WO2019124585A1 - Antisoil finishing agent composition and textile product using same - Google Patents

Abstract

The present invention relates to an antisoil finishing agent composition and a textile product using the same and, more particularly, to an antisoil finishing agent composition and a textile product using the same, wherein the antisoil finishing agent composition contains, as active ingredients in a monomer,: a perfluoroalkyl ester having a perfluoroalkyl group of less than 8 carbon atoms in the form of an aqueous dispersion containing almost no volatile organic solvent and having a specific structure; and a non-fluorine ester, thereby reducing an environmental load, and easily imparting not only an antisoil property but also wear-resistant antisoil performance.

Description

Antifouling processing compositions and textile products using the same

The present invention relates to an antifoulant processing composition and a fiber product using the same. More particularly, the present invention relates to an antifoulant composition capable of easily imparting anti-abrasion resistance and antifouling property, and a fiber product using the same.

The main causes for contamination of fabrics such as clothing, carpets, and car seats are lipid (lipid) generated from human body, oil caused by food, and dust in air. One of the causes of contamination is the phenomenon that the fibers are reattached to the fibers when they are once detached (laundered) during washing.

Fibrous anti-fouling treatment can be divided into a process that makes it difficult to adhere to contamination and a process that makes it easier to remove adhered contamination. Generally, the process that makes it difficult to attach contamination is to use a fluorine-based polymer to cover the surface of the fiber with a thin film, to make the unevenness of the surface of the fiber somewhat flat and to reduce the surface free energy extremely, .

In order to make the attached stain easily fall off, hydrophilic polymer is used to hydrophilize the fiber surface to easily fuse with the detergent solution during washing, thereby easily removing contaminants and preventing stain contamination due to oily stain during rinsing. Particularly, it is very important that a car seat used in an automobile is difficult to be washed after installation and that the contamination is difficult to adhere to the car seat, and that the attached contaminants easily fall off. Therefore, automobile companies of a certain size are evaluating the antifouling performance of the car seat in terms of contamination accessibility and decontamination performance by separately stipulating the anti-fouling standard suitable for each company for the car seat.

In this regard, the conventional antifouling fabric for vehicles has a water-repellent and oil-repellent property to prevent contamination, and a fluorine-based process having a soil releasing (SR) property to easily wipe away contamination once attached or to easily fall off by washing or the like I am used a lot.

For example, Japanese Patent No. 3320491 discloses a (meth) acrylate containing a polyfluoroalkyl group, a (meth) acrylate containing a polyoxyalkylene chain, and a (meth) acrylate containing a blocked isocyanate group (Meth) acrylate containing a polyfluoroalkyl group, a (meth) acrylate containing a polyoxyalkylene chain (meth) acrylate containing a polyoxyalkylene chain, And a copolymer of (meth) acrylate containing an acetacetyl group as an effective component. However, these fluorine-based antifouling processing agents contain a relatively large amount of an organic solvent in order to obtain a good dispersibility of the fluorine-containing copolymer, and thus the load on the environment during actual processing is large.

Japanese Patent No. 2777040 discloses a (meth) acrylate containing a polyfluoroalkyl group having 4 to 12 carbon atoms, a (meth) acrylate containing a polyoxyalkylene chain, and an amino group in which a hydrogen atom is substituted with an alkyl group (Meth) acrylate copolymerized with a monomer containing (meth) acrylate. It is described that the copolymer has water-dispersibility and an oil-repellent and waterproof finish comprising an aqueous dispersion can be obtained by using the copolymer.

However, in the finishing agent described in Japanese Patent No. 2777040, although the water dispersibility of the fluorocopolymer is obtained, there is a problem that the soil releasing property, easy-clean property, .

The polyfluoroalkyl monomer used in the conventional fluorine-based SR processing agent mainly contains a perfluoroalkyl group having 8 or more carbon atoms by the environmental group such as EPA (US Environmental Protection Agency) and Greenpeace, ZDHC It is pointed out that a compound having a hydroxyl group is decomposed in the environment or in a living body to accumulate decomposition products, that is, the environmental load is high. For this reason, it has been recommended to use perfluoroalkyl monomers having less than 8 carbon atoms in compounds having a perfluoroalkyl group, but perfluoroalkyl monomers having less than 8 carbon atoms are limited due to the limitations of basic, Water repellency, and oil repellency.

The main object of the present invention is to solve the above-mentioned problems, and it is an object of the present invention to provide a fluorinated copolymer having a perfluoroalkyl group having less than 8 carbon atoms in the form of an aqueous dispersion substantially containing no volatile organic solvent, Which is capable of reducing the load and imparting abrasion resistance as well as antifouling performance, and a fiber product using the same.

In order to achieve the above object, an embodiment of the present invention is an antifoulant composition comprising at least components A), B) and C), wherein the component A) is a perfluoroalkyl monomer represented by the general formula Mixtures thereof a1); A fluorine-free alkyl monomer a2) represented by the general formula (II); A fluorine-free alkyl monomer represented by the formula (III) or a mixture thereof a3); And a vinyl group-containing monomer represented by the formula (IV), or a mixture thereof a4) as monomer units, and the component B) is a copolymer having a hydrophile-lipophile balance (HLB) 19, and the component (C) is water. The antifoulant composition according to claim 1, wherein the component (C) is water.

(I)

CF ₃ CF ₂ (CF ₂ CF ₂ ) _n (CH ₂ CH ₂ ) _m OOCCR = CRCOO (CH ₂ CH ₂ ) _m (CF ₂ CF ₂ ) _n CF ₂ CF ₃

In formula I, n is 1 or 2, m is an integer of 1 to 10, wherein R is -H or -CH _3,

≪ RTI ID = 0.0 &

C _n H _{2n + 1} CH ₂ OOCCR = CH ₂

In formula II, n is an integer of 2 ~ 22, R is -H or -CH _3,

(III)

H ₂ C = C (R) COOX

In formula III, X is an aryl group or a cycloalkyl group having a carbon number of 6 ~ 18, R is -H or -CH _3,

(IV)

H ₂ C = CHCl

In a preferred embodiment of the present invention, the component A) comprises, relative to the total weight of the fluoropolymer, from 30% to 80% by weight of component a1), from 3% to 35% 35% by weight and component a4) 5% by weight to 50% by weight.

In one preferred embodiment of the present invention, the component B) is 6 parts by weight to 30 parts by weight based on 100 parts by weight of the fluoropolymer.

In a preferred embodiment of the present invention, the antifoulant processing composition comprises 5% to 35% by weight of component A), 1% to 20% by weight of component B) and 55% to 80% . ≪ / RTI >

In a preferred embodiment of the present invention, the component a1) is characterized in that m in the general formula (I) is an integer of 1 to 10.

In a preferred embodiment of the invention, the component a2) is selected from the group consisting of behenyl (meth) acrylate, butyl acrylate, t-butyl acrylate, 2-ethylhexyl acrylate, lauryl (meth) (Meth) acrylate, cetyl (meth) acrylate and stearyl (meth) acrylate.

In a preferred embodiment of the present invention, said component a3) is selected from the group consisting of benzyl (meth) acrylate, isobornyl (meth) acrylate, cyclohexyl (meth) acrylate, 1-naphthyl (Meth) acrylate, and the like.

Another embodiment of the present invention provides a method for producing a fiber product comprising the step of coating a fiber coating composition containing the antifouling processing composition on the surface of a fiber product, and a fiber product produced by the manufacturing method.

In another preferred embodiment of the present invention, the antifoulant processing composition may contain 0.3% to 20% by weight based on the total weight of the fiber coating composition.

The anti-fouling agent composition according to the present invention is a composition in which a perfluoroalkyl ester having a specific structure and a non-fluorine ester having a perfluoroalkyl group of less than 8 carbon atoms in the form of an aqueous dispersion substantially containing no volatile organic solvent By containing it as an effective component, it is possible to reduce the environmental load, and not only the antifouling property but also the abrasion resistance and antifouling performance can be easily given.

Further, when the coating layer is formed by the antifoulant processing composition according to the present invention, the contamination source is not easily adhered to the surface, and even if it is attached, it is easily removed so that the appearance of the product is not stained and the antifouling property is maintained even after the product is worn, State can be maintained.

Unless otherwise defined, 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 well known and commonly used in the art.

Throughout this specification, when an element is referred to as "including " an element, it is understood that the element may include other elements as well, without departing from the other elements unless specifically stated otherwise.

In the present invention, '(meth) acrylic acid ester' means an acrylic acid ester or a methacrylic acid ester or a mixture thereof. That is, '(meth) acrylic acid ester' should be understood to mean a single component of an acrylic acid ester compound or 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, Acrylic acid amide 'should be interpreted in the same sense.

The present invention relates to an antifoulant composition comprising at least components A), B) and C), wherein said component A) is a perfluorinated alkyl monomer represented by the general formula (I) or a mixture thereof a1); A fluorine-free alkyl monomer a2) represented by the general formula (II); A fluorine-free alkyl monomer represented by the formula (III) or a mixture thereof a3); And a vinyl group-containing monomer represented by the formula (IV), or a mixture thereof a4) as monomer units, and the component B) is a copolymer having a hydrophile-lipophile balance (HLB) 19, and the component (C) is water. The present invention relates to an antifoulant processing composition.

(I)

CF ₃ CF ₂ (CF ₂ CF ₂ ) _n (CH ₂ CH ₂ ) _m OOCCR = CRCOO (CH ₂ CH ₂ ) _m (CF ₂ CF ₂ ) _n CF ₂ CF ₃

In formula I, n is 1 or 2, m is an integer of 1 to 10, wherein R is -H or -CH _3,

≪ RTI ID = 0.0 &

C _n H _{2n + 1} CH ₂ OOCCR = CH ₂

In formula II, n is an integer of 2 ~ 22, R is -H or -CH _3,

(III)

H ₂ C = C (R) COOX

In formula III, X is an aryl group or a cycloalkyl group having a carbon number of 6 ~ 18, R is -H or -CH _3,

(IV)

H ₂ C = CHCl

More specifically, the antifoulant composition according to the present invention comprises a perfluorinated alkyl monomer of the above formula (I) or a mixture thereof [component a1)], a fluorine-free alkyl monomer of the above formula (II) A fluorine-containing polymer obtained by copolymerizing the fluorine-free alkyl monomer of the formula (III) or a mixture thereof [component a3)] and the vinyl group-containing monomer of the formula (IV) or V as a monomer unit, (Component B) in which the HLB value is adjusted to a desired value (e.g., A)). [0033] The composition can reduce the environmental load through the composition, and can also provide antifouling properties as well as antifouling properties And a fiber product using the same.

The component A) is a polymer which is coated on a textile product and imparts antifouling property, abrasion resistance, durability, water repellency, etc., a perfluorinated alkyl monomer represented by the formula (I) or a mixture thereof a1); A fluorine-free alkyl monomer represented by the formula (II) or a mixture thereof a2); A fluorine-free alkyl monomer represented by the formula (III) or a mixture thereof a3); And a vinyl group-containing monomer represented by the general formula (IV) or (V) or a mixture thereof a4) as a monomer unit, respectively, and a perfluoroalkyl group having less than 8 carbon atoms.

(I)

CF ₃ CF ₂ (CF ₂ CF ₂ ) _n (CH ₂ CH ₂ ) _m OOCCR = CRCOO (CH ₂ CH ₂ ) _m (CF ₂ CF ₂ ) _n CF ₂ CF ₃

In formula I, n is 1 or 2, m is an integer of 1 to 10, wherein R is -H or -CH _3,

≪ RTI ID = 0.0 &

C _n H _{2n + 1} CH ₂ OOCCR = CH ₂

In formula II, n is an integer of 2 ~ 22, R is -H or -CH _3,

(III)

H ₂ C = C (R) COOX

In formula III, X is an alkyl group having a carbon number of 6 to 18 aryl group or a cyclic aliphatic group of wherein R is -H or -CH _3,

(IV)

H ₂ C = CHCl

In the formula (I), m may be an integer of 1 to 10, and the content thereof is preferably 30% by weight or more, more preferably 30% by weight or less, based on the total weight of the fluoropolymer, To 80% by weight, preferably 60% by weight to 75% by weight. When the content of the component a1) is less than 30% by weight based on the total weight of the fluorine-based polymer, the antifouling property and the abrasion resistance of the fiber product coated with the antifoulant composition may not be sufficient, The adhesiveness to the fibers may be deteriorated and the antifouling property may be lowered after abrasion.

Examples of the fluorine-free alkyl monomer represented by the formula (II) or a mixture thereof include a monomer selected from the group consisting of t-butyl acrylate, 2-ethylhexyl acrylate, lauryl (meth) acrylate, tridecyl Acrylate, cetyl (meth) acrylate, stearyl (meth) acrylate, behenyl (meth) acrylate and the like and mixtures thereof.

The component a2) may contain 3 wt% to 35 wt%, preferably 3 wt% to 8 wt%, based on the total weight of the fluoropolymer. When the content of the component a2) is less than 3% by weight based on the total weight of the fluorine-based polymer, the antifouling property and the abrasion resistance of the fiber product coated with the antifouctant composition may not be sufficient, The fluorine content is relatively decreased, and the antifouling property is lowered. At the same time, the adhesiveness is lowered and the abrasion resistance is lowered.

The component a3) is a fluorine-free alkyl monomer represented by the formula (III) and a mixture thereof, and examples thereof include benzyl (meth) acrylate, isobornyl (meth) acrylate, cyclohexyl Naphthyl (meth) acrylate, phenyl (meth) acrylate, and mixtures thereof.

The component a3) may contain 3% by weight to 35% by weight, preferably 3% by weight to 15% by weight, based on the total weight of the fluoropolymer. When the content of the component a3) is less than 3% by weight based on the total weight of the fluorine-based polymer, the antifouling property and the abrasion resistance of the fiber product coated with the composition of the antifoulant composition may not be sufficient, The fluorine content is relatively low, so that the antifouling property is lowered, and the tactile feeling of the treated fiber becomes poor.

The component a4) is a vinyl group-containing monomer represented by the above formula (IV) or a mixture thereof, and the component a4) is 5% by weight to 50% by weight, preferably 10% by weight to 30% ≪ / RTI > When the content of the component a4) is less than 5% by weight based on the total weight of the fluorine-based polymer, the antifouling property and the abrasion resistance of the fiber product coated with the composition of the antifoulant composition may not be sufficient, The reaction is not properly performed, and a problem such that the antifouling property is lowered and the stability of the emulsion is lowered due to the generation of a large amount of homopolymer may occur.

The fluoropolymer of component A) obtained by copolymerizing the components a1) to a4) may contain 5 to 35% by weight, preferably 20 to 35% by weight, based on the total weight of the composition of the antifoulant composition, As shown in FIG. When the fluorine-based polymer is contained in an amount of less than 5% by weight based on the total weight of the composition of the antifoulant composition, the fluorine-based polymer may have a low concentration, resulting in a problem that the economical efficiency and the efficiency of the product are deteriorated. The ratio between the polymer and the water as a solvent is not appropriate, which may cause problems in the storage of the product due to the lowered stability of the product.

On the other hand, the component B) is for improving the dispersion stability of the antifoulant composition, and is a nonionic surfactant having a hydrophilic lipophile balance (HLB) of 7 to 19, , More specifically polyoxyalkylene straight chain alkyl ether, polyoxyalkylene branched alkyl ether, polyoxyalkylene alkenyl ether, polyoxyalkylene alkyl phenyl ether, polyoxyalkylene alkyl aryl phenyl ether, polyoxyalkylene Nonionic surfactants such as fatty acid esters, and mixtures thereof. Exemplary substituents of the polyoxyalkylene group may be polyoxyethylene group polyoxypropylene group, polyoxybutylene group, or the like.

The amphoteric surfactant has a hydrophile-lipophile balance (HLB) of 7 to 19 in terms of emulsion dispersibility and dispersion stability of the composition after O / W type emulsion polymerization using water as a base, And preferably from 7.3 to 18.4. If the HLB value of the component B) is less than 7, the hydrophobicity is strong and the emulsifying property of the monomer deteriorates. As a result, the polymerization may not proceed properly. If the HLB value is more than 19, And the antifouling property and the antifouling property to the lower alcohol may be lowered.

The HLB value is a value indicating the degree of affinity to water and oil as a proposed concept in accordance with a demand for finding a dispersant suitable for the purpose of use because there are many kinds of surfactants. The HLB value ranges from 0 to 20, The lipophilic property is better, and the closer to 20, the better the hydrophilic property.

The component B) may be contained in an amount of 1 to 20% by weight based on the total weight of the composition of the antifoulant composition. If the content of the component B) is less than 1% by weight based on the total weight of the composition of the antifoulant composition, the dispersion stability of the composition of the antifoulant composition may be deteriorated and the appearance and performance may deteriorate during polymerization If it exceeds 20% by weight, the abrasion resistance and antifouling property of the composition of the antifoulant processing agent may be lowered due to the excessive amount of the surfactant.

The content of the component B) may be 6 to 30 parts by weight based on 100 parts by weight of the fluoropolymer. If the content of the component B) is less than 6 parts by weight based on 100 parts by weight of the fluorine-based polymer, the dispersion stability of the composition of the antifoulant processing agent may deteriorate, resulting in poor appearance and performance during polymerization. The abrasion resistance and antifouling property of the composition of the antifoulant processing agent may be deteriorated due to an excessive amount of the surfactant.

Component C) is a polymerization medium, water conventionally used in the art and may comprise from 55% to 80% by weight, based on the total weight of the composition of the antifoulant composition. When the content of the component C) is less than 55% by weight based on the total weight of the composition of the antifoulant composition, the proportion of the polymerization medium is low and it is difficult or impossible to emulsify the monomer. When the content of the component C exceeds 80% The reaction rate is slow not only due to the low concentration, but also has a molecular weight distribution different from that of the intended composition, resulting in the problem that the performance is not developed.

In addition, the antifoulant processing composition according to the present invention may further include at least one selected from an organic solvent, an initiator, a chain transfer agent, an emulsifying auxiliary, and an additive, And additives such as known additives may be included. The additive may be an antimicrobial agent, a deodorant, a flame retardant, an antistatic agent, a softener or the like.

The organic solvent is not particularly limited as long as it is an organic solvent compatible with water. Examples of the organic solvent include alcohols such as methanol and ethanol, esters such as ethyl acetate, glycols such as propylene glycol, dipropylene glycol and tripropylene glycol And the ratio of water to organic solvent is not particularly limited.

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

The chain transfer agent may be dodecylmercaptan, t-butyl alcohol or the like for the purpose of adjusting the molecular weight in the polymerization reaction, and the content thereof is preferably 5 parts by weight or less based on 100 parts by weight of the fluoropolymer. If the content of the chain transfer agent is more than 5 parts by weight, the molecular weight of the fluorine-containing polymer may be lowered, and it may be difficult to efficiently produce a fluorine-based polymer having a weight average molecular weight of 500,000 g / mol or more. A polymerization inhibitor may be used for the purpose of adjusting the molecular weight. By adding the polymerization inhibitor, a fluorine-based polymer having a desired molecular weight can be easily obtained.

For the purpose of further improving the dispersion stability, the emulsifying aid may be a known emulsifying aid such as stearyldimethylamine hydrochloride, stearyltrimethylamine hydrochloride, etc. The content of the emulsifying aid may be, for example, It is preferably 10 parts by weight or less based on 100 parts by weight of the fluoropolymer in terms of stabilizing the dispersion state of the composition.

Such a method for producing an antifoulant processing composition according to the present invention is characterized in that it comprises the monomers of components a1) to a4) or a mixture thereof, a nonionic surfactant of component B), water of component C), an initiator, And then the mixture is emulsified or dispersed by a dispersing means such as a homomixer, a high-pressure emulsifier or an ultrasonic wave, and the mixture is polymerized to prepare an antifoulant composition according to the present invention.

When the polymerization temperature is lower than 50 캜, the polymerization is insufficient. When the polymerization temperature is higher than 80 캜, the reaction does not proceed as intended due to destruction of radicals under high temperature conditions.

The antifoulant processing composition according to the present invention contains a fluorinated copolymer having a perfluoroalkyl group having less than 8 carbon atoms in the form of an aqueous dispersion containing little volatile organic solvent as an effective component, And is excellent in film forming ability when it is coated on a textile product and can easily impart not only the antifouling property immediately after the antifouling treatment but also the antifouling performance after the abrasion wear.

The present invention also relates to a method of producing a fiber product comprising the step of coating a fiber coating composition containing the antifouling processing composition on the surface of a fiber product, and a fiber product produced by the manufacturing method.

The fiber coating composition is an antifoulant composition diluted with water. The antifoulant composition may be contained in an amount of 0.3% by weight to 20% by weight based on the total weight of the fiber coating composition. If the composition of the antifoulant composition is contained in an amount of less than 0.3% by weight based on the total weight of the fiber coating composition, antifouling property may not be exhibited due to insufficient content of the polymerized polymer, and if it exceeds 20% There is a problem that the polymerized polymer is excessively lost in physical properties inherent to the fabric and the feel is hard.

The fiber coating composition according to the present invention may further contain at least one selected from a softener, a penetrating agent and an antistatic agent in an antifoulant composition.

As the softening agent, any known softening agent can be used without limitation as long as it softens the tactile feel of the fiber product and does not cause the deterioration of the antifouling property. The softening agent can be selected from the group consisting of dimethyl silicone, hydrogen silicone, amino modified silicone, fatty acid amide, Can be used. The softener may be used in an amount of 0.5 to 20 parts by weight based on 100 parts by weight of the composition of the antifoulant composition.

The penetrating agent can be used without limitation as long as it is a known penetrating agent for the purpose of penetrating the antifouling processing composition into the inside of a thick material which is difficult to penetrate into the high-density fiber product, and preferably, the antifouling property is not lowered On the side, glycols such as butyl diglycol and monoethyleneglycol, isopropyl alcohol, butyl cellosolve, alcohol type solvents such as higher alcohol type and lower alcohol type can be used, and as the content of the penetrating agent, May be used in an amount of 0.5 to 10 parts by weight based on 100 parts by weight.

The antistatic agent may be any antistatic agent as long as it is a known antistatic agent and is preferably selected from the group consisting of stearylaralkyltrimethylaminomethosulfite, laurylalkyltriethylaminoethosulfate, octylalkyltrimethylamino chloride, stearyltrimethyl Cationic polymers such as ammonium chloride, stearyldimethylammonium chloride and lauryltrimethylammonium chloride, phosphoric acid ester compounds, guanidine hydrochloride compounds and the like can be used. As the antistatic agent content, 100 parts by weight of the antifoulant composition , And 0.5 part by weight to 5 parts by weight.

The amount of the above-mentioned fiber coating composition coated on the fiber target product surface can be easily adjusted according to the required degree of antifouling property. Typically, for 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. When the coating amount is less than 0.5 part by weight, the water repellency of the fiber product is not sufficient, and when the coating amount exceeds 6 parts by weight, the original material property may be lost.

The fiber product may be coated by a known method such as dipping, spraying, spraying, or coating, and the coated product may be dried and cured (cured) to obtain a fiber product treated with the antifoulant composition .

At this time, the fiber target product may include synthetic fibers such as natural vegetable natural fibers such as cotton, hemp, wool and silk, polyamide, polyester, polyvinyl alcohol, polyacrylonitrile, polyvinyl chloride, polypropylene, And inorganic fibers such as glass fibers, and mixed fibers thereof.

On the other hand, after the antifoulant composition is coated, it can be cured by heat treatment or the like, and there is no particular limitation on the temperature condition of the heat treatment, but it can be usually carried out at 120 to 170 DEG C for 150 to 300 seconds.

In the fiber product according to the present invention thus obtained, a film made of the antifoulant composition of the present invention is adhered to the surface of the product, and preferably the surface thereof is covered with the film.

The fiber product according to the present invention can exhibit sufficient antifouling property even when it is used outdoors for a long time and the fiber product is in the form of an aqueous dispersion containing little volatile organic solvent and at the same time having a perfluoroalkyl group having less than 8 carbon atoms It is possible to reduce the environmental load by containing the fluorocopolymer as an effective component and to exhibit excellent durability against washing and also exhibit sufficient early antifouling property and antifouling property after abrasion, and at the same time, .

Hereinafter, the present invention will be described in more detail with reference to Examples. These embodiments are only for illustrating the present invention, and thus the scope of the present invention should not be construed as being limited by these embodiments.

< Manufacturing example  I>

The components a1) to a3), component B), an emulsifying aid, an organic solvent, a chain transfer agent and a component C) shown in the following Table 1 were mixed in an autoclave and then emulsified and dispersed by ultrasonic wave at 45 ° C for 5 minutes . After replacing the inside of the autoclave with nitrogen, the reactor was closed, and azobis (amidine propane) dihydrochloride, which is an initiator, was added thereto, and the reaction was carried out at 60 ° C for 4 hours to obtain an antifoulant composition. The content of each of the above components is as shown in Table 1. At this time, each component in Table 1 is usually available, perfluorodiohexylethyl acrylate, perfluorohexyl methacrylate and stearyl acrylate are its products, and behenyl acrylate is a product of Nippon Yushi , Stearyl methacrylate and benzyl methacrylate are used in the raw materials, styrene is used in the raw material cube, isobornyl methacrylate is used in Morikoku, vinyl chloride is used in domestic raw materials, and component (B) And emulsifying agents were purchased from Dupont and Miwon. And tripropylene glycol were products of Dow, dodecyl mercaptan was Cevron Phillips Chemical International and azobis (amidine propane) dihydrochloride were products of Dupont.

< Manufacturing example  II to V>

An antifoulant composition was prepared in the same manner as in Preparation Example I except that the components and the contents shown in Table 1 below were used.

< Manufacturing example  VI to IX &gt;

An antifoulant composition was prepared in the same manner as in Preparation Example I except that the components and the contents shown in Table 2 were used.

< Comparative Manufacturing Example  I to V>

An antifoulant composition was prepared in the same manner as in Production Example I, except that the components and the contents described in Table 3 were used.

< Comparative Manufacturing Example  VI to XI &gt;

An antifoulant composition was prepared in the same manner as in Production Example I, except that the components and contents described in Table 4 were used.

< Comparative Manufacturing Example  XII- XV >

An antifoulant composition was prepared in the same manner as in Preparation Example I except that the components and the contents described in Table 5 were used.

< Example  1 to 9 and Comparative Example  1 to 15>

The antifoulant compositions obtained in the preparation examples and comparative production examples were diluted in water as shown in the following Table 6 and immersed in a PET 100% Tricot Car seat (lightness 50) fabric. At this time, the pick up was adjusted to about 60% by adjusting the pressure of the mesh, followed by drying and curing at 150 ° C. for 300 seconds in a mini tenter.

division	Type and content of antifoulant processing composition (g)	Thinner (water)
Example 1	Preparation Example I: 4 g	96g
Example 2	Preparation Example II: 4 g	96g
Example 3	Preparation Example III: 4 g	96g
Example 4	Preparation Example IV: 4 g	96g
Example 5	Production Example V: 4 g	96g
Example 6	Production Example VI: 4 g	96g
Example 7	Preparation Example VII: 4 g	96g
Example 8	Preparation VIII: 4 g	96g
Example 9	Production Example IX: 4 g	96g
Comparative Example 1	Comparative Preparation Example I: 4 g	96g
Comparative Example 2	Comparative Preparation Example II: 4 g	96g
Comparative Example 3	Comparative Preparation Example III: 4 g	96g
Comparative Example 4	Comparative Preparation Example IV: 4 g	96g
Comparative Example 5	Comparative Preparation Example V: 4 g	96g
Comparative Example 6	Comparative Preparation Example VI: 4 g	96g
Comparative Example 7	Comparative Preparation Example VII: 4 g	96g
Comparative Example 8	Comparative Preparation Example VIII: 4 g	96g
Comparative Example 9	Comparative Preparation Example IX: 4 g	96g
Comparative Example 10	Comparative Preparation Example X: 4 g	96g
Comparative Example 11	Comparative Preparation Example XI: 4 g	96g
Comparative Example 12	Comparative Preparation Example XII: 4 g	96g
Comparative Example 13	Comparative Preparation Example XIII: 4 g	96g
Comparative Example 14	Comparative Preparation Example XIV: 4 g	96g
Comparative Example 15	Comparative Preparation Example XV: 4 g	96g

[ Experimental Example  1: State antifouling property measurement]

The darts of Examples 1 to 9 and Comparative Examples 1 to 15 were placed and n-tetradecane (grade 4 reagent of AATC 18 foot induction test) having a surface tension of 26 dyne / cm was dripped into a 5 mm diameter droplet of 3 drops After 30 seconds, 3 drops of droplets were visually observed and determined according to the criteria shown in Table 7. The results are shown in Table 8.

Antifouling (oil repellency) measurement criteria

[ Experimental Example 2: 500 times  Antifouling property after abrasion]

The fabric of Examples 1 to 9 and Comparative Examples 1 to 15 was perforated in a center portion of a test piece having a diameter of about 150 mm by a Taber-type abrasion tester, and a load of 4.9 N (50 gf) was applied to the abrasive wheel CS-10 , Three drops of a 5-mm-diameter droplet of n-tetradecane (a fourth-grade reagent of the AATC 18 induction test) having a surface tension of 26 dynes / cm were dripped. After 30 seconds, 3 drops Was visually observed and determined according to the criteria shown in Table 7. The results are shown in Table 8. &lt; tb &gt; &lt; TABLE &gt;

[ Experimental Example  3: State room IPA castle  Measure]

After the fabrics of Examples 1 to 9 and Comparative Examples 1 to 15 were placed flat, three droplets of a water: IPA (60:40) mixture having a surface tension of 26.6 dyne / cm and a diameter of 5 mm were dropped, After 30 seconds, the droplet state of 3 drops was judged according to the same criteria as in Table 7. The results are shown in Table 8.

[ Experimental Example  4: Low-temperature cure state antifouling property measurement]

The antifoulant compositions obtained in the preparation examples and comparative production examples were diluted in water as shown in the following Table 6 and immersed in a PET 100% Tricot Car seat (lightness 50) fabric. At this time, the pick up was adjusted to about 60% by adjusting the pressure of the mesh, and then the curing was carried out at 110 ° C for 360 seconds in a mini tenter. The fabric thus fabricated was measured for stain-proofing properties in the same manner as in Experimental Example 1, and the results are shown in Table 8.

[ Experimental Example  5: Measurement of antifouling property at low concentration]

The antifoulant compositions obtained in the preparation examples and comparative preparation examples were diluted in water as shown in the following Table 6, except that 99.5 g of water was diluted with 0.5 g of the antifoulant composition, and a PET 100% Tricot Car seat (lightness 50) Lt; / RTI &gt; At this time, the pick up was adjusted to about 60% by adjusting the pressure of the mesh, followed by drying and curing at 150 ° C for 300 seconds in a mini tenter. The fabric thus fabricated was measured for stain-proofing properties in the same manner as in Experimental Example 1, and the results are shown in Table 8.

division	State Antifouling (grade / number)	Antifouling after abrasion (grade / number of times)	State-of-the-art IPA quality (rating / frequency)	Low Temperature Cure Antifouling (Grade / Number)	Low concentration of antifouling (grade / number of times)
Example 1	A / 3	A / 3	A / 3	A / 3	A / 3
Example 2	A / 3	A / 2, B / 1	A / 3	A / 3	A / 3
Example 3	A / 3	A / 3	A / 3	A / 3	A / 3
Example 4	A / 3	B / 3	A / 3	A / 1, B / 2	A / 3
Example 5	A / 3	A / 2, B / 1	A / 3	A / 3	A / 3
Example 6	A / 3	A / 2, B / 1	A / 3	B / 3	B / 3
Example 7	A / 3	A / 3	A / 3	B / 3	A / 1, B / 2
Example 8	A / 3	B / 3	A / 3	A / 3	A / 3
Example 9	A / 3	A / 3	A / 3	A / 3	A / 3
Comparative Example 1	B / 3	C / 3	A / 3	C / 3	B / 3
Comparative Example 2	A / 3	C / 3	A / 3	B / 3	B / 3
Comparative Example 3	A / 1, B / 2	C / 3	A / 3	B / 3	B / 2, C / 1
Comparative Example 4	C / 3	D / 3	C / 3	D / 3	D / 3
Comparative Example 5	B / 1, C / 2	D / 3	B / 3	C / 3	C / 3
Comparative Example 6	B / 3	C / 1, D / 2	C / 3	C / 3	D / 3
Comparative Example 7	C / 3	D / 3	C / 3	D / 3	C / 3
Comparative Example 8	C / 3	D / 3	C / 3	D / 3	D / 3
Comparative Example 9	B / 3	D / 3	C / 3	B / 1, C / 2	D / 3
Comparative Example 10	B / 3	B / 1, C / 2	B / 1, C / 2	D / 3	C / 3
Comparative Example 11	C / 3	D / 3	C / 3	D / 3	D / 3
Comparative Example 12	B / 3	D / 3	C / 3	D / 3	C / 3
Comparative Example 13	B / 3	D / 3	B / 1, C / 2	D / 3	C / 3
Comparative Example 14	B / 3	D / 3	C / 3	D / 3	D / 3
Comparative Example 15	C / 3	D / 3	C / 3	D / 3	D / 3

As shown in Table 8, in the cases of Examples 1 and 9, all of the stainproofing properties were grade A grade 3 or more, the antifouling properties after abrasion were grade B grade 3 or more, the state room IPA grade was grade B grade 3 or more, In the case of Comparative Examples 1 and 15, when the stainproofing property was more than 3 times in the A grade, all of the antifouling properties were 3 or more in the A grade and in the B grade, Respectively. Therefore, it was confirmed that the fiber product treated with the antifoulant processing composition according to the present invention was remarkably excellent in not only the antifouling property but also the abrasion resistance.

It will be understood by those skilled in the art that various changes in form and details may be made therein without departing from the spirit and scope of the invention as defined by the appended claims.

Claims (10)

1. An antifoulant composition comprising at least components A), B) and C)

   The component A) is a perfluorinated alkyl monomer represented by the formula (I) or a mixture thereof a1); A fluorine-free alkyl monomer a2) represented by the general formula (II); A fluorine-free alkyl monomer represented by the formula (III) or a mixture thereof a3); And a vinyl group-containing monomer represented by the formula (IV) or a mixture thereof a4) as a monomer unit,

   (I)

   CF ₃ CF ₂ (CF ₂ CF ₂ ) _n (CH ₂ CH ₂ ) _m OOCCR = CRCOO (CH ₂ CH ₂ ) _m (CF ₂ CF ₂ ) _n CF ₂ CF ₃

   (In the formula (I), n is 1 or 2, m is an integer of 1 to 10, and R is -H or -CH ₃ )

   &Lt; RTI ID = 0.0 &

   C _n H _{2n + 1} CH ₂ OOCCR = CH ₂

   (And in formula II, n is an integer of 2 ~ 22, R is -H or -CH ₃ Im)

   (III)

   H ₂ C = C (R) COOX

   (Wherein X is an aryl group or a cycloalkyl group having 6 to 18 carbon atoms and R is -H or -CH ₃ )

   (IV)

   H ₂ C = CHCl

   The component B) is a nonionic surfactant having a hydrophile-lipophile balance (HLB) of 7 to 19,

   Wherein the component C) is water.
2. The method according to claim 1,

   Based on the total weight of the fluorine-based polymer, from 30 wt% to 80 wt% of component a1), from 3 wt% to 35 wt% of component a2), from 3 wt% to 35 wt% of component a3) % To 50% by weight of the composition.
3. The method according to claim 1,

   Wherein the component B) is 6 to 30 parts by weight based on 100 parts by weight of the fluorine-based polymer.
4. The method according to claim 1,

   Wherein the antifoulant processing composition comprises 5 to 35% by weight of component A), 1 to 20% by weight of component B) and 55 to 80% by weight of component C).
5. The method according to claim 1,

   Wherein the component a1) is an integer of 1 to 10 in the formula (I).
6. The method according to claim 1,

   The component a2) is preferably selected from the group consisting of behenyl (meth) acrylate, butyl acrylate, t-butyl acrylate, 2-ethylhexyl acrylate, lauryl (meth) acrylate, tridecyl (meth) Acrylate, stearyl (meth) acrylate, and stearyl (meth) acrylate.
7. The method according to claim 1,

   The component a3) is selected from the group consisting of benzyl (meth) acrylate, isobornyl (meth) acrylate, cyclohexyl (meth) acrylate, 1-naphthyl (meth) acrylate and phenyl By weight based on the total weight of the composition.
8. A process for producing a fiber product comprising the step of coating a fiber coating composition containing the antifoulant composition according to any one of claims 1 to 7 on the surface of a fiber product.
9. 9. The method of claim 8,

   Wherein the antifoulant composition comprises 0.3% to 20% by weight, based on the total weight of the textile coating composition.
10. 9. A fiber product produced by the method of claim 8.