CH2＝C(－CN)－C(＝O)－O－(CH2)2－S－(CH2)2－Rf
CH2＝C(－CN)－C(＝O)－O－(CH2)2－SO2－Rf
CH2＝C(－CN)－C(＝O)－O－(CH2)2－SO2－(CH2)2－Rf
CH2＝C(－CN)－C(＝O)－NH－(CH2)2－Rf
CH2＝C(－CF2CF3)－C(＝O)－O－(CH2)2－S－Rf
CH2＝C(－CF2CF3)－C(＝O)－O－(CH2)2－S－(CH2)2－Rf
CH2＝C(－CF2CF3)－C(＝O)－O－(CH2)2－SO2－Rf
CH2＝C(－CF2CF3)－C(＝O)－O－(CH2)2－SO2－(CH2)2－Rf
CH2＝C(－CF2CF3)－C(＝O)－NH－(CH2)2－Rf
CH2＝C(－F)－C(＝O)－O－(CH2)3－S－Rf
CH2＝C(－F)－C(＝O)－O－(CH2)3－S－(CH2)2－Rf
CH2＝C(－F)－C(＝O)－O－(CH2)3－SO2－Rf
CH2＝C(－F)－C(＝O)－O－(CH2)3－SO2－(CH2)2－Rf
CH2＝C(－F)－C(＝O)－NH－(CH2)3－Rf
CH2＝C(－Cl)－C(＝O)－O－(CH2)3－S－Rf
CH2＝C(－Cl)－C(＝O)－O－(CH2)3－S－(CH2)2－Rf
CH2＝C(－Cl)－C(＝O)－O－(CH2)3－SO2－Rf
CH2＝C(－Cl)－C(＝O)－O－(CH2)3－SO2－(CH2)2－Rf
CH2＝C(－CF3)－C(＝O)－O－(CH2)3－S－Rf
CH2＝C(－CF3)－C(＝O)－O－(CH2)3－S－(CH2)2－Rf
CH2＝C(－CF3)－C(＝O)－O－(CH2)3－SO2－Rf
CH2＝C(－CF3)－C(＝O)－O－(CH2)3－SO2－(CH2)2－Rf
CH2＝C(－CF2H)－C(＝O)－O－(CH2)3－S－Rf
CH2＝C(－CF2H)－C(＝O)－O－(CH2)3－S－(CH2)2－Rf
CH2＝C(－CF2H)－C(＝O)－O－(CH2)3－SO2－Rf
CH2＝C(－CF2H)－C(＝O)－O－(CH2)3－SO2－(CH2)2－Rf
CH2＝C(－CN)－C(＝O)－O－(CH2)3－S－Rf
CH2＝C(－CN)－C(＝O)－O－(CH2)3－S－(CH2)2－Rf
CH2＝C(－CN)－C(＝O)－O－(CH2)3－SO2－Rf
CH2＝C(－CN)－C(＝O)－O－(CH2)3－SO2－(CH2)2－Rf
CH2＝C(－CF2CF3)－C(＝O)－O－(CH2)3－S－Rf
CH2＝C(－CF2CF3)－C(＝O)－O－(CH2)3－S－(CH2)2－Rf
CH2＝C(－CF2CF3)－C(＝O)－O－(CH2)3－SO2－Rf
CH2＝C(－CF2CF3)－C(＝O)－O－(CH2)2－SO2－(CH2)2－Rf
[ in the formula, Rf is a C1-20 fluoroalkyl group. ]
(b) Halogenated olefin monomer
The halogenated olefin monomer (halogenated olefin) preferably has no fluorine atom.
The halogenated olefin is preferably an olefin having 2 to 20 carbon atoms substituted with 1 to 10 chlorine, bromine or iodine atoms. The halogenated olefin is preferably a C2-20 chlorinated olefin, and particularly preferably a C2-5 olefin having 1-5 chlorine atoms. Preferred specific examples of the halogenated olefin are halogenated ethylenes such as vinyl chloride, vinyl bromide, vinyl iodide; vinylidene halides, such as vinylidene chloride, vinylidene bromide, vinylidene iodide. Vinyl chloride and vinylidene chloride are preferred, vinyl chloride being particularly preferred.
(c) Other monomers
The monomers (c) other than the monomers (a) and (b) are preferably free of fluorine. Examples of the other monomer (c) include: a non-fluorine non-crosslinkable monomer (c1) and a non-fluorine crosslinkable monomer (c 2).
(c1) Non-fluorine non-crosslinking monomer
The non-fluorine non-crosslinkable monomer (c1) is a monomer containing no fluorine atom. The non-fluorine non-crosslinkable monomer (c1) has no crosslinkable functional group. The non-fluorine non-crosslinkable monomer (c1) is not crosslinkable, unlike the crosslinkable monomer (c 2). The non-fluorine non-crosslinkable monomer (c1) is preferably a non-fluorine monomer having a carbon-carbon double bond. The non-fluorine non-crosslinkable monomer (c1) is preferably a vinyl monomer containing no fluorine. The non-fluorine non-crosslinkable monomer (c1) is usually a compound having 1 carbon-carbon double bond.
Preferred non-fluorine non-crosslinking monomers (c1) are of the formula: CH (CH)2A compound represented by CA-T.
[ wherein A is a hydrogen atom, a methyl group or a halogen atom other than a fluorine atom (for example, a chlorine atom, a bromine atom and an iodine atom),
t is a hydrogen atom, a chain or cyclic hydrocarbon group having 1 to 30 carbon atoms, or a chain or cyclic organic group having 1 to 31 carbon atoms and having an ester bond. ]
Examples of the chain or ring-like hydrocarbon group having 1 to 30 carbon atoms include a straight chain or branched aliphatic hydrocarbon group having 1 to 30 carbon atoms, a ring-like aliphatic group having 4 to 30 carbon atoms, an aromatic hydrocarbon group having 6 to 30 carbon atoms, and an araliphatic hydrocarbon group having 7 to 30 carbon atoms.
Examples of the chain or cyclic organic group having 1 to 31 carbon atoms and having an ester bond are — C (═ O) -O-Q and — O-C (═ O) -Q (here, Q is a linear or branched aliphatic hydrocarbon group having 1 to 30 carbon atoms, a cyclic aliphatic group having 4 to 30 carbon atoms, an aromatic hydrocarbon group having 6 to 30 carbon atoms, or an aromatic aliphatic hydrocarbon group having 7 to 30 carbon atoms).
Preferable examples of the non-fluorine-containing non-crosslinkable monomer (c1) include, for example, ethylene, vinyl acetate, acrylonitrile, styrene, polyethylene glycol (meth) acrylate, polypropylene glycol (meth) acrylate, methoxypolyethylene glycol (meth) acrylate, methoxypolypropylene glycol (meth) acrylate and vinyl alkyl ether. The non-fluorine non-crosslinkable monomer (c1) is not limited to these examples.
The non-fluorine non-crosslinkable monomer (c1) may be a (meth) acrylate having an alkyl group. The number of carbon atoms of the alkyl group may be 1 to 30, for example, 6 to 30 (for example, 10 to 30). For example, the non-fluorine non-crosslinkable monomer (c1) may be of the general formula: CH (CH)2＝CA1COOA2The acrylate shown.
[ in the formula, A1A halogen atom other than a hydrogen atom, a methyl group or a fluorine atom (for example, a chlorine atom, a bromine atom and an iodine atom),
A2is CnH2n+1And (n is 1 to 30).]
A2Preferred examples of the (B) are lauryl, stearyl and behenyl.
The non-fluorine non-crosslinkable monomer (c1) may be a (meth) acrylate monomer having a cyclic hydrocarbon group.
The cyclic hydrocarbyl group-containing acrylate monomer is preferably of the formula: CH (CH)2＝CA21-C(＝O)-O-A22The compounds shown.
[ in the formula, A21Is a hydrogen atom or a methyl group,
A22a cyclic hydrocarbon-containing group having 4 to 30 carbon atoms.]
The cyclic hydrocarbon group-containing acrylate monomer is a monomer having a homopolymer with a high glass transition temperature (for example, 50 ℃ or higher, particularly 80 ℃ or higher).
The cyclic hydrocarbon group-containing acrylate monomer does not have a fluoroalkyl group. The cyclic hydrocarbon group-containing acrylate monomer may also contain a fluorine atom, but preferably contains no fluorine atom.
A21Methyl is particularly preferred.
A22The hydrocarbon group may have a chain group (for example, a linear or branched hydrocarbon group). Examples of the cyclic hydrocarbon group include: saturated or unsaturated monocyclic groups, polycyclic groups, bridged cyclic groups, and the like. The cyclic hydrocarbon group is preferably saturated. The number of carbon atoms of the cyclic hydrocarbon group is 4 to 30, preferably 6 to 20. 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, a carbon atom7 to 20 aromatic aliphatic groups. The number of carbon atoms of the cyclic hydrocarbon group is particularly preferably 15 or less, for example 12 or less. The cyclic hydrocarbon group is preferably a saturated cyclic aliphatic group. Specific examples of the cyclic hydrocarbon group include cyclohexyl, tert-butylcyclohexyl, isobornyl, dicyclopentyl, dicyclopentenyl and adamantyl.
Specific examples of the cyclic hydrocarbon group-containing acrylate monomer include: cyclohexyl (meth) acrylate, t-butylcyclohexyl (meth) acrylate, benzyl (meth) acrylate, isobornyl (meth) acrylate, dicyclopentanyl (meth) acrylate, dicyclopentenyl (meth) acrylate, dicyclopentenyloxyethyl (meth) acrylate, tricyclopentanyl (meth) acrylate, adamantyl (meth) acrylate, 2-methyl-2-adamantyl (meth) acrylate, and 2-ethyl-2-adamantyl (meth) acrylate.
By the presence of the cyclic hydrocarbon group-containing acrylate monomer, the water repellency and oil repellency provided by the copolymer become high.
(c2) Non-fluorine crosslinkable monomer
The fluoropolymer of the present invention may have a repeating unit derived from the non-fluorine crosslinkable monomer (c 2). The non-fluorine crosslinkable monomer (c2) is a monomer containing no fluorine atom. The non-fluorine crosslinkable monomer (c2) may be a compound having at least 2 reactive groups and/or carbon-carbon double bonds and containing no fluorine. The non-fluorine crosslinkable monomer (c2) may be a compound having at least 2 carbon-carbon double bonds or a compound having at least 1 carbon-carbon double bond and at least 1 reactive group. Examples of reactive groups are hydroxyl, epoxy, chloromethyl, blocked isocyanate, amino, carboxyl, and the like. The non-fluorine crosslinkable monomer (c2) may be a mono (meth) acrylate, di (meth) acrylate or mono (meth) acrylamide having a reactive group. Alternatively, the non-fluorine crosslinkable monomer (c2) may be a di (meth) acrylate.
Examples of the non-fluorine crosslinkable monomer (c2) include: diacetone (meth) acrylamide, N-methylol (meth) acrylamide, methylol (meth) acrylate, hydroxyethyl (meth) acrylate, 3-chloro-2-hydroxypropyl (meth) acrylate, 2-acetoacetoxyethyl (meth) acrylate, butadiene, isoprene, chloroprene, glycidyl (meth) acrylate, 1, 6-hexanediol di (meth) acrylate, neopentyl glycol di (meth) acrylate, and the like.
By copolymerizing the non-fluorine non-crosslinkable monomer (c1) and/or the non-fluorine crosslinkable monomer (c2), various properties such as water-and oil-repellency, stain-proofing property, and cleaning resistance, washing resistance, solubility in a solvent, hardness, and touch of these properties can be improved as required.
In the present specification, in the case of being simply referred to as "acrylate" or "acrylamide", not only the compound having a hydrogen atom at position α but also a compound having a hydrogen atom at position α substituted with another group (for example, a monovalent organic group including a methyl group or a halogen atom) is included.
The monomer (a), the monomer (b) and the monomer (c) (for example, each of the monomers (c1) and (c 2)) may be used alone or in combination of 2 or more.
The amounts of the respective monomers in the 1 st fluoropolymer are as follows.
The amount of the fluoromonomer (a) in the 1 st fluoropolymer may be 20 to 100% by weight, preferably 30 to 90% by weight, based on the fluoropolymer.
In the 1 st fluorine-containing polymer, the amount of the halogenated olefin monomer (b) is 5 to 300 parts by weight, for example, 10 to 200 parts by weight, particularly 20 to 100 parts by weight, particularly 30 to 80 parts by weight, and the amount of the other monomer (c) may be 0 to 800 parts by weight, for example, 1 to 300 parts by weight, particularly 2 to 200 parts by weight, particularly 3 to 100 parts by weight, based on 100 parts by weight of the fluorine-containing monomer (a).
In the 1 st fluorine-containing polymer, the amount of the non-fluorine non-crosslinkable monomer (c1) may be 0 to 500 parts by weight, for example, 1 to 300 parts by weight, particularly 2 to 200 parts by weight, particularly 3 to 100 parts by weight, and the amount of the non-fluorine crosslinkable monomer (c2) may be 0 to 80 parts by weight, for example, 0 to 50 parts by weight, particularly 0.1 to 30 parts by weight, particularly 1 to 20 parts by weight, relative to 100 parts by weight of the fluorine-containing monomer (a).
The amounts of the respective monomers in the 2 nd fluoropolymer are as follows.
In the 2 nd fluoropolymer, the amount of the fluoromonomer (a) may be 20 to 100% by weight, preferably 30 to 90% by weight, based on the fluoropolymer.
The 2 nd fluoropolymer has no repeating units derived from a halogenated olefin.
The amount of the other monomer (c) in the 2 nd fluoropolymer may be 0 to 800 parts by weight, for example 1 to 300 parts by weight, particularly 2 to 200 parts by weight, particularly 3 to 100 parts by weight, relative to 100 parts by weight of the monomer (a).
In the 2 nd fluorine-containing polymer, the amount of the non-fluorine non-crosslinkable monomer (c1) may be 0 to 500 parts by weight, for example, 1 to 300 parts by weight, particularly 2 to 200 parts by weight, particularly 3 to 100 parts by weight, based on 100 parts by weight of the fluorine-containing monomer (a). The amount of the non-fluorine crosslinkable monomer (c2) may be 0 to 80 parts by weight, for example, 0 to 50 parts by weight, particularly 0.1 to 30 parts by weight, particularly 1 to 20 parts by weight.
The fluorine-containing monomer (a) and the other monomer (c) in the 1 st fluorine-containing polymer and the 2 nd fluorine-containing polymer may be the same or different, respectively.
The weight ratio of the 1. sup. th fluoropolymer to the 2. sup. nd fluoropolymer in the surface treatment composition may be 5: 95 to 95: 5, for example, 20: 80 to 20: 80.
In the mixture of the 1 st fluoropolymer and the 2 nd fluoropolymer, generally, the molecules of the 1 st fluoropolymer and the molecules of the 2 nd fluoropolymer are not chemically bonded.
(2) Surface active agent
In the treatment agent of the present invention, the surfactant includes one or both of a nonionic surfactant and a cationic surfactant. Further, the surfactant may contain an amphoteric surfactant. The surfactant is preferably free of anionic surfactants.
(2-1) nonionic surfactant
The nonionic surfactant is a nonionic surfactant having an oxyalkylene group. The number of carbon atoms of the alkylene group in the oxyalkylene group is preferably 2 to 10. The number of oxyalkylene groups in the molecule of the nonionic surfactant is preferably 2 to 100 in general.
The nonionic surfactant may be an alkylene oxide adduct of a linear and/or branched aliphatic (saturated and/or unsaturated) group, a polyalkylene glycol ester of a linear and/or branched fatty acid (saturated and/or unsaturated), a Polyoxyethylene (POE)/polyoxypropylene (POP) copolymer (random copolymer or block copolymer), an alkylene oxide adduct of acetylene glycol, or the like. Among them, the structures of the alkylene oxide addition moiety and the polyalkylene glycol moiety are preferably Polyoxyethylene (POE), polyoxypropylene (POP) or POE/POP copolymer (which may be a random copolymer or a block copolymer).
In addition, the nonionic surfactant is preferably a structure containing no aromatic group in view of environmental problems (biodegradability, environmental hormone, etc.).
The nonionic surfactant can be of the formula: r1O-(CH2CH2O)p-(R2O)q-R3The compounds shown.
[ in the formula, R1Is alkyl with 1-22 carbon atoms or alkenyl or acyl with 2-22 carbon atoms, R2An alkylene group having 3 or more carbon atoms (e.g., 3 to 10), R3Is a hydrogen atom, an alkyl group having 1 to 22 carbon atoms or an alkenyl group having 2 to 22 carbon atoms, p is a number of 2 or more, and q is a number of 0 or 1 or more.]
R1Preferably 8 to 20 carbon atoms, and particularly preferably 10 to 18 carbon atoms. As R1Preferred specific examples of (3) include: lauryl, tridecyl, oleyl.
R2Examples of (B) are propylene and butylene.
In the nonionic surfactant, p may be a number of 3 or more (for example, 5 to 200). q may be a number of 2 or more (e.g., 5 to 200). Namely, - (R)2O)qPolyoxyalkylene chains can be formed.
The nonionic surfactant may be a polyoxyethylene alkylene alkyl ether containing a hydrophilic polyoxyethylene chain and a hydrophobic oxyalkylene chain (in particular, a polyoxyalkylene chain) in the center. Examples of the hydrophobic oxyalkylene chain include: oxypropylene chains, oxybutylene chains, oxystyrene chains, and the like, among which, oxypropylene chains are preferred.
Preferred nonionic surfactants are of the formula: r1O-(CH2CH2O)pA surfactant represented by-H.
[ in the formula, R1And p and R as defined above1And p have the same meaning.]
Specific examples of the nonionic surfactant are
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-C12H25。
[ in the formula, p and q have the same meanings as those of p and q described above. ]
Specific examples of the nonionic surfactant may include ethylene oxide and hexylphenol, isooctylphenol, hexadecanol, oleic acid, alkane (C)12-C16) Thiol, sorbitan mono fatty acid (C)7-C19) Or alkyl (C)12-C18) And condensation products of amines and the like.
The proportion of the polyoxyethylene segment may be 5 to 80% by weight, for example, 30 to 75% by weight, particularly 40 to 70% by weight, based on the molecular weight of the nonionic surfactant (copolymer).
The average molecular weight of the nonionic surfactant is usually 300 to 5,000, for example 500 to 3,000.
The nonionic surfactant may be used alone in 1 kind, or may be used in combination of 2 or more kinds.
The nonionic surfactant is preferably a combination of 2 or more. In combinations of 2 or more, at least 1 nonionic surfactant can be R1Radical (and/or R)3Radical) is a branched alkyl radical (e.g. isotridecyl radical)1O-(CH2CH2O)p-(R2O)q-R3[ especially R ]1O-(CH2CH2O)p-H]The compounds shown. R1The amount of the nonionic surfactant having a branched alkyl group may be 5 to 100 parts by weight, for example, 8 to 50 parts by weight, particularly, 5 to 100 parts by weight based on 100 parts by weight of the total amount of the nonionic surfactants (B2)10 to 40 parts by weight. In combinations of 2 or more, the remaining nonionic surfactant may be R1Radical (and/or R)3Alkyl) is a (saturated and/or unsaturated) straight chain alkyl (e.g. lauryl (n-lauryl)) R1O-(CH2CH2O)p-(R2O)q-R3[ especially R ]1O-(CH2CH2O)p-H]The compounds shown.
Examples of the nonionic surfactant include: polyoxyethylene alkyl ethers, polyoxyethylene alkylphenyl ethers, polyoxyethylene fatty acid esters, sorbitan fatty acid esters, polyoxyethylene sorbitol fatty acid esters, glycerin fatty acid esters, polyoxyethylene glycerin fatty acid esters, polyglycerin fatty acid esters, sucrose fatty acid esters, polyoxyethylene alkylamines, polyoxyethylene fatty acid amides, fatty acid alkylolamides, acetylene glycols, ethylene oxide adducts of acetylene glycols, polyethylene glycol polypropylene glycol block copolymers, and the like.
Since the dynamic surface tension of the aqueous emulsion is low (that is, the aqueous emulsion easily penetrates into a substrate), an acetylene alcohol (particularly, acetylene glycol) or an oxyethylene adduct of an acetylene alcohol (particularly, acetylene glycol) is preferable as the nonionic surfactant.
Preferred nonionic surfactants are alcohols having an unsaturated triple bond or alkylene oxide adducts of the alcohols (both the alcohols and the alkylene oxide adducts are referred to as "acetylene alcohol compounds"). Particularly preferred nonionic surfactants are alkylene oxide adducts of monohydric or polyhydric alcohols having an unsaturated triple bond.
The acetylene alcohol compound is a compound containing 1 or more triple bonds and 1 or more hydroxyl groups. The acetylene alcohol compound may be a compound containing a polyoxyalkylene moiety. Examples of polyoxyalkylene moieties include: polyoxyethylene, polyoxypropylene, a random addition structure of polyoxyethylene and polyoxypropylene, and a block addition structure of polyoxyethylene and polyoxypropylene.
The acetylene alcohol compound is of the formula:
HO-CR11R12-C≡C-CR13R14-OH, or
HO-CR15R16-C ≡ C-H.
[ in the formula, R11、R12、R13、R14、R15、R16The alkyl groups may be the same or different and each represents a hydrogen atom or an alkyl group having 1 to 30 carbon atoms.]
The acetylene alcohol compound may be an alkylene oxide adduct of the compound represented by the formula. The alkyl group is preferably a linear or branched alkyl group having 1 to 12 carbon atoms, and particularly preferably a linear or branched alkyl group having 6 to 12 carbon atoms. Examples thereof include: methyl, ethyl, propyl, butyl, isobutyl, and the like. The alkylene oxide is preferably an alkylene oxide having 1 to 20 carbon atoms (particularly 2 to 5 carbon atoms) such as ethylene oxide and propylene oxide, and the number of addition of the alkylene oxide is preferably 1 to 50.
(2-2) cationic surfactant
The cationic surfactant is preferably a compound having no amide group.
The cationic surfactant can be amine salt, quaternary ammonium salt, or ethylene oxide addition type ammonium salt. Specific examples of the cationic surfactant are not particularly limited, and include: and quaternary ammonium salt surfactants such as alkylamine salts, aminoalcohol fatty acid derivatives, polyamine fatty acid derivatives, and imidazolines, alkyltrimethylammonium salts, dialkyldimethylammonium salts, alkyldimethylbenzylammonium salts, pyridinium salts, alkylisoquinolinium salts, and benzethonium chloride.
A preferred example of the cationic surfactant is R21-N+(-R22)(-R23)(-R24)X-The compound of (1).
[ in the formula, R21、R22、R23And R24A hydrocarbon group having 1 to 30 carbon atoms,
x is an anionic group. ]
R21、R22、R23And R24Specific examples thereof are alkyl groups (e.g., methyl, butyl, stearyl, and palmityl). Specific examples of X are halogen (e.g., chlorine) and acid (e.g., hydrochloric acid and acetic acid).
The cationic surfactant is particularly preferably a monoalkyltrimethylammonium salt (having 4 to 30 carbon atoms in the alkyl group).
The cationic surfactant is preferably an ammonium salt. The cationic surfactant may be of the formula: r1 p-N+R2 qX-The ammonium salts shown.
[ in the formula, R1Is above C12 (e.g. C)12～C50) The linear and/or branched aliphatic (saturated and/or unsaturated) group of (A),
R2h or C1-4 alkyl, benzyl, polyoxyethylene (the number of oxyethylene groups is, for example, 1 (particularly 2, particularly 3) to 50)
(particularly preferably CH)3、C2H5)，
X is a halogen atom (e.g., fluorine atom, chlorine atom, bromine atom, iodine atom, etc.), C1～C4The fatty acid salt group of (a) is,
p is 1 or 2, q is 2 or 3, and p + q is 4. ]
R1The number of carbon atoms in (b) may be 12 to 50, for example 12 to 30.
Specific examples of the cationic surfactant include dodecyltrimethylammonium acetate, trimethyltetradecylammonium chloride, hexadecyltrimethylammonium bromide, trimethyloctadecylammonium chloride, (dodecylmethylbenzyl) trimethylammonium chloride, benzyldodecyldimethylammonium chloride, methyldodecyldi (hydropolyoxyethylene) ammonium chloride, benzyldodecyldi (hydropolyoxyethylene) ammonium chloride, N- [2- (diethylamino) ethyl ] oleamide hydrochloride.
As the amphoteric surfactant, there can be mentioned: alanine, imidazolinium betaine, amidobetaine, acetobetaine, and the like, and specific examples thereof include: lauryl betaine, stearyl betaine, lauryl carboxymethyl hydroxyethyl imidazolinium betaine, lauryl dimethyl glycine betaine, fatty acid amide propyl dimethyl glycine betaine, etc.
The nonionic surfactant, the cationic surfactant and the amphoteric surfactant may be each 1 kind or a combination of 2 or more.
As the surfactant, only a nonionic surfactant or only a cationic surfactant may be used, but a combination of a nonionic surfactant and a cationic surfactant is preferably used. In the combination of the nonionic surfactant and the cationic surfactant, the weight ratio of the nonionic surfactant to the cationic surfactant is preferably 85: 15 to 20: 80, and more preferably 80: 20 to 40: 60.
The total amount of the surfactant may be 0.1 to 20 parts by weight, for example, 0.2 to 10 parts by weight, based on 100 parts by weight of the polymer.
(3) Liquid medium
The surface treatment agent composition is preferably a dispersion obtained by dispersing a polymer in a liquid medium.
The liquid medium may be an organic solvent, but is preferably an aqueous medium. In the present specification, the term "aqueous medium" refers to a medium composed of water alone and a medium containing an organic solvent (usually a water-soluble organic solvent) in addition to water (the amount of the organic solvent is 80 parts by weight or less, for example, 0.1 to 50 parts by weight, particularly 5 to 30 parts by weight, based on 100 parts by weight of water).
The amount of the aqueous medium may be 20 to 99% by weight, for example, 40 to 95% by weight, based on the surface treatment agent composition.
(4) Other ingredients
The surface treatment agent composition may contain a non-fluorine water-repellent compound as another component other than the fluorine-containing polymer and the surfactant.
Non-fluorine water repellent compound
The surface treatment agent composition may contain a water repellent compound containing no fluorine atom (non-fluorine water repellent compound).
The non-fluorine water repellent compound may be a non-fluorine acrylate polymer, a saturated or unsaturated hydrocarbon compound, or a silicone-based compound.
The non-fluorine acrylate polymer is a homopolymer composed of 1 non-fluorine acrylate monomer, or a copolymer composed of at least 2 non-fluorine acrylate monomers, or a copolymer composed of at least 1 non-fluorine acrylate monomer and at least 1 other non-fluorine monomer (ethylenic unsaturated compound, for example, ethylene, vinyl monomer).
The non-fluoroacrylate monomers that make up the non-fluoroacrylate polymer are of the formula: CH (CH)2A compound represented by CA-T.
[ wherein A represents a halogen atom other than a hydrogen atom, a methyl group or a fluorine atom (for example, a chlorine atom, a bromine atom or an iodine atom),
t is a hydrogen atom, a chain or cyclic hydrocarbon group having 1 to 30 carbon atoms, or a chain or cyclic organic group having 1 to 31 carbon atoms and having an ester bond. ]
Examples of the chain or ring-like hydrocarbon group having 1 to 30 carbon atoms include a straight chain or branched aliphatic hydrocarbon group having 1 to 30 carbon atoms, a ring-like aliphatic group having 4 to 30 carbon atoms, an aromatic hydrocarbon group having 6 to 30 carbon atoms, and an araliphatic hydrocarbon group having 7 to 30 carbon atoms.
Examples of the chain or cyclic organic group having 1 to 31 carbon atoms and having an ester bond are — C (═ O) -O-Q and — O-C (═ O) -Q (here, Q is a linear or branched aliphatic hydrocarbon group having 1 to 30 carbon atoms, a cyclic aliphatic group having 4 to 30 carbon atoms, an aromatic hydrocarbon group having 6 to 30 carbon atoms, or an aromatic aliphatic hydrocarbon group having 7 to 30 carbon atoms).
Examples of the non-fluorine acrylate monomer include, for example, alkyl (meth) acrylates, polyethylene glycol (meth) acrylates, polypropylene glycol (meth) acrylates, methoxypolyethylene glycol (meth) acrylates, methoxypolypropylene glycol (meth) acrylates.
The non-fluorinated acrylate monomer is preferably an alkyl (meth) acrylate. The number of carbon atoms of the alkyl group may be 1 to 30, for example, 6 to 30 (for example, 10 to 30). Specific examples of the non-fluorine-containing acrylate monomer are lauryl (meth) acrylate, stearyl (meth) acrylate and behenyl (meth) acrylate.
The non-fluoroacrylate polymer can be produced by the same polymerization method as the fluoropolymer.
The saturated or unsaturated hydrocarbon compound is preferably a saturated hydrocarbon. In the saturated or unsaturated hydrocarbon compound, the number of carbon atoms may be 15 or more, preferably 20 to 300, for example 25 to 100. Specific examples of the saturated or unsaturated hydrocarbon compound include paraffin wax and the like.
Silicone compounds are generally used as water-repellent agents. The silicone compound is not limited as long as it exhibits water repellency.
The amount of the non-fluorine-containing water-repellent compound may be 0 to 500 parts by weight, for example, 5 to 200 parts by weight, particularly 5 to 100 parts by weight, based on 100 parts by weight of the total of the 1 st fluoropolymer and the 2 nd fluoropolymer.
The fluoropolymer (the 1 st fluoromonomer and the 2 nd fluoromonomer) in the present invention can be produced by any of the usual polymerization methods, and the conditions of the polymerization reaction can be arbitrarily selected. Examples of such a polymerization method include: solution polymerization, suspension polymerization, emulsion polymerization.
The following method can be employed in the solution polymerization: in the presence of a polymerization initiator, a monomer is dissolved in an organic solvent to carry out nitrogen substitution, and then the mixture is heated and stirred at 30 to 120 ℃ for 1 to 10 hours. Examples of the polymerization initiator include: azobisisobutyronitrile, benzoyl peroxide, di-t-butyl peroxide, lauroyl peroxide, cumene hydroperoxide, t-butyl peroxypivalate, diisopropyl peroxydicarbonate, and the like. The polymerization initiator may be used in an amount of 0.01 to 20 parts by weight, for example, 0.01 to 10 parts by weight, based on 100 parts by weight of the monomer.
The organic solvent is a solvent which is inactive to the monomer and dissolves the monomer, and examples thereof include esters (e.g., esters having 2 to 30 carbon atoms, specifically ethyl acetate and butyl acetate), ketones (e.g., ketones having 2 to 30 carbon atoms, specifically methyl ethyl ketone and diisobutyl ketone), and alcohols (e.g., alcohols having 1 to 30 carbon atoms, specifically isopropyl alcohol). Specific examples of the organic solvent include: acetone, chloroform, HCHC225, isopropanol, pentane, hexane, heptane, octane, cyclohexane, benzene, toluene, xylene, petroleum ether, tetrahydrofuran, 1, 4-dioxane, methyl ethyl ketone, methyl isobutyl ketone, 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 may be used in an amount of 10 to 2000 parts by weight, for example, 50 to 1000 parts by weight, based on 100 parts by weight of the total monomers.
The following methods can be employed in the emulsion polymerization: in the presence of a polymerization initiator and an emulsifier, the monomers are emulsified in water, nitrogen substitution is performed, and then the monomers are copolymerized by stirring at 50 to 80 ℃ for 1 to 10 hours. As the polymerization initiator, there can be used water-soluble ones such as benzoyl peroxide, lauroyl peroxide, t-butyl peroxybenzoate, 1-hydroxycyclohexyl hydroperoxide, 3-carboxypropionyl peroxide, acetyl peroxide, azobisisobutylamidine dihydrochloride, azobisisobutyronitrile, sodium peroxide, potassium persulfate and ammonium persulfate, and oil-soluble ones such as azobisisobutyronitrile, benzoyl peroxide, di-t-butyl peroxide, lauroyl peroxide, cumene hydroperoxide, t-butyl peroxypivalate and diisopropyl peroxydicarbonate. The polymerization initiator may be used in an amount of 0.01 to 10 parts by weight based on 100 parts by weight of the monomer.
In order to obtain an aqueous polymer dispersion having excellent standing stability, it is preferable to polymerize the monomer by finely granulating the monomer in water using an emulsifying apparatus capable of imparting strong crushing energy such as a high-pressure homogenizer or an ultrasonic homogenizer. The emulsifier may be anionic, cationic or nonionic, and may be used in an amount of 0.5 to 20 parts by weight based on 100 parts by weight of the monomer. Anionic and/or nonionic and/or cationic emulsifiers are preferably used. In the case where the monomers are not completely compatible, it is preferable to add a compatibilizing agent capable of sufficiently compatibilizing these monomers, for example, a water-soluble organic solvent or a low-molecular-weight monomer. The addition of the compatibilizer can improve the emulsifiability and the copolymerizability.
Examples of the water-soluble organic solvent include: acetone, methyl ethyl ketone, ethyl acetate, propylene glycol, dipropylene glycol monomethyl ether, dipropylene glycol, tripropylene glycol, ethanol, and the like can be used in an amount of 1 to 50 parts by weight, for example, 10 to 40 parts by weight, based on 100 parts by weight of water. In addition, examples of the low molecular weight monomer include: methyl methacrylate, glycidyl methacrylate, 2,2, 2-trifluoroethyl methacrylate, and the like can be used in an amount of 1 to 50 parts by weight, for example, 10 to 40 parts by weight, based on 100 parts by weight of the total amount of the monomers.
In the polymerization, a chain transfer agent may also be used. The molecular weight of the polymer may be varied depending on the amount of chain transfer agent used. Examples of the chain transfer agent include thiol group-containing compounds (particularly, alkyl mercaptans (having 1 to 30 carbon atoms)) such as lauryl mercaptan, thioglycol, and thioglycerol, and inorganic salts such as sodium hypophosphite and sodium bisulfite. 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, based on 100 parts by weight of the total amount of the monomers.
The treatment agent composition of the present invention may be in the form of a solution, an emulsion (particularly, an aqueous dispersion liquid) or an aerosol, and is preferably an aqueous dispersion liquid. The treating agent composition contains a polymer (active ingredient of the surface treating agent) and a medium (particularly, a liquid medium such as an organic solvent and/or water). The amount of the medium may be, for example, 5 to 99.9% by weight, particularly 10 to 80% by weight, based on the treating agent composition.
The concentration of the polymer in the treating agent composition may be 0.01 to 95% by weight, for example, 5 to 50% by weight.
The treating agent composition of the present invention can be applied to the object to be treated by a conventionally known method. The treatment agent composition is usually diluted by dispersing in an organic solvent or water, and is attached to the surface of the object to be treated by a known method such as dip coating, spray coating, or bubble coating, followed by drying. In addition, if desired, it can also be applied simultaneously with a suitable crosslinking agent and cured. Further, an insect repellent, a softening agent, an antibacterial agent, a flame retardant, an antistatic agent, a paint fixative, an anti-wrinkle agent, and the like may be added to and used in combination with the treatment agent composition of the present invention. The concentration of the polymer in the treatment liquid to be 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 treating agent composition of the present invention (for example, water-and oil-repellent agent) include: fibrous products, stone, filters (e.g., electrostatic filters), dust covers, parts of fuel cells (e.g., gas diffusion electrodes and gas diffusion supports), glass, paper, wood, leather, fur, asbestos, bricks, cement, metals and oxides, ceramic industrial products, plastics, painted surfaces, and plaster, and the like. Various examples of the fiber product are given. Examples thereof include: animal and plant natural fibers such as cotton, hemp, wool, and silk, synthetic fibers such as polyamide, polyester, polyvinyl alcohol, polyacrylonitrile, polyvinyl chloride, and polypropylene, semisynthetic fibers such as rayon and acetate, inorganic fibers such as glass fibers, carbon fibers, and asbestos fibers, or a mixture thereof.
The fiber product may be in the form of fiber or cloth.
The treating agent composition of the present invention can also be used as an internal release agent or an external release agent.
The polymer can be applied to a fibrous substrate (e.g., a fibrous article, etc.) by any of the methods known for treating fibrous articles in liquids. When the fiber product is a cloth, the cloth may be soaked in the solution, or the solution may be attached to or sprayed on the cloth. In order to impart oil repellency to the treated textile product, the treated textile product is dried, and is preferably heated at, for example, 100 to 200 ℃.
Alternatively, the polymer may be applied to the fibrous article using a cleaning process, for example, washing may be applied or the fibrous article may be applied in a dry cleaning process or the like.
Typically, the fibrous products being treated are cloths, including woven, knitted, non-woven, cloth in the form of clothing and carpets, but also fibres or yarns or intermediate fibrous products (e.g. slivers or rovings, etc.). The fibrous article material may be natural fibers (e.g., cotton or wool, etc.), chemical fibers (e.g., viscose or Lyocell, etc.), or synthetic fibers (e.g., polyester, polyamide, or acrylic fibers, etc.), or may be a blend of fibers (e.g., a blend of natural and synthetic fibers, etc.). The polymer of the present invention is particularly effective in rendering cellulose-based fibers (e.g., cotton, rayon, or the like) oleophobic and oil repellent. In addition, the process of the present invention generally renders the fibrous product hydrophobic and water repellent.
Alternatively, the fibrous substrate may be leather. In order to render the leather hydrophobic and oleophobic, the make polymer may be applied to the leather from an aqueous solution or emulsion during various stages of the leather processing, for example during the wetting process of the leather or during the finishing process of the leather.
Alternatively, the fibrous substrate may be paper. The make polymer may be applied to a preformed paper, or may be applied during various stages of papermaking, such as during the drying of the paper.
The term "treatment" refers to applying a treatment agent to an object to be treated by dipping, spraying, coating, or the like. By the treatment, the polymer as an active ingredient of the treatment agent permeates into the inside of the object to be treated and/or adheres to the surface of the object to be treated.
[ examples ]
The present invention will be described in detail below with reference to examples. However, the present invention is not limited to these examples.
Hereinafter, unless otherwise specified, parts or% or ratio means parts or% or ratio by weight.
The procedure of the test is as follows.
Spray water repellency test
The spray water repellency test was carried out in accordance with JIS-L-1092. The spray water repellency test (shown in table 1 described below) is represented by water repellency No. below.
A glass funnel with a volume of at least 250ml and a nozzle capable of spraying 250ml of water in 20-30 seconds is used. The test piece frame is a metal frame with the diameter of 15 cm. 3 test piece sheets having a size of about 20cm × 20cm were prepared, and the sheets were fixed to a test piece holding frame so that the sheets were free from wrinkles. The center of the spray was placed in the center of the sheet. Water (250mL) at room temperature was added to the glass funnel, and the test piece sheet (for 25 to 30 seconds) was sprayed. And taking down the holding frame from the table, grasping one end of the holding frame to make the front surface at the lower side, and lightly knocking one end at the opposite side by using hard substances. The holding frame is rotated another 180 deg., and the same procedure is repeated, allowing excess water droplets to fall. In order to perform the scores of 0, 50, 70, 80, 90 and 100 in the order of poor to excellent water repellency, the wet test piece was compared with the wet comparison standard. The results were obtained from the average of 3 measurements.
Continuous workability of water repellency
10 test piece sheets having a size of about 20cm × 50cm were prepared and continuously treated with a water-and oil-repellent treatment liquid diluted to a predetermined concentration. The sheet was subjected to the spray water repellency test described above, and evaluated.
Production example 1
CF was placed in a 1000mL autoclave3CF2-(CF2CF2)n-CH2CH2OCOC(Cl)＝CH2(n-2.0) (13FC1A)108g, Lauryl Acrylate (LA)24.0g, isobornyl methacrylate (IBMA)57.7g, pure water 565g, water-soluble glycol solvent 47g, polyoxyethylene oleyl ether 2.5g, and polyoxyethylene alkyl ether 27.8g, which were emulsified and dispersed with ultrasonic waves at 60 ℃ for 15 minutes under stirring. After the autoclave was purged with nitrogen, 62g of Vinyl Chloride (VCM) was charged under pressure, 0.4g of a water-soluble initiator containing an azo group was added thereto, and the mixture was reacted at 60 ℃ for 20 hours to obtain an aqueous dispersion of a polymer. The composition of the polymer is substantially identical to the composition of the feed monomer.
Production example 2
CF was placed in a 500mL reaction flask3CF2-(CF2CF2)n-CH2CH2OCOC(Cl)＝CH2(n-2.0) (13FC1A)51.2g, stearyl acrylate (StA)85.4g, purified water 194g, water-soluble glycol solvent 34.1g, alkyltrimethylammonium chloride 6.3g, polyoxyethyleneThe alkylene ether (7.0 g) was emulsified and dispersed with stirring at 60 ℃ for 15 minutes by ultrasonic waves. After the reaction flask was purged with nitrogen, a solution of 0.4g of an azo group-containing water-soluble initiator and 9g of water was added thereto, and the mixture was reacted at 60 ℃ for 20 hours to obtain an aqueous dispersion of a polymer. The composition of the polymer is substantially identical to the composition of the feed monomer.
Production example 3
CF was placed in a 1000mL autoclave3CF2-(CF2CF2)n-CH2CH2OCOC(Cl)＝CH2(n-2.0) (13FC1A)108g, Lauryl Acrylate (LA)24.0g, isobornyl methacrylate (IBMA)57.7g, pure water 565g, water-soluble glycol solvent 47g, polyoxyethylene oleyl ether 2.5g, alkyltrimethylammonium chloride 3.9g, and polyoxyethylene alkyl ether 27.8g, which were emulsified and dispersed with ultrasonic waves at 60 ℃ for 15 minutes under stirring. After the autoclave was purged with nitrogen, 62g of Vinyl Chloride (VCM) was charged under pressure, 0.4g of a water-soluble initiator containing an azo group was added thereto, and the mixture was reacted at 60 ℃ for 20 hours to obtain an aqueous dispersion of a polymer. The composition of the polymer is substantially identical to the composition of the feed monomer.
Production example 4
CF was placed in a 500ml reaction flask3CF2-(CF2CF2)n-CH2CH2OCOC(CH3)＝CH251.2g of (n-2.0) (13FMA), 85.4g of stearyl acrylate (StA), 194g of purified water, 34.1g of a water-soluble glycol solvent, 6.3g of alkyltrimethylammonium chloride, and 7.0g of polyoxyethylene alkyl ether were emulsified and dispersed with ultrasonic waves at 60 ℃ for 15 minutes under stirring. After the reaction flask was purged with nitrogen, a solution of 0.4g of an azo group-containing water-soluble initiator and 9g of water was added thereto, and the mixture was reacted at 60 ℃ for 20 hours to obtain an aqueous dispersion of a polymer. The composition of the polymer is substantially identical to the composition of the feed monomer.
Production example 5
CF was placed in a 1000mL autoclave3CF2-(CF2CF2)n-CH2CH2OCOC(CH3)＝CH2(n-2.0) (13FMA)108g, lauryl acrylate (L)A)24.0g, 57.7g of isobornyl methacrylate (IBMA), 565g of pure water, 47g of a water-soluble glycol solvent, 2.5g of polyoxyethylene oleyl ether, and 27.8g of polyoxyethylene alkyl ether were emulsified and dispersed with ultrasonic waves at 60 ℃ for 15 minutes under stirring. After the autoclave was purged with nitrogen, 62g of Vinyl Chloride (VCM) was charged under pressure, 0.4g of a water-soluble initiator containing an azo group was added thereto, and the mixture was reacted at 60 ℃ for 20 hours to obtain an aqueous dispersion of a polymer. The composition of the polymer is substantially identical to the composition of the feed monomer.
Production example 6
A500 mL reaction flask was charged with 47.5g of stearyl acrylate (StA), 145g of pure water, 15g of a water-soluble glycol solvent, 1.5g of sorbitan monoalkyl ester, 2g of polyoxyethylene alkyl ether, and 1.5g of alkyldimethylammonium chloride, and emulsified and dispersed with stirring at 60 ℃ for 15 minutes by ultrasonic waves. After the reaction flask was purged with nitrogen, 0.5g of an azo group-containing water-soluble initiator was added thereto, and the mixture was reacted at 60 ℃ for 3 hours to obtain an aqueous dispersion of a polymer. Further, the solid content concentration was adjusted to 30% with pure water.
Production example 7
A500 mL autoclave was charged with 35g of stearyl acrylate (StA), 145g of pure water, 15g of a water-soluble glycol solvent, 1g of sorbitan monoalkyl ester, 2g of polyoxyethylene alkyl ether, and 2g of alkyldimethylammonium chloride, and emulsified and dispersed with ultrasonic waves at 60 ℃ for 15 minutes under stirring. After the autoclave was purged with nitrogen, 12.5g of vinyl chloride was introduced thereinto under pressure, 0.5g of 2, 2-azobis (2-amidinopropane) dihydrochloride was added thereto, and the mixture was reacted at 60 ℃ for 3 hours to obtain an aqueous dispersion of a polymer. Further, the solid content concentration was adjusted to 30% with pure water.
Comparative production example 1
CF was placed in a 500ml reaction flask3CF2-(CF2CF2)n-CH2CH2OCOCH＝CH251.2g of (n ═ 3.2) (NSFA), 85.4g of stearyl acrylate (StA), 194g of pure water, 34.1g of a water-soluble glycol solvent, 6.3g of alkyltrimethylammonium chloride, and 7.0g of polyoxyethylene alkyl ether were emulsified and dispersed with stirring at 60 ℃ for 15 minutes by ultrasonic waves. The reaction flask is internally provided withAfter the nitrogen substitution, a solution of 0.4g of a water-soluble initiator containing an azo group and 9g of water was added and the mixture was reacted at 60 ℃ for 20 hours to obtain an aqueous dispersion of a polymer. The composition of the polymer is substantially identical to the composition of the feed monomer.
Comparative production example 2
CF was placed in a 1000mL autoclave3CF2-(CF2CF2)n-CH2CH2OCOCH＝CH2(n-3.2) (NSFA)108g, stearyl acrylate (StA)81.7g, purified water 565g, water-soluble glycol solvent 47g, polyoxyethylene oleyl ether 2.5g, and polyoxyethylene alkyl ether 27.8g, and emulsified and dispersed with ultrasonic waves at 60 ℃ for 15 minutes under stirring. After the autoclave was purged with nitrogen, 62g of Vinyl Chloride (VCM) was charged under pressure, 0.4g of a water-soluble initiator containing an azo group was added thereto, and the mixture was reacted at 60 ℃ for 20 hours to obtain an aqueous dispersion of a polymer. The composition of the polymer is substantially identical to the composition of the feed monomer.
Comparative production example 3
A500 ml reaction flask was charged with 136.6g of paraffin (melting point: 50 ℃ C.), 194g of pure water, 34.1g of a water-soluble glycol solvent, 6.3g of alkyltrimethylammonium chloride and 7.0g of polyoxyethylene alkyl ether, and emulsified and dispersed with stirring at 60 ℃ for 15 minutes by ultrasonic waves to obtain an aqueous dispersion. The composition of the polymer is substantially identical to the composition of the feed monomer.
Example 1
The aqueous liquids prepared in preparation examples 1 and 2 were diluted with pure water so that the fluoropolymer concentration was 30% as a solid content, mixed and sufficiently stirred at a ratio of 50: 50, and further diluted with water so that the 30% dilution was 2%, thereby preparing a test solution (l00g) at 2.00%. 10 pieces of PET cloth (500 mm. times.200 mm) were continuously immersed in the test solution, passed through a calender and treated with a pin tenter at 170 ℃ for 1 minute. Then, a water repellency test was performed. The results are shown in Table A. Initial water repellency was also measured for test solutions having concentrations of 1.00%, 1.20%, and 1.40%, and the results are also shown in table a.
Example 2
The aqueous liquids produced in production examples 1 and 2 were diluted with pure water so that the fluoropolymer concentration was 30% solids, mixed at 30: 70 and sufficiently stirred, and then treated and evaluated in the same manner as in example 1. The results are shown in Table A.
Example 3
The aqueous liquids produced in production examples 2 and 3 were diluted with pure water so that the fluoropolymer concentration was 30% solids, mixed at 50: 50 and sufficiently stirred, and then treated and evaluated in the same manner as in example 1. The results are shown in Table A.
Example 4
The aqueous liquids produced in production examples 2 and 3 were diluted with pure water so that the fluoropolymer concentration was 30% solids, mixed at 70: 30 and sufficiently stirred, and then treated and evaluated in the same manner as in example 1. The results are shown in Table A.
Example 5
The aqueous liquids produced in production examples 4 and 5 were diluted with pure water so that the fluoropolymer concentration was 30% solids, mixed at 50: 50 and sufficiently stirred, and then treated and evaluated in the same manner as in example 1. The results are shown in Table A.
Example 6
The aqueous liquids prepared in production examples 1,2 and 6 were diluted with pure water so that the polymer concentration was 30% as a solid component, mixed and sufficiently stirred at 50: 17.5: 32.5, and then treated and evaluated in the same manner as in example 1. The results are shown in Table A.
Example 7
The aqueous liquids prepared in production examples 1,2 and 7 were diluted with pure water so that the polymer concentration was 30% as a solid component, mixed at 50: 25 and sufficiently stirred, and then treated and evaluated in the same manner as in example 1. The results are shown in Table A.
Comparative example 1
The aqueous liquid produced in production example 1 was diluted with pure water so that the fluoropolymer concentration was 30% solids, and then further diluted with water so that the proportion of the 30% diluted liquid was 2%, to prepare a test liquid (100g) of 2.00%. Thereafter, the treatment and evaluation were carried out in the same manner as in example 1. The results are shown in Table A.
Comparative example 2
The aqueous liquid produced in production example 2 was diluted with pure water so that the fluoropolymer concentration was 30% solids, and then further diluted with water so that the proportion of the 30% diluted liquid was 2%, to prepare a 2.00% test solution (100 g). Thereafter, the treatment and evaluation were carried out in the same manner as in example 1. The results are shown in Table A.
Comparative example 3
The aqueous liquid produced in production example 3 was diluted with pure water so that the fluoropolymer concentration was 30% solids, and then further diluted with water so that the proportion of the 30% diluted liquid was 2%, to prepare a test liquid (100g) of 2.00%. Thereafter, the treatment and evaluation were carried out in the same manner as in example 1. The results are shown in Table A.
Comparative example 4
The aqueous liquid produced in production example 4 was diluted with pure water so that the fluoropolymer concentration was 30% solids, and then further diluted with water so that the proportion of the 30% diluted liquid was 2%, to prepare a test liquid (100g) of 2.00%. Thereafter, the treatment and evaluation were carried out in the same manner as in example 1. The results are shown in Table A.
Comparative example 5
The aqueous liquid produced in production example 5 was diluted with pure water so that the fluoropolymer concentration was 30% solids, and then further diluted with water so that the proportion of the 30% diluted liquid was 2%, to prepare a test liquid (100g) of 2.00%. Thereafter, the treatment and evaluation were carried out in the same manner as in example 1. The results are shown in Table A.
Comparative example 6
The aqueous liquid produced in comparative production example 1 was diluted with pure water so that the fluoropolymer concentration was 30% as a solid content, and then further diluted with water so that the proportion of the 30% diluted liquid was 2%, thereby preparing a test liquid (100g) of 2.00%. Thereafter, the treatment and evaluation were carried out in the same manner as in example 1. The results are shown in Table A.
Comparative example 7
The aqueous liquid produced in comparative production example 2 was diluted with pure water so that the fluoropolymer concentration was 30% as a solid content, and then further diluted with water so that the proportion of the 30% diluted liquid was 2%, thereby preparing a test liquid (100g) of 2.00%. Thereafter, the treatment and evaluation were carried out in the same manner as in example 1. The results are shown in Table A.
Comparative example 8
The aqueous liquids prepared in production example 1 and comparative production example 3 were diluted with pure water so that the fluoropolymer concentration was 30% as a solid content, mixed at 75: 25 and sufficiently stirred, and further diluted with water so that the ratio of the 30% diluted liquid was 2%, thereby preparing 2.00% of a test solution (100 g). Thereafter, the treatment and evaluation were carried out in the same manner as in example 1. The results are shown in Table A.
The abbreviations have the following meanings.
Figure BDA0001522344680000261
[ Table 1]
TABLE A
Figure BDA0001522344680000271
[ Table 2]
Watch A (continuation)
Figure BDA0001522344680000281
Industrial applicability
The surface treatment agent composition of the present invention can be used, for example, as a water-and oil-repellent agent, an antifouling agent and a soil release agent.

Claims (11)

1. A surface treatment agent composition characterized by comprising:
(I) a 1 st fluoropolymer having repeating units derived from a fluoromonomer (a) and repeating units derived from a halogenated olefin (b);
(II) a 2 nd fluoropolymer having repeating units derived from the fluoromonomer (a) and not having repeating units derived from a halogenated olefin; and
(III) a liquid medium, wherein,
in the 1 st fluoropolymer and the 2 nd fluoropolymer, the fluoromonomer (a) is of the formula: CH (CH)2A compound represented by ═ C (-X) -C (═ O) -Y-Z-rf (i),
in the formula, X is a chlorine atom,
y is-O-or-NH-,
z is direct bonding;
a linear or branched aliphatic group having 1 to 20 carbon atoms;
an aromatic group or cyclic aliphatic group having 6 to 30 carbon atoms;
formula-R2(R1)N-SO2Or formula-R2(R1) A group represented by N-CO-, wherein R is1Is an alkyl group having 1 to 10 carbon atoms, R2A linear or branched alkylene group having 1 to 10 carbon atoms;
formula-CH2CH(OR3)CH2-(Ar-O)pA group represented by the formula (II) wherein R3Is a hydrogen atom or an acyl group having 1 to 10 carbon atoms, Ar is an arylene group having a substituent as required, and p represents 0 or 1;
formula-CH2-Ar-(O)q-a group represented by the formula (I), wherein Ar is an arylene group having a substituent as required, and q is 0 or 1; or
-(CH2)m-SO2-(CH2)n-radical or- (CH)2)m-S-(CH2)nA group, wherein m is 1 to 10, n is 0 to 10,
rf is a linear or branched fluoroalkyl group having 1 to 20 carbon atoms.
2. The surface treatment composition according to claim 1, characterized in that:
in the fluorine-containing monomer (a), Rf has 1 to 6 carbon atoms.
3. The surface treatment composition according to claim 1, characterized in that:
the halogenated olefin monomer (b) is vinyl chloride.
4. The surface treatment agent composition according to claim 1 or 2, characterized in that:
at least one of the 1 st fluoropolymer and the 2 nd fluoropolymer has a repeating unit derived from the other monomer (c),
the other monomer (c) is a non-fluorine non-crosslinkable monomer (c1),
the non-fluorine non-crosslinkable monomer (c1) is of the formula: CH (CH)2A compound represented by CA-T,
wherein A is a hydrogen atom, a methyl group or a halogen atom other than a fluorine atom, and T is a hydrogen atom, a chain or cyclic hydrocarbon group having 1 to 30 carbon atoms, or a chain or cyclic organic group having 1 to 31 carbon atoms and having an ester bond.
5. The surface treatment agent composition according to claim 1 or 2, characterized in that:
the amount of the halogenated olefin monomer (b) is 5 to 300 parts by weight and the amount of the other monomer (c) present as required is 0 to 800 parts by weight based on 100 parts by weight of the fluorine-containing monomer (a) in the 1 st fluorine-containing polymer,
the amount of the other monomer (c) present in the 2 nd fluorine-containing polymer is 0 to 800 parts by weight based on 100 parts by weight of the fluorine-containing monomer (a) as required.
6. The surface treatment agent composition according to claim 1 or 2, characterized in that:
the weight ratio of the 1 st fluoropolymer to the 2 nd fluoropolymer is 5: 95 to 95: 5.
7. The surface treatment agent composition according to claim 1 or 2, characterized in that:
the liquid medium (III) is water or a mixture of water and a water-soluble organic solvent.
8. The surface treatment agent composition according to claim 1 or 2, characterized in that:
the aqueous dispersion is an aqueous dispersion containing a nonionic surfactant and a cationic surfactant.
9. The surface treatment agent composition according to claim 1 or 2, characterized in that:
a water repellent compound containing no fluorine atom.
10. The surface treatment agent composition according to claim 1 or 2, characterized in that:
the surface treatment agent composition is a water-and oil-repellent agent composition, an antifouling agent composition or a soil release agent composition.
11. A substrate, characterized by:
which is obtained by treating the surface treating agent composition according to any one of claims 1 to 10.
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