KR20180011200A - Surface treatment agent composition - Google Patents

Abstract

(I) a first fluorine-containing polymer having a repeating unit derived from a fluorine-containing monomer (a) and a repeating unit derived from a halogenated olefin (b), (II) , A second fluorine-containing polymer having no repeating unit derived from a halogenated olefin, and (III) a liquid medium.

Description

Surface treatment agent composition

The present invention relates to a surface treating agent composition such as a water repellent or oil repellent composition comprising a treating agent, particularly a fluorine-containing polymer mixture. More specifically, the present invention relates to a water repellent fabric which is excellent in water repellency, oil repellency, antifouling property, especially continuous water repellent oil repellent finishing (for example, water repellent finishing) of a fiber product (for example, carpet), paper, nonwoven fabric, stone, electrostatic filter, dustproof mask, Water-repellent < / RTI >

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. The fluorine-containing compound is used, for example, as a water- and oil-repellent agent and an antifouling agent by using the property that the free energy of the fluorine-containing compound is low, that is, is difficult to adhere.

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. Practical treatment of the surface treatment agent with fibers shows that the dynamic contact angle, especially the receding contact angle, is important not as a static contact angle but as a surface property from various research results so far. 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 significantly smaller 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 number of carbon atoms in 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 carbon number of the side chain of not more than 7 (in particular, not more than 6) has a problem that practicality is not satisfied as it is because the crystallinity of the side chain is low. Further, in the water-repellent oil-repellent processing, continuous processing is common, and water-repellent and oil-repellent agents having high processing sustainability in terms of drainage and productivity have been demanded.

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 Drabbe wetting time and an aqueous medium (C) And the composition is an essential component. Japanese Patent Application Laid-Open No. 2004-262970 discloses a water- and oil-repellent aqueous composition containing a fluorine-based water- and oil-repellent agent (A), an emulsion (B) containing a paraffin wax and a carboxyl-containing polyethylene, and an organic acid (C).

These patents do not describe the machining continuity.

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 surface treatment agent composition excellent in machinability in water-repellent processing of fibers and the like.

According to the present invention,

(I) a first fluorine-containing polymer having a repeating unit derived from a fluorine-containing monomer (a) and a repeating unit derived from a halogenated olefin (b)

(II) a second fluorine-containing polymer having a repeating unit derived from the fluorine-containing monomer (a) and having no repeating unit derived from a halogenated olefin, and

(III) liquid medium

To a surface treating agent composition comprising the surface treatment agent composition.

The surface treatment agent composition of the present invention is excellent in the machining sustainability of the water repellent oil refining process.

According to the present invention, excellent durability of excellent water repellency, oil repellency, antifouling property and stain releasing property, for example, 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 contaminant desorbing agent composition.

(1) The fluorine-containing polymer

In the present invention, the fluorine-containing polymer is a combination of the first fluorine-containing polymer and the second fluorine-containing polymer.

As the monomer constituting the repeating unit of the fluorine-containing polymer,

The fluorine-containing monomer (a), the halogenated olefin monomer (b) and the other monomer (c) other than the monomers (a) and (b) are used.

In the present invention, the first fluorine-containing polymer and the second fluorine-containing polymer act as an active ingredient of the water- and oil-repellent agent, the antifouling agent and the contaminant desorbing agent.

(a) a fluorine-containing monomer

The fluorine-containing monomer is generally a polymerizable compound having a perfluoroalkyl group or a perfluoroalkenyl group and an acrylic acid group, a methacrylic acid group or an alpha -substituted acrylic acid group.

The fluorine-containing monomer (a) is, for example,

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,

And Rf is a fluoroalkyl group having 1 to 20 carbon atoms]

.

The fluorine-containing monomer (a)

Wherein X is a hydrogen atom, a straight 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 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, or a substituted or unsubstituted phenyl group;

Y is -O- or -NH-;

Z is a direct bond, or

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 - (wherein x is 1 to 10)

An aromatic group or a cyclic aliphatic group having 6 to 30 carbon atoms,

Formula ^{-R 2 (R 1) N-} SO 2 - , and or a group represented by the formula -R ² (R ¹⁾ of the group (wherein a represents N-CO-, R ¹ is an alkyl group having 1 to 10, R ² is C 1 -C 10 straight-chain alkylene group or branched alkylene group)

Formula _{-CH 2 CH (OR 3) CH} 2 - (Ar-O) p - ( wherein, R ³ is an acyl group of a hydrogen atom, or 1 to 10 carbon atoms (e.g., formyl or acetyl), Ar Represents an arylene group optionally having substituent (s), and p represents 0 or 1)

A group represented by the formula -CH ₂ -Ar- (O) _q - (wherein Ar represents an arylene group optionally having a substituent and q is 0 or 1)

- (CH ₂ ) _m --SO ₂ - (CH ₂ ) _n - group or - (CH ₂ ) _m -S- (CH ₂ ) _n- group wherein m is 1 to 10 and n is 0 to 10, ego;

And Rf is a straight or branched fluoroalkyl group having 1 to 20 carbon atoms]

Is preferable.

Representative specific examples of X are Cl, Br, I, F, CN, CF 3, and preferably Cl. Particularly, when the? -Position is a chlorine atom, the surface treatment agent composition is excellent in practical water repellency (especially spray repellency).

In the fluorine-containing monomer, it is preferable that the Rf group is a perfluoroalkyl group. The carbon number of the Rf group is preferably 1 to 12, for example, 1 to 6, particularly 4 to 6, more preferably 6. Examples of Rf groups _{include, -CF 3, -CF 2 CF 3} , -CF 2 CF 2 CF 3, -CF (CF 3) 2, -CF 2 CF 2 CF 2 CF 3, -CF 2 CF (CF 3) _{2, -C (CF 3) 3} , - (CF 2) 4 CF 3, - (CF 2) 2 CF (CF 3) 2, -CF 2 C (CF 3) 3, -CF (CF 3) CF 2 CF ₂ CF ₃ , - (CF ₂ ) ₅ CF ₃ , - (CF ₂ ) ₃ CF (CF ₃ ) ₂ , - (CF ₂ ) ₄ CF (CF ₃ ) ₂ and -C ₈ F ₁₇ .

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 (provided that m is 1 to 10, and n is 0 to 10). The aliphatic group is preferably an alkylene group (especially 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 SO ₂ group may be bonded directly to the R f group.

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

[Wherein Rf is a fluoroalkyl group having 1 to 20 carbon atoms]

(b) Halogenated olefin monomers

The halogenated olefin monomer (halogenated olefin) preferably has no fluorine atom.

The halogenated olefin is preferably an olefin having 2 to 20 carbon atoms which is substituted with 1 to 10 chlorine, bromine or iodine atoms. The halogenated olefin is preferably a chlorinated olefin having 2 to 20 carbon atoms, especially an olefin having 2 to 5 carbon atoms and having 1 to 5 chlorine atoms. Preferred examples of halogenated olefins are vinyl halides such as vinyl chloride, vinyl bromide, vinyl iodide, vinylidene halides such as vinylidene chloride, vinylidene bromide, and vinylidene iodide. Vinyl chloride and vinylidene chloride are preferable, and vinyl chloride is particularly preferable.

(c) Other monomers

The monomer (c) other than the monomers (a) and (b) is preferably free of fluorine. As the other monomer (c), non-fluorine-free cross-linking monomer (c1) and non-fluorine-crosslinking monomer (c2) can be mentioned.

(c1) Non-fluorine Incompatible  Monomer

The non-fluorine-free non-crosslinking monomer (c1) is a monomer not containing a fluorine atom. The non-fluorine-free crosslinkable monomer (c1) has no crosslinkable functional group. Unlike the crosslinkable monomer (c2), the non-fluorine-free crosslinkable monomer (c1) is incompatible. The non-fluorine-incompatible monomer (c1) is preferably a non-fluorine monomer having a carbon-carbon double bond. The non-fluorine-incompatible monomer (c1) is preferably a vinyl monomer containing no fluorine. The non-fluorine-incompatible monomer (c1) is generally a compound having one carbon-carbon double bond.

The preferred non-fluorine-free crosslinkable monomer (c1)

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 straight or cyclic hydrocarbon group having 1 to 30 carbon atoms, or a straight or cyclic organic group having 1 to 31 carbon atoms and having an ester bond]

.

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.

Examples of the chain or cyclic organic group having 1 to 31 carbon atoms having an ester bond include -C (= O) -OQ and -OC (= O) -Q wherein Q is a straight or branched An aliphatic hydrocarbon group, a cyclic aliphatic group having 4 to 30 carbon atoms, an aromatic hydrocarbon group having 6 to 30 carbon atoms, and an aromatic aliphatic hydrocarbon group having 7 to 30 carbon atoms).

Preferable examples of the non-fluorine-incompatible monomer (c1) include ethylene, vinyl acetate, acrylonitrile, styrene, polyethylene glycol (meth) acrylate, polypropylene glycol (meth) acrylate, methoxypolyethylene glycol ) Acrylate, methoxypolypropylene glycol (meth) acrylate, and vinyl alkyl ether. The non-fluorine-incompatible monomer (c1) is not limited to these examples.

The non-fluorine-free crosslinkable monomer (c1) may be a (meth) acrylate ester having an alkyl group. 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). For example, the non-fluorine-containing non-crosslinking monomer (c1)

CH ₂ = CA ¹ COOA ²

Wherein A ¹ is a hydrogen atom, a methyl group, or a halogen atom other than a fluorine atom (for example, a chlorine atom, a bromine atom and an iodine atom)

A ² is an alkyl group represented by C _n H _{2n + 1} (n = 1 to 30)

May be used.

Preferred examples of A ² are lauryl, stearyl, and behenyl.

The non-fluorine-incompatible monomer (c1) may be a (meth) acrylate monomer having a cyclic hydrocarbon group.

The cyclic hydrocarbon group-containing acrylate ester monomer may be,

expression:

CH ₂ = CA ²¹ -C (= O) -OA ²²

Wherein A ²¹ is a hydrogen atom or a methyl group,

A ²² is a cyclic hydrocarbon-containing group having 4 to 30 carbon atoms]

Is preferable.

The cyclic hydrocarbon group-containing acrylate ester monomer is a monomer whose homopolymer has a high glass transition point (for example, 50 ° C or more, particularly 80 ° C or more).

The cyclic hydrocarbon group-containing acrylate ester monomer does not have a fluoroalkyl group. The cyclic hydrocarbon group-containing acrylate ester monomer may contain a fluorine atom, but preferably contains no fluorine atom.

It is particularly preferable that A ²¹ is a methyl group.

A ²² is a cyclic hydrocarbon group which may have a chain (for example, a linear or branched hydrocarbon group). Examples of the cyclic hydrocarbon group include saturated or unsaturated, monocyclic, polycyclic, and bridged groups. The cyclic hydrocarbon group is preferably saturated. The number of carbon atoms of the cyclic hydrocarbon group is preferably 4 to 30, and more preferably 6 to 20. The cyclic hydrocarbon group includes a cyclic aliphatic group having 4 to 20 carbon atoms, particularly 5 to 12 carbon atoms, an aromatic group having 6 to 20 carbon atoms, and an aromatic aliphatic group having 7 to 20 carbon atoms. The number of carbon atoms in the cyclic hydrocarbon group is particularly preferably 15 or less, for example, 12 or less. The cyclic hydrocarbon group is preferably a saturated cyclic aliphatic group. Specific examples of the cyclic hydrocarbon group include a cyclohexyl group, a t-butylcyclohexyl group, an isobornyl group, a dicyclopentanyl group, a dicyclopentenyl group and an adamantyl group.

Specific examples of cyclic hydrocarbon group-containing acrylate ester monomers 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 -Adamantyl (meth) acrylate, 2-ethyl-2-adamantyl (meth) acrylate and the like.

The presence of the cyclic hydrocarbon group-containing acrylate ester monomer increases the water repellency and oil repellency imparted by the copolymer.

(c2) Non-fluorine Crosslinkability  Monomer

The fluorine-containing polymer of the present invention may have a repeating unit derived from a non-fluorine-crosslinkable monomer (c2). The non-fluorine-crosslinkable monomer (c2) is a monomer not containing a fluorine atom. The non-fluorine-crosslinkable monomer (c2) may be a compound having at least two reactive groups and / or carbon-carbon double bonds and not containing fluorine. The non-fluorine-crosslinkable monomer (c2) may be a compound having at least two carbon-carbon double bonds, or a compound having at least one carbon-carbon double bond and at least one reactive group. 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 (c2) may be mono (meth) acrylate, di (meth) acrylate or mono (meth) acrylamide having a reactive group. Alternatively, the non-fluorine-crosslinkable monomer (c2) may be di (meth) acrylate.

Examples of the nonfluorine-crosslinkable monomer (c2) include diacetone (meth) acrylamide, (meth) acrylamide, N-methylol (meth) acrylamide, hydroxymethyl (meth) acrylate, (Meth) acrylate, butadiene, isoprene, chloroprene, glycidyl (meth) acrylate, 1,6-cyclohexanedimethylacrylate -Hexanediol di (meth) acrylate, neopentyl glycol di (meth) acrylate, and the like.

By copolymerizing the non-fluorine-free crosslinkable monomer (c1) and / or the non-fluorine crosslinkable monomer (c2), water repellency and antifouling property, Various properties can be improved as needed.

In the present specification, when it is simply referred to as "acrylate" or "acrylamide", not only a compound having a hydrogen atom at the α-position but also a group having a different substituent (eg, a monovalent organic group containing a methyl group or a halogen atom ). ≪ / 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) (for example, each of the monomers (c1) and (c2)) may be singly or in combination of two or more.

The amount of each monomer in the first fluorine-containing polymer is as follows.

In the first fluorine-containing polymer, the amount of the fluorine-containing monomer (a) may be 20% by weight to 100% by weight, preferably 30% by weight to 90% by weight, based on the fluorine-containing polymer.

In the first fluorine-containing polymer, with respect to 100 parts by weight of the fluorine-containing monomer (a)

The amount of the halogenated olefin monomer (b) is 5 to 300 parts by weight, for example, 10 to 200 parts by weight, particularly 20 to 100 parts by weight, particularly 30 to 80 parts by weight,

The amount of the other monomer (c) may be 0 to 800 parts by weight, for example, 1 to 300 parts by weight, particularly 2 to 200 parts by weight, and particularly 3 to 100 parts by weight.

In the first fluorine-containing polymer, with respect to 100 parts by weight of the fluorine-containing monomer (a)

The amount of the non-fluorine-free crosslinkable monomer (c1) is 0 to 500 parts by weight, for example, 1 to 300 parts by weight, particularly 2 to 200 parts by weight, particularly 3 to 100 parts by weight,

The amount of the non-fluorine-crosslinkable monomer (c2) may be 0 to 80 parts by weight, for example, 0 to 50 parts by weight, particularly 0.1 to 30 parts by weight, particularly 1 to 20 parts by weight.

The amount of each monomer in the second fluorine-containing polymer is as follows.

In the second fluorine-containing polymer, the amount of the fluorine-containing monomer (a) may be 20 wt% to 100 wt%, preferably 30 wt% to 90 wt% with respect to the fluorine-containing polymer.

The second fluorine-containing polymer does not have a repeating unit derived from a halogenated olefin.

In the second fluorine-containing polymer, relative to 100 parts by weight of the monomer (a)

The amount of the other monomer (c) may be 0 to 800 parts by weight, for example, 1 to 300 parts by weight, particularly 2 to 200 parts by weight, and particularly 3 to 100 parts by weight.

In the second fluorine-containing polymer, with respect to 100 parts by weight of the fluorine-containing monomer (a)

The amount of the non-fluorine-free cross-linking monomer (c1) may be 0 to 500 parts by weight, for example, 1 to 300 parts by weight, particularly 2 to 200 parts by weight, and particularly 3 to 100 parts by weight.

The amount of the non-fluorine-crosslinkable monomer (c2) may be 0 to 80 parts by weight, for example, 0 to 50 parts by weight, particularly 0.1 to 30 parts by weight, particularly 1 to 20 parts by weight.

The fluorine-containing monomer (a) and the other monomer (c) in the first fluorine-containing polymer and the second fluorine-containing polymer may be the same or different.

In the surface treatment agent composition, the weight ratio of the first fluorine-containing polymer and the second fluorine-containing polymer may be 5:95 to 95: 5, for example, 20:80 to 20:80.

Generally, in the mixture of the first fluorine-containing polymer and the second fluorine-containing polymer, molecules of the first fluorine-containing polymer and molecules of the second fluorine-containing polymer are not chemically bonded.

(2) Surfactants

In the treatment agent of the present invention, the surfactant includes one or both of a nonionic surfactant and a cationic surfactant. In addition, the surfactant may include a positive surfactant. It is preferred that the surfactant does not contain an anionic surfactant.

(2-1) Nonionic  Surfactants

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

The nonionic surfactant may be selected from alkylene oxide adducts of linear and / or branched aliphatic (saturated and / or unsaturated) groups, polyalkylene glycol esters of linear and / or branched fatty acids (saturated and / or unsaturated) , Polyoxyethylene (POE) / polyoxypropylene (POP) copolymers (random copolymers or block copolymers), and alkylene oxide adducts of acetylene glycol. Among them, the structure of the alkylene oxide addition moiety and polyalkylene glycol moiety is preferably polyoxyethylene (POE), polyoxypropylene (POP) or POE / POP copolymer (may be a random copolymer or a block copolymer) Do.

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, R ² is an alkylene group having 3 or more carbon atoms (for example, 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 2 or more and q is 0 or 1 or more]

.

R ^{1 preferably} has 8 to 20 carbon atoms, 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 (e.g., 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 oxystyrene chain. Among them, 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 have the same meaning as above,

Lt; / RTI >

Examples of nonionic surfactants include,

[Wherein p and q are as defined above]

.

Specific examples of the nonionic surfactant include ethylene oxide and its derivatives such as hexylphenol, isooctatylphenol, 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 alone or in combination of two or more.

The nonionic surfactant is preferably a combination of two or more. In the combination of two or more, a non-ionic surface active agent at least one kind of the group R ¹ (and / or R ³ group), an alkyl group (e.g., isopropyl tree decyl group) in R ¹ O- (CH ₂ CH branched 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, particularly 10 to 40 parts by weight per 100 parts by weight of the total amount of the nonionic surfactant (B2) . In the combination of two or more kinds, the remaining nonionic surfactants are those 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 (CH ₂ CH ₂ O) _p --H], which is represented by R ¹ O- (CH ₂ CH ₂ O) _p - (R ² O) _q -R ³ [in particular, R ¹ O-

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.

Examples of the nonionic surfactant include acetylene alcohols (especially, acetylene glycol) or oxyethylene adducts of acetylenic alcohols (particularly, acetylene glycol), since the dynamic surface tension of the aqueous emulsion is low (i.e. the aqueous emulsion tends to penetrate the substrate) Water is preferred.

A preferred nonionic surfactant is an alcohol having an unsaturated triple bond or an alkylene oxide adduct of the alcohol (both the alcohol and the alkylene oxide adduct are referred to as " acetylene alcohol compounds "). Particularly preferred nonionic surfactants are alkylene oxide adducts of monools or polyols having unsaturated triple bonds.

An acetylene alcohol compound is a compound containing at least one triple bond and at least one hydroxyl group. The acetylene alcohol compound may be a compound containing a polyoxyalkylene moiety. Examples of polyoxyalkylene moieties include random addition structures of polyoxyethylene, polyoxypropylene, polyoxyethylene and polyoxypropylene, and block addition structures of polyoxyethylene and polyoxypropylene.

The acetylene alcohol compound has the formula:

HO-CR ¹¹ R ¹² -C? C-CR ¹³ R ¹⁴ -OH, or

HO-CR ¹⁵ R ¹⁶ -C≡CH

Wherein R ¹¹ , R ¹² , R ¹³ , R ¹⁴ , R ¹⁵ and R ¹⁶ may be the same or different and each is a hydrogen atom or an alkyl group having 1 to 30 carbon atoms]

. The acetylene alcohol compound may be an alkylene oxide adduct of a compound represented by the formula. The alkyl group is preferably a linear or branched alkyl group having 1 to 12 carbon atoms, particularly preferably a linear or branched alkyl group having 6 to 12 carbon atoms. For example, a methyl group, an ethyl group, a propyl group, a butyl group, and an isobutyl group. The alkylene oxide is preferably an alkylene oxide having 1 to 20 carbon atoms (particularly 2 to 5 carbon atoms) such as ethylene oxide or propylene oxide, and the addition number of the alkylene oxide is preferably 1 to 50.

(2-2) Cationic  Surfactants

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]

≪ / RTI >

Specific examples of R ²¹ , R ²² , R ²³ and -R ²⁴ are an alkyl group (for example, methyl group, butyl group, stearyl group, palmity group). Specific examples of X are halogen (for example, chlorine), acid (for example, 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 (e.g., C ₁₂ to C ₅₀ )

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

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

X represents a halogen atom (e.g., a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, etc.), a C ₁ to C ₄ fatty acid base,

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

Or a salt thereof. 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, Methyldodecyldi (hydro- polyoxyethylene) ammonium chloride, benzyldodecyldi (hydro- polyoxyethylene) ammonium chloride, N- [2- (diethylamino) ethyl] oleamide hydrochloride.

Examples of the amphoteric surfactant include alanine, imidazolinium betaine, amide betaine, and betaine acetate. Specific examples thereof include lauryl betaine, stearyl betaine, lauryl carboxymethyl hydroxyethyl imide Lauryldimethylaminoacetic acid betaine, fatty acid amidopropyl dimethylaminoacetate betaine, and the like.

Each of the nonionic surfactant, the cationic surfactant and the amphoteric surfactant may be one or a combination of two or more.

As the surfactant, only a nonionic surfactant or a cationic surfactant may be used, but it is preferable to use a combination of a nonionic surfactant and a cationic surfactant. In the combination of the nonionic surfactant and the cationic surfactant, the weight ratio of the nonionic surfactant to the cationic surfactant is preferably 85:15 to 20:80, more preferably 80:20 to 40:60 .

The total amount of the surfactant may be 0.1 to 20 parts by weight, for example, 0.2 to 10 parts by weight based on 100 parts by weight of the polymer.

(3) Liquid media

The surface treatment agent composition is preferably a dispersion in which the polymer is dispersed in a liquid medium.

The liquid medium may be an organic solvent, but is preferably an aqueous medium. In the present specification, the term "aqueous medium" means an organic solvent (usually a water-soluble organic solvent) added to a water-based medium and water, wherein the amount of the organic solvent is 80 parts by weight or less, 50 parts by weight, especially 5 to 30 parts by weight).

The amount of the aqueous medium may be from 20 to 99% by weight, for example from 40 to 95% by weight, based on the surface treating agent composition.

(4) Other components

The surface treatment agent composition may contain a fluorine-containing water-repellent compound as a component other than the fluorine-containing polymer and the surfactant.

Non-fluorine  Water repellent compound

The surface treatment agent composition may contain a water-repellent compound containing no fluorine atom (non-fluorine-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-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 at least Is a copolymer composed of one kind of another 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 straight or cyclic hydrocarbon group having 1 to 30 carbon atoms, or a straight or cyclic organic group having 1 to 31 carbon atoms and having an ester bond]

.

Examples of the straight 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 aromatic hydrocarbon group having 7 to 30 carbon atoms Aromatic aliphatic hydrocarbon group.

Examples of the chain or cyclic organic group having 1 to 31 carbon atoms having an ester bond include -C (= O) -OQ and -OC (= O) -Q wherein Q is a linear or branched aliphatic group having 1 to 30 carbon atoms A hydrocarbon group, a cyclic aliphatic group having 4 to 30 carbon atoms, an aromatic hydrocarbon group having 6 to 30 carbon atoms, and an aromatic aliphatic hydrocarbon group having 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 0 to 500 parts by weight, for example, 5 to 200 parts by weight, particularly 5 to 100 parts by weight per 100 parts by weight of the total of the first fluorine-containing polymer and the second fluorine-

The fluorine-containing polymer (the first fluorine-containing monomer and the second fluorine-containing monomer) in the present invention can be produced by any of ordinary polymerization methods, 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 of dissolving the monomer in an organic solvent in the presence of a polymerization initiator, substituting with nitrogen, and heating and stirring the solution 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 one which is inert to the monomer and dissolves them. Examples thereof include esters (e.g., esters having 2 to 30 carbon atoms, specifically, ethyl acetate, butyl acetate), ketones (e.g., Ketone, specifically, methyl ethyl ketone, diisobutyl ketone), an alcohol (for example, an alcohol 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, a method of emulsifying monomers in water in the presence of a polymerization initiator and an emulsifier, and performing polymerization after the replacement with nitrogen and stirring at 50 to 80 ° C for 1 to 10 hours is employed. 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 crushing 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 completely compatible, 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, ethanol and the like. , 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 treating composition of the present invention may be in the form of a solution, an emulsion (especially an aqueous dispersion) or an aerosol, but is preferably an aqueous dispersion. The treating composition comprises a polymer (the active component of the surface treatment agent) and a medium (especially 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 the object to be treated by conventional methods. Usually, a method is employed in which the treating composition is dispersed in an organic solvent or water and diluted, adhered to the surface of the material to be treated by a known method such as immersion coating, spray coating, or air bubble coating and dried. 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, plaster and plaster. Various examples of textile products are available. 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 treating composition of the present invention can also 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 a cloth, the cloth may be immersed in the solution, or the solution may be attached or sprayed on the cloth. The treated fiber product is dried and preferably heated, for example, at 100 ° C to 200 ° C to develop oil repellency.

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

The textile product to be treated is typically a fabric, which includes fabrics, knits and non-wovens, garments in the form of garments, and carpets, but may also include fibers or yarns or intermediate fiber products (e.g., 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 leucel), 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 render 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.

Example

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 expressed 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 are used. The specimen frame is a metal frame with 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 sheet was fixed to the test piece holder frame so that the sheet was free of wrinkles. 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 boulevard, one end of the holding frame is held, the front surface is downwardly, and the opposite end is lightly knocked with a hard material. The retaining frame is further rotated by 180 DEG, the same procedure is repeated, and excess water drops are dropped. Moisture test specimens are compared to wet comparison standards to give a rating of 0, 50, 70, 80, 90 and 100 in good order from poor water repellency. Results are obtained from the average of three measurements.

Water-repellent  Continuous processability

Ten sheets of test pieces each having a size of about 20 cm x 50 cm are prepared and treated successively with a water- and oil-repellent treatment solution diluted to a predetermined concentration. Each sheet was subjected to the above-described shower repellency test and evaluated.

Production Example 1

A 1000 mL autoclave was charged with 108 g of CF ₃ CF ₂ - (CF ₂ CF ₂ ) _n --CH ₂ CH ₂ OCOC (Cl) = CH ₂ (n = 2.0) (13FCIA), 24.0 g of lauryl acrylate 57.7 g of neil methacrylate (IBMA), 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 charged and emulsified and dispersed by ultrasonic wave at 60 DEG C for 15 minutes . After replacing the inside of the autoclave with nitrogen, 62 g of vinyl chloride (VCM) was press-filled and 0.4 g of an 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 matched the composition of the input monomers.

Production Example 2

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) (13FClA), 85.4 g of stearyl acrylate 344 g of a water-soluble 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 캜 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 the mixture was reacted at 60 DEG C for 20 hours to obtain an aqueous dispersion of the polymer. The composition of the polymer almost matched the composition of the input monomers.

Production Example 3

A 1000 mL autoclave was charged with 108 g of CF ₃ CF ₂ - (CF ₂ CF ₂ ) _n --CH ₂ CH ₂ OCOC (Cl) = CH ₂ (n = 2.0) (13FCIA), 24.0 g of lauryl acrylate 57.7 g of neil methacrylate (IBMA), 565 g of pure water, 47 g of a water-soluble glycol solvent, 2.5 g of polyoxyethylene oleyl ether, 3.9 g of alkyltrimethylammonium chloride and 27.8 g of polyoxyethylene alkyl ether were placed, And emulsified and dispersed by ultrasonic wave for 15 minutes. After replacing the inside of the autoclave with nitrogen, 62 g of vinyl chloride (VCM) was press-filled and 0.4 g of an 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 matched the composition of the input monomers.

Production Example 4

In a 500 ml reaction flask, 51.2 g of CF ₃ CF ₂ - (CF ₂ CF ₂ ) _n -CH ₂ CH ₂ OCOC (CH ₃ ) = CH ₂ (n = 2.0) (13FMA), 85.4 g of stearyl acrylate 34.1 g of a pure water 194 g water-soluble glycol 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 캜 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 the mixture was reacted at 60 DEG C for 20 hours to obtain an aqueous dispersion of the polymer. The composition of the polymer almost matched the composition of the input monomers.

Production Example 5

To a 1000 mL autoclave were added 108 g of CF ₃ CF ₂ - (CF ₂ CF ₂ ) _n --CH ₂ CH ₂ OCOC (CH ₃ ) = CH ₂ (n = 2.0) (13 FMA), 24.0 g of lauryl acrylate 57.7 g of boron methacrylate (IBMA), 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 were charged and emulsified by ultrasonic at 60 캜 for 15 minutes under stirring Lt; / RTI > After replacing the inside of the autoclave with nitrogen, 62 g of vinyl chloride (VCM) was press-filled and 0.4 g of an 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 matched the composition of the input monomers.

Production Example 6

47.5 g of stearyl acrylate (StA), 145 g of pure water, 15 g of a water-soluble glycol solvent, 1.5 g of sorbitan monoalkyl ester, 2 g of polyoxyethylene alkyl ether and 1.5 g of alkyldimethylammonium chloride were placed in a 500 mL reaction flask, And emulsified and dispersed by ultrasonic wave at 60 캜 for 15 minutes. After the inside of the reaction flask was purged with nitrogen, 0.5 g of an azo group-containing water-soluble initiator was added, and the mixture was reacted at 60 ° C for 3 hours to obtain an aqueous dispersion of the polymer. In addition, the solid content was adjusted to 30% with pure water.

Production Example 7

35 g of stearyl acrylate (StA), 145 g of pure water, 15 g of water-soluble glycol solvent, 1 g of sorbitan monoalkyl ester, 2 g of polyoxyethylene alkyl ether and 2 g of alkyldimethylammonium chloride were placed in a 500 mL autoclave, Minute, and emulsified and dispersed by ultrasonic waves. After the inside of the autoclave was purged with nitrogen, 12.5 g of vinyl chloride was injected thereinto, 0.5 g of 2,2-azobis (2-amidinopropane) dihydrochloride was added, and the reaction was allowed to proceed at 60 ° C for 3 hours, To obtain a dispersion. In addition, the solid content was adjusted to 30% with pure water.

Comparative Preparation Example 1

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 OCOCH═CH ₂ (n = 3.2) (NSFA), 85.4 g of stearyl acrylate (StA) , 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 캜 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 the mixture was reacted at 60 DEG C for 20 hours to obtain an aqueous dispersion of the polymer. The composition of the polymer almost matched the composition of the input monomers.

Comparative Production Example 2

A 1000 mL autoclave was charged with 108 g of CF ₃ CF ₂ - (CF ₂ CF ₂ ) _n --CH ₂ CH ₂ OCOCH═CH ₂ (n = 3.2) (NSFA), 81.7 g of stearyl acrylate (StA), 565 g of pure water, 47 g of a phenol-based solvent, 2.5 g of polyoxyethylene oleyl ether and 27.8 g of polyoxyethylene alkyl ether were put and emulsified and dispersed by ultrasonic wave at 60 캜 for 15 minutes under stirring. After replacing the inside of the autoclave with nitrogen, 62 g of vinyl chloride (VCM) was press-filled and 0.4 g of an 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 matched the composition of the input monomers.

Comparative Production Example 3

In a 500 ml reaction flask, paraffin (melting point 50 ° C), 136.6 g of pure water, 34.1 g of water-soluble glycol solvent, 6.3 g of alkyltrimethylammonium chloride and 7.0 g of polyoxyethylene alkyl ether were charged and emulsified by ultrasonic at 60 ° C for 15 minutes And an aqueous dispersion was obtained. The composition of the polymer almost matched the composition of the input monomers.

Example 1

The aqueous liquid prepared in Preparation Examples 1 and 2 was diluted with purified water to a solid content of 30% of the fluorine-containing polymer, mixed at a ratio of 50:50 and sufficiently stirred. Thereafter, the ratio of the 30% And further diluted with water to make a 2.00% test liquid (100 g). 10 pieces of PET cloth (500 mm x 200 mm) were continuously immersed in this test solution, passed through mangles, and treated with a pin tenter at 170 캜 for 1 minute. After that, it was subjected to a water repellency test. The results are shown in Table A. The initial water repellency was also measured for the test liquids having the concentrations of 1.00%, 1.20%, and 1.40%.

Example 2

The aqueous liquid prepared in Preparation Examples 1 and 2 was diluted with purified water to a solid content of 30% of the fluorine-containing polymer, mixed at a ratio of 30:70 and sufficiently stirred. Thereafter, did. The results are shown in Table A.

Example 3

The aqueous liquid prepared in Production Examples 2 and 3 was diluted with pure water to a solid content of 30% of the fluorine-containing polymer, mixed at a ratio of 50:50 and sufficiently stirred. Thereafter, did. The results are shown in Table A.

Example 4

The aqueous liquid prepared in Production Examples 2 and 3 was diluted with pure water to a solid content of 30% of the fluorine-containing polymer, mixed at 70:30 and sufficiently stirred. Thereafter, did. The results are shown in Table A.

Example 5

The aqueous liquid prepared in Production Examples 4 and 5 was diluted with purified water to a solid content of 30% of the fluorine-containing polymer, mixed at a ratio of 50:50 and sufficiently stirred. Thereafter, did. The results are shown in Table A.

Example 6

The aqueous liquids prepared in Production Examples 1, 2 and 6 were diluted with pure water to a solid content of 30%, and then mixed at 50: 17.5: 32.5 and sufficiently stirred. Thereafter, Respectively. The results are shown in Table A.

Example 7

The aqueous liquids prepared in Preparation Examples 1, 2 and 7 were diluted with pure water to a solid content of 30%, and then mixed at 50:25:25 and sufficiently stirred. Thereafter, the same procedure as in Example 1 was repeated Respectively. The results are shown in Table A.

Comparative Example 1

The aqueous liquid prepared in Preparation Example 1 was diluted with pure water to a solid content of 30% of the fluorine-containing polymer, diluted further with water such that the proportion of the 30% diluent became 2%, and 2.00% . Thereafter, the evaluation was carried out in the same manner as in Example 1. The results are shown in Table A.

Comparative 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, diluted further with water such that the proportion of the 30% diluent became 2%, and 2.00% . Thereafter, the evaluation was carried out in the same manner as in Example 1. The results are shown in Table A.

Comparative 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, and further diluted with water such that the proportion of the 30% diluted solution became 2%, and 2.00% . Thereafter, the evaluation was carried out in the same manner as in Example 1. The results are shown in Table A.

Comparative Example 4

The aqueous liquid prepared in Production Example 4 was diluted with purified water to a solid content of 30% of the fluorine-containing polymer, and further diluted with water such that the proportion of the 30% diluted solution became 2%, and 2.00% . Thereafter, the evaluation was carried out in the same manner as in Example 1. The results are shown in Table A.

Comparative 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, diluted further with water such that the proportion of the 30% diluted solution became 2%, and 2.00% . Thereafter, the evaluation was carried out in the same manner as in Example 1. The results are shown in Table A.

Comparative Example 6

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, and further diluted with water such that the proportion of the 30% diluted solution became 2% to prepare 2.00% . Thereafter, the evaluation was carried out in the same manner as in Example 1. The results are shown in Table A.

Comparative Example 7

The aqueous liquid prepared in Comparative Preparation Example 2 was diluted with pure water to a solid content of 30% of the fluorine-containing polymer, diluted further with water such that the proportion of the 30% diluted solution became 2%, and 2.00% . Thereafter, the evaluation was carried out in the same manner as in Example 1. The results are shown in Table A.

Comparative Example 8

The aqueous liquid prepared in Preparative Example 1 and Comparative Preparative Example 3 was diluted with pure water to a solid content of 30% and then mixed at 75:25 and sufficiently stirred. Thereafter, the ratio of the 30% diluted liquid was 2% And further diluted with water to make a 2.00% test liquid (100 g). Thereafter, the evaluation was carried out in the same manner as in Example 1. The results are shown in Table A.

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)

(I) a first fluorine-containing polymer having a repeating unit derived from a fluorine-containing monomer (a) and a repeating unit derived from a halogenated olefin (b)
(II) a second fluorine-containing polymer having a repeating unit derived from the fluorine-containing monomer (a) and having no repeating unit derived from a halogenated olefin, and
(III) liquid medium
Wherein the surface treatment agent composition is a surface treatment agent composition. The fluorine-containing polymer according to claim 1, wherein the fluorine-containing monomer (a)

Wherein X is a hydrogen atom, a straight 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 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, or a substituted or unsubstituted phenyl group;
Y is -O- or -NH-;
Z is a direct bond,
A linear or branched aliphatic group having 1 to 20 carbon atoms,
An aromatic group or a cyclic aliphatic group having 6 to 30 carbon atoms,
Formula ^{-R 2 (R 1) N-} SO 2 - , and or a group represented by the formula -R ² (R ¹⁾ of the group (wherein a represents N-CO-, R ¹ is an alkyl group having 1 to 10, R ² is C 1 -C 10 straight-chain alkylene group or branched alkylene group),
Formula ^{_{-CH 2 CH (OR 3) CH}} 2 - (Ar-O) p - ( wherein, R ³ is an acyl group of a hydrogen atom, or a carbon number of 1 to 10, Ar is a substituent having, depending on the needs arylene group, p Represents 0 or 1,
A group represented by the formula -CH ₂ -Ar- (O) _q - (wherein Ar represents an arylene group optionally having a substituent and q is 0 or 1)
- (CH ₂ ) _m --SO ₂ - (CH ₂ ) _n - group or - (CH ₂ ) _m -S- (CH ₂ ) _n- group wherein m is 1 to 10 and n is 0 to 10, ego;
And Rf is a straight or branched fluoroalkyl group having 1 to 20 carbon atoms]
Is a compound represented by the general formula (1). The surface treatment agent composition according to any one of claims 1 to 3, wherein the fluorine-containing monomer (a) is an acrylate in which the? -Phosphorus is substituted with a chlorine atom. The surface treating agent composition according to claim 2, wherein the fluorine-containing monomer (a) has 1 to 6 carbon atoms in Rf. The surface treatment agent composition according to claim 1, wherein the halogenated olefin monomer (b) is vinyl chloride. The fluorine-containing polymer according to any one of claims 1 to 5, wherein at least one of the first fluorine-containing polymer and the second fluorine-containing polymer has a repeating unit derived from the other monomer (c)
The other monomer (c) is a non-fluorine-free cross-linking monomer (c1)
The non-fluorine-containing non-crosslinking monomer (c1)
CH ₂ = CA-T
Wherein A is a hydrogen atom, a methyl group, or a halogen atom other than a fluorine atom,
T represents a hydrogen atom, a straight or cyclic hydrocarbon group having 1 to 30 carbon atoms, or a straight or cyclic organic group having 1 to 31 carbon atoms and having an ester bond]
Is a compound represented by the general formula (1). 7. The fluorine-containing polymer according to any one of claims 1 to 6, wherein the amount of the halogenated olefin monomer (b) is 5 to 300 parts by weight based on 100 parts by weight of the fluorine-containing monomer (a) The amount of other monomer (c) present, if necessary, is 0 to 800 parts by weight,
Wherein the amount of the other monomer (c) present in the second fluorine-containing polymer, if necessary, relative to 100 parts by weight of the fluorine-containing monomer (a) is 0 to 800 parts by weight. The surface treating agent composition according to any one of claims 1 to 7, wherein the weight ratio of the first fluorine-containing polymer and the second fluorine-containing polymer is 5:95 to 95: 5. 9. The surface treatment agent composition according to any one of claims 1 to 8, wherein the liquid medium (III) is water or a mixture of water and a water-soluble organic solvent. 10. The surface treatment agent composition according to any one of claims 1 to 9, which is an aqueous dispersion comprising a nonionic surfactant and a cationic surfactant. 11. The surface treatment agent composition according to any one of claims 1 to 10, which contains a water-repellent compound containing no fluorine atom. 12. The surface treating agent composition according to any one of claims 1 to 11, wherein the surface treating agent composition is a water- and oil-repellent agent composition, an antifouling agent composition or a contaminant desorbing agent composition. 12. A substrate treated by the surface treatment agent composition according to any one of claims 1 to 12.