KR20210103971A - Fluorine Based Stain-proofing Agent Composition with Improved Water-repellant, Oil-repellant and Antifouling Performance and Fabric Products Using the Same - Google Patents

Abstract

The present invention provides a fluorine-based processing agent composition containing a fluorinated copolymer comprising a perfluoroalkyl group derived from an HFP as an active ingredient, a textile product using the same, and a manufacturing method thereof, wherein by containing, as an active ingredient in the monomer, a perfluoroalkyl ester and a non-fluorine ester having a specific structure but having a perfluoroalkyl group in the form of an aqueous dispersion containing almost no volatile organic solvent, the fluorine-based processing agent composition according to the present invention reduces an environmental load and has excellent water-repellency, oil-repellency, and antifouling performance.

Description

Fluorine Based Stain-proofing Agent Composition with Improved Water-repellant, Oil-repellant and Antifouling Performance and Fabric Products Using the Same

The present invention relates to a fluorine-based processing agent composition having improved water-repellent, oil-repellent and antifouling performance, and textile products using the same.

The main causes of contamination of fabrics such as clothes, carpets, and car seats are lipids generated from the human body, oil components from food, and dust in the air. Another cause of contamination is the phenomenon of re-attaching to the fabric when it is detached (contaminants) once during washing.

The antifouling treatment for textiles can be divided into a process for making it difficult for dirt to adhere and a process for making the attached dirt easy to fall off. In general, in the process of making it difficult for contamination to adhere, the fiber surface is covered with a thin film using a fluorine-based polymer, the unevenness of the fiber surface is flattened to some extent, and at the same time, the surface free energy is extremely lowered to reduce the fiber and oiliness. Reduce contact with contaminants.

In the process of making the attached contamination easy to fall off, the surface of the fiber is made hydrophilic with a hydrophilic polymer and easily fuses with the detergent solution during washing to easily drop off the contaminants and prevents recontamination due to oily contamination during rinsing. In particular, since it is difficult to wash a car seat used in a car once installed, it is difficult for contaminants to adhere to the car seat, and antifouling treatment in which the attached contaminants easily fall is very important. Therefore, automobile companies of a certain size are evaluating the antifouling performance of the pollution accessibility and pollution removal performance of the car seat by separately stipulating the antifouling standard suitable for each company for the car seat.

In this regard, the conventional antifouling-treated fabric for vehicles has water and oil repellency to prevent contaminants from sticking well, and a soil release or stain release (SR) that makes it easy to peel off easily by wiping or washing once attached contaminants. ), a fluorine-based processing agent that has both properties is widely used.

For example, Japanese Patent No. 3320491 discloses (meth)acrylate containing a polyfluoroalkyl group, (meth)acrylate containing a polyoxyalkylene chain, and (meth)acrylate containing a blocked isocyanate group. A fluorine-based antifouling agent having a copolymer as an active ingredient has been proposed. However, these fluorine-based antifouling agents are fluorinated copolymers and are derived from TFE (Tetra-fluoro ethylene). ) contains a group of chemical substances of Substances of Very High Concern, so the load on the environment during actual processing is large, and there is a problem of accumulating in the human body of consumers who use it.

Japanese Laid-Open Publication No. 5351023 discloses a water and oil repellent agent of a copolymer component comprising a mixture of perfluoroalkylethyl methacrylate having less than 8 carbon atoms, alkyl (meth)acrylate, an isocyanate-reactive monomer, and vinyl chloride and/or vinylidene chloride. Although disclosed, there is a problem in that it contains a trace amount of environmentally harmful substances such as PFOA.

On the other hand, when a conventional HFP (Hexafluoro propylene)-derived fluorine compound without environmental load is used as a component of a fluorine-based processing agent, not a TFE-derived fluorine-based processing agent, the crystallinity is low and high water-repellent, oil-repellent and antifouling like TFE-derived fluorine-based processing agent. There is a problem in that it is difficult to implement the performance, so there is a need for continuous research and development for a fluorine-based processing agent composition with improved crystallinity.

Japanese Patent No. 3320491 (published on October 4, 1994) Japanese Patent No. 5351023 (published on: 2010.01.21.)

The fluorine-based processing agent of the present invention is intended to solve the above problems, and it is in the form of an aqueous dispersion containing almost no volatile organic solvents and at the same time contains a fluorinated copolymer having a perfluoroalkyl group derived from HFP as an active ingredient. no load

In addition, the present invention includes a fluorine-free monomer having a ring strain structure as an active ingredient of the fluorine-based processing agent, so that the crystallinity of the conventional fluorine-based processing agent containing a perfluoroalkyl group derived from HFP is low, and high water repellency, oil repellency and An object of the present invention is to provide a fluorine-based processing agent composition capable of solving the problem of difficulty in implementing antifouling performance, a textile product using the same, and a manufacturing method thereof.

In order to solve the above problems, the present invention provides a fluorine-based processing agent composition comprising at least components (A), (B) and (C), wherein the component (A) is a perfluorinated alkyl monomer represented by the following formula (1) or the perfluorinated a mixture (a1) comprising two or more alkyl monomers; and a fluorine-free monomer represented by the following Chemical Formula 2 or a mixture (a2) comprising two or more of the fluorine-free monomers; A fluorine-based polymer copolymerized by including each as a monomer unit,

[Formula 1]

CF ₃ CF ₂ CF ₂ O(CFCF ₃ CF ₂ O) _n CFCF ₃₍ C=O)OL ₁ -O(C=O)C(R)=CH ₂

(In Formula 1, n is 1 to 5,

L ₁ is a substituted or unsubstituted straight-chain, branched or cyclic alkylene group having 2 to 6 carbon atoms,

R is -H or -CH ₃ )

[Formula 2]

H ₂ C=C(R ₁ )-(Y)mX or H ₂ C=CH(C ₆ H ₅ )

(In Formula 2,

Y is -(C=O)O-, -O-, -(C=O)OL ₂ -, -(C=O)OL ₂ -O- Any one linking group selected from, wherein L ₂ is substituted or unsubstituted a straight-chain, branched or cyclic alkylene group having 1 to 6 carbon atoms,

m is 0 or 1,

X is a substituted or unsubstituted aromatic aryl group having 6 to 18 carbon atoms, a substituted or unsubstituted cyclic aliphatic group having 4 to 30 carbon atoms, and a substituted or unsubstituted cyclic aliphatic group having 4 to 30 carbon atoms, having 1 to 10 carbon atoms Any one of the substituents selected from the alkyl group, R ₁ is -H or -CH ₃ )

The component (B) is a nonionic surfactant having a hydrophilic-lipophile balance (HLB) of 5.0 to 19.0 or a mixture of the nonionic surfactant and a cationic surfactant, and the component (C) is water It provides a fluorine-based processing agent composition characterized in that.

In one embodiment of the present invention, the fluorine-based polymer component (A) is a perfluorinated alkyl monomer represented by Formula 1 or a mixture (a1) comprising two or more of the perfluorinated alkyl monomers; and a fluorine-free alkyl monomer represented by Formula 2 or a mixture (a2) comprising two or more of the fluorine-free monomers; In the case of a fluorine-based polymer copolymerized by including each as a monomer unit, it may contain 15 wt% to 80 wt% of component (a1) and 20 wt% to 85 wt% of component (a2) with respect to the total weight of the fluorine-based polymer have.

In one embodiment of the present invention, the fluorine-based polymer component (A) is a vinyl group-containing monomer represented by the following Chemical Formula 3A or Chemical Formula 3B or a mixture thereof (a3); It may be a fluorine-based polymer copolymerized by additionally including as a monomer unit.

[Formula 3A] [Formula 3B]

H ₂ C=CH(R ₂ ) H ₂ C=C(R ₂ )(R ₃ )

(In Formulas 3A and 3B, R ₂ and R ₃ are the same or different from each other, and independently of each other are -F or -Cl)

In one embodiment of the present invention, the fluorine-based polymer component (A) is a perfluorinated alkyl monomer represented by Formula 1 or a mixture (a1) comprising two or more of the perfluorinated alkyl monomers; and a fluorine-free alkyl monomer represented by Formula 2 or a mixture (a2) comprising two or more of the fluorine-free monomers; and a vinyl group-containing monomer represented by Formula 3A or Formula 3B or a mixture thereof (a3) as a monomer unit, respectively; in the case of a copolymerized fluorine-based polymer, it is based on the total weight of the fluorine-based polymer, component (a1) 20 weight % to 60% by weight, 20% to 50% by weight of component (a2) and 15% to 40% by weight of component (a3).

In another embodiment of the present invention, the component (B) may be in the range of 1 wt% to 20 wt%, based on the total weight of the fluorine-based processing agent composition.

In another embodiment of the present invention, the fluorine-based processing agent composition may include 5% by weight to 50% by weight of the component (A) based on the total weight of the fluorine-based processing agent composition.

In another embodiment of the present invention, the component (a2) is styrene or a compound including an alkyl group to which a cyclic aliphatic group having at least two or more rings or a cyclic aliphatic group having at least two or more rings is bonded. do it with

In another embodiment of the present invention, the component (a2) is selected from the group consisting of isoboronyl (meth) acrylate, norbornyl (meth) acrylate, dicyclopentadienyl (meth) acrylate and styrene It is characterized in that it is one or more types.

In addition, the present invention provides a method of manufacturing a textile product comprising the step of coating the fiber coating composition containing the fluorine-based processing agent composition on the surface of the fiber target product.

In one embodiment of the present invention, the fluorine-based processing agent composition may be contained in an amount of 0.3 wt% to 20 wt%, based on the total weight of the fiber coating composition.

In addition, the present invention can provide a textile product manufactured by the method for manufacturing the textile product.

The fluorine-based processing agent composition according to the present invention is in the form of an aqueous dispersion containing almost no volatile organic solvent, and at the same time, a perfluoroalkyl ester having an asymmetric structure including a perfluoroalkyl group derived from HFP and a non-fluorine-free fluorine-containing compound having a strain structure. By containing the ester as an active ingredient in the monomer, it has excellent water repellency, oil repellency and antifouling performance while reducing the environmental load.

In addition, when the coating layer is formed on the textile product by the fluorine-based processing agent composition according to the present invention, the contamination source does not adhere well to the surface, so that a clean state can be maintained.

Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. In general, the nomenclature used herein is those well known and commonly used in the art.

Throughout this specification, when a part "includes" a certain component, it means that other components may be further included, rather than excluding other components, unless otherwise stated.

Meanwhile, in the present invention, '(meth)acrylic acid ester' means acrylic acid ester, methacrylic acid ester, or a mixture thereof. That is, the '(meth)acrylic acid ester' should be regarded as meaning a single component of an acrylic acid ester compound, a single component of a methacrylic acid ester compound, or a mixed component of the acrylic acid ester compound and a methacrylic acid ester compound, and also '(meth) 'Acrylic acid amide' should be interpreted in the same sense.

The present invention is a fluorine-based processing agent composition comprising at least components (A), (B) and (C), wherein the component (A) is a perfluorinated alkyl monomer represented by the following formula (1) or two or more of the perfluorinated alkyl monomers A mixture comprising (a1); and a fluorine-free monomer represented by the following formula (2) or a mixture (a2) comprising two or more of the fluorine-free monomers;

[Formula 1]

CF ₃ CF ₂ CF ₂ O(CFCF ₃ CF ₂ O) _n CFCF ₃₍ C=O)OL ₁ -O(C=O)C(R)=CH ₂

(In Formula 1, n is 1 to 5,

L ₁ is a substituted or unsubstituted straight-chain, branched or cyclic alkylene group having 2 to 6 carbon atoms,

R is -H or -CH ₃ )

[Formula 2]

H ₂ C=C(R ₁ )-(Y)mX or H ₂ C=CH(C ₆ H ₅ )

(In Formula 2,

Y is -(C=O)O-, -O-, -(C=O)OL ₂ -, -(C=O)OL ₂ -O- Any one linking group selected from, wherein L ₂ is a substituted or unsubstituted straight-chain, branched or cyclic alkylene group having 1 to 6 carbon atoms,

m is 0 or 1,

X is a substituted or unsubstituted aromatic aryl group having 6 to 18 carbon atoms, a substituted or unsubstituted cyclic aliphatic group having 4 to 30 carbon atoms, and a substituted or unsubstituted cyclic aliphatic group having 4 to 30 carbon atoms, having 1 to 10 carbon atoms Any one of the substituents selected from the alkyl group, R ₁ is -H or -CH ₃ )

The component (B) is a nonionic surfactant having a hydrophilic-lipophile balance (HLB) of 5.0 to 19.0 or a mixture of the nonionic surfactant and a cationic surfactant, and the component (C) is water It provides a fluorine-based processing agent composition characterized in that.

More specifically, the fluorine-based processing agent composition of the first feature according to the present invention is a perfluorinated alkyl monomer of Formula 1 or a mixture containing two or more of the perfluorinated alkyl monomers [component (a1)], and Formula 2 Component (A) each containing as a monomer unit a fluorine-free monomer of or a mixture containing two or more of the fluorine-free monomers [component (a2)], the hydrophilic-lipophile balance (HLB) is A composition comprising 5.0 to 19.0 of a nonionic surfactant alone or a mixture of the nonionic surfactant and a cationic surfactant [component (B)] and water [component (C)], wherein each in the component (A) The fluorine-based polymer obtained by copolymerizing the monomers and the fluorine-based processing agent composition comprising the components (B) and (C) can have excellent water repellency, oil repellency and antifouling performance while reducing environmental load.

Here, when each monomer component in the component (A) is copolymerized with a fluorine-based polymer, it is coated on a textile product to provide water repellency, oil repellency and antifouling properties, etc., and component (A) is perfluorinated from HFP. Having an alkyl group, the perfluorinated alkyl monomer represented by Formula 1 or a mixture (a1) containing two or more of the perfluorinated alkyl monomers; A fluorine-free monomer represented by Formula 2 or a mixture (a2) comprising two or more of the fluorine-free monomers; each as a monomer component.

[Formula 1]

CF ₃ CF ₂ CF ₂ O(CFCF ₃ CF ₂ O) _n CFCF ₃₍ C=O)OL ₁ -O(C=O)C(R)=CH ₂

(In Formula 1, n is 1 to 5,

L ₁ is a substituted or unsubstituted straight-chain or branched or cyclic alkylene group having 2 to 6 carbon atoms,

R is -H or -CH ₃ )

[Formula 2]

H ₂ C=C(R ₁ )-(Y)mX or H ₂ C=CH(C ₆ H ₅ )

(In Formula 2,

Y is -(C=O)O-, -O-, -(C=O)OL ₂ -, -(C=O)OL ₂ -O- Any one linking group selected from, wherein L ₂ is a substituted or unsubstituted straight-chain, branched or cyclic alkylene group having 1 to 6 carbon atoms,

m is 0 or 1,

X is a substituted or unsubstituted aromatic aryl group having 6 to 18 carbon atoms, a substituted or unsubstituted cyclic aliphatic group having 4 to 30 carbon atoms, and a substituted or unsubstituted cyclic aliphatic group having 4 to 30 carbon atoms, having 1 to 10 carbon atoms Any one of the substituents selected from the alkyl group, R ₁ is -H or -CH ₃ )

Here, 'substitution' in 'substituted or unsubstituted' means deuterium, a cyano group, a halogen group, a nitro group, a linear, branched or cyclic alkyl group having 1 to 10 carbon atoms, a halogenated straight group having 1 to 10 carbon atoms. A chain, branched or cyclic alkyl group, an aryl group having 6 to 18 carbon atoms, an arylalkyl group having 7 to 18 carbon atoms, an alkylaryl group having 7 to 18 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, an alkylsilyl group having 1 to 24 carbon atoms , means substituted with one or more substituents selected from the group consisting of an arylsilyl group having 6 to 24 carbon atoms, an aryloxy group having 6 to 24 carbon atoms, and more preferably, it is deuterium, a cyano group, a halogen group, a carbon number 1 to 6 straight chain, branched or cyclic alkyl group, halogenated straight chain, branched or cyclic alkyl group having 1 to 6 carbon atoms, aryl group having 6 to 12 carbon atoms, arylalkyl group having 7 to 12 carbon atoms, 7 to 12 carbon atoms Substituted with one or more substituents selected from the group consisting of an alkylaryl group, an alkoxy group having 1 to 6 carbon atoms, an alkylsilyl group having 1 to 12 carbon atoms, an arylsilyl group having 6 to 18 carbon atoms, and an aryloxy group having 6 to 12 carbon atoms. it may be

Meanwhile, in the present invention, when considering the range of the alkylene group in the “substituted or unsubstituted alkylene group having 1 to 6 carbon atoms”, etc., the range of carbon number of the alkylene group having 1 to 6 carbon atoms is that the substituent is It refers to the total number of carbon atoms constituting the alkylene moiety when viewed as unsubstituted without considering the substituted moiety. _{For example, a butylene (-C 4} H ₈ -) group substituted with a methyl group at the 2-position should be regarded as corresponding to an alkylene group having 4 carbon atoms substituted with a methyl group having 1 carbon atom.

In addition, the aromatic aryl group, which is a substituent used in the compound of the present invention, is an organic radical derived from an aromatic hydrocarbon (arene) by removal of one hydrogen. When the aryl group has a substituent, it is fused with neighboring substituents. A ring may be further formed.

Specific examples of the aryl group include a phenyl group, o-biphenyl group, m-biphenyl group, p-biphenyl group, o-terphenyl group, m-terphenyl group, p-terphenyl group, naphthyl group, anthryl group, phenanthryl group, and aromatic groups such as pyrenyl, indenyl, fluorenyl, tetrahydronaphthyl, peryleneyl, chrysenyl, naphthacenyl, fluoranthenyl, and the like, wherein at least one hydrogen atom of the aryl group is deuterium, cyano group, A halogen group, a nitro group, a linear, branched or cyclic alkyl group having 1 to 10 carbon atoms, a halogenated straight chain, branched or cyclic alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 18 carbon atoms, 7 to 18 carbon atoms of an arylalkyl group, an alkylaryl group having 7 to 18 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, an alkylsilyl group having 1 to 24 carbon atoms, an arylsilyl group having 6 to 24 carbon atoms, an aryloxy group having 6 to 24 carbon atoms can

Unless otherwise defined, the alkyl group as a substituent used in the present invention is a linear, branched or cyclic saturated aliphatic hydrocarbon group, and is a saturated hydrocarbon alkane or cycloalkane. One hydrogen in a molecule An organic radical derived by removal, wherein the cyclic type includes not only a cyclic alkyl group but also a straight-chain or branched alkyl group to which a cyclic alkyl group is connected.

For example, a straight-chain, branched alkyl group having 1 to 5 carbon atoms has 1 to 5 carbon atoms in the alkyl chain, i.e., the alkyl chain is methyl, ethyl, propyl, isopropyl, isobutyl, n-butyl, sec-butyl , tert-butyl, pentyl, n-isopentyl, sec-pentyl, iso-amyl, hexyl and t-butylmethyl, etc. may be selected from the group consisting of, and at least one hydrogen atom of the alkyl group is an atom of the aryl group It can be substituted with the same substituent as in the case of

Specific examples of the cyclic alkyl group as a substituent used in the compound of the present invention include cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, methylcyclopentyl, methylcyclohexyl, ethylcyclopentyl, ethylcyclohexyl, adamantyl, deca hydronaphthyl, norbornyl, bornyl, isobornyl, and the like, and at least one hydrogen atom in the cyclic alkyl group may be substituted with the same substituent as in the case of the aryl group.

In addition, the alkylene group used in the present invention is an organic radical induced by the removal of two hydrogens in alkane or cycloalkane molecules that are linear or branched or cyclic saturated hydrocarbons, In addition, it may be an organic radical formed when one hydrogen is further removed from the alkyl group.

Specific examples of the alkylene group include a methylene group, an ethylene group, a propylene group, an isopropylene group, an isobutylene group, a sec-butylene group, a tert-butylene group, a pentylene group, an iso-amylene group, a hexylene group, and the like. and one or more hydrogen atoms in the alkylene group may be substituted with the same substituents as in the case of the aryl group.

In addition, the cyclic aliphatic group used in the present invention means a cyclic alkyl group as an organic radical derived by the removal of one hydrogen in an aliphatic hydrocarbon molecule containing at least one saturated or unsaturated ring, preferably a saturated or unsaturated It may mean a cyclic alkyl group as an organic radical derived by the removal of one hydrogen in an aliphatic hydrocarbon molecule containing 1 to 6 rings, more preferably saturated or by containing 1 to 3 double bonds. It means an unsaturated, cyclic alkyl group as an organic radical derived by the removal of one hydrogen in an aliphatic hydrocarbon molecule containing 2 to 4 condensed rings.

Specific examples of the arylalkyl group as a substituent used in the compound of the present invention include phenylmethyl (benzyl), phenylethyl, phenylpropyl, naphthylmethyl naphthylethyl, and the like, and at least one hydrogen atom of the arylalkyl group is the aryl It can be substituted with the same substituent as in the case of the group.

Here, the component (a1), which is a technical characteristic part of the present invention, is a perfluorinated alkyl monomer derived from hexafluoro propylene (HFP), and the structure of the monomer is asymmetric in the residue region centered on the unsaturated bond between carbons. A long carbon chain is formed, and the carbon chain includes a hexafluoro propylene (HFP) unit repeating structure.

The HFP-derived perfluorinated alkyl monomer having the above structure is compared to the tetrafluoro ethylene (hereinafter, TFE)-based monomer, which is a type of fluorine-based monomer. It contains no environmental impact at all. However, the perfluorinated alkyl monomer derived from HFP has a repeating ester group in the structure, so it has low crystallinity during polymerization and contains a hydrophilic group in the structure. This has been used for the purpose of imparting stain resistance, but the present inventors solved the problems of the prior art by copolymerizing with the fluorine-free monomer component (a2) represented by Formula 2 to be described later.

The component (a1) is a perfluorinated alkyl monomer represented by Formula 1 or a mixture comprising two or more of the above-mentioned perfluorinated alkyl monomers, and preferably, in Formula 1, n is perfluoro having an integer range of 1 to 5. It may be a roalkyl acrylate.

In addition, the component (a1) may be contained in an amount of 15 wt% to 80 wt%, preferably 20 wt% to 60 wt%, more preferably 30 wt% to 50 wt%, based on the total weight of the fluorine-based polymer . When the component (a1) contains less than 15% by weight based on the total weight of the component (A), the antifouling property of the textile product coated with the fluorine-based composition may not be sufficient, and when it exceeds 80% by weight, Since the hydrophobicity of the polymer becomes strong and prevents emulsion polymerization, a problem in which water and oil repellency performance is deteriorated may occur.

Wherein the component (a1) within the L ₁ in Formula 1 is a substituted or unsubstituted straight-chain or branched or cyclic alkylene group of 2 to 6 carbon atoms ring, preferably unsubstituted methylene, unsubstituted ethylene (- It may be any one selected from _{C 2} H ₄ -), unsubstituted propylene (-C ₃ H ₆ -), and unsubstituted butylene (-C ₄ H _{8 -).}

On the other hand, component (a2) is a fluorine-free monomer represented by Formula 2 or a mixture comprising two or more of the fluorine-free monomers, and may be H ₂ C=C(R ₁ )-(Y)mX or styrene. And, when the component (a2) is _{a monomer represented by H 2} C=C(R ₁ )-(Y)mX, Y is -(C=O)O-, -O-, -(C=O )OL ₂ -, -(C=O)OL ₂ -O- Any one linking group selected from, wherein L ₂ is a substituted or unsubstituted straight-chain or branched or cyclic alkylene group having 1 to 6 carbon atoms, m is 0 or 1,

X is a substituted or unsubstituted aromatic aryl group having 6 to 18 carbon atoms, a substituted or unsubstituted cyclic aliphatic group having 4 to 30 carbon atoms, or an alkyl group having 1 to 10 carbon atoms having a substituted or unsubstituted cyclic aliphatic group having 4 to 30 carbon atoms and R ₁ may be —H or —CH ₃ .

That is, when component (a2) is _{a monomer represented by H 2} C=C(R ₁ )-(Y)mX, preferably Y is an ester group (-(C=O)O-), an ether group (- O-), a form in which a substituted or unsubstituted alkylene group having 1 to 6 carbon atoms is bonded to an ester group (-(C=O)OL ₂ -), or a substituted or unsubstituted alkylene group having 1 to 6 carbon atoms is bonded to an ester group and an oxygen atom bonded thereto (-(C=O)OL ₂ -O-).

In addition, X is preferably an alkyl group having 1 to 6 carbon atoms having a substituted or unsubstituted cyclic aliphatic group having 5 to 20 carbon atoms or a substituted or unsubstituted cyclic aliphatic group having 5 to 20 carbon atoms. can be

Here, as a preferred example of the component (a2), it is styrene, or a substituted or unsubstituted cyclic aliphatic group having 5 to 20 carbon atoms having at least two or more rings or a substituted or unsubstituted group having at least two or more rings It may be an alkyl group having 1 to 6 carbon atoms to which a cyclic aliphatic group having 5 to 20 carbon atoms is bonded, wherein the two or more rings may be those having a ring strain.

More preferably, a substituted or unsubstituted C5-C20 cyclic aliphatic group containing a condensed ring of 2 to 4, which is styrene, or saturated or unsaturated by including 1 to 3 double bonds, or saturated or It may be an alkyl group having 1 to 6 carbon atoms to which a substituted or unsubstituted cyclic aliphatic group having 5 to 20 carbon atoms including a condensed ring of 2 to 4, which is unsaturated by including 1 to 3 double bonds, is bonded.

Here, as the compound containing a cyclic aliphatic group having two or more rings, isoboronyl (meth) acrylate, norbornyl (meth) acrylate, dicyclopentadienyl (meth) acrylate, etc. selected from the group consisting of One or more may be used, and preferably, one or more selected from the group consisting of isoboronyl (meth)acrylate and norbornyl (meth)acrylate may be used.

Therefore, when the fluorine-free monomer, which is the polycyclic compound having the styrene or the ring strain, is included in the fluorine-based processing agent composition as a monomer component of the fluorine-based copolymer, the crystallinity of the copolymer is increased so that the processing agent composition is treated The surface orientation of the treated material is improved, and the water repellency, oil repellency and antifouling performance are increased.

In addition, the content of component (a2) may be contained in an amount of 20 wt% to 85 wt%, preferably 20 wt% to 50 wt%, more preferably 20 wt% to 40 wt%, based on the total weight of the fluorine-based polymer. have. When the component (a2) contains less than 20% by weight based on the total weight of the fluorine-based polymer, the water-repellent, oil-repellent and antifouling performance of the textile product coated with the fluorine-based processing agent composition may not be sufficient, and 85% by weight When it exceeds, the adhesion to the fibers is lowered, and washing durability and oil repellency may be deteriorated.

In addition, in the present invention, the fluorine-based polymer component (A) is a perfluorinated alkyl monomer represented by Formula 1 or a mixture (a1) comprising two or more of the perfluorinated alkyl monomers; and a fluorine-free alkyl monomer represented by Formula 2 or a mixture (a2) comprising two or more of the fluorine-free monomers; In the case of a fluorine-based polymer copolymerized by including each as a monomer unit, it may contain 15 wt% to 80 wt% of component (a1) and 20 wt% to 85 wt% of component (a2) with respect to the total weight of the fluorine-based polymer And according to this configuration, it is possible to improve the water repellency performance well.

On the other hand, in the present invention, the component (A) is a vinyl group-containing monomer represented by the following Chemical Formula 3A or Chemical Formula 3B or a mixture thereof (a3); It may be a fluorine-based polymer copolymerized by additionally including as a monomer unit.

[Formula 3A] [Formula 3B]

H ₂ C=CH(R ₂ ) H ₂ C=C(R ₂ )(R ₃ )

(In Formulas 3A and 3B, R ₂ and R ₃ are each the same or different and independently of each other are -F or -Cl)

That is, the component (a3) is a vinyl group-containing monomer represented by Formula 3 or a mixture thereof, and contains 15 wt% to 40 wt%, preferably 20 wt% to 30 wt%, based on the total weight of the fluorine-based polymer can do. When the component (a3) contains less than 15% by weight based on the total weight of the fluorine-based polymer, the antifouling property of the textile product coated with the fluorine-based processing agent composition may not be sufficient, and when it exceeds 40% by weight, the reaction This is not done properly, and there may be problems in that antifouling properties and stability of the emulsion are deteriorated due to the generation of a large amount of homopolymer, etc.

In the present invention, the fluorine-based polymer component (A) is a perfluorinated alkyl monomer represented by Formula 1 or a mixture (a1) comprising two or more of the perfluorinated alkyl monomers; and a fluorine-free alkyl monomer represented by Formula 2 or a mixture (a2) comprising two or more of the fluorine-free monomers; and a vinyl group-containing monomer represented by Formula 3A or Formula 3B or a mixture thereof (a3) as a monomer unit, respectively; in the case of a copolymerized fluorine-based polymer, it is based on the total weight of the fluorine-based polymer, component (a1) 20 weight % to 60% by weight, component (a2) 20% to 50% by weight, and component (a3) 15% to 40% by weight, according to this configuration can be improved

The fluorine-based polymer of component (A) obtained by copolymerizing the components (a1) to (a3) in the fluorine-based processing agent composition according to the present invention may be included in 5 wt% to 50 wt%, based on the total weight of the fluorine-based processing agent composition, Preferably, it may be included in the range of 20% by weight to 40% by weight. When the fluorine-based polymer is included in an amount of less than 5% by weight based on the total weight of the fluorine-based processing agent, the concentration of the fluorine-based polymer is low and a problem of lowering oil repellency may occur, and when it exceeds 50% by weight, the polymer crystal Due to the lack of performance, the water repellency, oil repellency, and antifouling performance of the product may be deteriorated.

On the other hand, component (B) is to improve the dispersion stability of the fluorine-based processing agent composition, and is a nonionic surfactant having a hydrophile-lipophile balance (HLB) of 5.0 to 19.0, or a cationic surfactant with the nonionic surfactant. Mixtures of surfactants may be used.

As examples of the nonionic surfactant, polyoxyalkylene straight chain alkyl ether, polyoxyalkylene branched alkyl ether, polyoxyalkylene alkenyl ether, polyoxyalkylene alkylphenyl ether, polyoxyalkylene alkylarylphenyl ether, Nonionic surfactants such as polyoxyalkylene fatty acid esters and mixtures thereof may be used, wherein exemplary substituents of polyoxyalkylene groups include polyoxyethylene groups, polyoxypropylene groups, polyoxybutylene groups, and the like. .

The nonionic surfactant is an average hydrophilic-lipophile balance (HLB) of a single component or mixture in terms of emulsion dispersing power and dispersion stability of the composition after polymerization during O/W type emulsion polymerization based on water. ) may be 5.0 to 19.0, preferably 9.0 to 17.0. If the HLB value of the component (B) is less than 5.0, the hydrophobicity is strong and the emulsification of the monomer is lowered, which may cause a problem that polymerization does not proceed properly, and when it exceeds 19.0, the hydrophilicity increases The adsorption degree of the processing agent composition to the material to be treated is lowered, which may cause a problem in that water repellency, oil repellency and antifouling performance are lowered.

The HLB value is a concept proposed in response to the need to find a dispersant suitable for the purpose of use because there are many types of surfactant, and is a value indicating the degree of affinity for water and oil. The higher the lipophilicity, the better the hydrophilicity.

The component (B) may be included in the range of 1 wt% to 20 wt%, based on the total weight of the fluorine-based processing agent composition. If the content of the component (B) is less than 1% by weight based on the total weight of the fluorine-based processing agent composition, the dispersion stability of the fluorine-based processing agent composition is lowered, resulting in deterioration in appearance and performance during polymerization. And, if it exceeds 20% by weight, the antifouling property of the fluorine-based processing agent composition may be reduced due to an excess of surfactant.

On the other hand, the component (B) may be characterized in that the nonionic surfactant contains a cationic surfactant having an amine group and having 12 to 22 carbon atoms. When the cationic surfactant is introduced together with a nonionic surfactant during emulsion polymerization, it induces electrical repulsion between particles dispersed in the mixed solution in an emulsified state, thereby improving product stability and processing stability.

Examples of the cationic surfactant include stearyl dimethyl amine hydrochloride, alkyl trimethyl ammonium chloride, stearyl trimethyl ammonium chloride, lauryl trimethyl ammonium chloride, cetyl trimethyl ammonium chloride, tallow alkyltrimethyl ammonium chloride, behenyl trimethyl ammonium chloride, bromide Stearyl trimethyl ammonium, behenyl trimethyl ammonium bromide, distearyl dimethyl ammonium chloride, dicocoyl dimethyl ammonium chloride, dioctyl dimethyl ammonium chloride, di(POE) oleyl methyl ammonium (2EO) chloride, benzalkonium chloride, alkyl chloride Benzalkonium, alkyl dimethyl benzalkonium chloride, benzethonium chloride, stearyl dimethyl benzylammonium chloride, lanolin-derived quaternary ammonium salt, diethylaminoethyl stearate, dimethyl aminopropyl stearate, amidopropyl behenate chloride At least one selected from dimethylhydroxypropyl ammonium, stearoyl coraminoformyl methylpyridinium chloride, cetylpyridinium chloride, tall oil chloride alkyl benzyl hydroxyethyl imidazolinium, and benzyl ammonium salt may be used.

In addition, when included, the cationic surfactant may be included in an amount of 0.15 wt% to 1.8 wt%, preferably 0.15 wt% to 1.5 wt%, based on the total weight of the fluorine-based processing agent composition. If the content of the cationic surfactant is less than 0.15 wt% with respect to the total weight of the fluorine-based processing agent composition, the addition amount is insignificant, so the stability and processing stability of the fluorine-based processing agent composition product may not be increased, and 1.8 wt% %, the water repellency, oil repellency, antifouling performance or durable water repellency of the fluorine-based processing agent composition may be deteriorated due to an excess of surfactant.

Component (C) is a polymerization medium, water commonly used in the art, and may be included in an amount of 49 wt% to 94 wt%, based on the total weight of the fluorine-based processing agent composition.

When the content of the component (C) is less than 49% by weight based on the total weight of the fluorine-based processing agent composition, it is difficult or impossible to emulsify the monomer because the ratio of the polymerization medium is low, and when it exceeds 94% by weight, the monomer Due to the low concentration of , not only the reaction rate is slow, but also it has a molecular weight distribution different from that of the intended composition, which may cause a problem in that performance cannot be expressed.

In addition, the fluorine-based processing agent composition according to the present invention may further include at least one selected from an organic solvent, an initiator, a chain transfer agent, an emulsification aid, and an additive, if necessary, and the additive includes the properties of the fluorine-based processing agent composition Well-known additives may be included in the dimension of not changing the , and the additives may be antibacterial agents, deodorants, flame retardants, antistatic agents, softeners, and the like.

The organic solvent is not particularly limited as long as it is an organic solvent compatible with water. For example, alcohols such as methanol and ethanol, esters such as ethyl acetate, glycols such as propylene glycol, dipropylene glycol, tripropylene glycol, etc. may be used, and the ratio of water and organic solvent is not particularly limited.

The initiator may be selected from known polymerization initiators such as azo-based, peroxide-based, and redox-based initiators, and the content of the initiator may be determined in consideration of the molecular weight of the polymer to be polymerized. It may be in the range of 0.1 parts by weight to 10 parts by weight based on 100 parts by weight of the fluorine-based polymer.

The chain transfer agent may use dodecyl mercaptan, t-butyl alcohol, etc. for the purpose of molecular weight adjustment in the polymerization reaction, and the content thereof is preferably 5 parts by weight or less based on 100 parts by weight of the fluorine-based polymer. When the content of the chain transfer agent exceeds 5 parts by weight, a decrease in molecular weight may be severe, making it difficult to efficiently prepare a fluorine-based polymer implementing excellent water repellency, oil repellency, and antifouling performance.

A polymerization inhibitor can be used in order to add molecular weight adjustment. A fluorine-based polymer having a desired level of molecular weight can be easily obtained by adding a polymerization inhibitor.

As the emulsification aid, a known emulsifying aid such as glycolic acid may be used for the purpose of further improving dispersion stability, and the content thereof is preferably 10 parts by weight or less based on 100 parts by weight of the fluorine-based polymer.

The method for producing the fluorine-based processing agent composition according to the present invention as described above is a monomer component of component (a1) and component (a2) (or, when the monomer is a component of component (a1) to component (a3), component (a1) to component (a3) a mixture of the monomer component), the nonionic surfactant of component (B), or a mixture of a nonionic surfactant and a cationic surfactant, and a mixed solution containing the water of component (C), an initiator, an additive, etc. Next, the fluorine-based processing agent composition according to the present invention is prepared by emulsifying or dispersing with a known dispersing means, for example, a homomixer, a high-pressure emulsifier, or a dispersion means such as ultrasonic waves and polymerization.

The polymerization temperature is 50 °C to 80 °C. When the polymerization temperature is less than 50 °C, polymerization is insufficient, and when it exceeds 80 °C, the reaction does not proceed as intended due to the destruction of radicals depending on high temperature conditions.

The fluorine-based processing agent composition according to the present invention is in the form of an aqueous dispersion containing almost no volatile organic solvent and at the same time contains a fluorinated copolymer having a perfluoroalkyl group derived from HFP as an active ingredient, thereby reducing the environmental load and , when coated on textile products, the film-forming ability is excellent, so that water repellency, oil repellency and antifouling performance can be easily imparted.

In addition, the present invention may provide a method for manufacturing a textile product comprising the step of coating the fiber coating composition containing the fluorine-based processing agent composition on the surface of the textile target product, and also a textile product manufactured by the manufacturing method can provide

The fiber coating composition is obtained by diluting the fluorine-based processing agent composition in water, and the fluorine-based processing agent composition may be contained in an amount of 0.3 wt% to 20 wt%, based on the total weight of the fiber coating composition. If the fluorine-based processing agent composition is contained in an amount of less than 0.3% by weight based on the total weight of the fiber coating composition, a problem in that antifouling properties are not expressed due to insufficient content of the polymerized polymer may occur, and when it exceeds 20% by weight If the polymer content is excessive, the inherent physical properties of the fabric may be lost and the touch may become hard.

The fiber coating composition according to the present invention may be used by further mixing one or more selected from a softening agent, a penetrating agent, and an antistatic agent in the fluorine-based processing agent composition.

As the softening agent, any known softening agent can be used without limitation for the purpose of softening the feel of textile products and not causing deterioration of antifouling properties, preferably dimethyl silicone, hydrogen silicone, amino-modified silicone, fatty acid amide, epoxy-modified silicone, etc. can be used The content of the softening agent may be used in an amount of 0.5 parts by weight to 20 parts by weight based on 100 parts by weight of the fluorine-based processing agent composition.

In addition, the penetrant can be used without limitation as long as it is a known penetrant for the purpose of allowing the fluorine-based processing agent composition to penetrate to the inside of the thick material that is difficult to penetrate into the inside of the high-density textile product, preferably water repellent, oil repellent and antifouling In terms of not reducing the performance, glycols such as butyl diglycol and monoethylene glycol, isopropyl alcohol, butyl cellosolve, alcohol solvents such as higher alcohols and lower alcohols can be used, and the penetrant content may be used in an amount of 0.1 to 10 parts by weight based on 100 parts by weight of the fluorine-based processing agent composition.

In addition, the antistatic agent may be used without limitation as long as it is a known antistatic agent, and preferably stearil archirtrimethylaminomethsarphite, lauryl alkyltriethyl aminoethosulphite, octyl alkyl trimethyl aminochloride, stearyl trimethyl Cationic polymers such as ammonium chloride, stearyl dimethylammonium chloride, lauryl trimethyl ammonium chloride, phosphate ester compounds, guanidine hydrochloride compounds, etc. may be used, and the content of the antistatic agent is based on 100 parts by weight of the fluorine-based processing agent composition. , 0.1 parts by weight to 5 parts by weight can be used.

The amount of the above-described fiber coating composition to be coated on the surface of the fiber target product can be easily adjusted according to the required degree of water repellency, oil repellency and antifouling performance. Typically, based on 100 parts by weight of the textile product, the fiber coating composition is adjusted in the range of 0.5 to 6 parts by weight. If the coating amount is less than 0.5 parts by weight, the water repellency of the textile product is not sufficient, and if it exceeds 6 parts by weight, the properties of the textile fabric may be lost.

As a method of coating the mixture on the textile product, it can be coated according to a known method such as dipping, spraying, spraying, or applying, and after coating, drying and curing (curing) to obtain a textile product treated with a fluorine-based processing agent composition can

At this time, the subject textile products are natural fibers of animal and plant origin such as cotton, hemp, wool, silk, etc., synthetic fibers such as polyamide, polyester, polyvinyl alcohol, polyacrylonitrile, polyvinyl chloride, polypropylene, and rayon. , semi-synthetic fibers such as acetate, inorganic fibers such as glass fibers, and mixed fibers thereof.

On the other hand, after the fluorine-based processing agent composition is coated, it can be cured using heat treatment, etc., and there is no particular limitation on the temperature conditions of the heat treatment, but it can be usually carried out at 120 ° C. to 200 ° C. for 60 seconds to 300 seconds.

The textile product according to the present invention thus obtained has a film made of the fluorine-based processing agent composition of the present invention attached to the surface of the product, and preferably the surface is covered with the film.

The textile product according to the present invention can exhibit sufficient water-repellent, oil-repellent and anti-fouling performance even when used outdoors for a long period of time. By containing the fluorinated copolymer having an alkyl group as an active ingredient, the environmental load can be reduced, and high-functional textile products can be manufactured with good economical efficiency according to low unit cost.

Hereinafter, the present invention will be described in more detail through examples. These examples are only for illustrating the present invention and should not be construed as limiting the scope of the present invention by these examples.

<Production Example 1>

Component (a1) to component (a3), component (B), emulsifying aid, organic solvent, chain transfer agent, and component (C) described in Preparation Example 1 in Table 1 below were stirred and mixed in an autoclave, followed by mixing at 45 ° C. It was emulsified and dispersed by ultrasonication for 5 min. After replacing the inside of the autoclave with nitrogen, the reactor was closed, and then, azobis(amidinepropane)dihydrochloride as an initiator was added thereto, and then reacted at 60° C. for 4 hours to obtain a fluorine-based processing agent composition. The content of each component is as described in Table 1. At this time, most of the components in Table 1 are commonly available, among them, the perfluorinated alkyl monomer component (a1) represented by Formula 1 is their product, and isoboronyl methacrylate is from Moriroku, benzyl methacryl Late and stearyl acrylate were purchased from Miwon Trading Co., styrene from Wonik Cube, and vinyl chloride and vinylidene chloride from Korea Standard Gas. In addition, polyoxyethyl alkyl ether was purchased from Han Nong-Hwaseong, stearyl dimethyl amine hydrochloride was purchased from Miwon Corporation, tripropylene glycol was from Dow, and dodecyl mercaptan was Sevron Phillips Chemical International. Dupont's product and azobis(amidinepropane)dihydro hydrochloride were used.

<Preparation Examples 2 to 6>

A fluorine-based processing agent composition was prepared in the same manner as in Preparation Example 1, but with the components and contents described in Preparation Examples 2 to 6 in Table 1 below.

division Ingredient name Preparation Example 1
(weight%) Preparation 2
(weight%) Preparation 3
(weight%) Preparation 4
(weight%) Preparation 5
(weight%) Preparation 6
(weight%) ingredient
(a1) Perfluorinated alkyl monomers represented by the formula (1)
n = 3, R = CH3 12 12 12 8 15 12 ingredient
(a2) Isoboronyl methacrylate 9 - - 13 6 11 benzyl methacrylate - 9 - - - - styrene - - 9 - - - stearyl acrylate - - - - - - ingredient
(a3) vinyl chloride 8 8 8 8 8 6 vinylidene chloride - - - - - - non-ion
interface
activator
(B) polyoxyethylene
Alkyl ether (HLB: 11.5) One One One One One One polyoxyethylene
Alkyl ether (HLB: 13.0) One One One One One One polyoxyethylene
Alkyl ether (HLB: 14.5) 0.9 0.9 0.9 0.9 0.9 0.9 cation
interface
activator
(B) Stearyl dimethyl amine hydrochloride (active ingredient 15%) One One One One One One oil paint
supplements glycolic acid 0.1 0.1 0.1 0.1 0.1 0.1 abandonment
solvent tripropylene glycol 9 9 9 9 9 9 chain
transfer agent dodecyl mercaptan 0.1 0.1 0.1 0.1 0.1 0.1 ingredient
(C) water 57.6 57.6 57.6 57.6 57.6 57.6 initiator Azobis(amidinepropane)dihydrohydrochloride 0.3 0.3 0.3 0.3 0.3 0.3

<Preparation Examples 7 to 11>

A fluorine-based processing agent composition was prepared in the same manner as in Preparation Example 1, but with the components and contents described in Preparation Examples 7 to 11 in Table 2 below.

Ingredient name Preparation 7
(weight%) Preparation 8
(weight%) Preparation 9
(weight%) Preparation 10
(weight%) Preparation 11
(weight%) Component (a1) Perfluorinated alkyl monomers represented by the formula (1)
n = 3, R = CH3 12 12 5 13.5 15 Component (a2) Isoboronyl methacrylate 8.5 9 16 10 14 benzyl methacrylate - - - - - styrene - - - - - stearyl acrylate - - - - - Component (a3) vinyl chloride 8.5 - 8 5.5 - vinylidene chloride - 8 - - - nonionic interface
Activator (B) Polyoxyethylene alkyl ether (HLB:11.5) One One One One One Polyoxyethylene alkyl ether (HLB:13.0) One One One One One Polyoxyethylene alkyl ether (HLB: 14.5) 0.9 0.9 0.9 0.9 0.9 cationic interface
Activator (B) Stearyl Dimethyl Amine Hydrochloride
(active ingredient 15%) One One One One One emulsifying aid glycolic acid 0.1 0.1 0.1 0.1 0.1 organic solvent tripropylene glycol 9 9 9 9 9 chain transfer agent dodecyl mercaptan 0.1 0.1 0.1 0.1 0.1 Component (C) water 57.6 57.6 57.6 57.6 57.6 initiator Azobis(amidinepropane)dihydrohydrochloride 0.3 0.3 0.3 0.3 0.3

<Comparative Preparation Examples 1 to 2>

A fluorine-based processing agent composition was prepared in the same manner as in Preparation Example 1, but with the components and contents described in Comparative Preparation Examples 1 and 2 in Table 3 below.

division Ingredient name comparison
Preparation Example 1
(weight%) comparison
Preparation 2
(weight%) Component (a1) Perfluorinated alkyl monomers represented by the formula (1)
n = 3, R = CH3 12 18 Component (a2) Isoboronyl methacrylate - 3 benzyl methacrylate - - styrene - - stearyl acrylate 9 - Component (a3) vinyl chloride 8 8 vinylidene chloride - - non-ion
Surfactant (B) polyoxyethylene alkyl ether
(HLB:11.5) One One polyoxyethylene alkyl ether
(HLB:13.0) One One polyoxyethylene alkyl ether
(HLB:14.5) 0.9 0.9 cation
Surfactant (B) Stearyl dimethyl amine hydrochloride (active ingredient 15%) One One emulsifying aid glycolic acid 0.1 0.1 organic solvent tripropylene glycol 9 9 chain transfer agent dodecyl mercaptan 0.1 0.1 Component (C) water 57.6 57.6 initiator Azobis(amidinepropane)dihydrohydrochloride 0.3 0.3

<Examples 1 to 11 and Comparative Examples 1 to 2>

The fluorine-based processing agent composition obtained in Preparation Examples and Comparative Preparation Examples was diluted in water as shown in Table 4 below, and PET 100% Tricot Car seat (hereinafter referred to as PET fabric) having a brightness of 50 and for clothing in order to check the performance as a car seat use In order to check the performance for use, a total of three types of fabrics were immersed in 100% PET Dewspo and Nylon Rib (hereinafter NYLON fabric). At this time, by adjusting the pressure of the mangle, the pick up was adjusted to about 60% for car seat applications, and then dried and cured at 150 ° C for 300 seconds in a mini tenter. Then, drying and curing were performed at 180° C. for 60 seconds in a mini tenter.

division Type and content of processing agent composition (g) water (g) Example 1 Preparation Example 1: 4g 96 Example 2 Preparation Example 2: 4g 96 Example 3 Preparation Example 3: 4g 96 Example 4 Preparation Example 4: 4g 96 Example 5 Preparation Example 5: 4g 96 Example 6 Preparation Example 6: 4g 96 Example 7 Preparation Example 7: 4g 96 Example 8 Preparation 8: 4g 96 Example 9 Preparation Example 9: 4g 96 Example 10 Preparation 10: 4g 96 Example 11 Preparation Example 11: 4g 96 Comparative Example 1 Comparative Preparation Example 1: 4g 96 Comparative Example 2 Comparative Preparation Example 2: 4g 96

[Experimental Example 1: Measurement of antifouling (oil repellency)]

Place the fabric for car seat use coated with the fluorine-based processing agent composition of Examples 1 to 11 and Comparative Examples 1 to 2, and measure the diameter of n-tetradecane (AATCC 18 oil repellency test grade 4 determination reagent) with a surface tension of 26 dyne/cm After dripping 3 drops of 5 mm in size, after 30 seconds, the state of the 3 drops was visually observed and determined according to the criteria in Table 5, and the results are shown in Table 6.

Antifouling (oil repellency) measurement criterion

[Experimental Example 2: Room IPA (water repellency) measurement]

After laying flat the fabric coated with the fluorine-based processing agent composition of Examples 1 to 11 and Comparative Examples 1 to 2, 3 drops of a water:IPA (60:40) mixture having a surface tension of 26.6 dyne/cm to a diameter of 5 mm After dropping the droplet, the state of the 3 drops after 30 seconds was determined according to the same criteria as in Table 5, and the results are shown in Table 6.

[Experimental Example 3: Measurement of SPRAY water repellency]

For the fabrics for clothing coated with the fluorine-based processing agent compositions of Examples 1 to 11 and Comparative Examples 1 to 2, the results of measurement of SPRAY water repellency through a test method conforming to the AATCC-25 standard are described in Table 6, and when the SPRAY water repellency is good 5, and 1 in the case of defective.

[Experimental Example 4: Measurement of oil repellency]

The results of measuring oil repellency through a test method conforming to the AATCC-118 standard for the fabrics for clothing coated with the fluorine-based processing agent compositions of Examples 1 to 11 and Comparative Examples 1 to 2 are shown in Table 6, and when the oil repellency is good 3, and 0 when defective.

division antifouling
(oil repellency)
(grade/number of times) Room IPA Castle
(Water repellency)
(grade/number of times) SPRAY water repellency oil repellency PET PET PET NYLON PET NYLON Example 1 A/3 A/3 5 5 3 3 Example 2 B/3 A/1, B/2 3.5 3.0 2.0 2.0 Example 3 A/1, B/2 A/1, B/2 3.5 3.5 1.5 1.5 Example 4 A/1, B/2 A/3 5 5 2.5 2 Example 5 A/2, B/1 A/1, B/2 4 4.5 2.5 2.5 Example 6 A/2, B/1 A/2, B/1 4.5 4.5 2.5 3 Example 7 A/2, B/1 A/2, B/1 4.5 5 3 2.5 Example 8 A/2, B/1 A/2, B/1 4.5 5 2.5 2.5 Example 9 C/3 A/1, B/2 4 4.5 0.5 One Example 10 C/2, D/1 B/2, C/1 3 2.5 One 0.5 Example 11 A/1, B/2 A/1, B/2 3 3 2 2 Comparative Example 1 D/3 C/1, D/2 1.5 One 0 0 Comparative Example 2 C/1, D/2 C/1, D/2 One 1.5 0.5 0.5

As shown in Table 6, it can be confirmed that the antifouling properties, IPA resistance (water repellency), SPRAY water repellency and oil repellency of Examples 1 to 11 are superior to those of Comparative Examples.

All simple modifications or changes of the present invention can be easily carried out by those skilled in the art, and all such modifications or changes can be considered to be included in the scope of the present invention.

Claims (11)

A fluorine-based processing agent composition comprising at least components (A), (B) and (C),
The component (A) may be a perfluorinated alkyl monomer represented by the following formula (1) or a mixture (a1) comprising two or more of the perfluorinated alkyl monomers; and,
A fluorine-free monomer represented by the following Chemical Formula 2 or a mixture (a2) comprising two or more of the fluorine-free monomers; A fluorine-based polymer copolymerized by including each as a monomer unit,
[Formula 1]
CF ₃ CF ₂ CF ₂ O(CFCF ₃ CF ₂ O) _n CFCF ₃₍ C=O)OL ₁ -O(C=O)C(R)=CH ₂
(In Formula 1, n is 1 to 5,
L ₁ is a substituted or unsubstituted straight-chain or branched or cyclic alkylene group having 2 to 6 carbon atoms,
R is -H or -CH ₃ )
[Formula 2]
H ₂ C=C(R ₁ )-(Y)mX or H ₂ C=CH(C ₆ H ₅ )
(In Formula 2,
Y is -(C=O)O-, -O-, -(C=O)OL ₂ -, -(C=O)OL ₂ -O- Any one linking group selected from, wherein L ₂ is a substituted or unsubstituted straight-chain, branched or cyclic alkylene group having 1 to 6 carbon atoms,
m is 0 or 1,
X is a substituted or unsubstituted aromatic aryl group having 6 to 18 carbon atoms, a substituted or unsubstituted cyclic aliphatic group having 4 to 30 carbon atoms, and a substituted or unsubstituted cyclic aliphatic group having 4 to 30 carbon atoms, having 1 to 10 carbon atoms Any one of the substituents selected from the alkyl group, R ₁ is -H or -CH ₃ )
The component (B) is a nonionic surfactant having a hydrophilic-lipophile balance (HLB) of 5.0 to 19.0 or a mixture of the nonionic surfactant and a cationic surfactant,
The component (C) is a fluorine-based processing agent composition, characterized in that water.
According to claim 1,
The component (A) may be a vinyl group-containing monomer represented by the following Chemical Formula 3A or Chemical Formula 3B or a mixture thereof (a3); A fluorine-based processing agent composition, characterized in that it is a copolymerized fluorine-based polymer by additionally including as a monomer unit.
[Formula 3A] [Formula 3B]
H ₂ C=CH(R ₂ ) H ₂ C=C(R ₂ )(R ₃ )
(In Formulas 3A and 3B, R ₂ and R ₃ are each the same or different and independently of each other are -F or -Cl)
According to claim 1,
The component (A) is a fluorine-based processing agent composition, characterized in that it comprises 15% by weight to 80% by weight of component (a1) and 20% to 85% by weight of component (a2) based on the total weight of the fluorine-based polymer.
3. The method of claim 2,
The component (A) comprises 20% to 60% by weight of component (a1), 20% to 50% by weight of component (a2), and 15% to 40% by weight of component (a3), based on the total weight of the fluorine-based polymer Fluorine-based processing agent composition, characterized in that.
According to claim 1,
The component (B) is a fluorine-based processing agent composition, characterized in that in the range of 1% to 20% by weight based on the total weight of the fluorine-based processing agent composition.
According to claim 1,
The composition of the fluorine-based processing is with respect to the total composition weight of a fluorine-based processing, the components (A) 5% to 50 fluorine-based processing agent composition characterized in that it comprises, by weight%.
According to claim 1,
The component (a2) is styrene or a fluorine-based processing agent composition, characterized in that it is a compound comprising an alkyl group to which a cyclic aliphatic group having at least two or more rings or a cyclic aliphatic group having at least two or more rings is bonded.
According to claim 1,
The component (a2) is fluorine-based processing, characterized in that at least one selected from the group consisting of isoboronyl (meth) acrylate, norbornyl (meth) acrylate dicyclopentadienyl (meth) acrylate and styrene my composition.
A method of manufacturing a textile product comprising the step of coating the fiber coating composition containing the fluorine-based processing agent composition of any one of claims 1 to 8 on the surface of the textile target product.
10. The method of claim 9,
The fluorine-based processing agent composition is a method of manufacturing a textile product, characterized in that it contains 0.3 wt% to 20 wt%, based on the total weight of the fiber coating composition.
A textile product manufactured by the manufacturing method of claim 10.