CN107177982B - Surface treatment agent composition - Google Patents

Surface treatment agent composition Download PDF

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Publication number
CN107177982B
CN107177982B CN201610137414.8A CN201610137414A CN107177982B CN 107177982 B CN107177982 B CN 107177982B CN 201610137414 A CN201610137414 A CN 201610137414A CN 107177982 B CN107177982 B CN 107177982B
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fluorine
monomer
carbon atoms
atom
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CN107177982A (en
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南晋一
福森正树
井置正人
榎本孝司
山本育男
周斌
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Daikin Industries Ltd
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Daikin Industries Ltd
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Priority to JP2017045264A priority patent/JP6866699B2/en
Priority to KR1020170030429A priority patent/KR20170106236A/en
Publication of CN107177982A publication Critical patent/CN107177982A/en
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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
    • 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
    • D06M15/277—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of unsaturated carboxylic acids; Salts or esters thereof containing fluorine
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    • 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
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    • 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
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    • 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
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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
    • C09D5/1656—Antifouling paints; Underwater paints characterised by the film-forming substance
    • C09D5/1662—Synthetic film-forming substance
    • C09D5/1668—Vinyl-type polymers
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    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
    • D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
    • D06M15/37—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • D06M15/643—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds containing silicon in the main chain
    • D06M15/6436—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds containing silicon in the main chain containing amino groups
    • 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
    • C08F220/1812—C12-(meth)acrylate, e.g. lauryl (meth)acrylate
    • 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
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M2101/00—Chemical constitution of the fibres, threads, yarns, fabrics or fibrous goods made from such materials, to be treated
    • D06M2101/16—Synthetic fibres, other than mineral fibres
    • D06M2101/30—Synthetic polymers consisting of macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • D06M2101/32—Polyesters
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    • D06M2101/00—Chemical constitution of the fibres, threads, yarns, fabrics or fibrous goods made from such materials, to be treated
    • D06M2101/16—Synthetic fibres, other than mineral fibres
    • D06M2101/30—Synthetic polymers consisting of macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • D06M2101/34—Polyamides
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M2200/00—Functionality of the treatment composition and/or properties imparted to the textile material
    • D06M2200/10—Repellency against liquids
    • D06M2200/11—Oleophobic properties
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M2200/00—Functionality of the treatment composition and/or properties imparted to the textile material
    • D06M2200/10—Repellency against liquids
    • D06M2200/12—Hydrophobic properties
    • 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
    • D06M2200/50—Modified hand or grip properties; Softening compositions

Abstract

The invention provides a fluorine-containing treatment agent which can provide excellent water and oil repellency when used together with an auxiliary agent such as a softening agent and/or an antistatic agent in the water and oil repellency processing of fibers and the like. The fluorine-containing treatment agent contains: (1) a fluorine-containing polymer having a repeating unit derived from (a) a fluorine-containing monomer having a fluoroalkyl group and having 1 to 6 carbon atoms and a repeating unit derived from (b) a non-fluorine-crosslinkable monomer as a vinyl monomer having a hydroxyl group; and (2) a liquid medium, wherein the fluorine-containing treatment agent is combined with (3) at least one auxiliary agent selected from a softening agent and an antistatic agent.

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 can impart excellent water repellency, oil repellency, and stain resistance to parts of fiber products (e.g., carpets), paper, nonwoven fabrics, stone materials, electrostatic filters, dust masks, and fuel cells, and particularly can impart excellent water-and oil repellency even when a softener or an antistatic agent is used in water-and oil-repellent processing of fibers.
Background
At present, various fluorine-containing compounds have been proposed. The fluorine-containing compound has an advantage of excellent characteristics such as heat resistance, oxidation resistance and weather resistance. The fluorine-containing compound is used as, for example, a water-and oil-repellent agent and an antifouling agent by utilizing its low free energy, i.e., its property of being difficult to adhere.
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 structural monomer. In practical treatment of fibers with a surface treatment agent, various research results to date have shown that: as the surface characteristics thereof, not a static contact angle but a dynamic contact angle, particularly a receding contact angle, is important. Namely, the following are displayed: the advancing contact angle with water is not dependent on the number of carbon atoms of the side chain of the fluoroalkyl group, but the receding contact angle with water becomes significantly smaller at 7 or less than that of the fluoropolymer having 8 or more carbon atoms in the side chain. In contrast, 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 is correlated with side chain crystallinity, and that the mobility of the surface treatment agent molecule is an important factor for developing practical performance (for example, proChuanlong Mao, precise chemistry (ファインケミカル), Vol23, No.6, P12 (1994)). For the above reasons, the (meth) acrylate polymer having a fluoroalkyl group having a side chain having 7 or less (particularly 6 or less) carbon atoms has the following problems: since the side chain has low crystallinity, the side chain sometimes fails to satisfy practical properties when used as it is. In addition, in water and oil repellent processing, processing using a softening agent and an auxiliary agent for an antistatic agent in combination is increasing, and when these agents are used in combination, there is a problem that practical performance cannot be satisfied.
Japanese patent application laid-open No. 2001-98257 discloses a composition comprising, as essential components, a polymer (A) containing polymerized units of a polymerizable monomer having a polyfluoroalkyl group, a surfactant (B) having a specific Draves 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 publications, the processing of the co-additives 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
An object of the present invention is to provide a fluorine-containing treatment agent which can impart excellent water-and oil-repellency when used in combination with an auxiliary agent such as a softening agent and/or an antistatic agent in the water-and oil-repellent processing of fibers and the like.
Means for solving the problems
The present invention provides a fluorine-containing treatment agent, which contains:
(1) a fluorine-containing polymer having a repeating unit derived from (a) a fluorine-containing monomer having 1 to 6 carbon atoms in a fluoroalkyl group and a repeating unit derived from (b) a non-fluorine-crosslinkable monomer as a vinyl monomer having a hydroxyl group, and
(2) a liquid medium;
a fluorine-containing treating agent in combination with (3) at least one auxiliary agent selected from a softening agent and an antistatic agent.
Further, the present invention provides a surface treatment agent composition comprising:
(1) a fluorine-containing polymer having a repeating unit derived from (a) a fluorine-containing monomer having a fluoroalkyl group and having 1 to 6 carbon atoms and a repeating unit derived from (b) a non-fluorine-crosslinkable monomer as a vinyl monomer having a hydroxyl group,
(2) a liquid medium, and
(3) at least one auxiliary agent selected from the group consisting of softeners and antistatic agents.
Further, the present invention provides a method for producing a surface treatment agent composition, comprising:
a step of adding (3) at least one auxiliary agent selected from a softening agent and an antistatic agent to a fluorine-containing treatment agent, the fluorine-containing treatment agent containing:
(1) a fluorine-containing polymer having a repeating unit derived from (a) a fluorine-containing monomer having 1 to 6 carbon atoms in a fluoroalkyl group and a repeating unit derived from (b) a non-fluorine-crosslinkable monomer as a vinyl monomer having a hydroxyl group, and
(2) a liquid medium.
ADVANTAGEOUS EFFECTS OF INVENTION
The fluorine-containing treatment agent of the present invention can impart excellent water-and oil-repellency when used in combination with an auxiliary agent such as a softening agent and an antistatic agent.
According to the present invention, excellent water repellency, oil repellency, stain resistance and stain release properties, for example, excellent durability of water repellency 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 detergent composition.
Detailed Description
The fluorine-containing treatment agent comprises a fluorine-containing polymer (1) and a liquid medium (2).
The surface treatment agent composition contains a fluoropolymer (1), a liquid medium (2), and an auxiliary agent (3). The surface treatment agent composition is a combination (mixture) of a fluorine-containing treatment agent and an auxiliary agent (3). The surface treatment agent composition is prepared by adding the auxiliary (3) to the fluorine-containing treatment agent before the treatment of the substrate.
(1) Fluorine-containing polymer
The fluoropolymer has repeating units derived from a monomer such as a fluoromonomer.
The fluoropolymer may be a homopolymer or a copolymer of the fluoromonomer (a). The fluorine-containing polymer may have a repeating unit derived from a non-fluorine monomer (b) in addition to a repeating unit derived from a fluorine-containing monomer. The fluorine-containing monomer (a) and other monomers can be used in 1 type or in combination of 2 or more.
(a) Fluorine-containing monomer
The fluorine-containing monomer is generally a polymerizable compound having a fluoroalkyl group or a fluorine-containing alkenyl group, and an acrylic group, a methacrylic group, or an α -substituted acrylic group. "alpha-substituted acrylic group" means that the hydrogen atom at the alpha position of the acrylic group is replaced with Cl, Br, I, F, CN, CF3And the like.
The fluoroalkyl group is preferably a perfluoroalkyl group having 1 to 6 carbon atoms. The fluorine-containing alkenyl group is preferably a perfluoroalkenyl group having 2 to 6 carbon atoms.
The fluorine-containing monomer is preferably a compound represented by the formula (I).
CH2＝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 bond or a divalent organic group,
rf is a fluoroalkyl group having 1 to 6 carbon atoms. ]
In the general formula (I) of the fluorine-containing monomer, X is preferably 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 linear or branched fluoroalkyl group having 1 to 21 carbon atoms, a substituted or unsubstituted benzyl group, or a substituted or unsubstituted phenyl group. Specific examples of X are hydrogen atom, methyl group, Cl, Br, I, F, CN, CF3. X is preferably Cl.
Y is preferably-O-.
Z may be a bond, a linear or branched aliphatic group (particularly an alkylene group) having 1 to 20 carbon atoms, for example, a formula- (CH)2)xWherein x is 1 to 10, 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. ) 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 of the formula or-CH2-Ar-(O)qWherein Ar is an arylene group optionally having a substituent, q is 0 or 1, and- (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).
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.
The Rf group is preferably a perfluoroalkyl group. The Rf group has 1 to 6 carbon atoms, preferably 4 to 6 carbon atoms, and particularly preferably 6 carbon atoms. A fluorine-containing monomer having 1 to 20 carbon atoms in the Rf group can be used, and the fluorine-containing monomer is preferably composed of a compound having 4 to 6 carbon atoms in the Rf group alone, and particularly preferably 6 carbon atoms.
Specific examples of the fluorine-containing monomer 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 fluoroalkyl group having 1 to 6 carbon atoms. ]
(b) Non-fluorine monomer
The non-fluorine monomer (b) is a monomer having no fluorine atom. The non-fluorine monomer (b) is a compound having at least 1 ethylenically unsaturated double bond.
The non-fluorine monomer (b) may be a non-fluorine non-crosslinkable monomer (b1) or a non-fluorine crosslinkable monomer (b 2).
Examples of the non-fluorine non-crosslinkable monomer (b1) may be compounds represented by the following formula.
CH2＝CA-T
[ wherein A represents 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 halogen atom other than a fluorine atom (for example, a chlorine atom, a bromine atom, and an iodine atom), a chain or cyclic hydrocarbon group having 1 to 30 carbon atoms, or a chain or cyclic organic group having 1 to 30 carbon atoms and having an ester bond. ]
Examples of the chain or cyclic hydrocarbon group having 1 to 30 carbon atoms include a linear or branched saturated or unsaturated (e.g., ethylenically unsaturated) aliphatic hydrocarbon group having 1 to 30 carbon atoms, a saturated or unsaturated (e.g., ethylenically unsaturated) cyclic 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 30 carbon atoms and having an ester bond are — C (═ O) -O-Q and — O-C (═ O) -Q (here, Q is a linear or branched, saturated or unsaturated (e.g., ethylenically unsaturated) aliphatic hydrocarbon group having 1 to 20 carbon atoms, a saturated or unsaturated (e.g., ethylenically unsaturated) cyclic aliphatic group having 4 to 20 carbon atoms, an aromatic hydrocarbon group having 6 to 20 carbon atoms, or an araliphatic hydrocarbon group having 7 to 20 carbon atoms).
The non-fluorine non-crosslinkable monomer (b1) may be a (meth) acrylate monomer (b1-1), a halogenated olefin monomer (b1-2), or the like.
Examples of the (meth) acrylate monomer (b1-1) may be compounds represented by the following formula.
CH2＝CA21-C(＝O)-O-A22
[ in the formula, A21Is a hydrogen atom, a monovalent organic group, or a halogen atom other than a fluorine atom, A22Is a hydrocarbon group having 1 to 30 carbon atoms.]
A21Preferably a hydrogen atom, a methyl group, or a chlorine atom.
A22The (hydrocarbon group) may be an acyclic aliphatic hydrocarbon group having 1 to 30 carbon atoms, a cyclic hydrocarbon-containing group having 4 to 30 carbon atoms, or the like. Specific examples of the acyclic aliphatic hydrocarbon group are lauryl group, cetyl group, stearyl group and behenyl group. Specific examples of the cyclic hydrocarbon group are cyclohexyl, t-butylcyclohexyl, isobornyl, dicyclopentanyl, dicyclopentenyl and adamantyl.
Specific examples of the (meth) acrylate monomer having an acyclic aliphatic hydrocarbon group include lauryl (meth) acrylate, cetyl (meth) acrylate, stearyl (meth) acrylate, and behenyl (meth) acrylate.
Specific examples of the (meth) acrylate monomer having a cyclic hydrocarbon-containing group include cyclohexyl (meth) acrylate, t-butylcyclohexyl (meth) acrylate, benzyl (meth) acrylate, isobornyl (meth) acrylate, dicyclopentanyl (meth) acrylate, dicyclopentenyl (meth) acrylate, dicyclopentanyloxyethyl (meth) acrylate, tricyclopentanyl (meth) acrylate, adamantyl (meth) acrylate, 2-methyl-2-adamantyl (meth) acrylate, and 2-ethyl-2-adamantyl (meth) acrylate.
The halogenated olefin monomer (b1-2) has no fluorine atom.
The halogenated olefin monomer may be an olefin having 2 to 20 carbon atoms substituted with 1 to 10 chlorine, bromine or iodine atoms. The halogenated olefin monomer is preferably a chlorinated olefin having 2 to 20 carbon atoms, particularly an olefin having 2 to 5 carbon atoms and having 1 to 5 chlorine atoms. Preferred examples of the halogenated olefin monomer (b1-2) are halogenated ethylenes such as vinyl chloride, vinyl bromide, vinyl iodide, and vinylidene halides such as vinylidene chloride, vinylidene bromide, and vinylidene iodide. Since the water-and oil-repellency (particularly, durability of the water-and oil-repellency) is improved, vinyl chloride and vinylidene chloride are preferable.
(b2) Non-fluorine crosslinkable monomer
The non-fluorine crosslinkable monomer (b2) is a monomer containing no fluorine atom. The non-fluorine crosslinkable monomer may be a compound having at least 2 reactive groups and/or an olefinic carbon-carbon double bond (preferably a (meth) acrylate group) and not containing fluorine. The non-fluorine crosslinkable monomer may be a compound having at least 2 olefinic carbon-carbon double bonds (preferably a (meth) acrylate group), or a compound having at least 1 olefinic 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 may be a mono (meth) acrylate, di (meth) acrylate or mono (meth) acrylamide having a reactive group. Alternatively, the non-fluorine crosslinkable monomer may be a di (meth) acrylate.
A vinyl monomer having a hydroxyl group (particularly, an acrylate monomer or an acrylamide monomer) is used as the non-fluorine crosslinkable monomer.
Preferred vinyl monomers having a hydroxyl group are compounds represented by the following formula.
CH2＝CD1-C(＝O)-D2-D3-OH
[ in the formula, D1A 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),
D2is-O-or-NH-,
D3an organic group having 1 to 20 carbon atoms, for example, 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)xIn the formula, x is a group represented by 1 to 10.]
Examples of the vinyl monomer having a hydroxyl group include N-methylol (meth) acrylamide, N-2-hydroxypropyl (meth) acrylamide, N-hydroxybutyl (meth) acrylamide, and hydroxyethyl (meth) acrylate.
The amount of the vinyl monomer having a hydroxyl group may be 0.1 to 20 parts by weight, for example, 0.5 to 10 parts by weight, based on 100 parts by weight of the fluorine-containing monomer (a).
The non-fluorine crosslinkable monomer may be a vinyl monomer (particularly, an acrylate monomer or an acrylamide monomer) having a reactive group (a reactive group other than a hydroxyl group) such as an epoxy group, a chloromethyl group, a blocked isocyanate group, an amino group and/or a carboxyl group, or the like.
The preferable non-fluorine crosslinkable monomer is a compound represented by the following formula.
CH2＝CE1-C(＝O)-E2-E3
[ in the formula, E1A 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),
E2is-O-or-NH-,
E3hydroxyl, epoxy, chloromethyl, blocked isocyanate, amino and carboxyl.]
Examples of the non-fluorine crosslinkable monomer (b2) include diacetone (meth) acrylamide, 3-chloro-2-hydroxypropyl (meth) acrylate, 2-acetoacetoxyethyl (meth) acrylate, butadiene, isoprene, chloroprene, glycidyl (meth) acrylate, 1, 6-hexanediol di (meth) acrylate, and neopentyl glycol di (meth) acrylate.
(c) Other monomers
The fluoropolymer may contain monomers other than the monomers (a) and (b).
Examples of the other monomer (c) include, for example, ethylene, vinyl acetate, acrylonitrile, styrene, polyethylene glycol (meth) acrylate, polypropylene glycol (meth) acrylate, methoxypolyethylene glycol (meth) acrylate, methoxypolypropylene glycol (meth) acrylate, vinyl alkyl ether and the like. The other monomers are not limited to these examples.
The monomers (a) to (c) may be used alone or in a mixture of 2 or more.
The amount of the monomer (a) may be 10% by weight or more, for example, 40% by weight or more, based on the polymer. The amount of the monomer (a) may be 95% by weight or less, for example 80% by weight or less, or 75% by weight or less, or 70% by weight or less, based on the polymer.
In the polymer, with respect to 100 parts by weight of the monomer (a),
the amount of the repeating unit (b1) may be 0 to 200 parts by weight, preferably 1 to 40 parts by weight,
the amount of the repeating unit (b2) may be 0.1 to 100 parts by weight, preferably 1 to 30 parts by weight,
the amount of the repeating unit (c) may be 0 to 100 parts by weight, preferably 1 to 30 parts by weight.
In the polymer, with respect to 100 parts by weight of the monomer (a),
the amount of the repeating unit (b1-1) may be 0 to 150 parts by weight, preferably 1 to 30 parts by weight,
the amount of the repeating unit (b1-2) may be 0 to 50 parts by weight, preferably 1 to 10 parts by weight.
The amount of the fluoropolymer (solid content) may be about 0.01 to 60% by weight, preferably about 0.1 to 40% by weight, and particularly preferably about 5 to 35% by weight, based on the fluorine-containing treatment agent or the surface treatment agent composition.
The fluoropolymer may be present in the form of a solution dissolved in an organic solvent, and is preferably present in the form of an aqueous dispersion.
In the present specification, the term "acrylate" or "acrylamide" is used simply to include not only compounds in which the α -position is a hydrogen atom, but also compounds in which the α -position is substituted with another group (for example, a monovalent organic group containing a methyl group or a halogen atom). In the present specification, "(meth) acrylate" means acrylate or methacrylate, and "(meth) acrylamide" means acrylamide or methacrylamide.
The monomer (a), the monomer (b) and the monomer (c) (for example, the monomers (c1) and (c2) may be used alone in 1 kind or in combination of 2 or more kinds, respectively.
(2) Liquid medium
The liquid medium may be an aqueous medium. The liquid medium may be water alone or a mixture of water and a (water-soluble) organic solvent. The amount of the organic solvent may be 30% by weight or less, for example, 10% by weight or less (preferably 0.1% or more) based on the liquid medium. The liquid medium is preferably water alone. The liquid medium may be only an organic solvent.
The amount of the liquid medium may be 30 to 99.1% by weight, particularly 50 to 99% by weight, based on the fluorine-containing treatment agent (or surface treatment agent composition).
(3) Auxiliary agent
The surface treatment agent composition of the present invention contains at least 1 kind of auxiliary agent selected from a softening agent and an antistatic agent. Generally, the coagent is added to the fluoropolymer (or fluorochemical treatment) after the polymerization reaction is complete.
The auxiliary (softener and/or antistatic agent) may be a surfactant. In the case where the auxiliary is a surfactant, the auxiliary is added after the completion of the polymerization reaction, and therefore, the auxiliary can be distinguished from a surfactant (surfactant for polymerization) used in polymerizing the monomer.
The surfactant may be contained in the fluorine-containing treatment agent (surfactant for polymerization). When the fluorine-containing treatment agent contains a surfactant, the fluorine-containing polymer is well dispersed in the liquid medium.
In the present invention, the surfactant may be at least 1 selected from the group consisting of a nonionic surfactant, a cationic surfactant, an anionic surfactant and an amphoteric surfactant.
(3-1) nonionic surfactant
Examples of the nonionic surfactant include ethers, esters, ester ethers, alkanolamides, polyhydric alcohols, and amine oxides.
Examples of ethers are compounds having oxyalkylene groups, preferably polyoxyethylene groups.
Examples of esters are esters of alcohols with fatty acids. Examples of the alcohol include alcohols having 1 to 50 carbon atoms (particularly 3 to 30 carbon atoms) having 1 to 6 valences (particularly 2 to 5 valences) (for example, aliphatic alcohols). Examples of the fatty acid include saturated or unsaturated fatty acids having 2 to 50 carbon atoms, particularly 5 to 30 carbon atoms.
Examples of the ester ether are compounds in which an alkylene oxide (particularly ethylene oxide) is added to an ester of an alcohol with a fatty acid. Examples of the alcohol include alcohols having 1 to 50 carbon atoms (particularly 3 to 30 carbon atoms) having 1 to 6 valences (particularly 2 to 5 valences) (for example, aliphatic alcohols). Examples of the fatty acid include saturated or unsaturated fatty acids having 2 to 50 carbon atoms, particularly 5 to 30 carbon atoms.
Alkanolamides are formed from fatty acids and alkanolamines. The alkanolamide may be a monoalkanolamide or a dialkanolamide. Examples of the fatty acid include saturated or unsaturated fatty acids having 2 to 50 carbon atoms, particularly 5 to 30 carbon atoms. The alkanolamine may be an alkanol having 2 to 50 carbon atoms, particularly 5 to 30 carbon atoms, having 1 to 3 amino groups and 1 to 5 hydroxyl groups.
The polyhydric alcohol may be an alcohol having 2 to 5 valences and 3 to 30 carbon atoms.
The amine oxide may be an oxide (e.g., 5 to 50 carbon atoms) of an amine (secondary or preferably tertiary).
The nonionic surfactant is preferably a nonionic surfactant having an oxyalkylene group (preferably a polyoxyethylene group). The alkylene group of the oxyalkylene group preferably has 2 to 10 carbon atoms. The number of oxyalkylene groups in the molecule of the nonionic surfactant is preferably 2 to 100 in general.
The nonionic surfactant is selected from ethers, esters, ester ethers, alkanolamides, polyhydric alcohols, and amine oxides, and is preferably a nonionic surfactant having an oxyalkylene group.
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 (Acetylene glycol), or the like. Among these, the structures of the alkylene oxide addition moiety and the polyalkylene glycol moiety are preferably those of Polyoxyethylene (POE), polyoxypropylene (POP), or POE/POP copolymer (which may be a random copolymer or a block copolymer).
In addition, from the viewpoint of environmental problems (biodegradability, environmental hormones, and the like), the nonionic surfactant preferably has a structure that does not contain an aromatic group.
The nonionic surfactant may be a compound represented by the following formula.
R1O-(CH2CH2O)p-(R2O)q-R3
[ in the formula, R1Is an alkyl group having 1 to 22 carbon atoms or an alkenyl group or acyl group having 2 to 22 carbon atoms,
R2independently, the same or different, an alkylene group having 3 or more carbon atoms (for example, 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,
q is 0 or a number of 1 or more. ]
R1Preferably 8 to 20 carbon atoms, and particularly preferably 10 to 18 carbon atoms. As R1As a preferred example of (3), lauryl, tridecyl and oleyl groups are mentioned.
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)qIt is possible to form a polyoxyalkylene chain.
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 an oxyalkylene chain, an oxybutylene chain, and a styrene chain, and among them, an oxyalkylene chain is preferable.
Preferred nonionic surfactants are those of the formula.
R1O-(CH2CH2O)p-H
[ in the formula, R1And p has the same meaning as above.]
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-C12H25And the like.
[ in the formula, p and q have the same meanings as described above. ]
Specific examples of the nonionic surfactant include ethylene oxide, hexylphenol, isooctylphenol, cetyl alcohol, oleic acid, and 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 block 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 generally 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 as a base may be 5 to 100 parts by weight, for example, 8 to 50 parts by weight, particularly 10 to 40 parts by weight, based on 100 parts by weight of the total of the nonionic surfactants. In combinations of 2 or more, the remaining nonionic surfactant may be R1Radical (and/or R)3Radical) is a (saturated and/or unsaturated) straight-chain alkyl radical (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 alkanolamides, alkyl alkanolamides, acetylene glycols, ethylene oxide adducts of acetylene glycols, polyethylene glycol-polypropylene glycol block copolymers, and the like. Polyoxyethylene alkyl ethers and polyoxyethylene sorbitan fatty acid esters are preferred. More preferred are polyoxyethylene alkyl ethers.
(3-2) cationic surfactant
The cationic surfactant is preferably a compound having no amide group.
The cationic surfactant may be amine salt, quaternary ammonium salt, or ethylene oxide addition type ammonium salt. Specific examples of the cationic surfactant are not particularly limited, and examples thereof include amine salt type surfactants such as alkylamine salts, aminoalcohol fatty acid derivatives, polyamine fatty acid derivatives, and imidazolines, quaternary ammonium salt type surfactants such as alkyltrimethylammonium salts, dialkyldimethylammonium salts, alkyldimethylbenzylammonium salts, pyridinium salts, alkylisoquinolinium salts, and benzylammonium chlorides.
Preferred examples of the cationic surfactant are compounds represented by the following formula.
R21-N+(-R22)(-R23)(-R24)X-
[ 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 cetyl). 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 an ammonium salt represented by the following formula.
R1 p-N+R2 qX-
[ in the formula, R1Is C12Above (e.g. C)12～C50) The linear and/or branched aliphatic (saturated and/or unsaturated) group of (A),
R2is H or C1～C4Alkyl groups, benzyl groups, polyoxyethylene groups (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.), 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 (a) 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 (hydrogenpolyoxyethylene) ammonium chloride, benzyldodecyldihydrogenpolyoxyethylene ammonium chloride, N- [2- (diethylamino) ethyl ] oleamide hydrochloride, and dialkyl (reduced tallow) dimethylammonium chloride. Cationic emulsifiers having an ammonium chloride structure are preferred. Further preferred is a cationic emulsifier having an ammonium chloride structure and having a long-chain (for example, 10 to 30 carbon atoms, particularly 14 to 24 carbon atoms) hydrocarbon group (particularly an alkyl group) such as an octadecyl group or a hexadecyl group.
(3-3) anionic surfactant
Specific examples of the anionic surfactant include sodium lauryl sulfate, triethanolamine lauryl sulfate, sodium polyoxyethylene lauryl ether sulfate, sodium polyoxyethylene nonylphenyl ether sulfate, triethanolamine polyoxyethylene lauryl ether sulfate, sodium cocoyl sarcosinate, sodium N-cocoyl methyltaurate, sodium polyoxyethylene cocoyl ether sulfate, sodium diether hexyl sulfosuccinate, sodium alpha-olefin sulfonate, sodium lauryl phosphate, sodium polyoxyethylene lauryl ether phosphate, and perfluoroalkyl carboxylate (trade name: UNIDYNE DS-101, 102, manufactured by Daiki industries, Ltd.). The anionic surfactant is preferably a salt of an organic acid (e.g., a salt of an organic acid with an inorganic base or an amine). Further preferred are alkyl sulfate salts (e.g., ROSO)3 -M+) The number of carbon atoms of the (alkyl (R group) is, for example, 8 to 30. M is an alkali metal (e.g., sodium or potassium). ).
(3-4) amphoteric surfactant
Specific examples of the amphoteric surfactant include amine oxides, alanine acids, imidazolium betaines, amidobetaines, and acetate betaines, and specific examples thereof include lauryl betaine, stearyl betaine, lauryl carboxymethylhydroxyethyl imidazolium betaine, lauryl dimethylamino acetic acid betaine, and fatty acid amidopropyl dimethylamino acetic acid betaine. Preference is given to amine oxides (e.g. R)3N ═ O (each R group is, for example, a hydrocarbon group (particularly an alkyl group) having 1 to 30 carbon atoms)).
The nonionic surfactant, the cationic surfactant, the anionic surfactant and the amphoteric surfactant may be each 1 kind or a combination of 2 or more.
The auxiliaries, in particular surfactants, are preferably compounds having long-chain alkyl and/or long-chain alkenyl groups. The long-chain alkyl group and the long-chain alkenyl group preferably have 10 to 30 carbon atoms, for example, 14 to 24 carbon atoms. The long chain alkyl and long chain alkenyl groups are preferably interrupted by ester or amide linkages. The auxiliary may be an amine compound or an ammonium compound having a long-chain alkyl group and/or a long-chain alkenyl group.
Examples of the softening agent include silicone-based softening agents (for example, dimethyl silicone (generally an emulsion) having at least 1 functional group such as an epoxy group, a primary amino group, a secondary amino group, a vinyl group), polyethylene-based softening agents (for example, polyethylene wax (generally an emulsion)), cationic softening agents such as ester-type quaternary ammonium salts obtained by quaternizing an ester compound of triethanolamine and a long-chain fatty acid (a fatty acid having 10 to 30 carbon atoms) with an alkylating agent such as methyl chloride or dimethyl sulfuric acid, anionic softening agents such as alkyl sulfosuccinates, nonionic softening agents such as polyol fatty acid esters, polyethylene glycol fatty acid esters, and polyethylene glycol alkyl ethers. Silicone-based softeners and polyethylene wax-based softeners are preferred. More preferably a silicone softener comprising an emulsion of dimethyl silicone having at least 1 functional group such as an epoxy group, a primary or secondary amino group, or a vinyl group.
The antistatic agent is preferably a surfactant. Examples of the antistatic agent are a nonionic antistatic agent (nonionic surfactant), a cationic antistatic agent (cationic surfactant), an anionic antistatic agent (anionic surfactant), an amphoteric antistatic agent (amphoteric surfactant), and a polymer type antistatic agent.
Examples of the nonionic antistatic agent include glycerin fatty acid esters, polyoxyethylene alkyl ethers, polyoxyethylene alkylphenyl ethers, fatty alcohol phosphate esters, higher alcohol sulfate esters, and the like;
examples of the cationic antistatic agent include tetraalkylammonium salts represented by (. beta. -lauramidopropionyl) trimethylammonium sulfonate, trialkylbenzylammonium salts, alkylurea-type compounds represented by monoalkyltrimethylaminoalkyl ureas, and alkylamide-type compounds represented by monoalkyltrimethylaminoalkyl amides;
examples of the anionic antistatic agent include fatty acid salts, alkylsulfonic acid salts, alkylbenzenesulfonic acid salts typified by dodecylbenzenesulfonic acid salt and tridecylbenzenesulfonic acid salt, and alkylphosphoric acid salts typified by distearylphosphoric acid salt;
examples of the amphoteric antistatic agent include alkyl betaines and alkyl imidazolium betaines;
examples of the polymer type antistatic agent include salts such as polyoxyethylene glycol (polyethylene glycol), polyetheresteramide, and polyetheramideimide, and for example, sulfates of aliphatic amines and amides, and salts of aliphatic amines.
Nonionic antistatic agents and cationic antistatic agents are preferred. Further preferred are glycerin fatty acid esters, polyethylene glycol, alkyl urea compounds, alkylamide compounds, and trialkylbenzylammonium salts (having 1 to 30 carbon atoms in the alkyl group).
The softener and the antistatic agent may be only 1 kind, or a combination of at least 2 kinds, respectively.
The amount of the auxiliary (generally as a solid) may be 0.1 to 20% by weight, for example, 0.2 to 10% by weight, based on the surface treatment agent composition.
(4) Other ingredients
The surface treatment agent composition may contain at least 1 of the non-fluorine water-repellent compound and the additive as other components than the fluorine-containing polymer, the liquid medium and the auxiliary.
(4-1) 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 compound.
The non-fluoroacrylate polymer is a homopolymer composed of 1 non-fluoroacrylate monomer, or a copolymer composed of at least 2 non-fluoroacrylate monomers, or a copolymer composed of at least 1 non-fluoroacrylate monomer and at least 1 other non-fluoroacrylate monomer (ethylenically unsaturated compound, e.g., ethylene, vinyl monomer).
The non-fluoroacrylate monomer constituting the non-fluoroacrylate polymer is a compound represented by the following formula.
CH2＝CA-T
[ wherein A represents 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).
Examples of the non-fluorine-containing acrylate monomer include, for example, alkyl (meth) acrylates, polyethylene glycol (meth) acrylates, polypropylene glycol (meth) acrylates, methoxypolyethylene glycol (meth) acrylates, and methoxypolypropylene glycol (meth) acrylates.
The non-fluoroacrylate monomer is preferably an alkyl (meth) acrylate. The number of carbon atoms in the alkyl group may be 1 to 30, for example, 6 to 30 (for example, 10 to 30). Specific examples of the non-fluorine 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.
The silicone compound is generally used as a water-repellent agent. The silicone compound is not limited as long as it exhibits water repellency.
The amount of the non-fluorine water-repellent compound may be 500 parts by weight or less, for example, 5 to 200 parts by weight, particularly 5 to 100 parts by weight, based on 100 parts by weight of the fluorine-containing polymer.
(4-2) additives
Examples of the additives are silicon-containing compounds, waxes, acrylic latex, and the like. Other examples of the additives are other fluorine-containing polymers, drying rate modifiers, crosslinking agents, film-forming aids, compatibilizers, surfactants, anti-freezing agents, viscosity modifiers, ultraviolet absorbers, antioxidants, pH modifiers, antifoaming agents, hand feeling modifiers, slip property modifiers, antistatic agents, hydrophilizing agents, antibacterial agents, preservatives, insect repellents, fragrances, flame retardants, and the like.
The fluoropolymer and the non-fluoropolymer in the present invention can be produced by any of the usual polymerization methods, and the conditions for the polymerization reaction can be arbitrarily selected. Examples of such a polymerization method include solution polymerization, suspension polymerization, and emulsion polymerization.
In the solution polymerization, a method of dissolving a monomer in an organic solvent in the presence of a polymerization initiator, replacing nitrogen, and then heating at 30 to 120 ℃ for 1 to 10 hours with stirring is employed. Examples of the polymerization initiator include azobisisobutyronitrile, benzoyl peroxide, di-t-butyl peroxide, lauryl peroxide, cumene hydroperoxide, t-butyl peroxyvalerate, and diisopropyl peroxydicarbonate. The polymerization initiator is 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 inert to the monomer and dissolves these substances, 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, isopropyl alcohol, pentane, hexane, pentane, 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 is 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.
In the emulsion polymerization, a method of emulsifying a monomer in water in the presence of a polymerization initiator and an emulsifier, displacing nitrogen, and then stirring and polymerizing at 50 to 80 ℃ for 1 to 10 hours is adopted. 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, lauryl peroxide, cumene hydroperoxide, t-butyl peroxyvalerate and diisopropyl peroxydicarbonate. The polymerization initiator is 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 use an emulsifying apparatus capable of imparting strong pulverization energy such as a high-pressure homogenizer or an ultrasonic homogenizer to atomize and polymerize a monomer in water. As the emulsifier, various anionic, cationic or nonionic emulsifiers can be used, and the amount of the emulsifier is in the range of 0.5 to 20 parts by weight per 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 completely incompatible, it is preferable to add a compatibilizing agent, such as a water-soluble organic solvent or a low-molecular-weight monomer, to these monomers to make them sufficiently compatible. 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, and ethanol, and the water-soluble organic solvent 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. Examples of the low-molecular-weight monomer include methyl methacrylate, glycidyl methacrylate, and 2,2, 2-trifluoroethyl methacrylate, and the monomer 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 be used. The molecular weight of the polymer can be varied depending on the amount of the 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, mercaptoethanol, and thioglycerol, and inorganic salts such as sodium hypophosphite and sodium bisulfite. The amount of the chain transfer agent to be used may be in the range 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 composition of the present invention may be in the form of a solution, a latex (particularly an aqueous dispersion) or an aerosol, and is preferably an aqueous dispersion. 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 wt%, particularly 10 to 80 wt%, 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 treatment agent composition of the present invention can be applied to an 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 foam coating, followed by drying. In addition, if desired, it can be applied simultaneously with a suitable crosslinking agent and cured. Further, the treatment agent composition of the present invention may be used in combination with an insect repellent, a softening agent, an antibacterial agent, a flame retardant, an antistatic agent, a paint fixer, an anti-wrinkle agent, and the like. 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 (for example, water and oil repellent) of the present invention include fiber products, stone materials, filters (for example, electrostatic filters), dust masks, parts of fuel cells (for example, gas diffusion electrodes and gas diffusion supports), glass, paper, wood, leather, fur, asbestos, bricks, cement, metals and oxides, ceramic products, plastics, painted surfaces, and plasters. Various examples of the fiber product are listed. Examples thereof include natural fibers of animals and plants 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, and mixed fibers 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 known methods for treating fibrous articles in a liquid. When the fiber product is a cloth, the cloth may be impregnated with the solution, or the solution may be attached to or sprayed on the cloth. The treated fiber product is dried to exhibit oil repellency, 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, in a laundry application or dry cleaning process, etc.
The treated fibrous products are typically cloths, including woven, knitted and non-woven fabrics, cloths in the form of clothing and carpets, and may be fibers or filaments 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., viscos rayon or rayon, etc.), or synthetic fibers (e.g., polyester, polyamide, acrylic, etc.), or may be a mixture of fibers (e.g., a mixture of natural and synthetic fibers, etc.). The polymer of the present invention is particularly effective in rendering a cellulose-based fiber (e.g., cotton or rayon) oil-repellent 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 manufacturing polymer may be applied to the leather from an aqueous solution or emulsion at various stages of the leather processing, for example during the wet processing of the leather, or during the finishing of the leather.
Alternatively, the fibrous substrate may be paper. The manufacturing polymer may be applied to pre-formed paper, or may also be applied in 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, but 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 is represented by water repellency No. (shown in table 1 described below).
A glass funnel having a volume of at least 250ml and a spray nozzle capable of spraying 250ml of water over a period of 20 to 30 seconds are used. The test piece frame is a metal frame with a diameter of 15 cm. 3 test pieces having a size of about 20cm × 20cm were prepared, and the sheet was fixed to the test piece holder frame so that no wrinkles were formed on the sheet. The center of the spray was placed in the center of the sheet. Water (250mL) at room temperature was placed in a glass funnel and the test piece was sprayed (over a period of 25 to 30 seconds). The holding frame was removed from the base, one end of the holding frame was grasped with the front surface being the lower side, and the opposite end was lightly tapped with a hard substance. The holding frame is then rotated 180 deg., and the same procedure is repeated, allowing excess water droplets to fall. In order to score the wet test piece for water repellency in the order of poor to excellent 0, 50, 70, 80, 90 and 100, a comparison was made with a wet comparison standard. The results were obtained from the average of 3 measurements.
Production example 1
CF was placed in a 500ml reaction flask3CF2-(CF2CF2)n-CH2CH2OCOC(Cl)＝ CH2(N-2.0) (13FClA)51.2g, lauryl acrylate 85.4g, N-methylolacrylamide 2.7g, 3-chloro-2-hydroxypropyl methacrylate 1.3g, purified water 194g, water-soluble ethylene glycol solvent 34.1g, alkyltrimethylammonium chloride 6.3g, and polyoxyethylene alkyl ether 7.0g, and they were emulsified and dispersed with ultrasonic waves at 60 ℃ for 15 minutes under stirring. After the reaction flask was purged with nitrogen, a solution containing 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 nearly identical to that of the feed monomer.
Production example 2
CF was placed in a 1000mL autoclave3CF2-(CF2CF2)n-CH2CH2OCOC(Cl)＝ CH2(N-2.0) (13FClA)138g, Lauryl Acrylate (LA)51.0g, N-methylolacrylamide 5.2g, 3-chloro-2-hydroxypropyl methacrylate 2.6g, purified water 565g, water-soluble ethylene glycol solvent 47g, polyoxyethylene oleyl ether 2.5g, and polyoxyethylene alkyl ether 27.8g, and they were emulsified and dispersed with ultrasonic waves at 60 ℃ for 15 minutes under stirring. After the flask 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 nearly identical to that of the feed monomer.
Production example 3
Put into a 1000mL autoclaveInto CF3CF2-(CF2CF2)n-CH2CH2OCOC(Cl)＝ CH2(N-2.0) (13FClA)138g, stearyl acrylate (StA)51.0g, N-methylolacrylamide 5.2g, 3-chloro-2-hydroxypropyl methacrylate 2.6g, purified water 565g, water-soluble ethylene glycol solvent 47g, polyoxyethylene oleyl ether 2.5g, and polyoxyethylene alkyl ether 27.8g, and they were emulsified and dispersed with ultrasonic waves at 60 ℃ for 15 minutes under stirring. After the flask 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 nearly identical to that of the feed monomer.
Production example 4
CF was placed in a 500ml reaction flask3CF2-(CF2CF2)n-CH2CH2OCOC(Cl)＝CH2(N-2.0) (13FClA)51.2g, stearyl acrylate 85.4g, N-methylolacrylamide 2.7g, 3-chloro-2-hydroxypropyl methacrylate 1.3g, purified water 194g, water-soluble ethylene glycol solvent 34.1g, alkyltrimethylammonium chloride 6.3g, and polyoxyethylene alkyl ether 7.0g, and they were ultrasonically emulsified and dispersed at 60 ℃ for 15 minutes under stirring. After the reaction flask was purged with nitrogen, a solution containing 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 nearly identical to that of the feed monomer.
Production example 5
CF was placed in a 1000mL autoclave3CF2-(CF2CF2)n-CH2CH2OCOC(CH3)＝ CH2(N-2.0) (13FMA)138g, Lauryl Acrylate (LA)51.0g, N-methylolacrylamide 5.2g, 3-chloro-2-hydroxypropyl methacrylate 2.6g, purified water 565g, water-soluble ethylene glycol solvent 47g, polyoxyethylene oleyl ether 2.5g, and polyoxyethylene alkyl ether 27.8g, and they were emulsified and dispersed with ultrasonic waves at 60 ℃ for 15 minutes under stirring. After nitrogen substitution was performed in the flask, 62g of Vinyl Chloride (VCM) was charged under pressure, 0.4g of water-soluble initiator containing an azo group was added thereto, and the mixture was reacted at 60 ℃ for 20 minutesIn the course of time, an aqueous polymer dispersion was obtained. The composition of the polymer is nearly identical to that of the feed monomer.
Production example 6
CF was placed in a 1000mL autoclave3CF2-(CF2CF2)n-CH2CH2OCOC(CH3)＝ CH2(N-2.0) (13FMA)138g, stearyl acrylate (StA)51.0g, N-methylolacrylamide 5.2g, 3-chloro-2-hydroxypropyl methacrylate 2.6g, purified water 565g, water-soluble ethylene glycol solvent 47g, polyoxyethylene oleyl ether 2.5g, and polyoxyethylene alkyl ether 27.8g, and they were emulsified and dispersed with ultrasonic waves at 60 ℃ for 15 minutes under stirring. After the flask 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 nearly identical to that of the feed monomer.
Production example 7
CF was placed in a 1000mL autoclave3CF2-(CF2CF2)n-CH2CH2OCOC(Cl)＝ CH2(N-2.0) (13FClA)138g, Lauryl Acrylate (LA)51.0g, N-methylolacrylamide 5.2g, pure water 565g, water-soluble glycol solvent 47g, polyoxyethylene oleyl ether 2.5g, and polyoxyethylene alkyl ether 27.8g, and they were emulsified and dispersed with ultrasonic waves at 60 ℃ for 15 minutes under stirring. After the flask 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 nearly identical to that of the feed monomer.
Comparative production example 1
CF was placed in a 500ml reaction flask3CF2-(CF2CF2)n-CH2CH2OCOC(Cl)＝ CH251.2g of (n-2.0) (13FClA), 85.4g of lauryl acrylate, 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 ultrasonic waves at 60 ℃ for 15 minutes under stirring. Putting the reaction flask inAfter the nitrogen substitution, a solution containing 0.4g of an azo group-containing water-soluble initiator 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 nearly identical to that of the feed monomer.
Comparative production example 2
CF was placed in a 1000mL autoclave3CF2-(CF2CF2)n-CH2CH2OCOC(Cl)＝ CH2(n-2.0) (13FClA)138g, Lauryl Acrylate (LA)51.0g, purified water 565g, water-soluble glycol solvent 47g, polyoxyethylene oleyl ether 2.5g, and polyoxyethylene alkyl ether 27.8g, and they were emulsified and dispersed with ultrasonic waves at 60 ℃ for 15 minutes under stirring. After the flask 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 nearly identical to that of the feed monomer.
Comparative production example 3
CF was placed in a 1000mL autoclave3CF2-(CF2CF2)n-CH2CH2OCOC(Cl)＝ CH2(n-2.0) (13FClA)138g, stearyl acrylate (StA)51.0g, purified water 565g, water-soluble ethylene glycol solvent 47g, polyoxyethylene oleyl ether 2.5g, and polyoxyethylene alkyl ether 27.8g, and they were emulsified and dispersed with ultrasonic waves at 60 ℃ for 15 minutes under stirring. After the flask 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 nearly identical to that of the feed monomer.
Example 1
The aqueous liquid prepared in production example 1 was diluted with pure water so that the fluoropolymer concentration became 30% solids, and then diluted with water so that the proportion of the 30% dilution became 3%, and an amino group-containing dimethylsilicone latex softener was added so that the content became 2.5%, to prepare a test solution (100g) containing 3.00% of the aqueous liquid and 2.5% of the softener. PET, Nylon cloth (500 mm. times.200 mm) was immersed in the test solution, passed through a roller mill, and treated with a pin tenter (pin tenter) at 170 ℃ for 1 minute. Thereafter, a water repellency test was performed. The results are shown in Table A.
Example 2
The aqueous liquid prepared in preparation example 2 was diluted with pure water so that the fluoropolymer concentration became 30% solids, and then diluted with water so that the proportion of the 30% dilution became 3%, and an amino group-containing dimethylsilicone latex softener was added so that the content became 2.5%, to prepare a test solution (100g) containing 3.00% of the aqueous liquid and 2.5% of the softener. PET, Nylon cloth (500 mm. times.200 mm) was immersed in the test solution, passed through a roller mill, and treated with a pin tenter at 170 ℃ for 1 minute. Thereafter, a water repellency test was performed. The results are shown in Table 1.
Example 3
The aqueous liquid prepared in preparation example 3 was diluted with pure water so that the fluoropolymer concentration became 30% solids, and then diluted with water so that the proportion of the 30% dilution became 3%, and an amino group-containing dimethylsilicone latex softener was added so that the content became 2.5%, to prepare a test solution (100g) of 3.00% aqueous liquid and 2.5% softener. PET, Nylon cloth (500 mm. times.200 mm) was immersed in the test solution, passed through a roller mill, and treated with a pin tenter at 170 ℃ for 1 minute. Thereafter, a water repellency test was performed. The results are shown in Table 1.
Example 4
After diluting the aqueous liquid prepared in pure water production example 4 so that the fluoropolymer concentration became 30% solids, the aqueous liquid was further diluted with water so that the proportion of the 30% diluted liquid became 3%, and an amino group-containing dimethylsilicone latex softener was added so that the content became 2.5%, to prepare a test liquid (100g) containing 3.00% of the aqueous liquid and 2.5% of the softener. PET, Nylon cloth (500 mm. times.200 mm) was immersed in the test solution, passed through a roller mill, and treated with a pin tenter at 170 ℃ for 1 minute. Thereafter, a water repellency test was performed. The results are shown in Table 1.
Example 5
The aqueous liquid prepared in production example 5 was diluted with pure water so that the fluoropolymer concentration became 30% solids, and then diluted with water so that the proportion of the 30% dilution became 3%, and an amino group-containing dimethylsilicone latex softener was added so that the content became 2.5%, to prepare a test solution (100g) containing 3.00% of the aqueous liquid and 2.5% of the softener. PET, Nylon cloth (500 mm. times.200 mm) was immersed in the test solution, passed through a roller mill, and treated with a pin tenter at 170 ℃ for 1 minute. Thereafter, a water repellency test was performed. The results are shown in Table 1.
Example 6
The aqueous liquid prepared in preparation example 6 was diluted with pure water so that the fluoropolymer concentration became 30% solids, and then diluted with water so that the proportion of the 30% dilution became 3%, and an amino group-containing dimethylsilicone latex softener was added so that the content became 2.5%, to prepare a test solution (100g) containing 3.00% of the aqueous liquid and 2.5% of the softener. PET, Nylon cloth (500 mm. times.200 mm) was immersed in the test solution, passed through a roller mill, and treated with a pin tenter at 170 ℃ for 1 minute. Thereafter, a water repellency test was performed. The results are shown in Table 1.
Example 7
The aqueous liquid prepared in preparation example 7 was diluted with pure water so that the fluoropolymer concentration became 30% solids, and then diluted with water so that the proportion of the 30% dilution became 3%, and an amino group-containing dimethylsilicone latex softener was added so that the content became 2.5%, to prepare a test solution (100g) containing 3.00% of the aqueous liquid and 2.5% of the softener. PET, Nylon cloth (500 mm. times.200 mm) was immersed in the test solution, passed through a roller mill, and treated with a pin tenter at 170 ℃ for 1 minute. Thereafter, a water repellency test was performed. The results are shown in Table 1.
Example 8
The aqueous liquid produced in production example 1 was diluted with pure water so that the fluoropolymer concentration became 30% solids, and then diluted with water so that the proportion of the 30% dilution became 3%, and an antistatic agent comprising polyethylene glycol and a glycerin fatty acid ester (weight ratio 50: 50) was added so that the amount of the antistatic agent became 1.5%, to prepare a test solution (100g) containing 3.00% of the aqueous liquid and 1.5% of the antistatic agent. PET, Nylon cloth (500 mm. times.200 mm) was immersed in the test solution, passed through a roller mill, and treated with a pin tenter at 170 ℃ for 1 minute. Thereafter, a water repellency test was performed. The results are shown in Table 1.
Example 9
The aqueous liquid produced in production example 2 was diluted with pure water so that the fluoropolymer concentration became 30% solids, and then diluted with water so that the proportion of the 30% dilution became 3%, and an antistatic agent comprising polyethylene glycol and a glycerin fatty acid ester (weight ratio 50: 50) was added so that the amount of the antistatic agent became 1.5%, to prepare a test solution (100g) containing 3.00% of the aqueous liquid and 1.5% of the antistatic agent. PET, Nylon cloth (500 mm. times.200 mm) was immersed in the test solution, passed through a roller mill, and treated with a pin tenter at 170 ℃ for 1 minute. Thereafter, a water repellency test was performed. The results are shown in Table 1.
Example 10
The aqueous liquid produced in production example 3 was diluted with pure water so that the fluoropolymer concentration became 30% solids, and then diluted with water so that the proportion of the 30% dilution became 3%, and an antistatic agent comprising polyethylene glycol and a glycerin fatty acid ester (weight ratio 50: 50) was added so that the amount of the antistatic agent became 1.5%, to prepare a test solution (100g) containing 3.00% of the aqueous liquid and 1.5% of the antistatic agent. PET, Nylon cloth (500 mm. times.200 mm) was immersed in the test solution, passed through a roller mill, and treated with a pin tenter at 170 ℃ for 1 minute. Thereafter, a water repellency test was performed. The results are shown in Table 1.
Example 11
The aqueous liquid produced in production example 4 was diluted with pure water so that the fluoropolymer concentration became 30% solids, and then diluted with water so that the proportion of the 30% dilution became 3%, and an antistatic agent comprising polyethylene glycol and a glycerin fatty acid ester (weight ratio 50: 50) was added so that the amount of the antistatic agent became 1.5%, to prepare a test solution (100g) containing 3.00% of the aqueous liquid and 1.5% of the antistatic agent. PET, Nylon cloth (500 mm. times.200 mm) was immersed in the test solution, passed through a roller mill, and treated with a pin tenter at 170 ℃ for 1 minute. Thereafter, a water repellency test was performed. The results are shown in Table 1.
Example 12
The aqueous liquid produced in production example 5 was diluted with pure water so that the fluoropolymer concentration became 30% solids, and then diluted with water so that the proportion of the 30% dilution became 3%, and an antistatic agent comprising polyethylene glycol and a glycerin fatty acid ester (weight ratio 50: 50) was added so that the amount of the antistatic agent became 1.5%, to prepare a test solution (100g) containing 3.00% of the aqueous liquid and 1.5% of the antistatic agent. PET, Nylon cloth (500 mm. times.200 mm) was immersed in the test solution, passed through a roller mill, and treated with a pin tenter at 170 ℃ for 1 minute. Thereafter, a water repellency test was performed. The results are shown in Table 1.
Example 13
The aqueous liquid produced in production example 6 was diluted with pure water so that the fluoropolymer concentration became 30% solids, and then diluted with water so that the proportion of the 30% dilution became 3%, and an antistatic agent comprising polyethylene glycol and a glycerin fatty acid ester (weight ratio 50: 50) was added so that the amount of the antistatic agent became 1.5%, to prepare a test solution (100g) containing 3.00% of the aqueous liquid and 1.5% of the antistatic agent. PET, Nylon cloth (500 mm. times.200 mm) was immersed in the test solution, passed through a roller mill, and treated with a pin tenter at 170 ℃ for 1 minute. Thereafter, a water repellency test was performed. The results are shown in Table 1.
Example 14
The aqueous liquid prepared in production example 7 was diluted with pure water so that the fluoropolymer concentration became 30% solid content, and then diluted with water so that the proportion of the 30% diluted liquid became 3%, and an antistatic agent comprising polyethylene glycol and a glycerin fatty acid ester (weight ratio 50: 50) was added so that the amount of the antistatic agent became 1.5%, to prepare a test solution (100g) containing 3.00% of the aqueous liquid and 1.5% of the antistatic agent. PET, Nylon cloth (500 mm. times.200 mm) was immersed in the test solution, passed through a roller mill, and treated with a pin tenter at 170 ℃ for 1 minute. Thereafter, a water repellency test was performed. The results are shown in Table 1.
Comparative example 1
The aqueous liquid prepared in comparative preparation example 1 was diluted with pure water so that the fluoropolymer concentration became 30% solids, and then diluted with water so that the proportion of the 30% dilution became 3%, and an amino group-containing dimethylsilicone latex softener was added so that the content became 2.5%, to prepare a test solution (100g) of 3.00% aqueous liquid and 2.5% softener. PET, Nylon cloth (500 mm. times.200 mm) was immersed in the test solution, passed through a roller mill, and treated with a pin tenter at 170 ℃ for 1 minute. Thereafter, a water repellency test was performed. The results are shown in Table 1.
Comparative example 2
The aqueous liquid prepared in comparative preparation example 2 was diluted with pure water so that the fluoropolymer concentration became 30% solids, and then diluted with water so that the proportion of the 30% dilution became 3%, and an amino group-containing dimethylsilicone latex softener was added so that the content became 2.5%, to prepare a test solution (100g) of 3.00% aqueous liquid and 2.5% softener. PET, Nylon cloth (500 mm. times.200 mm) was immersed in the test solution, passed through a roller mill, and treated with a pin tenter at 170 ℃ for 1 minute. Thereafter, a water repellency test was performed. The results are shown in Table 1.
Comparative example 3
The aqueous liquid prepared in comparative preparation example 3 was diluted with pure water so that the fluoropolymer concentration became 30% solids, and then diluted with water so that the proportion of the 30% dilution became 3%, and an amino group-containing dimethylsilicone latex softener was added so that the content became 2.5%, to prepare a test solution (100g) of 3.00% aqueous liquid and 2.5% softener. PET, Nylon cloth (500 mm. times.200 mm) was immersed in the test solution, passed through a roller mill, and treated with a pin tenter at 170 ℃ for 1 minute. Thereafter, a water repellency test was performed. The results are shown in Table 1.
Comparative example 4
The aqueous liquid produced in comparative production example 1 was diluted with pure water so that the fluoropolymer concentration became 30% solids, and then further diluted with water so that the proportion of the 30% dilution became 3%, and an antistatic agent comprising polyethylene glycol and a glycerin fatty acid ester (weight ratio 50: 50) was added so that the amount of the antistatic agent became 1.5%, to prepare a test solution (100g) containing 3.00% of the aqueous liquid and 1.5% of the antistatic agent. PET, Nylon cloth (500 mm. times.200 mm) was immersed in the test solution, passed through a roller mill, and treated with a pin tenter at 170 ℃ for 1 minute. Thereafter, a water repellency test was performed. The results are shown in Table 1.
Comparative example 5
The aqueous liquid produced in comparative production example 2 was diluted with pure water so that the fluoropolymer concentration became 30% solids, and then further diluted with water so that the proportion of the 30% dilution became 3%, and an antistatic agent comprising polyethylene glycol and a glycerin fatty acid ester (weight ratio 50: 50) was added so that the amount of the antistatic agent became 1.5%, to prepare a test solution (100g) containing 3.00% of the aqueous liquid and 1.5% of the antistatic agent. PET, Nylon cloth (500 mm. times.200 mm) was immersed in the test solution, passed through a roller mill, and treated with a pin tenter at 170 ℃ for 1 minute. Thereafter, a water repellency test was performed. The results are shown in Table 1.
Comparative example 6
The aqueous liquid produced in comparative production example 3 was diluted with pure water so that the fluoropolymer concentration became 30% solids, and then further diluted with water so that the proportion of the 30% dilution became 3%, and an antistatic agent comprising polyethylene glycol and a glycerin fatty acid ester (weight ratio 50: 50) was added so that the amount of the antistatic agent became 1.5%, to prepare a test solution (100g) containing 3.00% of the aqueous liquid and 1.5% of the antistatic agent. PET, Nylon cloth (500 mm. times.200 mm) was immersed in the test solution, passed through a roller mill, and treated with a pin tenter at 170 ℃ for 1 minute. Thereafter, a water repellency test was performed. The results are shown in Table 1.
The abbreviation means as follows.
Figure BDA0000939133970000311
[ TABLE 1 ]
Figure BDA0000939133970000321
Industrial applicability of the invention
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 (12)

1. A fluorine-containing treating agent characterized by comprising,
which is a fluorine-containing treating agent for use in combination with (3) at least one auxiliary selected from a softening agent and an antistatic agent,
the fluorine-containing treatment agent contains:
(1) a fluorine-containing polymer having a repeating unit derived from (a) a fluorine-containing monomer having 1 to 6 carbon atoms in a fluoroalkyl group and a repeating unit derived from (b) a non-fluorine-containing monomer,
the fluorine-containing monomer (a) is a compound represented by the formula (I),
CH2＝C(-X)-C(＝O)-Y-Z-Rf (I)
wherein X is 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, CFX1X2A cyano group, a linear or branched fluoroalkyl group having 1 to 21 carbon atoms, a substituted or unsubstituted benzyl group, or a substituted or unsubstituted phenyl group, wherein X is1And X2Is hydrogen atom, fluorine atom, chlorine atom, bromine atom or iodine atom;
y is-O-or-NH-;
z is an aliphatic group having 1 to 10 carbon atoms, an aromatic group or a cyclic aliphatic group having 6 to 18 carbon atoms,
-CH2CH2N(R1)SO2A group in which R1An alkyl group having 1 to 4 carbon atoms,
-CH2CH(OZ1)CH2-(Ph-O)pA group, wherein Z1Is a hydrogen atom or an acetyl group, Ph is a phenylene group, p is 0 or 1,
-(CH2)n-Ph-O-group, wherein Ph is phenylene, n is 0 to 10,
-(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 6 carbon atoms,
the non-fluorine monomer is non-fluorine non-crosslinking monomer (b1) and non-fluorine crosslinking monomer (b2),
the non-fluorine non-crosslinkable monomer (b1) comprises a (meth) acrylate monomer having a non-cyclic aliphatic hydrocarbon group, wherein the (meth) acrylate monomer having a non-cyclic aliphatic hydrocarbon group is at least 1 monomer selected from the group consisting of lauryl (meth) acrylate, cetyl (meth) acrylate, stearyl (meth) acrylate and behenyl (meth) acrylate,
the non-fluorine crosslinkable monomer (b2) is a vinyl monomer having a hydroxyl group,
the vinyl monomer having a hydroxyl group is a compound represented by the following formula,
CH2＝CD1-C(＝O)-D2-D3-OH
in the formula, D1A halogen atom other than a hydrogen atom, a methyl group or a fluorine atom including a chlorine atom, a bromine atom and an iodine atom,
D2is-O-or-NH-,
D3is an organic group having 1 to 20 carbon atoms, and
(2) a liquid medium.
2. A fluorine-containing treatment agent according to claim 1, wherein:
the fluorine-containing monomer (a) is an acrylate in which the alpha position is substituted with a chlorine atom.
3. A fluorine-containing treatment agent according to claim 1, wherein:
in the fluorine-containing monomer (a), Rf has 6 carbon atoms.
4. A fluorine-containing treatment agent according to claim 1, wherein:
the auxiliary (3) is added to the fluoropolymer or the fluorine-containing treating agent after the completion of the polymerization reaction.
5. A fluorine-containing treatment agent according to claim 1, wherein:
the softening agent is at least one selected from silicone softening agents and polyethylene wax softening agents.
6. A fluorine-containing treatment agent according to claim 1, wherein:
the antistatic agent is a cationic surfactant and a nonionic surfactant.
7. A fluorine-containing treatment agent according to claim 1, wherein:
a water repellent compound containing no fluorine atom.
8. A fluorine-containing treatment agent according to claim 1, wherein:
the amount of the fluorine-containing monomer (a) in the fluorine-containing polymer is 95% by weight or less based on the polymer,
relative to 100 parts by weight of the fluorine-containing monomer (a),
the amount of the non-fluorine non-crosslinkable monomer (b1) is 1 to 40 parts by weight, and the amount of the non-fluorine crosslinkable monomer (b2) is 1 to 30 parts by weight.
9. A surface treatment agent composition characterized by comprising:
(1) a fluorine-containing polymer having a repeating unit derived from (a) a fluorine-containing monomer having 1 to 6 carbon atoms in a fluoroalkyl group and a repeating unit derived from (b) a non-fluorine-containing monomer,
the fluorine-containing monomer (a) is a compound represented by the formula (I),
CH2＝C(-X)-C(＝O)-Y-Z-Rf (I)
wherein X is 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, CFX1X2A cyano group, a linear or branched fluoroalkyl group having 1 to 21 carbon atoms, a substituted or unsubstituted benzyl group, or a substituted or unsubstituted phenyl group, wherein X is1And X2Is hydrogen atom, fluorine atom, chlorine atom, bromine atom or iodine atom;
y is-O-or-NH-;
z is an aliphatic group having 1 to 10 carbon atoms, an aromatic group or a cyclic aliphatic group having 6 to 18 carbon atoms,
-CH2CH2N(R1)SO2A group in which R1An alkyl group having 1 to 4 carbon atoms,
-CH2CH(OZ1)CH2-(Ph-O)pA group, wherein Z1Is a hydrogen atom or an acetyl group, Ph is a phenylene group, p is 0 or 1,
-(CH2)n-Ph-O-group, wherein Ph is phenylene, n is 0 to 10,
-(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 6 carbon atoms,
the non-fluorine monomer is non-fluorine non-crosslinking monomer (b1) and non-fluorine crosslinking monomer (b2),
the non-fluorine non-crosslinkable monomer (b1) comprises a (meth) acrylate monomer having a non-cyclic aliphatic hydrocarbon group, wherein the (meth) acrylate monomer having a non-cyclic aliphatic hydrocarbon group is at least 1 monomer selected from the group consisting of lauryl (meth) acrylate, cetyl (meth) acrylate, stearyl (meth) acrylate and behenyl (meth) acrylate,
the non-fluorine crosslinkable monomer (b2) is a vinyl monomer having a hydroxyl group,
the vinyl monomer having a hydroxyl group is a compound represented by the following formula,
CH2＝CD1-C(＝O)-D2-D3-OH
in the formula, D1A halogen atom other than a hydrogen atom, a methyl group or a fluorine atom including a chlorine atom, a bromine atom and an iodine atom,
D2is-O-or-NH-,
D3is an organic group having 1 to 20 carbon atoms,
(2) a liquid medium, and
(3) at least one auxiliary agent selected from the group consisting of softeners and antistatic agents.
10. The surface treatment composition according to claim 9, characterized in that:
the surface treatment agent composition is a water-and oil-repellent agent composition, an antifouling agent composition or a detergent composition.
11. A method for producing a surface treatment agent composition, characterized by comprising:
comprising the step of adding (3) at least one auxiliary selected from a softening agent and an antistatic agent to a fluorine-containing treatment agent,
the fluorine-containing treatment agent contains:
(1) a fluorine-containing polymer having a repeating unit derived from (a) a fluorine-containing monomer having 1 to 6 carbon atoms in a fluoroalkyl group and a repeating unit derived from (b) a non-fluorine-containing monomer,
the fluorine-containing monomer (a) is a compound represented by the formula (I),
CH2＝C(-X)-C(＝O)-Y-Z-Rf (I)
wherein X is 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, CFX1X2A cyano group, a linear or branched fluoroalkyl group having 1 to 21 carbon atoms, a substituted or unsubstituted benzyl group, or a substituted or unsubstituted phenyl group, wherein X is1And X2Is hydrogen atom, fluorine atom, chlorine atom, bromine atom or iodine atom;
y is-O-or-NH-;
z is an aliphatic group having 1 to 10 carbon atoms, an aromatic group or a cyclic aliphatic group having 6 to 18 carbon atoms,
-CH2CH2N(R1)SO2A group in which R1An alkyl group having 1 to 4 carbon atoms,
-CH2CH(OZ1)CH2-(Ph-O)pA group, wherein Z1Is a hydrogen atom or an acetyl group, Ph is a phenylene group, p is 0 or 1,
-(CH2)n-Ph-O-group, wherein Ph is phenylene, n is 0 to 10,
-(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 6 carbon atoms,
the non-fluorine monomer is non-fluorine non-crosslinking monomer (b1) and non-fluorine crosslinking monomer (b2),
the non-fluorine non-crosslinkable monomer (b1) comprises a (meth) acrylate monomer having a non-cyclic aliphatic hydrocarbon group, wherein the (meth) acrylate monomer having a non-cyclic aliphatic hydrocarbon group is at least 1 monomer selected from the group consisting of lauryl (meth) acrylate, cetyl (meth) acrylate, stearyl (meth) acrylate and behenyl (meth) acrylate,
the non-fluorine crosslinkable monomer (b2) is a vinyl monomer having a hydroxyl group,
the vinyl monomer having a hydroxyl group is a compound represented by the following formula,
CH2＝CD1-C(＝O)-D2-D3-OH
in the formula, D1A halogen atom other than a hydrogen atom, a methyl group or a fluorine atom including a chlorine atom, a bromine atom and an iodine atom,
D2is-O-or-NH-,
D3is an organic group having 1 to 20 carbon atoms, and
(2) a liquid medium.
12. A method of manufacturing a substrate, comprising:
comprising the step of applying the surface treatment agent composition as set forth in claim 9 or 10 to a substrate.
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