KR100322937B1 - Textile product treatment method - Google Patents

Abstract

The present invention is a fiber which imparts water / oil repellency by treating a fiber product with a salt of a divalent or higher metal, and then treating the fiber product with a fluorine-containing polymer having a hydrophilic functional group selected from a coordinating phosphate group and a sulfonic acid group. The product treatment method stably imparts excellent initial water and oil repellency and durable water and oil repellency for the fiber product.

Description

Textile product processing method

[Industrial use]

The present invention relates to a method for processing a textile product. More particularly, the present invention relates to a method for treating a fibrous product that imparts excellent initial water and oil repellency and durable water and oil repellency in modifying the fibrous product, particularly a hydrophilic fibrous product.

[Prior art]

In general, it is known that fluorine-containing compounds exhibit excellent performance as water and oil repellents. In particular, treatment agents consisting of polymers of vinyl monomers containing fluoroalkyl groups have been provided practically. These polymers may be homopolymers of vinyl monomers containing fluoroalkyl groups, but in most cases they consist of copolymers with various non-fluorine vinyl monomers. Non-fluorinated vinyl monomers used herein include those that exhibit hydrophilicity. For example, Japanese Patent Laid-Open No. 62-47466 discloses a water and oil repellent agent comprising a phosphoric acid group-containing monomer and a perfluoroalkyl group-containing vinyl monomer. However, in the case of using a copolymer with a hydrophilic vinyl monomer such as a phosphoric acid group-containing monomer, the polymer charges due to the hydrophilicity or the electrical properties of the functional group, in particular, have difficulty in adhesion to hydrophilic fiber products, for example, nylon, and water / oil repellent. There is no performance at all.

The gist of the invention

An object of the present invention is to impart excellent initial and oil repellent and durable water and oil repellency to fiber products, particularly hydrophilic fiber products, by stabilizing the performance expression of water and oil repellent properties of the fluorine-containing polymer.

An object of the present invention is to provide a method for treating a fiber product, characterized in that the fiber product is treated with a salt of a divalent or higher metal and then treated with a fluorine-containing polymer containing a hydrophilic functional group that can coordinate with the metal.

Another object of the present invention is to provide a fiber product treated with the above treatment method.

In the present invention, [treatment] means contacting a textile product with a treatment liquid containing a metal salt or a fluorine-containing polymer. [Treatment] includes immersion, impregnation, pad method, and coating method.

The hydrophilic functional group is preferably selected from the group consisting of a phosphoric acid group and a sulfonic acid group.

Preferably, the fluorine-containing polymer is a copolymer consisting of:

(a) repeating units derived from fluorine-containing vinyl monomers,

(b) a repeating group derived from an acid group-containing monomer represented by the following general formula:

[Wherein R ¹ is a hydrogen atom or a methyl group, R ² is an alkylene group or a substituted alkylene group having 6 or less carbon atoms, or a divalent linking group to which an ether group, an ester group, an amide group and the like are connected, X is PO or SO ₂ , M is hydrogen or an alkali metal atom, when X is PO, p is 1, n, m is 1 or 2, and n + m = 3, and when X is -SO _2- , p is 0, n = m = 1], and

(c) if necessary, repeating units derived from non-fluorine-based monomers containing no phosphate or sulfonic acid groups, provided that the total amount of components (b) and (c) is 100 parts by weight based on 100 parts by weight of component (a) Or less).

The fluorine-containing vinyl monomer (a) is a compound having a polyfluoroalkyl group (particularly perfluoroalkyl group) or a polyfluoroalkenyl group (particularly perfluoroalkenyl group) and a polymerizable unsaturated double bond (particularly a carbon double bond). Examples of the fluorine-containing vinyl monomer (a) include the following compounds.

[Wherein, R ¹¹ is hydrogen or a methyl group, R ¹² is a lower alkyl group, and X is a divalent organic group. M is an integer of 1 to 4, n is an integer of 5 to 21;

Carbon number of R <^12> is 1-6 normally. X is a C1-C10 alkyleneoxy group, an oxygen atom, a sulfur atom, a C1-C6 lower alkyl substituted or unsubstituted amino group, etc., for example.

The acid group-containing monomer (b) is anionic and has a functional group capable of coordinating with a metal. It is preferable that especially this functional group is a phosphoric acid group and a sulfonic acid group. The following compound is mentioned as a specific example of an acidic radical containing monomer (b).

Mono (2-hydroxyethylacrylate) acid phosphate,

Mono (2-hydroxyethylmethacrylate) acid phosphate,

Mono (2-hydroxypropylacrylate) acid phosphate sodium salt,

Mono (3-hydroxypropylmethacrylate) acid phosphate,

Mono (allyl alcohol) acid phosphate,

Mono (3-chloro-2-hydroxypropylmethacrylate) acid phosphate,

Mono (2-hydroxyethylvinylether) acid phosphate,

Mono (3-hydroxypropylmethacrylamide) acid phosphate,

(2-hydroxyethylacrylate) acid phosphate,

2-acrylamide-2-methylpropane sulfonic acid,

2-methacrylamide-2-ethylpropane sulfonic acid,

2-acrylamidebutane sulfonic acid, and

2- (acrylcarbonyloxy) ethylsulfonic acid and the like.

The copolymerization ratio of the fluorine-containing vinyl monomer (a) and the acid group-containing monomer (b) may be any range that does not adversely affect the water / oil repellent performance. The amount of the acid group-containing monomer (b) is usually 50 parts by weight or less, preferably 0.2 to 30 parts by weight with respect to 100 parts by weight of the fluorine-containing vinyl monomer (a).

In addition, the fluorine-containing polymer may contain at least one non-fluorine monomer (c) which does not contain any of a phosphoric acid group or a sulfone group. The quantity of a non-fluorine-type monomer (c) is less than 100 weight part with respect to 100 weight part of fluorine-containing vinyl monomers (a), Preferably it is 0-50 weight part.

Specific examples of the non-fluorine monomer (c) are as follows: ethylene, propylene, isobutene, 3-chloro-1-isobutene, butadiene, isoprene, chloro- and dichlorobutadiene, 2,5-dimethyl-1 Lower olefin halogenated or non-halogenated hydrocarbons such as, 5-hexadiene and diisobutylene; Vinyl or allyl or vinylidene halides such as vinyl chloride or vinylidene chloride, vinylidene or vinylidene fluoride, allyl bromide and metaallyl chloride; Styrene and styrene derivatives such as vinyltoluene, α-methylstyrene, α-cyanomethylstyrene, divinylbenzene and N-vinylcarbazole; Vinyl acetate, vinyl propionate, vinyl esters of acids known under the trade name [Versatic acids], vinyl isobutylate, vinyl senesioate, vinyl succinate, vinyl isodecanoate, vinyl stearate, Vinyl esters such as divinyl carbonate; Allyl esters such as allyl acetate and heptanoate; Halogenated or non-halogenated alkylvinyl or alkylallyl ethers such as cetyl vinyl ether, dodecyl vinyl ether, isobutyl vinyl ether, ethyl vinyl ether, 2-chloroethyl vinyl ether, tetraallyloxy ethane; Vinyl alkyl ketones such as vinyl methyl ketone; Unsaturated acids such as acrylic acid, methacrylic acid, α-chloroacrylic acid, clotonic acid, maleic acid, fumaric acid, itaconic acid, citraconic acid, sesenoic acid, acid anhydrides thereof and esters thereof such as vinyl, allyl, Methyl, butyl, isobutyl, hexyl, heptyl, 2-ethylhexyl, cyclohexyl, lauryl, stearyl ester or, 2-isocyaniite ethyl acrylate and methacrylate, dimethylmaleate, ethyl chlorotonate, mono Diacrylates and dimethacrylates, methacryloyloxypropyltrimethoxysilane of glycols or polyalkylene glycols such as methyl maleate, monobutyl itaconate, ethylene glycol or triethylene glycol dimethacrylate; Alkyl cyano, such as acrylonitrile, methacrylonitrile, 2-chloro- acrylonitrile, 2-cyanoethyl acrylate or methacrylate, methylene glutaronitrile, vinylidene cyanide, isopropyl cyano acrylate Acrylate, trisacryloyl-hexahydro-s-triazine, vinyltrichlorosilane, vinyltrimethoxysilane, vinyltriethoxysilane and N-vinyl-2-pyrrolidone; Hydroxyalkyl acrylates and methacrylates such as ethylene glycol monoacrylate and propylene glycol monomethacrylate, acrylates and methacrylates of polyalkylene glycols, allyl alcohols, allyl glycolates, isobutenediol and allyloxyethanol , o-allylphenol, divinylcarbinol, glycerin α-allylether, acrylamide, methacrylamide, maleamide and maleimide, N- (cyanoethyl) -acrylamide, N-isopropylacrylamide, diacetone Acrylamide, N- (hydroxymethyl) -acrylamide and N- (hydroxymethyl) -methacrylamide, N- (alkoxymethyl) -acrylamide and N- (alkoxymethyl) -methacrylamide, glyoxalbis Acrylamide, sodium acrylate or methacrylate, vinylsulfonic acid and styrene-p-sulfonic acid and their alkali metal salts, 3-aminoclotonnitrile, monoallylamine, vinylpyridine , Glycidyl acrylate or methacrylate, allyl glycidyl ether, acrolein and N, N-dimethylaminoethyl or N-t-butylaminoethyl methacrylate and the like.

There is no restriction | limiting in particular in the manufacturing method of a fluoropolymer, It can obtain by the solution polymerization, emulsion polymerization, etc. which are generally used. In the polymerization, a radical initiator can be used. The molecular weight of the fluorine-containing polymer of the present invention is usually 1,000 to 1,000,000.

Metal salt treatment means immersing a fiber product in the solution containing the salt of a bivalent or more metal, and is used as a one-step process in this invention. Preferred metals are chromium, zirconium, titanium, aluminum and the like, and preferred metal salts are sulfates, nitrates, chlorides and the like. Among these, basic chromium sulfate is recommended at the point of especially strong binding force with anionic functional group.

In a preferred embodiment of the present invention, the fiber product is immersed in a solution containing a metal salt (the liquid is 20 to 70 ° C), and the pH is adjusted to 5 to 7, more preferably 5.5 to 6.5, if necessary, Do it. The metal salt solution is an aqueous solution or an aqueous suspension containing the metal salt in an amount of 0.01 to 50% by weight, more preferably 0.5 to 10% by weight of the fiber product. Immersion time of a fiber product is 10 second or more normally, Preferably it is 1 to 120 minutes. The pH can be adjusted using sodium acetate, sodium formate, sodium hydrogen carbonate and the like.

Thereafter, the dried fiber product is treated with a fluorine-containing polymer. The treatment with the fluorine-containing polymer is a two-step treatment in the present invention, and the same method as the conventional method can be used. For example, the treatment is performed by impregnation, pad method or coating method, and then dried.

In addition, it is also possible to perform a fluorine-containing polymer treatment with the same solution after the metal surface treatment. In this case, after the metal salt treatment, pH preparation, and water washing, 0.01 to 50% by weight, more preferably 5 to 25% by weight of the weight of the fiber product is added to the solution as a solid component, and then 10 seconds or more, preferably Is immersed for 1 to 120 minutes. At this time, when the fluorine-containing polymer is neutralized with an organic amine such as ammonia or triethylamine, or an inorganic base such as sodium hydroxide or potassium hydroxide, it is particularly effective in the treatment of thick textile products. In the case of using a neutralized product, after immersion, 0.1% to 5% of acidic solution such as hydrochloric acid and sulfuric acid or organic acid solution such as formic acid, acetic acid and propionic acid are added to pH 1-4, more preferably, 2.5. It is prepared in -3.5. After water washing and water removal, it is the same as the processing method of the normal fluorine-containing water and oil repellent agent. The weight ratio of the metal salt and the fluorine-containing polymer in the solution is usually 1:10 to 10: 1.

A fluorine-containing polymer may be used with various combination agents, As a combination agent, a melamine resin, urea resin, block isocyanate, glyoxal etc. are mentioned, for example. If necessary, heat treatment and calendering may be performed. Moreover, it can also use together with processing agents other than a fluorine-type compound, for example, a silicone type compound.

Textile products subjected to the metal salt treatment / fluorine-containing polymer treatment of the present invention can also be treated with other water and oil repellents thereon, and treatment with a fluorine-containing water and oil repellent agent is particularly preferred. Homopolymers or copolymers of fluorine-containing monomers that do not contain anionic functional groups are particularly preferred for improving the durability of fiber products.

The fiber products provided in the present invention include not only in the form of the fibers themselves, but also yarns, fabrics, knits, nonwovens, and the like formed from the fibers. The fiber may be any of chemical fibers including natural fibers such as cotton, wool and silk and synthetic fibers such as acrylic, polyamide, cellulose, and polyester. Blends of natural fibers and synthetic oil can be used. It is preferred that the fiber product is hydrophilic. Particularly preferred hydrophilic fiber products are polyamides and polyesters. Further, in recent years, textiles, artificial leather, etc., which are made of ultrafine fibers, which are remarkably developed, are also preferable in the present disclosure as textile products. The ultrafine fibers are usually 1 denier or less, preferably 1 to 0.0001, more preferably 0 1 to 0.001 denier.

Example

Hereinafter, the present invention will be described in detail with reference to Examples and Comparative Examples.

The water repellency shown in the Example and the comparative example is measured by JIS-L-1092-1977, and is represented by the same number as shown in Table 1. In addition, oil repellency is measured by the method according to AATTC TM-118-1975, the oil of which surface tension shown in Table 2 is dripped, and let the highest number of oil which shows no penetration after 30 second as an index of oil repellency. .

In addition, washing durability was measured according to JIS-L-0217-103, and was shown by water repellency and oil repellency before and after washing 10 times. In addition, when the water-repellent and oil-repellent indications are marked with +, the performance is slightly better, respectively, and if-is indicated, the performance is slightly inferior.

Preparation Example 1 (Preparation of Fluorine-Containing Polymer)

90.2 g of fluorine-containing vinyl monomers (Structure Formula a), non-fluorine monomers: 2-ethylhexyl methacrylate [trade name: Light ester EH, Ippaosha Co., Ltd.] 10.25 g, acid group-containing monomers: (2-hydroxyethyl acrylate) Acid phosphate [brand name: light ester PM, Ippo Shayu Co., Ltd.] 2.05 g, lauryl mercaptan 0.1 g, polyoxyethylene octyl phenyl ether. HS-220, manufactured by Nihon Yushi Co., Ltd.] 6.23 g, ion-exchanged water 170.8 g, and acetone 36.75 g were emulsified with a homogenizer for 1 minute and further with an ultrasonic emulsifier for 5 minutes. The obtained emulsion was transferred to a four neck flask, and 0.51 g of azobisisobutylamidine hydrochloride was added, and the gas phase was copolymerized at 55 ° C. for 5 hours after nitrogen substitution. The obtained emulsion was diluted with 229.8 g of ion-exchanged water to obtain a fluorine-containing copolymer emulsion having a solid content of 20%.

Structural Formula a:

(molar ratio 5: 3: 2: 1 mixture of n being 3, 4, 5, 6)

Production Examples 2 to 4 (Preparation of Fluorine-Containing Copolymer)

The type and weight ratio of the non-fluorine monomer and the acid group-containing monomer were changed, and a fluorine-containing copolymer emulsion was obtained in the same manner as in Production Example 1. This composition is shown in Table 3.

Metal salt treatment test fabric production example 1

6 nylon taffeta for dyeing test was immersed in an aqueous solution at 30 ° C. (bath ratio 10: 1) containing 5% by weight of basic chromium sulfate (registered trademark: Bichrome F, manufactured by Bayer Corporation) based on the weight of the test cloth, and was dyed. After spin-processing for 120 minutes using the base industry Co., Ltd., sodium neutral formate and sodium hydrogencarbonate were added by 0.2weight%, respectively, and were neutralized. Subsequently, the resultant was further subjected to rotation treatment at 20 ° C. for 20 minutes, followed by water removal, washed with water, and then dried at room temperature to obtain a sample.

Examples 1-4

Each of the fluorine-containing copolymer emulsions prepared in Production Examples 1 to 4 was diluted with tap water so that the solid content concentration was 1%, and 3% of isopropyl alcohol was further added to form a treatment liquid. The test fabric prepared in Preparation Example 1 of the metal salt-treated test cloth was immersed in the treatment solution, mixed with mangle, wet pick up was 25%, dried at 110 ° C. for 3 minutes, and further heat-treated at 160 ° C. for 1 minute. The water repellency and oil repellency before and after washing 10 times of the sample were measured. The results are shown in Table 4.

Comparative Examples 1 to 4

It carried out by the method similar to Examples 1-4 except using 6 nylon taffeta for the dyeing test which did not give metal salt treatment. The water repellency and oil repellency before and after washing 10 times of the sample were measured. The results are shown in Table 4.

Examples 5-6

In the metal salt-treated test fabric preparation example 1, 6 nylon taffeta was subjected to the same process until the neutralization treatment, followed by bathing, and containing 15% of the emulsion of Preparation Example 1 or 2 (represented in Examples 5 or 6, respectively) by weight of the test fabric. It was immersed in 50 degreeC dilution water (bath ratio 10: 1), and rotated for 60 minutes. 3% of formic acid was added to the weight of the test cloth in the same solution, followed by further rotating treatment at 40 ° C for 20 minutes. After bathing, water washing was performed, water was removed, dried at 110 ° C. for 3 minutes, and further heat-treated at 160 ° C. for 1 minute. With respect to the obtained sample, water repellency and oil repellency before and after washing 10 times were measured. Each result is shown in Table 5 by Examples 5 and 6.

Examples 7-8

Tex Guard TG-5431 (manufactured by Daisheng Co., Ltd.), a fluorine-based water and oil repellent, was diluted with tap water so that the solid content concentration was 1%, and 3% of isopropyl alcohol was added to form a treatment liquid. Examples 5 and 6 The test cloth obtained in the above was immersed in this, mixed with mangle, the wet pickup was 25%, dried at 110 ° C for 3 minutes, and further heat-treated at 160 ° C for 1 minute. The obtained sample was measured for water and oil repellency before and after washing 10 times. Each result is shown in Table 5 as Examples 7 and 8.

Comparative Example 5

Tex Guard TG-5431 (manufactured by Daiseng Co., Ltd.), a fluorine-based water and oil repellent, was diluted with tap water so that the solid content concentration was 1%, and 3% of isopropyl alcohol was added to prepare a treatment liquid. 6 nylon tarpants for untreated dyeing test were immersed therein, mixed with mangle, and the wet pickup was 25%, dried at 110 ° C for 3 minutes, and further heat-treated at 160 ° C for 1 minute. The water repellency and oil repellency before and after washing 10 times were measured about the obtained sample. The results are shown in Table 5.

Metal salt treatment test cloth production example 2

Instead of basic chromium sulfate, the same treatment was carried out as in Metal Salt Treatment Test Fabric Preparation Example 1, except that basic zirconium sulfate (trade name: zircotan, manufactured by Rohm & Hurs) was used.

Example 9

It processed similarly to Example 1 using the fluorine-containing copolymer emulsion prepared by manufacture 4 except having used the test fabric prepared by the said metal salt treatment test fabric preparation example 2. About the sample, the water repellency and oil repellency before and after washing 10 times were measured. The results are shown in Table 6.

Effects of the Invention

The present invention can impart excellent initial water / oil repellency to fiber products, especially hydrophilic fiber products, and can easily and stably provide durable water / oil repellency to withstand long-term use including washing and friction.

Claims (5)

Treating a fibrous product with a fluorine-containing polymer having a hydrophilic functional group selected from phosphoric acid groups and sulfonic acid groups that are coordinable with the metal and then treating the fibrous product with a salt of a divalent or higher metal. The method of claim 1, wherein the divalent or more metal is selected from the group consisting of chromium, titanium, zirconium, and aluminum. The process of claim 1 wherein the fluorine-containing polymer is a copolymer consisting of: (a) repeating units derived from fluorine-containing vinyl monomers, (b) repeating units derived from an acid group-containing monomer represented by the following general formula: [In the meal, R ¹ is a hydrogen atom or a methyl group, R ² is a C6 or less alkylene group or a substituted alkylene group, or a divalent bonding group to which an ether group, an ester group, an amide group or the like is connected, X is PO or SO ₂ , M is hydrogen or an alkali metal atom, when X is PO, p is 1, n, m is 1 or 2, and n + m = 3 and X is SO ₂ , p is 0 and n = m = 1], and (c) If necessary, repeating units derived from non-fluorine-based monomers containing no phosphate group or sulfonic acid group, provided that the total amount of components (b) and (c) is 100% by weight based on 100 parts by weight of component (a) Part or less). A fiber product treated by the method of claim 1. 6. The fibrous product of claim 5, wherein the fibers of the fibrous product are polyamide or polyester.