KR20170106236A - Surface treatment agent composition - Google Patents

Abstract

Provided is a fluorine-containing treatment agent capable of assigning excellent water and oil repellency when a softening agent for water-repellent oil-working processing such as a fiber or the like and/or an auxiliary agent such as an antistatic agent is used together. The fluorine-containing treatment agent comprises: (1) (a) a repeating unit derived from a fluorine-containing monomer having a carbon number of 1-6 of a fluoroalkyl group, and (b) a fluorine-containing polymer having a repeating unit derived from a non-fluorine crosslinking monomer which is a vinyl monomer having a hydroxyl group; and (2) a liquid medium. (3). The fluorine-containing treating agent is combined with at least one auxiliary agent selected from a group composed of the softening agent and the antistatic agent.

Description

[0001] SURFACE TREATMENT AGENT COMPOSITION [0002]

The present invention relates to a surface treatment composition such as a water- and oil-repellent composition comprising a treating agent, particularly a fluorine-containing polymer mixture. More specifically, the present invention relates to a water repellent, oil repellent, and antifouling property, particularly a water repellent property of a fiber product (such as a carpet), paper, nonwoven fabric, stone, electrostatic filter, dustproof mask, Oil repellent composition which can impart excellent water repellency and oil repellency even when a softener or an antistatic agent is used in combination.

Conventionally, various fluorine-containing compounds have been proposed. The fluorine-containing compound has an advantage of excellent properties such as heat resistance, oxidation resistance and weather resistance. Using the characteristic that the free energy of the fluorine-containing compound is low, that is, it is difficult to adhere, the fluorine-containing compound is used, for example, as a water- and oil- repellent agent and an antifouling agent.

As the fluorine-containing compound which can be used as a water- and oil-repellent agent, a fluorine-containing polymer having a (meth) acrylate ester having a fluoroalkyl group as a constituent monomer can be given. In the practical treatment of the surface treatment agent with the fibers, from various research results so far, it is shown that the dynamic contact angle, especially the receding contact angle, is important as the surface property thereof, not the static contact angle. That is, although the advancing contact angle of water does not depend on the number of carbon atoms in the side chain of the fluoroalkyl group, the receding contact angle of water is remarkably small at 7 or less as compared with 8 or more carbon atoms in the side chain. Corresponding to this, the X-ray analysis shows that crystallization of the side chain occurs when the carbon number of the side chain is 7 or more. It has been known that practical water repellency has a correlation with the crystallinity of the side chain and that the mobility of the surface treatment agent molecule is an important factor for manifesting practical performance (for example, Maekawa Takashige, Fine Chemical, Vol 23, No. 6, P12 (1994)). For this reason, the (meth) acrylate polymer having a short fluoroalkyl group with a number of carbon atoms in the side chain of not more than 7 (in particular, not more than 6) has a low crystallinity of the side chain, . Further, in the water-repellent oil-repellent processing, there are many processing for the auxiliary agent combination with the softening agent and the antistatic agent, and there is a problem that the practical performance is not satisfied when these agents are used together.

Japanese Patent Application Laid-Open No. 2001-98257 discloses a polymer (A) containing polymerized units of a polymerizable monomer having a polyfluoroalkyl group, a surfactant (B) having a specific Dreve wetting time, and an aqueous medium ) As an essential component.

Japanese Patent Application Laid-Open No. 2004-262970 discloses a water- and oil-repellent aqueous composition containing a fluorinated water- and oil-repellent agent (A), an emulsion (B) containing paraffin wax and a carboxyl-containing polyethylene, and an organic acid (C).

These publications do not describe the processing for combining auxiliary agents.

Japanese Patent Application Laid-Open No. 2001-98257 Japanese Patent Application Laid-Open No. 2004-262970

It is an object of the present invention to provide a fluorine-containing treatment agent capable of imparting excellent water-repellent and oil-repellent properties when a softening agent for water-repellent oil-working processing such as fibers and / or an auxiliary agent such as an antistatic agent is used in combination.

The present invention

(1) a copolymer comprising (a) a repeating unit derived from a fluorine-containing monomer having 1 to 6 carbon atoms in a fluoroalkyl group, and

(b) a fluorine-containing polymer having a repeating unit derived from a non-fluorine-crosslinkable monomer which is a vinyl monomer having a hydroxyl group,

(2) Liquid media

Containing treatment agent,

The fluorine-

(3) at least one auxiliary agent selected from the group consisting of a softening agent and an antistatic agent.

In addition,

(1) a copolymer comprising (a) a repeating unit derived from a fluorine-containing monomer having 1 to 6 carbon atoms in a fluoroalkyl group, and

(b) a fluorine-containing polymer having a repeating unit derived from a non-fluorine-crosslinkable monomer which is a vinyl monomer having a hydroxyl group,

(2) a liquid medium,

(3) at least one auxiliary agent selected from the group consisting of a softener and an antistatic agent.

In addition,

(1) a copolymer comprising (a) a repeating unit derived from a fluorine-containing monomer having 1 to 6 carbon atoms in a fluoroalkyl group, and

(b) a fluorine-containing polymer having a repeating unit derived from a non-fluorine-crosslinkable monomer which is a vinyl monomer having a hydroxyl group,

(2) Liquid media

A fluorine-containing treating agent,

(3) adding at least one auxiliary agent selected from the group consisting of a softener and an antistatic agent to the surface treatment agent composition.

The fluorine-containing treating agent of the present invention can impart excellent water repellency and oil repellency when used together with adjuvants such as a softening agent and an antistatic agent.

According to the present invention, durability excellent in excellent water repellency, oil repellency, antifouling property and stain releasing property, for example, water repellency and oil repellency is 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 decontamination agent composition.

The fluorine-containing treatment agent includes the fluorine-containing polymer (1) and the liquid medium (2).

The surface treatment agent composition includes a fluorine-containing polymer (1), a liquid medium (2) and an auxiliary agent (3). The surface treatment agent composition is a combination (mixture) of the fluorine-containing treatment agent and the auxiliary agent (3). The surface treating agent composition is prepared by adding the auxiliary agent (3) to the fluorine-containing treating agent before treating the substrate.

(1) The fluorine-containing polymer

The fluorine-containing polymer has a repeating unit derived from a monomer such as a fluorine-containing monomer.

The fluorine-containing polymer may be a homopolymer or a copolymer of the fluorine-containing monomer (a). The fluorine-containing polymer may have, in addition to the repeating unit derived from the fluorine-containing monomer, a repeating unit derived from the non-fluorine monomer (b). Each of the monomers such as the fluorine-containing monomer (a) may be used alone or in combination of two or more.

(a) a fluorine-containing monomer

The fluorine-containing monomer is generally a polymerizable compound having a fluoroalkyl group or a fluoroalkenyl group and an acrylic acid group or a methacrylic acid group or an? -Substituted acrylic acid group. The term "? -Substituted acrylic acid group" means a group in which a hydrogen atom at? -Position of an acrylic acid group is substituted with a group such as Cl, Br, I, F, CN, CF ₃ or the like.

The fluoroalkyl group is preferably a perfluoroalkyl group and has 1 to 6 carbon atoms. The fluoroalkenyl group is preferably a perfluoroalkenyl group and has 2 to 6 carbon atoms.

The fluorine-containing monomer has the formula:

CH ₂ = C (-X) -C (= O) -YZ-Rf (I)

Wherein X is a hydrogen atom, a monovalent organic group or a halogen atom,

Y is -O- or -NH-,

Z is a direct bond or a divalent organic group,

Rf is a fluoroalkyl group having 1 to 6 carbon atoms]

Is preferable.

In the formula (I) in the fluorine-containing monomer, X is a hydrogen atom, a C 1 -C 21 linear or branched alkyl group, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, a CFX ¹ X ² group (where the , X ¹ and X ² are each a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom or an iodine atom), a cyano group, a straight or branched fluoroalkyl group having 1 to 21 carbon atoms, a substituted or unsubstituted benzyl group, It is preferably a substituted or unsubstituted phenyl group. Representative examples of X are a hydrogen atom, a methyl group, Cl, Br, I, F, CN, CF ₃ . X is preferably Cl.

Y is preferably -O-.

Z is, for example, a direct bond, a linear or branched aliphatic group having 1 to 20 carbon atoms (particularly an alkylene group) such as a group of the formula - (CH ₂ ) _x - wherein x is 1 to 10, A group represented by the formula -R ² (R ¹ ) N-SO ₂ - or a group represented by the formula -R ² (R ¹ ) N-CO- (wherein R ¹ represents an alkyl group having 1 to 10 carbon atoms and, R ² has 1 to 10 carbon atoms of the linear alkylene group or branched alkylene group), or the formula ^{_{-CH 2 CH (oR 3) CH}} 2 - (Ar-O) p - ( wherein, R ³ is A hydrogen atom or an acyl group having 1 to 10 carbon atoms (for example, formyl or acetyl), Ar represents an arylene group optionally having substituent (s), p represents 0 or 1, (CH ₂ ) _m -SO ₂ - (CH ₂ ) _m -SO ₂ - (CH ₂ ) _m- , -CH ₂ -Ar- (O) _q - wherein Ar represents an arylene group optionally having substituents and q is 0 or 1, CH ₂ ) _n - group or - (CH ₂ ) _m -S- (CH ₂ ) _n - group (provided that m is 1 to 10 and n is 0 to 10).

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, -CH ₂ CH ₂ N (R ¹ ) SO ₂ - group (wherein R ¹ is an alkyl group having 1 to 4 carbon atoms ^{_{), -CH 2 CH (OZ 1}} ) CH 2 - (Ph-O) p - group (where, Z ¹ is a hydrogen atom or an acetyl group, Ph is a phenylene group, p is 0 or 1), - (CH ₂ ) _n -Ph-O- group (where, Ph is a phenylene group, n is _{0-10), - (CH 2) m} -SO 2 - (CH 2) n - group or a - (CH _{2) m} -S - (CH ₂ ) _n - group (provided that m is 1 to 10 and n is 0 to 10). The aliphatic group is preferably an alkylene group (especially having 1 to 4 carbon atoms, for example 1 or 2). The aromatic group or the cyclic aliphatic group may be substituted or unsubstituted. The S group or the SO ₂ group may be bonded directly to the R f group.

The Rf group is preferably a perfluoroalkyl group. The carbon number of the Rf group is 1 to 6, preferably 4 to 6, especially 6. Containing monomer having 1 to 20 carbon atoms in the Rf group may be used, but it is preferable that the fluorine-containing monomer is composed only of a compound having an Rf group of 4 to 6, especially 6, carbon atoms.

Specific examples of the fluorine-containing monomer include, but are not limited to, the following.

[Wherein Rf is a fluoroalkyl group having 1 to 6 carbon atoms]

(b) a 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 one ethylenically unsaturated double bond.

The non-fluorine monomer (b) may be a non-fluorine-containing monomer (b1) or a non-fluorine-crosslinkable monomer (b2).

Examples of the non-fluorine-incompatible monomer (b1)

CH ₂ = CA-T

[Wherein A is a hydrogen atom, a methyl group, or a halogen atom (e.g., a chlorine atom, a bromine atom and an iodine atom) other than a fluorine atom,

T represents a hydrogen atom, a halogen atom other than a fluorine atom (for example, a chlorine atom, a bromine atom and an iodine atom), a straight or cyclic hydrocarbon group having 1 to 30 carbon atoms, or a straight or cyclic C1- To 31 (or 1 to 30)

May be used.

Examples of the straight or branched chain hydrocarbon group of 1 to 30 carbon atoms include linear or branched saturated or unsaturated (for example, ethylenic unsaturated) aliphatic hydrocarbon groups of 1 to 30 carbon atoms, saturated or unsaturated (For example, ethylenic unsaturation), an aromatic hydrocarbon group having 6 to 30 carbon atoms, and an aromatic aliphatic hydrocarbon group having 7 to 30 carbon atoms.

-C (= O) -OQ and -OC (= O) -Q (wherein Q represents an organic group having 1 to 30 carbon atoms, (Or ethylenically unsaturated) aliphatic hydrocarbon group of 1 to 30 (or 1 to 20) linear or branched, saturated or unsaturated (e.g., ethylenically unsaturated), saturated or unsaturated (Or unsaturated) cyclic aliphatic group, an aromatic hydrocarbon group having 6 to 30 (or 6 to 20) carbon atoms, and an aromatic aliphatic hydrocarbon group having 7 to 30 (or 7 to 20) carbon atoms.

The non-fluorine-containing non-crosslinking monomer (b1) may be a (meth) acrylate ester monomer (b1-1) and a halogenated olefin monomer (b1-2).

Examples of the (meth) acrylate ester monomer (b1-1)

CH ₂ = CA ²¹ -C (= O) -OA ²²

Wherein A ²¹ is a hydrogen atom, a monovalent organic group or a halogen atom other than a fluorine atom, and A ²² is a hydrocarbon group having 1 to 30 carbon atoms]

May be used.

A ²¹ is preferably a hydrogen atom, a methyl group or a chlorine atom.

A ²² (hydrocarbon group) may be a non-cyclic aliphatic hydrocarbon group having 1 to 30 carbon atoms and a cyclic hydrocarbon-containing group having 4 to 30 carbon atoms. Specific examples of the acyclic aliphatic hydrocarbon group include lauryl, cetyl, stearyl and behenyl. Specific examples of the cyclic hydrocarbon group include a cyclohexyl group, a t-butylcyclohexyl group, an isobornyl group, a dicyclopentanyl group, a dicyclopentenyl group and an adamantyl group.

Specific examples of the (meth) acrylate ester monomer having an acyclic aliphatic hydrocarbon group include lauryl (meth) acrylate, cetyl (meth) acrylate, stearyl (meth) acrylate, behenyl to be.

Specific examples of the (meth) acrylate ester monomer having a cyclic hydrocarbon-containing group include cyclohexyl (meth) acrylate, t-butylcyclohexyl (meth) acrylate, benzyl (meth) acrylate, isobornyl Acrylate, dicyclopentanyl (meth) acrylate, dicyclopentanyl (meth) acrylate, dicyclopentenyl (meth) acrylate, dicyclopentenyl Methyl-2-adamantyl (meth) acrylate, 2-ethyl-2-adamantyl (meth) acrylate and the like.

The halogenated olefin monomer (b1-2) has no fluorine atom.

The halogenated olefin monomer may be an olefin having 2 to 20 carbon atoms which is 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 vinyl halides such as vinyl chloride, vinyl bromide, vinyl iodide, vinylidene halides such as vinylidene chloride, vinylidene bromide, and vinylidene iodide. Water repellency and oil repellency (in particular, durability of water repellency and oil repellency) becomes high, vinyl chloride and vinylidene chloride are preferable.

(b2) a non-fluorine-crosslinkable monomer

The non-fluorine-crosslinkable monomer (b2) is a monomer that does not contain a fluorine atom. The non-fluorine-crosslinkable monomer may be a compound having at least two reactive groups and / or olefinic carbon-carbon double bonds (preferably, a (meth) acrylate group) and not containing fluorine. The non-fluorine-crosslinkable monomer is a compound having at least two olefinic carbon-carbon double bonds (preferably (meth) acrylate groups), or a compound having at least one olefinic carbon-carbon double bond and at least one reactive group Compound. Examples of the reactive group include a hydroxyl group, an epoxy group, a chloromethyl group, a block isocyanate group, an amino group, and a carboxyl group.

The non-fluorine-crosslinkable monomer may be mono (meth) acrylate, di (meth) acrylate or mono (meth) acrylamide having a reactive group. Alternatively, the non-fluorine-crosslinkable monomer may be di (meth) acrylate.

A vinyl monomer having a hydroxyl group (particularly, an acrylate monomer or an acrylamide monomer) is used as a non-fluorine-crosslinkable monomer.

The preferred vinyl monomer having a hydroxyl group is represented by the formula:

CH ₂ = CD ¹ -C (═O) -D ² -D ³ -OH

[In the formula, D ¹ represents a hydrogen atom, a methyl group, or a halogen atom other than a fluorine atom (e.g., a chlorine atom, a bromine atom and an iodine atom)

D ² is -O- or -NH-,

D ³ represents an organic group having 1 to 20 carbon atoms, for example, a linear or branched aliphatic group having 1 to 20 carbon atoms (particularly an alkylene group) such as a group represented by the formula - (CH ₂ ) _x - Is 1 to 20, especially 1 to 10)

≪ / RTI >

Examples of the vinyl monomer having a hydroxyl group include N-methylol (meth) acrylamide, N-2-propanol (meth) acrylamide, N-butylol (meth) acrylamide, hydroxyethyl The rate is exemplified.

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 per 100 parts by weight of the fluorine-containing monomer (a).

The nonfluorine-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 block isocyanate group, an amino group and / do.

Preferred non-fluorine crosslinking monomers are those having the formula:

CH ₂ = CE ¹ -C (= O) -E ² -E ³

[Wherein E ¹ represents a hydrogen atom, a methyl group, or a halogen atom other than a fluorine atom (e.g., a chlorine atom, a bromine atom and an iodine atom)

E ² is -O- or -NH-,

E ³ is a hydroxyl group, an epoxy group, a chloromethyl group, a block isocyanate group, an amino group, or a carboxyl group]

≪ / RTI >

Examples of the nonfluorine-crosslinkable monomer (b2) include diacetone (meth) acrylamide, (meth) acrylamide, 3-chloro-2-hydroxypropyl (meth) acrylate, 2-acetoacetoxyethyl (Meth) acrylate, 1,6-hexanediol di (meth) acrylate, neopentyl glycol di (meth) acrylate, and the like.

(c) Other monomers

The fluorine-containing polymer may contain monomers other than the monomers (a) and (b).

Examples of other monomers (c) include monomers such as ethylene, vinyl acetate, acrylonitrile, styrene, polyethylene glycol (meth) acrylate, polypropylene glycol (meth) acrylate, methoxypolyethylene glycol (meth) Methoxypolypropylene glycol (meth) acrylate, vinyl alkyl ether, and the like. Other monomers are not limited to these examples.

Each of monomers (a) to (c) may be a single monomer or a mixture of two or more monomers.

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 wt% or less, for example, 80 wt% or less, or 75 wt% or less, or 70 wt% or less with respect to the polymer.

In the polymer, relative to 100 parts by weight of the monomer (a)

The amount of the repeating unit (b1) is 0 to 200 parts by weight, preferably 1 to 40 parts by weight,

The amount of the repeating unit (b2) is 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, relative to 100 parts by weight of the monomer (a)

The amount of the repeating unit (b1-1) is 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 fluorine-containing polymer (solid content) may be about 0.01 to 60% by weight, preferably about 0.1 to 40% by weight, particularly preferably about 5 to 35% by weight, based on the fluorine-containing treating agent or the surface treatment agent composition .

The fluorine-containing polymer may be present in the form of a solution dissolved in an organic solvent, but is preferably present in the form of an aqueous dispersion.

In the present specification, when it is simply referred to as "acrylate" or "acrylamide", not only a compound in which the α-position is a hydrogen atom but also a compound having an α-position in another group (eg, a monovalent organic group containing a methyl group or halogen Atoms). ≪ / RTI > In the present specification, "(meth) acrylate" means acrylate or methacrylate, and "(meth) acrylamide" means acrylamide or methacrylamide.

Each of the monomer (a), the monomer (b) and the monomer (c) may be a single type, or a combination of two or more types.

(2) Liquid media

The liquid medium may be an aqueous medium. The liquid medium may be water alone or a mixture of water and (water-miscible) organic solvent. The amount of the organic solvent may be 30 wt% or less, for example, 10 wt% or less (preferably 0.1 wt% or more) with respect to 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 the surface treatment agent composition).

(3) Supplements

The surface treatment agent composition of the present invention contains at least one auxiliary agent selected from the group consisting of softening agents and antistatic agents. Generally, the adjuvant is added to the fluorine-containing polymer (or the fluorine-containing treatment agent) after completion of the polymerization reaction.

The adjuvant (softening agent and / or antistatic agent) may be a surfactant. In the case where the adjuvant is a surfactant, since the adjuvant is added after completion of the polymerization reaction, the adjuvant can be distinguished from the surfactant (polymerization surfactant) used for polymerizing the monomer.

The surfactant may be contained in the fluorine-containing treating agent (surfactant for polymerization). When the fluorine-containing treating 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 one selected from a nonionic surfactant, a cationic surfactant, an anionic surfactant and a positive surfactant.

(3-1) Nonionic surfactant

Examples of the nonionic surfactant include ethers, esters, ester ethers, alkanolamides, polyhydric alcohols and amine oxides.

An example of an ether is a compound having an oxyalkylene group (preferably a polyoxyethylene group).

Examples of esters are esters of alcohols and fatty acids. Examples of alcohols are alcohols having 1 to 6 carbon atoms (especially 2 to 5 carbon atoms) and 1 to 50 carbon atoms (particularly 3 to 30 carbon atoms) (for example, aliphatic alcohols). Examples of fatty acids are saturated or unsaturated fatty acids having 2 to 50 carbon atoms, especially 5 to 30 carbon atoms.

Examples of ester ethers are compounds obtained by adding an alkylene oxide (particularly, ethylene oxide) to an ester of an alcohol and a fatty acid. Examples of alcohols are alcohols having 1 to 6 carbon atoms (especially 2 to 5 carbon atoms) and 1 to 50 carbon atoms (particularly 3 to 30 carbon atoms) (for example, aliphatic alcohols). Examples of fatty acids are saturated or unsaturated fatty acids having 2 to 50 carbon atoms, especially 5 to 30 carbon atoms.

Examples of alkanolamides are formed with fatty acids and alkanolamines. The alkanolamide may be a monoalkanolamide or a dialkanolamide. Examples of fatty acids are saturated or unsaturated fatty acids having 2 to 50 carbon atoms, especially 5 to 30 carbon atoms. The alkanolamine may be an alkanol having 2 to 50 carbon atoms, especially 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 from 2 to 5 carbon atoms and having from 15 to 30 carbon atoms.

The amine oxides may be oxides of amines (secondary amines or preferably tertiary amines) (for example, 5 to 50 carbon atoms).

The nonionic surfactant is preferably a nonionic surfactant having an oxyalkylene group (preferably a polyoxyethylene group). The number of carbon atoms of the alkylene group in the oxyalkylene group is preferably 2 to 10. The number of oxyalkylene groups in the molecule of the nonionic surfactant is generally preferably from 2 to 100.

The nonionic surfactant is preferably selected from the group consisting of 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 selected from alkylene oxide adducts of straight chain and / or branched aliphatic (saturated and / or unsaturated) groups, linear or branched fatty acids (saturated and / or unsaturated) Glycol esters, polyoxyethylene (POE) / polyoxypropylene (POP) copolymers (random copolymers or block copolymers), and alkylene oxide adducts of acetylene glycol. Of these, polyoxyethylene (POE), polyoxypropylene (POP) or POE / POP copolymer (which may be a random copolymer or a block copolymer) may be used as the structure of the alkylene oxide addition moiety and polyalkylene glycol moiety desirable.

The nonionic surfactant is preferably a structure free from aromatic groups from environmental problems (biodegradability, environmental hormones, etc.).

The nonionic surfactant has the formula:

R ¹ O- (CH ₂ CH ₂ O) _p - (R ² O) _q -R ³

Wherein R ¹ is an alkyl group having 1 to 22 carbon atoms or an alkenyl group or an acyl group having 2 to 22 carbon atoms,

Each of R < ² > is independently the same or different and is an alkylene group having 3 or more carbon atoms (e.g., 3 to 10 carbon atoms)

R ³ is 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]

May be used.

R ^{1 preferably} has 8 to 20 carbon atoms, and more preferably 10 to 18 carbon atoms. Specific preferred examples of R ¹ include a lauryl group, a tridecyl group and an oleyl group.

Examples of R ² are a propylene group and a butylene group.

In the nonionic surfactant, p may be 3 or more (e.g., 5 to 200). q may be 2 or more (for example, 5 to 200). That is, - (R ² O) _q - may form a polyoxyalkylene chain.

The nonionic surfactant may be a polyoxyethylene alkylene alkyl ether having a hydrophilic polyoxyethylene chain at the center and a hydrophobic oxyalkylene chain (particularly, a polyoxyalkylene chain). Examples of the hydrophobic oxyalkylene chain include oxypropylene chain, oxybutylene chain and styrene chain. Of these, oxypropylene chain is preferable.

Preferred nonionic surfactants have the formula:

R ¹ O- (CH ₂ CH ₂ O) _p -H

Wherein R < ¹ > and p are as defined above,

Lt; / RTI >

Examples of nonionic surfactants include,

[Wherein p and q are as defined above]

.

Specific examples of the nonionic surfactant include a mixture of ethylene oxide and at least one of hexylphenol, isooctylphenol, hexadecanol, oleic acid, alkane (C ₁₂ -C ₁₆ ) thiol, sorbitan mono fatty acid (C ₇ -C ₁₉ ) C ₁₂ -C ₁₈ ) amine, and the like.

The proportion of the polyoxyethylene block may be from 5 to 80% by weight, for example from 30 to 75% by weight, in particular from 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 from 300 to 5,000, for example from 500 to 3,000.

The nonionic surfactants may be used singly or in combination of two or more.

The nonionic surfactant is preferably a combination of two or more. In at least one of the combinations, the at least one nonionic surfactant is at least one nonionic surfactant selected from the group consisting of R ¹ O- (CH ₂ ) (where R ¹ group and / or R ³ group is a branched alkyl group CH ₂ O) _p - (R ² O) _q -R ³ [particularly, R ¹ O- (CH ₂ CH ₂ O) _p -H]. The amount of the nonionic surfactant in which the R ¹ group is an alkyl group in the branch may be 5 to 100 parts by weight, for example 8 to 50 parts by weight, especially 10 to 40 parts by weight, based on 100 parts by weight of the total amount of the nonionic surfactant. In the combination of two or more kinds, the remaining nonionic surfactant is a nonionic surfactant in which the R ¹ group (and / or the R ³ group) is a linear alkyl group (saturated or unsaturated) (for example, a lauryl group group)) of _{^{R 1 O- (CH 2 CH 2}} O) p - (R 2 O) q -R 3 may be a compound represented by the following [in _{^{particular, R 1 O- (CH 2 CH}} 2 O) p -H] .

Examples of the nonionic surfactant include polyoxyethylene alkyl ethers, polyoxyethylene alkyl phenyl ethers, polyoxyethylene fatty acid esters, sorbitan fatty acid esters, polyoxyethylene sorbitan fatty acid esters, polyoxyethylene sorbitol fatty acid esters, glycerin fatty acid esters A polyoxyethylene alkylamine, a polyoxyethylene fatty acid amide, a fatty acid alkylolamide, an alkylalkanolamide, an acetylene glycol, an oxyethylene adduct of acetylene glycol, a polyoxyethylene alkylene oxide adduct, a polyoxyethylene alkylene oxide adduct, a polyoxyethylene sorbitan fatty acid ester, a polyoxyethylene glycerin fatty acid ester, a polyglycerin fatty acid ester, , Polyethylene glycol polypropylene glycol block copolymer, and the like. Polyoxyethylene alkyl ethers and polyoxyethylene sorbitan fatty acid esters are preferred. And polyoxyethylene alkyl ethers are more preferred.

(3-2) Cationic surfactant

The cationic surfactant is preferably a compound having no amide group.

The cationic surfactant may be an amine salt, a quaternary ammonium salt or an oxyethylene addition type ammonium salt. Specific examples of the cationic surfactant include, but are not limited to, alkylamine salts, aminoalcohol fatty acid derivatives, polyamine fatty acid derivatives, amine salt type surfactants such as imidazoline, alkyltrimethylammonium salts, dialkyldimethylammonium salts, alkyldimethylbenzylammonium salts, Quaternary ammonium salt type surfactants such as pyridinium salts, alkylisoquinolinium salts and benzethonium chloride, and the like.

Preferable examples of the cationic surfactant include,

^{R 21 -N + (-R 22)} (- R 23) (- R 24) X -

Wherein R ²¹ , R ²² , R ²³ and R ²⁴ represent a hydrocarbon group having 1 to 30 carbon atoms,

X is an anionic group]

Lt; / RTI >

Specific examples of R ²¹ , R ²² , R ²³ and R ²⁴ are alkyl groups (for example, methyl group, butyl group, stearyl group, palmity group). Specific examples of X are halogen (e.g., chlorine), acid (e.g., hydrochloric acid, acetic acid).

It is particularly preferred that the cationic surfactant is a monoalkyltrimethylammonium salt (alkyl having 4 to 30 carbon atoms).

The cationic surfactant is preferably an ammonium salt. The cationic surfactant has the formula:

R ¹ _p -N ⁺ R ² _q X ^-

Wherein R ¹ is a straight chain and / or branched aliphatic (saturated and / or unsaturated) group of C ₁₂ or more (for example, C ₁₂ to C ₅₀ )

R ² is H or a C ₁ to C ₄ alkyl group, a benzyl group, a polyoxyethylene group (the number of oxyethylene groups is, for example, 1 (particularly 2, particularly 3) to 50)

(CH ₃ , C ₂ H ₅ being particularly preferred),

X is a halogen atom (e.g., a chlorine atom), a C ₁ to C ₄ fatty acid base,

p is 1 or 2, q is 2 or 3, and p + q = 4.

May be an ammonium salt. The carbon number of R ¹ 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, methyl (Diethylamino) ethyl] oleamide hydrochloride, dialkyl (reduced Uji) dimethylammonium chloride, and the like can be used in combination with a base such as sodium hydride, sodium hydride, sodium hydride, sodium hydride, . Cationic emulsifiers having an ammonium chloride structure are preferred. More preferred are cationic emulsifiers having an ammonium chloride structure having a long-chain (e.g., 10 to 30, especially 14 to 24) hydrocarbon groups (particularly alkyl groups) such as octadecyl or hexadecyl.

(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 methyl taurine, sodium polyoxyethylene palmitoyl ether sulfate, sodium diethylhexyl sulfosuccinate, sodium alpha -olefin sulfonate, sodium lauryl phosphate, sodium polyoxyethylene lauryl ether phosphate, perfluoroalkyl carboxylate (Trade name: Unidyne DS-101, 102 (manufactured by Daikin Industries, Ltd.)). The anionic surfactant is preferably a salt of an organic acid (for example, a salt with an organic acid and an inorganic base or an amine). Alkyl sulfate ester salts (e.g., ROSO ₃ ^- M ⁺⁾ (. The number of carbon atoms of the alkyl group (R group), for example 8 to 30 Im M is an alkali metal (e.g., sodium or potassium) Im) are more desirable.

(3-4) Amphoteric surfactant

Specific examples of the amphoteric surfactant include amine oxides, alanines, imidazolinium betaines, amide betaines, and betaine acetate. Specific examples thereof include lauryl betaine, stearyl betaine, lauryl carboxy Methylhydroxyethylimidazolium betaine, lauryldimethylaminoacetic acid betaine, fatty acid amidopropyldimethylaminoacetic acid betaine, and the like. Amine oxides (for example, R ₃ N = O (each R group is, for example, a hydrocarbon group (especially an alkyl group) having 1 to 30 carbon atoms)) is preferable.

The nonionic surfactant, the cationic surfactant, the anionic surfactant, and the amphoteric surfactant may each be used alone or in combination of two or more.

The adjuvant (particularly, surfactant) is preferably a compound having a long-chain alkyl group and / or a long-chain alkenyl group. The long-chain alkyl group and long-chain alkenyl group preferably have 10 to 30 carbon atoms, for example, 14 to 24 carbon atoms. The long-chain alkyl group and the long-chain alkenyl group are preferably interrupted by an ester bond or an amide bond. The adjuvant 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 a silicone type softening agent (for example, dimethylsilicone (generally an emulsion) having at least one functional group such as an epoxy group, a primary or secondary amino group or a vinyl group), a polyethylene type softening agent (for example, polyethylene wax Cationic softening agents such as ester type quaternary ammonium salts quaternized with an alkylating agent such as methyl chloride or dimethyl sulfate, ester compounds of triethanolamine and long chain fatty acids (fatty acids having 10 to 30 carbon atoms) Anionic softening agents such as ester salts, polyhydric alcohol fatty acid esters, polyethylene glycol fatty acid esters, and nonionic softening agents such as polyethylene glycol alkyl ethers. Silicone type softening agent and polyethylene wax type softening agent are preferable. More preferably a silicone type softening agent which is an emulsion of dimethyl silicone having at least one functional group of 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 include a nonionic antistatic agent (nonionic surfactant), a cationic antistatic agent (cationic surfactant), an anionic antistatic agent (anionic surfactant), a positive antistatic agent (amphoteric surfactant) Antistatic agent.

Examples of the nonionic antistatic agent include glycerin fatty acid esters, polyoxyethylene alkyl ethers, polyoxyethylene alkylphenyl ethers, aliphatic alcohol phosphate esters, and higher alcohol sulfate esters,

Examples of the cationic antistatic agent include alkyl urea compounds typified by tetraalkylammonium salts, trialkylbenzylammonium salts, monoalkyltrimethylaminoalkyl elements and the like represented by (? - laurapropopropionyl) trimethylammonium sulfate, monoalkyltrimethyl Alkylamide-type compounds represented by aminoalkylamides,

Examples of the anionic antistatic agent include alkylbenzenesulfonic acid salts represented by fatty acid salts, alkylsulfonic acid salts, dodecylbenzenesulfonic acid salts, and tridecylbenzenesulfonic acid salts, and alkylphosphates typified by distearyl phosphate,

Examples of positive antistatic agents include alkylbetaines, alkylimidazoliumbetaines,

Examples of the polymer type antistatic agent include salts such as polyoxyethylene glycol (polyethylene glycol), polyetheresteramide and polyetheramideimide, for example, sulfates and aliphatic amine salts of aliphatic amines and amides.

Nonionic antistatic agents and cationic antistatic agents are preferred. Glycerin fatty acid esters, polyethylene glycol, alkyl urea type compounds, alkyl amide type compounds and trialkyl benzyl ammonium salts (having 1 to 30 carbon atoms in the alkyl group) are more preferred.

Each of the softening agent and the antistatic agent may be a single kind or a combination of at least two kinds.

The amount of the auxiliary agent (generally as a solid) may be from 0.1 to 20% by weight, for example, from 0.2 to 10% by weight, based on the surface treating agent composition.

(4) Other components

The surface treatment agent composition may contain at least one of a non-fluorine water repellent compound and an additive as a component other than the fluorine-containing polymer, the liquid medium and the auxiliary agent.

(4-1) Non-fluorine-repellent compound

The surface treatment agent composition may contain a water-repellent compound containing no fluorine atom (non-fluorine-repellent compound).

The non-fluorine water repellent compound may be a non-fluorine acrylate polymer, a saturated or unsaturated hydrocarbon compound, or a silicon compound.

The non-fluorine acrylate polymer may be a homopolymer composed of one kind of non-fluorine acrylate monomer or a copolymer composed of at least two kinds of non-fluorine acrylate monomers, or a copolymer composed of at least one kind of non-fluorine acrylate monomer and Is a copolymer composed of at least one kind of other non-fluorine monomer (ethylenically unsaturated compound, for example, ethylene, vinyl monomer).

The non-fluorine acrylate monomer constituting the non-fluorine acrylate polymer is represented by the formula:

CH ₂ = CA-T

[Wherein A is a hydrogen atom, a methyl group, or a halogen atom (e.g., a chlorine atom, a bromine atom and an iodine atom) other than a fluorine atom,

T represents 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 having an ester bond]

≪ / RTI >

Examples of the straight chain or branched aliphatic hydrocarbon group having 1 to 30 carbon atoms, the cyclic aliphatic group having 4 to 30 carbon atoms, the aromatic hydrocarbon group having 6 to 30 carbon atoms, the carbon chain having 7 to 30 carbon atoms Lt; / RTI > aliphatic hydrocarbon group.

-C (= O) -OQ and -OC (= O) -Q (wherein Q represents a linear or branched alkyl group having 1 to 30 carbon atoms or an alkenyl group having 1 to 30 carbon atoms) An aliphatic hydrocarbon group of 4 to 30 carbon atoms, a cyclic aliphatic group of 4 to 30 carbon atoms, an aromatic hydrocarbon group of 6 to 30 carbon atoms, and an aromatic aliphatic hydrocarbon group of 7 to 30 carbon atoms.

Examples of nonfluorinated acrylate monomers include, for example, alkyl (meth) acrylates, polyethylene glycol (meth) acrylates, polypropylene glycol (meth) acrylates, methoxypolyethylene glycol (meth) acrylates, methoxypolypropylene Glycol (meth) acrylate.

The non-fluorine acrylate monomer is preferably an alkyl (meth) acrylate ester. The number of carbon atoms of the alkyl group may be 1 to 30, and may be, for example, 6 to 30 (for example, 10 to 30). Examples of non-fluorine acrylate monomers are lauryl (meth) acrylate, stearyl (meth) acrylate and behenyl (meth) acrylate.

The non-fluorine acrylate polymer can be produced by the same polymerization method as the fluorine-containing polymer.

The saturated or unsaturated hydrocarbon-based compound is preferably a saturated hydrocarbon. In a saturated or unsaturated hydrocarbon-based 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-based compound include paraffin and the like.

The silicone compound is generally used as a water repellent agent. The silicone compound is not limited as long as it is a compound exhibiting water repellency.

The amount of the non-fluorine-repellent compound may be 500 parts by weight or less, for example, 5-200 parts by weight, particularly 5-100 parts by weight, based on 100 parts by weight of the fluorine-containing polymer.

(4-2) Additive

Examples of the additive include silicon-containing compounds, waxes, acrylic emulsions and the like. Other examples of the additive include a fluorine-containing polymer, a drying rate-adjusting agent, a crosslinking agent, a coagulation assistant, a compatibilizing agent, a surfactant, a cryoprotectant, a viscosity adjusting agent, an ultraviolet absorber, an antioxidant, a pH adjusting agent, An antistatic agent, a hydrophilic agent, an antibacterial agent, an antiseptic, an insecticide, a fragrance, and a flame retardant.

The fluorine-containing polymer and the non-fluorine polymer in the present invention can be produced by any ordinary polymerization method, and the conditions of the polymerization reaction can be arbitrarily selected. Such polymerization methods include solution polymerization, suspension polymerization and emulsion polymerization.

In the solution polymerization, a method in which monomers are dissolved in an organic solvent and substituted with nitrogen in the presence of a polymerization initiator, followed by heating and stirring at 30 to 120 ° C for 1 to 10 hours is employed. As the polymerization initiator, for example, azobisisobutyronitrile, benzoyl peroxide, di-t-butyl peroxide, lauryl peroxide, cumene hydroperoxide, t-butyl peroxypivalate, diisopropyl peroxydicar And the like. 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 inert to the monomers and dissolves them, for example, an ester (for example, an ester having 2 to 30 carbon atoms, specifically, ethyl acetate, butyl acetate), a ketone (for example, Ketones such as methyl ethyl ketone and diisobutyl ketone), alcohols (for example, alcohols having 1 to 30 carbon atoms, specifically, isopropyl alcohol). Specific examples of the organic solvent include acetone, chloroform, HCHC225, isopropyl alcohol, pentane, hexane, heptane, octane, cyclohexane, benzene, toluene, xylene, petroleum ether, tetrahydrofuran, , Methyl isobutyl ketone, diisobutyl ketone, ethyl acetate, butyl acetate, 1,1,2,2-tetrachloroethane, 1,1,1-trichloroethane, trichlorethylene, perchlorethylene, tetrachlorodi Fluoroethane, 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 amount of the monomers.

In the emulsion polymerization, the monomer is emulsified in water and substituted with nitrogen in the presence of a polymerization initiator and an emulsifier, and then the mixture is stirred for 1 to 10 hours at 50 to 80 캜. The polymerization initiator may be at least one selected from the group consisting of benzoyl peroxide, lauroyl peroxide, t-butyl perbenzoate, 1-hydroxycyclohexyl hydroperoxide, 3-carboxypropionyl peroxide, acetyl peroxide, azobisisobutylamidine- But are not limited to, water-soluble ones such as butyronitrile, sodium peroxide, potassium persulfate and ammonium persulfate, azobisisobutyronitrile, benzoyl peroxide, di-t-butyl peroxide, lauryl peroxide, cumene hydroperoxide, Butyl peroxypivalate, diisopropyl peroxydicarbonate, and the like. The polymerization initiator is used in the range of 0.01 to 10 parts by weight based on 100 parts by weight of the monomer.

In order to obtain a polymer aqueous dispersion liquid excellent in stability of standing, it is preferable to polymerize monomers into water by using an emulsifying apparatus capable of imparting strong breaking energy such as a high-pressure homogenizer or an ultrasonic homogenizer. As the emulsifier, various emulsifiers such as anionic, cationic or nonionic emulsifiers can be used, and they are used in the range of 0.5 to 20 parts by weight based on 100 parts by weight of the monomers. It is preferred to use anionic and / or nonionic and / or cationic emulsifiers. When the monomers are not fully used, it is preferable to add a compatibilizing agent sufficiently compatible with these monomers, for example, a water-soluble organic solvent or a low molecular weight monomer. By the addition of the compatibilizing agent, it is possible to improve emulsification and copolymerization.

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. , For example, 10 to 40 parts by weight. Examples of the monomer having a low molecular weight include methyl methacrylate, glycidyl methacrylate, 2,2,2-trifluoroethyl methacrylate and the like. The amount of the monomer 50 parts by weight, for example, 10 to 40 parts by weight.

In the polymerization, a chain transfer agent may be used. Depending on the amount of chain transfer agent used, the molecular weight of the polymer can be varied. Examples of the chain transfer agent include mercaptan group-containing compounds such as lauryl mercaptan, thioglycol, thioglycerol and the like (particularly, alkyl mercaptans such as (for example, 1 to 30 carbon atoms)), sodium hypophosphite, sodium hydrogen sulfite Salt. The chain transfer agent may be used in an amount of 0.01 to 10 parts by weight, for example, 0.1 to 5 parts by weight, based on 100 parts by weight of the total amount of the monomers.

The treatment composition of the present invention may be in the form of a solution, an emulsion (particularly, an aqueous dispersion) or an aerosol, but is preferably an aqueous dispersion. The treating composition includes a polymer (an active ingredient of a surface treating agent) and a medium (particularly, a liquid medium such as an organic solvent and / or water). The amount of the medium may be, for example, 5 to 99.9% by weight, particularly 10 to 80% by weight, based on the treating composition.

In the treating composition, the concentration of the polymer may be from 0.01 to 95% by weight, for example, from 5 to 50% by weight.

The treating composition of the present invention can be applied to a subject to be treated by a conventional method. Usually, a method is employed in which the treating composition is dispersed in an organic solvent or water to be diluted, adhered to the surface of the material to be treated by a known method such as immersion coating, spray coating, air bubble coating and the like, followed by drying. If necessary, curing may be carried out with appropriate crosslinking agent. It is also possible to add a repellent, a softener, an antibacterial agent, a flame retardant, an antistatic agent, a paint fixer, an anti-wrinkle agent, etc. to the treatment composition of the present invention. The concentration of the polymer in the treatment liquid to be brought into contact with the substrate may be 0.01 to 10% by weight (particularly in the case of immersion coating), for example, 0.05 to 10% by weight.

Examples of the object to be treated with the treating composition of the present invention (for example, a water- and oil-repellent agent) include textile products, stones, filters (for example, electrostatic filters) Glass, paper, wood, leather, fur, asbestos, bricks, cement, metals and oxides, ceramics, plastics, coated surfaces and plasters. There are many examples of fiber products. For example, synthetic vegetable natural fibers such as cotton, hemp, wool, and silk, synthetic fibers such as polyamide, polyester, polyvinyl alcohol, polyacrylonitrile, polyvinyl chloride, and polypropylene, semi- Inorganic fibers such as fibers, glass fibers, carbon fibers and asbestos fibers, and mixed fibers thereof.

The fiber product may be in the form of fiber, cloth or the like.

The treatment composition of the present invention can be used as an internal release agent or an external release agent.

The polymer may be applied to fibrous substrates (e.g., textile products, etc.) by any of the methods known for treating textile products with liquids. When the fiber product is foiled, the bubble may be immersed in the solution, or the solution may be attached or sprayed on the bubble. The treated fiber product is dried to exhibit oil repellency and is preferably heated, for example, at 100 to 200 ° C.

Alternatively, the polymer may be applied to a fiber product by a cleaning method, and may be applied to a fiber product, for example, in a laundry application or a dry cleaning method.

The textile product to be treated is typically a foil, which includes fabrics, knit and non-woven fabrics, garment-type blanks and carpets, but may be fabric or yarn or intermediate fiber products (e.g., sliver or roving) Or the like). The fiber product material may be selected from natural fibers (such as cotton or wool), chemical fibers (such as viscose rayon or lyocell), or synthetic fibers (such as polyester, polyamide or acrylic fibers , Or a mixture of fibers (for example, a mixture of natural fibers and synthetic fibers). The production polymer of the present invention is particularly effective in making cellulose-based fibers (for example, cotton or rayon) to be oleophobic and oil repellent. In addition, the process of the present invention generally makes the textile product hydrophobic and water repellent.

 Alternatively, the fibrous substrate may be a leather. The preparation polymer may also be applied to the leather from aqueous solutions or aqueous emulsions at various stages of leather processing, for example during the wet processing period of the leather, or during the finishing period of the leather, in order to make the leather hydrophobic and oleophobic .

Alternatively, the fibrous substrate may be paper. The preparation polymer may be applied to preformed paper or may be applied at various stages of paper making, for example during the drying of paper.

By " treatment " is meant applying the treating agent to the material to be treated by immersion, spraying, coating, or the like. By the treatment, the polymer which is an effective component of the treatment agent is allowed to penetrate into the inside of the treatment subject and adhere to the surface of the treatment subject.

<Examples>

Hereinafter, the present invention will be described in detail by way of examples, but the present invention is not limited to these examples.

In the following, parts or percentages or percentages refer to parts by weight or weight percentages or weight ratios, unless otherwise specified.

The procedure of the test is as follows.

Shower water repellency test

The water repellency test of the shower was performed in accordance with JIS-L-1092. The water repellency test of the shower was indicated by the water repellency No. (as shown in Table 1 described below).

A glass funnel having a volume of at least 250 ml, and a spray nozzle capable of spraying 250 ml of water for 20 seconds to 30 seconds. The test piece frame is a metal frame having a diameter of 15 cm. Three pieces of test piece sheets each having a size of about 20 cm x 20 cm were prepared, and the sheets were fixed to the test piece holder frame to prevent wrinkles on the sheets. The center of the spray is placed at the center of the sheet. Water (250 mL) at room temperature is placed in a glass funnel and sprayed onto the test piece sheet (over a period of 25 seconds to 30 seconds). The holding frame is removed from the die, one end of the holding frame is held, the front surface is downwardly, and the opposite end is tap lightly with a hard material. The holding frame is further rotated by 180 DEG, and the same procedure is repeated to drop excessive droplets of water. Wet specimens are compared to a wet comparison standard to give a rating of 0, 50, 70, 80, 90 and 100 in order of poor water repellency to good order. Results are obtained from the average of three measurements.

Production Example 1

In a 500 ml reaction flask, 51.2 g of CF ₃ CF ₂ - (CF ₂ CF ₂ ) _n --CH ₂ CH ₂ OCOC (Cl) = CH ₂ (n = 2.0) (13FCIA), 85.4 g of lauryl acrylate, Acrylamide, 1.3 g of 3-chloro-2-hydroxypropyl methacrylate, 194 g of pure water, 34.1 g of a water-soluble glycol solvent, 6.3 g of alkyltrimethylammonium chloride and 7.0 g of polyoxyethylene alkyl ether, RTI ID = 0.0 &gt; C &lt; / RTI &gt; for 15 minutes. After the inside of the reaction flask was purged with nitrogen, a solution of 0.4 g of an azo group-containing water-soluble initiator and 9 g of water was added and reacted at 60 DEG C for 20 hours to obtain an aqueous dispersion of the polymer. The composition of the polymer almost coincided with the composition of the input monomers.

Production Example 2

To 1000mL autoclave _{CF 3 CF 2 - (CF 2} CF 2) n -CH 2 CH 2 OCOC (Cl) = CH 2 (n = 2.0) (13FClA) 138g, lauryl acrylate (LA) 51.0g, N- 2.6 g of methylol acrylamide, 2.6 g of 3-chloro-2-hydroxypropyl methacrylate, 565 g of pure water, 47 g of a water-soluble glycol solvent, 2.5 g of polyoxyethylene oleyl ether and 27.8 g of polyoxyethylene alkyl ether, And emulsified and dispersed by ultrasonic wave at 60 캜 for 15 minutes under stirring. After the inside of the flask was purged with nitrogen, 62 g of vinyl chloride (VCM) was press-filled and 0.4 g of azo group-containing water-soluble initiator was added and reacted at 60 DEG C for 20 hours to obtain an aqueous dispersion of the polymer. The composition of the polymer almost coincided with the composition of the input monomers.

Production Example 3

To 1000mL autoclave _{CF 3 CF 2 - (CF 2} CF 2) n -CH 2 CH 2 OCOC (Cl) = CH 2 (n = 2.0) (13FClA) 138g, stearyl acrylate (StA) 51.0g, N- 2.6 g of methylol acrylamide, 2.6 g of 3-chloro-2-hydroxypropyl methacrylate, 565 g of pure water, 47 g of a water-soluble glycol solvent, 2.5 g of polyoxyethylene oleyl ether and 27.8 g of polyoxyethylene alkyl ether, And emulsified and dispersed by ultrasonic wave at 60 캜 for 15 minutes under stirring. After the inside of the flask was purged with nitrogen, 62 g of vinyl chloride (VCM) was press-filled and 0.4 g of azo group-containing water-soluble initiator was added and reacted at 60 DEG C for 20 hours to obtain an aqueous dispersion of the polymer. The composition of the polymer almost coincided with the composition of the input monomers.

Production Example 4

A 500 ml reaction flask was charged with 51.2 g of CF ₃ CF ₂ - (CF ₂ CF ₂ ) _n --CH ₂ CH ₂ OCOC (Cl) = CH ₂ (n = 2.0) (13FCIA), 85.4 g of stearyl acrylate, Acrylamide, 1.3 g of 3-chloro-2-hydroxypropyl methacrylate, 194 g of pure water, 34.1 g of a water-soluble glycol solvent, 6.3 g of alkyltrimethylammonium chloride and 7.0 g of polyoxyethylene alkyl ether, RTI ID = 0.0 &gt; C &lt; / RTI &gt; for 15 minutes. After the inside of the reaction flask was purged with nitrogen, a solution of 0.4 g of an azo group-containing water-soluble initiator and 9 g of water was added and reacted at 60 DEG C for 20 hours to obtain an aqueous dispersion of the polymer. The composition of the polymer almost coincided with the composition of the input monomers.

Production Example 5

To 1000mL autoclave _{CF 3 CF 2 - (CF 2} CF 2) n -CH 2 CH 2 OCOC (CH 3) = CH 2 (n = 2.0) (13FMA) 138g, lauryl acrylate (LA) 51.0g, N , 2.6 g of methylol acrylamide, 2.6 g of 3-chloro-2-hydroxypropyl methacrylate, 565 g of pure water, 47 g of water-soluble glycol solvent, 2.5 g of polyoxyethylene oleyl ether and 27.8 g of polyoxyethylene alkyl ether And emulsified and dispersed by ultrasonic wave at 60 캜 for 15 minutes under stirring. After the inside of the flask was purged with nitrogen, 62 g of vinyl chloride (VCM) was press-filled and 0.4 g of azo group-containing water-soluble initiator was added and reacted at 60 DEG C for 20 hours to obtain an aqueous dispersion of the polymer. The composition of the polymer almost coincided with the composition of the input monomers.

Production Example 6

To 1000mL autoclave _{CF 3 CF 2 - (CF 2} CF 2) n -CH 2 CH 2 OCOC (CH 3) = CH 2 (n = 2.0) (13FMA) 138g, stearyl acrylate (StA) 51.0g, N , 2.6 g of methylol acrylamide, 2.6 g of 3-chloro-2-hydroxypropyl methacrylate, 565 g of pure water, 47 g of water-soluble glycol solvent, 2.5 g of polyoxyethylene oleyl ether and 27.8 g of polyoxyethylene alkyl ether And emulsified and dispersed by ultrasonic wave at 60 캜 for 15 minutes under stirring. After the inside of the flask was purged with nitrogen, 62 g of vinyl chloride (VCM) was press-filled and 0.4 g of azo group-containing water-soluble initiator was added and reacted at 60 DEG C for 20 hours to obtain an aqueous dispersion of the polymer. The composition of the polymer almost coincided with the composition of the input monomers.

Production Example 7

To 1000mL autoclave _{CF 3 CF 2 - (CF 2} CF 2) n -CH 2 CH 2 OCOC (Cl) = CH 2 (n = 2.0) (13FClA) 138g, lauryl acrylate (LA) 51.0g, N- 5.2 g of methylol acrylamide, 565 g of pure water, 47 g of water-soluble glycol solvent, 2.5 g of polyoxyethylene oleyl ether and 27.8 g of polyoxyethylene alkyl ether were emulsified and dispersed by ultrasonic wave at 60 캜 for 15 minutes under stirring. After the inside of the flask was purged with nitrogen, 62 g of vinyl chloride (VCM) was press-filled and 0.4 g of azo group-containing water-soluble initiator was added and reacted at 60 DEG C for 20 hours to obtain an aqueous dispersion of the polymer. The composition of the polymer almost coincided with the composition of the input monomers.

Comparative Preparation Example 1

A 500ml reaction flask, _{CF 3 CF 2 - (CF 2} CF 2) n -CH 2 CH 2 OCOC (Cl) = CH 2 (n = 2.0) (13FClA) 51.2g, 85.4g lauryl acrylate, 194g of pure, water-soluble 34.1 g of a glycol-based solvent, 6.3 g of alkyltrimethylammonium chloride and 7.0 g of polyoxyethylene alkyl ether were put and emulsified and dispersed by ultrasonic wave at 60 DEG C for 15 minutes under stirring. After the inside of the reaction flask was purged with nitrogen, a solution of 0.4 g of an azo group-containing water-soluble initiator and 9 g of water was added and reacted at 60 DEG C for 20 hours to obtain an aqueous dispersion of the polymer. The composition of the polymer almost coincided with the composition of the input monomers.

Comparative Production Example 2

A 1000 mL autoclave was charged with 138 g of CF ₃ CF ₂ - (CF ₂ CF ₂ ) _n --CH ₂ CH ₂ OCOC (Cl) = CH ₂ (n = 2.0) (13FCIA), 51.0 g of lauryl acrylate (LA) , 47 g of a water-soluble glycol solvent, 2.5 g of polyoxyethylene oleyl ether and 27.8 g of polyoxyethylene alkyl ether, and emulsified and dispersed by ultrasonic wave at 60 캜 for 15 minutes under stirring. After the inside of the flask was purged with nitrogen, 62 g of vinyl chloride (VCM) was press-filled and 0.4 g of azo group-containing water-soluble initiator was added and reacted at 60 DEG C for 20 hours to obtain an aqueous dispersion of the polymer. The composition of the polymer almost coincided with the composition of the input monomers.

Comparative Production Example 3

A 1000 mL autoclave was charged with 138 g of CF ₃ CF ₂ - (CF ₂ CF ₂ ) _n -CH ₂ CH ₂ OCOC (Cl) = CH ₂ (n = 2.0) (13FCIA), 51.0 g of stearyl acrylate (StA) , 47 g of a water-soluble glycol solvent, 2.5 g of polyoxyethylene oleyl ether and 27.8 g of polyoxyethylene alkyl ether, and emulsified and dispersed by ultrasonic wave at 60 캜 for 15 minutes under stirring. After the inside of the flask was purged with nitrogen, 62 g of vinyl chloride (VCM) was press-filled and 0.4 g of azo group-containing water-soluble initiator was added and reacted at 60 DEG C for 20 hours to obtain an aqueous dispersion of the polymer. The composition of the polymer almost coincided with the composition of the input monomers.

Example 1

The aqueous liquid prepared in Preparation Example 1 was diluted with purified water to a solid content of 30% of the fluorine-containing polymer, further diluted with water such that the ratio of the 30% diluted solution became 3%, and the dimethyl silicone emulsion softener containing amino group was diluted to 2.5 % To prepare a test liquid (100 g) having an aqueous liquid concentration of 3.00% (fluorine-containing polymer: 0.9%) and a softener concentration of 2.5%. PET and nylon bubbles (500 mm x 200 mm) were immersed in this test liquid, passed through mangles, and treated with a pin tenter at 170 캜 for 1 minute. Thereafter, it was used for water repellency test. The results are shown in Table 1.

Example 2

The aqueous liquid prepared in Preparation Example 2 was diluted with purified water to a solid content of 30% of the fluorine-containing polymer, further diluted with water so that the proportion of the 30% diluent became 3%, 2.5 % To prepare a test liquid (100 g) of 3.00% aqueous liquid and 2.5% softener. PET and nylon bubbles (500 mm x 200 mm) were immersed in this test liquid, passed through mangles, and treated with a pin tenter at 170 캜 for 1 minute. Thereafter, it was used for water repellency test. 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 concentration of the fluorine-containing polymer became 30% solids, further diluted with water such that the proportion of the 30% diluted solution became 3%, the dimethyl silicone emulsion softener containing amino groups was diluted to 2.5 % To prepare a test liquid (100 g) of 3.00% aqueous liquid and 2.5% softener. PET and nylon bubbles (500 mm x 200 mm) were immersed in this test liquid, passed through mangles, and treated with a pin tenter at 170 캜 for 1 minute. Thereafter, it was used for water repellency test. The results are shown in Table 1.

Example 4

The aqueous liquid prepared in Preparation Example 4 was diluted with purified water to a solid content of 30% of the fluorine-containing polymer, further diluted with water so that the proportion of the 30% diluted solution became 3%, and the dimethyl silicone emulsion softener containing amino groups was diluted to 2.5 % To prepare a test liquid (100 g) of 3.00% aqueous liquid and 2.5% softener. PET and nylon bubbles (500 mm x 200 mm) were immersed in this test liquid, passed through mangles, and treated with a pin tenter at 170 캜 for 1 minute. Thereafter, it was used for water repellency test. The results are shown in Table 1.

Example 5

The aqueous liquid prepared in Preparation Example 5 was diluted with purified water to a solid content of 30% of the fluorine-containing polymer, further diluted with water such that the proportion of the 30% diluted liquid became 3%, and the dimethyl silicone emulsion softener containing amino groups was diluted to 2.5 % To prepare a test liquid (100 g) of 3.00% aqueous liquid and 2.5% softener. PET and nylon bubbles (500 mm x 200 mm) were immersed in this test liquid, passed through mangles, and treated with a pin tenter at 170 캜 for 1 minute. Thereafter, it was used for water repellency test. The results are shown in Table 1.

Example 6

The aqueous liquid prepared in Preparation Example 6 was diluted with purified water to a solid content of 30% of the fluorine-containing polymer, further diluted with water such that the proportion of the 30% diluted liquid became 3%, and the dimethyl silicone emulsion softener containing amino groups was diluted to 2.5 % To prepare a test liquid (100 g) of 3.00% aqueous liquid and 2.5% softener. PET and nylon bubbles (500 mm x 200 mm) were immersed in this test liquid, passed through mangles, and treated with a pin tenter at 170 캜 for 1 minute. Thereafter, it was used for water repellency test. 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 concentration of the fluorine-containing polymer became 30% solids, further diluted with water such that the proportion of the 30% diluted solution became 3%, the dimethyl silicone emulsion softener containing amino groups was diluted to 2.5 % To prepare a test liquid (100 g) of 3.00% aqueous liquid and 2.5% softener. PET and nylon bubbles (500 mm x 200 mm) were immersed in this test liquid, passed through mangles, and treated with a pin tenter at 170 캜 for 1 minute. Thereafter, it was used for water repellency test. The results are shown in Table 1.

Example 8

The aqueous liquid prepared in Preparation Example 1 was diluted with purified water to a solid content of 30% of the fluorine-containing polymer, further diluted with water so that the proportion of the 30% diluent became 3%, and the ratio of polyethylene glycol and glycerin fatty acid ester 50:50) was added so as to have a concentration of 1.5% to prepare a test liquid (100 g) containing 3.00% of an aqueous liquid and 1.5% of an antistatic agent. PET and nylon bubbles (500 mm x 200 mm) were immersed in this test liquid, passed through mangles, and treated with a pin tenter at 170 캜 for 1 minute. Thereafter, it was used for water repellency test. The results are shown in Table 1.

Example 9

The aqueous liquid prepared in Preparation Example 2 was diluted with pure water to a concentration of 30% solids of fluorine-containing polymer, further diluted with water such that the proportion of the 30% diluent became 3%, and a mixture of polyethylene glycol and glycerin fatty acid ester 50:50) was added so as to have a concentration of 1.5% to prepare a test liquid (100 g) containing 3.00% of an aqueous liquid and 1.5% of an antistatic agent. PET and nylon bubbles (500 mm x 200 mm) were immersed in this test liquid, passed through mangles, and treated with a pin tenter at 170 캜 for 1 minute. Thereafter, it was used for water repellency test. The results are shown in Table 1.

Example 10

The aqueous liquid prepared in Preparation Example 3 was diluted with purified water to a solid content of 30% of the fluorine-containing polymer, further diluted with water such that the proportion of the 30% diluent became 3%, and the ratio of polyethylene glycol and glycerin fatty acid ester 50:50) was added so as to have a concentration of 1.5% to prepare a test liquid (100 g) containing 3.00% of an aqueous liquid and 1.5% of an antistatic agent. PET and nylon bubbles (500 mm x 200 mm) were immersed in this test liquid, passed through mangles, and treated with a pin tenter at 170 캜 for 1 minute. Thereafter, it was used for water repellency test. The results are shown in Table 1.

Example 11

The aqueous liquid prepared in Preparation Example 4 was diluted with purified water to a solid content of 30% of the fluorine-containing polymer, further diluted with water such that the proportion of the 30% diluent became 3%, and the ratio of polyethylene glycol and glycerin fatty acid ester 50:50) was added so as to have a concentration of 1.5% to prepare a test liquid (100 g) containing 3.00% of an aqueous liquid and 1.5% of an antistatic agent. PET and nylon bubbles (500 mm x 200 mm) were immersed in this test liquid, passed through mangles, and treated with a pin tenter at 170 캜 for 1 minute. Thereafter, it was used for water repellency test. The results are shown in Table 1.

Example 12

The aqueous liquid prepared in Preparation Example 5 was diluted with purified water to a solid content of 30% of the fluorine-containing polymer, further diluted with water such that the proportion of the 30% diluted solution became 3%, and the ratio of polyethylene glycol and glycerin fatty acid ester 50:50) was added so as to have a concentration of 1.5% to prepare a test liquid (100 g) containing 3.00% of an aqueous liquid and 1.5% of an antistatic agent. PET and nylon bubbles (500 mm x 200 mm) were immersed in this test liquid, passed through mangles, and treated with a pin tenter at 170 캜 for 1 minute. Thereafter, it was used for water repellency test. The results are shown in Table 1.

Example 13

The aqueous liquid prepared in Preparation Example 6 was diluted with pure water so that the concentration of the fluorine-containing polymer became 30% solids, further diluted with water such that the proportion of the 30% diluent became 3%, and the ratio of polyethylene glycol and glycerin fatty acid ester 50:50) was added so as to have a concentration of 1.5% to prepare a test liquid (100 g) containing 3.00% of an aqueous liquid and 1.5% of an antistatic agent. PET and nylon bubbles (500 mm x 200 mm) were immersed in this test liquid, passed through mangles, and treated with a pin tenter at 170 캜 for 1 minute. Thereafter, it was used for water repellency test. The results are shown in Table 1.

Example 14

The aqueous liquid prepared in Preparation Example 7 was diluted with purified water to a solid content of 30% of the fluorine-containing polymer, further diluted with water such that the proportion of the 30% diluent became 3%, and the ratio of polyethylene glycol and glycerin fatty acid ester 50:50) was added so as to have a concentration of 1.5% to prepare a test liquid (100 g) containing 3.00% of an aqueous liquid and 1.5% of an antistatic agent. PET and nylon bubbles (500 mm x 200 mm) were immersed in this test liquid, passed through mangles, and treated with a pin tenter at 170 캜 for 1 minute. Thereafter, it was used for water repellency test. The results are shown in Table 1.

Comparative Example 1

The aqueous liquid prepared in Comparative Production Example 1 was diluted with purified water to a solid content of 30% of the fluorine-containing polymer, further diluted with water such that the proportion of the 30% diluted liquid became 3%, and an amino group-containing dimethyl silicone emulsion softener 2.5%, to prepare a test liquid (100 g) of 3.00% aqueous liquid and 2.5% softener. PET and nylon bubbles (500 mm x 200 mm) were immersed in this test liquid, passed through mangles, and treated with a pin tenter at 170 캜 for 1 minute. Thereafter, it was used for water repellency test. The results are shown in Table 1.

Comparative Example 2

The aqueous liquid prepared in Comparative Preparation Example 2 was diluted with purified water to a solid content of 30% of the fluorine-containing polymer, further diluted with water such that the proportion of the 30% diluted solution became 3%, and an amino group- 2.5%, to prepare a test liquid (100 g) of 3.00% aqueous liquid and 2.5% softener. PET and nylon bubbles (500 mm x 200 mm) were immersed in this test liquid, passed through mangles, and treated with a pin tenter at 170 캜 for 1 minute. Thereafter, it was used for water repellency test. The results are shown in Table 1.

Comparative Example 3

The aqueous liquid prepared in Comparative Preparation Example 3 was diluted with purified water to a solid content of fluorine-containing polymer of 30%, further diluted with water such that the proportion of the 30% diluted liquid became 3%, and an amino group-containing dimethyl silicone emulsion softener 2.5%, to prepare a test liquid (100 g) of 3.00% aqueous liquid and 2.5% softener. PET and nylon bubbles (500 mm x 200 mm) were immersed in this test liquid, passed through mangles, and treated with a pin tenter at 170 캜 for 1 minute. Thereafter, it was used for water repellency test. The results are shown in Table 1.

Comparative Example 4

The aqueous liquid prepared in Comparative Preparation Example 1 was diluted with pure water so that the concentration of the fluorine-containing polymer became 30% solids, further diluted with water such that the proportion of the 30% diluent became 3%, and the mixture was diluted with polyethylene glycol and glycerin fatty acid ester (Weight ratio 50:50) was added to 1.5% to prepare a test liquid (100 g) containing 3.00% of an aqueous liquid and 1.5% of an antistatic agent. PET and nylon bubbles (500 mm x 200 mm) were immersed in this test liquid, passed through mangles, and treated with a pin tenter at 170 캜 for 1 minute. Thereafter, it was used for water repellency test. The results are shown in Table 1.

Comparative Example 5

The aqueous liquid prepared in Comparative Preparation Example 2 was diluted with purified water to a solid content of fluorine-containing polymer of 30%, further diluted with water such that the proportion of the 30% diluent became 3%, and the mixture was diluted with polyethylene glycol and glycerin fatty acid ester (Weight ratio 50:50) was added to 1.5% to prepare a test liquid (100 g) containing 3.00% of an aqueous liquid and 1.5% of an antistatic agent. PET and nylon bubbles (500 mm x 200 mm) were immersed in this test liquid, passed through mangles, and treated with a pin tenter at 170 캜 for 1 minute. Thereafter, it was used for water repellency test. The results are shown in Table 1.

Comparative Example 6

The aqueous liquid prepared in Comparative Preparation Example 3 was diluted with pure water to a solid content of fluorine-containing polymer of 30%, further diluted with water such that the proportion of the 30% diluent became 3%, and the mixture was diluted with polyethylene glycol and glycerin fatty acid ester (Weight ratio 50:50) was added to 1.5% to prepare a test liquid (100 g) containing 3.00% of an aqueous liquid and 1.5% of an antistatic agent. PET and nylon bubbles (500 mm x 200 mm) were immersed in this test liquid, passed through mangles, and treated with a pin tenter at 170 캜 for 1 minute. Thereafter, it was used for water repellency test. The results are shown in Table 1.

The meaning of the abbreviation is as follows.

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 decontamination agent.

Claims (13)

(1) a copolymer comprising (a) a repeating unit derived from a fluorine-containing monomer having 1 to 6 carbon atoms in a fluoroalkyl group, and
(b) a fluorine-containing polymer having a repeating unit derived from a non-fluorine-crosslinkable monomer which is a vinyl monomer having a hydroxyl group,
(2) Liquid media
Containing treatment agent,
The fluorine-
(3) at least one auxiliary agent selected from the group consisting of softening agents and antistatic agents
Wherein the fluorine-containing treating agent is combined with the fluorine-containing treating agent. The fluorine-containing polymer according to claim 1, wherein the fluorine-containing monomer (a)
CH ₂ = C (-X) -C (= O) -YZ-Rf (I)
Wherein X represents a hydrogen atom, a linear or branched alkyl group having 1 to 21 carbon atoms, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, a CFX ¹ X ² group (provided that X ¹ and X ² are, A hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom or an iodine atom), a cyano group, a straight or branched fluoroalkyl group having 1 to 21 carbon atoms, a substituted or unsubstituted benzyl group or a substituted or unsubstituted phenyl group;
Y is -O- or -NH-;
Z represents an aliphatic group having 1 to 10 carbon atoms, an aromatic group or a cyclic aliphatic group having 6 to 18 carbon atoms,
-CH ₂ CH ₂ N (R ¹ ) SO ₂ - group (provided that R ¹ is an alkyl group having 1 to 4 carbon atoms)
^{_{-CH 2 CH (OZ 1) CH}} 2 - (Ph-O) p - group (where, Z ¹ is a hydrogen atom or an acetyl group, Ph is a phenylene group, p is 0 or 1), - (CH _{2) n} -Ph-O- group (where, Ph is a phenylene group, n is _{0-10), - (CH 2) m} -SO 2 - (CH 2) n - group or a - (CH _{2) m} -S- ( CH ₂ ) _n - group ( _where m is 1 to 10 and n is 0 to 10)
Rf is a straight or branched fluoroalkyl group having 1 to 6 carbon atoms]
Is a compound represented by the general formula (1). The fluorine-containing treatment agent according to any one of claims 1 to 3, wherein the fluorine-containing monomer (a) is an acrylate in which the position? Is substituted with a chlorine atom. The fluorine-containing treatment agent according to claim 2, wherein the fluorine-containing monomer (a) has 6 carbon atoms in Rf. The vinyl monomer having a hydroxyl group according to any one of claims 1 to 4,
CH ₂ = CD ¹ -C (═O) -D ² -D ³ -OH
[In the formula, D ¹ represents a hydrogen atom, a methyl group, or a halogen atom other than a fluorine atom (e.g., a chlorine atom, a bromine atom and an iodine atom)
D ² is -O- or -NH-,
D ³ is an organic group having 1 to 20 carbon atoms]
Is a compound represented by the general formula (1). 6. The fluorine-containing treatment agent according to any one of claims 1 to 5, wherein the auxiliary agent (3) is added to the fluorine-containing polymer or the fluorine-containing treatment agent after completion of the polymerization reaction. The fluorine-containing treatment agent according to any one of claims 1 to 6, wherein the softening agent is at least one selected from the group consisting of a silicone-based softening agent and a polyethylene wax-type softening agent. The fluorine-containing treatment agent according to any one of claims 1 to 6, wherein the antistatic agent is a cationic surfactant and a nonionic surfactant. 9. The fluorine-containing treatment agent according to any one of claims 1 to 8, which contains a water-repellent compound containing no fluorine atom. (1) a copolymer comprising (a) a repeating unit derived from a fluorine-containing monomer having 1 to 6 carbon atoms in a fluoroalkyl group, and
(b) a fluorine-containing polymer having a repeating unit derived from a non-fluorine-crosslinkable monomer which is a vinyl monomer having a hydroxyl group,
(2) a liquid medium,
(3) at least one auxiliary agent selected from the group consisting of a softener and an antistatic agent. The surface treating agent composition according to claim 10, wherein the surface treating agent composition is a water and oil repellent composition, an antifouling agent composition or a contaminant desizing agent composition. (1) a copolymer comprising (a) a repeating unit derived from a fluorine-containing monomer having 1 to 6 carbon atoms in a fluoroalkyl group, and
(b) a fluorine-containing polymer having a repeating unit derived from a non-fluorine-crosslinkable monomer which is a vinyl monomer having a hydroxyl group,
(2) Liquid media
A fluorine-containing treating agent,
(3) at least one auxiliary agent selected from the group consisting of a softener and an antistatic agent is added to the surface treatment agent composition. A method for producing a treated substrate, comprising applying the surface treatment agent composition according to claim 10 or 11 to the substrate.