JP3284672B2 - Textile processing method - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a method for treating textile products. More specifically, the present invention relates to a method for treating a fiber product, which imparts excellent initial water and oil repellency and durable water and oil repellency when modifying a fiber product, particularly a hydrophilic fiber product.

[0002]

2. Description of the Related Art It has been known that a fluorine-containing compound exhibits excellent performance as a water / oil repellent. In particular,
A treating agent comprising a polymer of a vinyl monomer containing a fluoroalkyl group has been put to practical use. These polymers may be homopolymers of a vinyl monomer containing a fluoroalkyl group, but often consist of copolymers with various non-fluorinated vinyl monomers. Among the non-fluorinated vinyl monomers used here, those exhibiting hydrophilicity are also included. For example, Japanese Patent Publication No. 62-47466 discloses a phosphate group-containing monomer and a perfluoroalkyl monomer. A water and oil repellent comprising a group-containing vinyl monomer is described. However, when a copolymer with a hydrophilic vinyl monomer such as a phosphoric acid group-containing monomer is used, the hydrophilicity and the charge of the polymer due to the electrical properties of the functional groups cause the hydrophilicity of the copolymer to be particularly high. In some cases, adhesion to textiles, for example, nylon, is difficult, and water / oil repellency is not obtained at all.

[0003]

SUMMARY OF THE INVENTION An object of the present invention is to stabilize the expression of the water- and oil-repellency of a fluoropolymer and thereby to provide an excellent initial water- and oil-repellency for textiles, especially hydrophilic textiles. And durable water and oil repellency.

[0004]

SUMMARY OF THE INVENTION According to one aspect, the present invention provides a method of treating a textile with a salt of a divalent or higher valent metal.
The present invention provides a method for treating a fiber product, which comprises treating with a fluoropolymer containing a hydrophilic functional group capable of coordinating with the metal. According to another aspect, the present invention provides a textile product treated by the treatment method.

[0005] In the present specification, the term "treatment" means that a fiber product is brought into contact with a treatment solution containing a metal salt or a fluoropolymer. "Treatment" includes dipping, impregnation, padding, and coating. Preferably, the hydrophilic functional group is selected from the group consisting of a phosphate group and a sulfonic acid group.

The fluorinated polymer comprises (a) a repeating unit derived from a fluorinated vinyl monomer, and (b) a general formula:

Embedded image [Wherein, R ¹ is a hydrogen atom or a methyl group, and R ² is a carbon atom having 6 carbon atoms.
The following alkylene group or substituted alkylene group, or a divalent linking group obtained by linking them to an ether group, an ester group, an amide group, or the like, X is PO or SO ₂ , M is a hydrogen or alkali metal atom, X is PO Then, p is 1, n and m are 1 or 2, and n + m = 3,
X is -SO ₂ - when, p is 0, a n = m = 1. A repeating unit derived from an acid group-containing monomer represented by the formula: and (c) a repeating unit derived from a non-fluorine-based monomer containing neither a phosphate group nor a sulfonic acid group, if necessary. Unit (however, components (b) and (c)
Is 100 parts by weight or less with respect to 100 parts by weight of the component (a).

[0007] The fluorine-containing vinyl monomer (a) comprises a perfluoroalkyl group or a perfluoroalkenyl group,
A compound having a polymerizable unsaturated double bond at the same time. Examples of the fluorine-containing vinyl monomer (a) include the following compounds.

[0008]

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

The carbon number of R ¹² is usually 1-6. X
Is, for example, an alkyleneoxy group having 1 to 10 carbon atoms, an oxygen atom, a sulfur atom, a lower alkyl-substituted or unsubstituted amino group having 1 to 6 carbon atoms, and the like.

The acid group-containing monomer (b) has an anionic functional group capable of coordinating with a metal. This functional group is particularly preferably a phosphoric acid group or a sulfonic acid group. Specific examples of the acid group-containing monomer (b) include the following compounds.

[0011]

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Mono (2-hydroxyethyl acrylate)
Acid phosphate, mono (2-hydroxyethyl methacrylate) acid phosphate, mono (2-hydroxypropyl acrylate) acid phosphate sodium salt, mono (3-hydroxypropyl methacrylate) acid phosphate, mono (allyl alcohol) acid phosphate Fate, mono (3-chloro-2
-Hydroxypropyl methacrylate) acid phosphate, mono (2-hydroxyethyl vinyl ether)
Acid phosphate, mono (3-hydroxypropyl methacrylamide) acid phosphate, (2-hydroxyethyl acrylate) acid phosphate, 2-acrylamide-2-methylpropanesulfonic acid, 2-methacrylamide-2-ethylpropanesulfonic acid , 2-acrylamidobutanesulfonic acid, 2- (acrylcarbonyloxy) ethylsulfonic acid, and the like.

The copolymerization ratio between the fluorine-containing vinyl monomer (a) and the acid group-containing monomer (b) may be within a range that does not adversely affect the water / oil repellency. 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, based on 100 parts by weight of the fluorinated vinyl monomer (a).

The fluoropolymer may also contain at least one non-fluorinated monomer (c) containing neither a phosphate group nor a sulfone group. The amount of the non-fluorinated monomer (c) is 100 parts by weight or less, preferably 0 to 50 parts by weight, based on 100 parts by weight of the fluorinated vinyl monomer (a).

Specific examples of the non-fluorinated monomer (c) include:
Ethylene, propylene, isobutene, 3-chloro-1-
Halogenated or non-halogenated lower olefinic hydrocarbons such as isobutene, butadiene, isoprene, chloro- and dichlorobutadiene, fluoro and difluorobutadiene, 2,5-dimethyl-1,5-hexadiene and diisobutylene; vinyl chloride Or vinyl or allyl or vinylidene halides, such as vinylidene chloride, vinyl or vinylidene fluoride, allyl bromide and methallyl chloride;

Vinyl toluene, α-methylstyrene, α
-Cyanomethylstyrene, divinylbenzene and N-
Styrene and styrene derivatives such as vinyl carbazole; vinyl acetate, vinyl propionate, vinyl esters of acids known under the trade name "Versatic acids", vinyl isobutyrate, vinyl sensioate, vinyls Succinate,
Vinyl esters such as vinyl isodecanoate, vinyl stearate, divinyl carbonate; allyl esters such as allyl acetate and heptanoate; cetyl vinyl ether, dodecyl vinyl ether, isobutyl vinyl ether, ethyl vinyl ether, 2-chloroethyl vinyl ether, tetraallyloxy Halogenated or non-halogenated alkylvinyl or alkylallyl esters such as ethane;

Vinyl alkyl ketones such as vinyl methyl ketone; unsaturated acids such as acrylic acid, methacrylic acid, α-chloroacrylic acid, crotonic acid, maleic acid, fumaric acid, itaconic acid, citraconic acid and sensioic acid; Acid anhydrides and esters thereof, for example vinyl,
Allyl, methyl, butyl, isobutyl, hexyl, heptyl, 2-ethylhexyl, cyclohexyl, lauryl, stearyl ester or 2-isocyanatoethyl acrylate and methacrylate, dimethyl maleate, ethyl crotonate, monomethyl maleate, monobutyl itaconate, ethylene Glycol or polyalkylene glycol diacrylates and dimethacrylates such as glycol or triethylene glycol dimethacrylate, methacryloyloxypropyltrimethoxysilane;

Acrylonitrile, methacrylonitrile,
Alkyl cyanoacrylates such as 2-chloro-acrylonitrile, 2-cyanoethyl acrylate or methacrylate, methylene glutaronitrile, vinylidene cyanide, isopropyl cyanoacrylate, trisacryloyl-hexahydro-s-triazine, vinyl trichlorosilane, vinyl trimethoxysilane, vinyl Triethoxysilane and N-vinyl-2-pyrrolidone;

Hydroxyalkyl acrylates and methacrylates such as ethylene glycol monoacrylate and propylene glycol monomethacrylate, acrylates and methacrylates of polyalkylene glycol, allyl alcohol, allyl glycolate, isobutenediol, allyloxyethanol, o-allylphenol, divinylcarbinol Glycerin α-allyl ether, acrylamide, methacrylamide, maleamide and maleimide, N- (cyanoethyl) -acrylamide, N-isopropylacrylamide, diacetone acrylamide, N- (hydroxymethyl) -acrylamide and N- (hydroxymethyl) -methacryl Amide, N- (alkoxymethyl) -acrylamide and N
-(Alkoxymethyl) -methacrylamide, glyoxal bisacrylamide, sodium acrylate or methacrylate, vinyl sulfonic acid and styrene
p-sulfonic acid and alkali metal salts thereof, 3-aminocrotonitrile, monoallylamine, vinylpyridine, glycidyl acrylate or methacrylate,
Allyl glycidyl ether, acrolein and N, N
-Dimethylaminoethyl or N-tert-butylaminoethyl methacrylate.

The method for producing the fluorinated polymer is not particularly limited, and it can be obtained by commonly used solution polymerization, emulsion polymerization or the like. Upon polymerization, a radical initiator can be used.

The metal salt treatment refers to immersing the fiber product in a liquid containing a salt of a divalent or higher-valent metal, and is used as a first-stage treatment in the present invention. Preferred metals are chromium, zirconium, titanium, aluminum and the like. Preferred metal salts are sulfates, nitrates, chlorides and the like. Among them, basic chromium sulfate is recommended because it has a particularly strong bonding force with an anionic functional group.

In a preferred embodiment of the present invention, the textile is immersed in a liquid containing a metal salt (liquid temperature of 20 to 70 ° C.), and if necessary, the pH is adjusted to 5 to 7, more preferably 5.5 to 6.5. And wash with water. The metal salt solution is an aqueous solution or suspension containing metal salt in an amount of 0.01 to 50% by weight, more preferably 0.5 to 10% by weight based on the weight of the textile. The immersion time of the fiber product is usually 10 seconds or more, preferably 1 to 120 minutes. The pH can be adjusted using sodium acetate, sodium formate, sodium hydrogen carbonate, or the like.

Thereafter, the dried fiber product is treated with a fluoropolymer. The treatment with the fluorinated polymer is the second stage treatment in the present invention, and may be the same as that conventionally performed, for example, by impregnation, padding or coating, and then drying.

After the metal salt treatment, it is also possible to carry out a fluoropolymer treatment in the same bath. In that case, after the metal salt treatment, pH adjustment, and water washing, after adding 0.01 to 50% by weight, more preferably 5 to 25% by weight of the fluoropolymer as a solid content to the bath as a solid content, , 10 seconds or more,
Preferably, soak for 1 to 120 minutes. At this time, when a fluorine-containing polymer neutralized with an organic amine such as ammonia or triethylamine, or an inorganic base such as sodium hydroxide or potassium hydroxide is used, it is particularly effective in treating a thick textile. . When a neutralized product is used, after immersion, 0.1% to 5% of a mineral acid solution such as hydrochloric acid or sulfuric acid or an organic acid solution such as formic acid, acetic acid or propionic acid is added to adjust the pH to 1%. ~ 4, more preferably 2.
Prepare 5 to 3.5. After washing with water and draining, it is the same as the usual method of treating a fluorinated water / oil repellent. The weight ratio between the metal salt and the fluoropolymer in the bath is usually 1:10.
10 to 10.

The fluoropolymer may be used together with various concomitant agents, such as melamine resin,
Urea resin, blocked isocyanate, glyoxal and the like can be mentioned. If necessary, heat treatment or calendering may be performed. It is also possible to use a treating agent other than the fluorine compound, for example, a silicon compound in combination.

The fiber product treated with the metal salt / fluorinated polymer of the present invention can be further treated with another water / oil repellent, and particularly preferably treated with a fluorinated water / oil repellent. A homopolymer or copolymer of a fluorine-containing monomer containing no anionic functional group is particularly preferred for improving the durability of textile products.

In the present invention, the fiber product to be provided is:
In addition to those in the form of fibers themselves, yarns, woven fabrics, knits, nonwoven fabrics and the like formed from fibers are included. As the fiber, any of natural fibers such as cotton, wool, and silk, and synthetic fibers including synthetic fibers such as acryl, polyamide, cellulose, and polyester can be used. A blend of natural and synthetic fibers can be used. Preferably, the textile is hydrophilic. Particularly preferred hydrophilic textiles are polyamides and polyesters. In addition, woven fabrics and artificial leathers made of ultrafine fibers whose development has been remarkable in recent years are also preferred as fiber products for the present invention.
The ultrafine fiber is usually 1 denier or less, preferably 1 to
0.0001, more preferably 0.1 to 0.001 denier.

[0028]

The present invention will be specifically described below with reference to examples and comparative examples.

The water repellency shown in Examples and Comparative Examples was measured according to JIS-L-1092-1977.
It is indicated by a number as shown in Table 1. The oil repellency is
The oil was measured by a method according to AATTC TM-118-1975, and oils having different surface tensions shown in Table 2 were added dropwise.
The highest number of the oil in which no penetration is observed after 0 seconds is used as an index of oil repellency.

[0030]

Table 1 Water - repellent state 100 No surface adhesion and wetting 90 Surface with slight adhesion and wetting 80 Surface with partial wetting 70 Surface with wetting 50 Surface with wetting 50 Thing 0 Both sides are completely wet.

[0031]

TABLE 2 Oil-repellent surface tension test solution 0-1 or less 1 31.45 Nujol 2 29.6 Nujol / n-hexadecane = 65/35 (vol%) 327.3 n-hexadecane 4 26.35 n-tetradecane 5 24.7 n-dodecane 6 23.5 n-decane 7 21.4 n-octane 8 19.9.75 n-heptane

The washing durability was determined according to JIS-L-021.
The water repellency and oil repellency before and after washing 10 times were measured according to 7-103. In addition, those marked with + in the water repellency and oil repellency display indicate slightly better performance, and those marked with-indicate slightly poor performance.

Production Example 1 (Preparation of fluorinated copolymer) 90.2 g of fluorinated vinyl monomer (structural formula a), non-fluorinated monomer: 2-ethylhexyl methacrylate [trade name: light ester EH, one side Made of company oil and fat] 10.25
g, acid group-containing monomer: (2-hydroxyethyl acrylate) acid phosphate [trade name: light ester PM, manufactured by Yoko Co., Ltd.] 2.05 g, lauryl mercaptan 0.1 g, polyoxyethylene octyl phenyl ether [product Name: HS-220, manufactured by NOF CORPORATION] 6.
23 g, ion-exchanged water 170.8 g, acetone 36.75
The mixture consisting of g was emulsified for 1 minute with a homogenizer and further for 5 minutes with an ultrasonic emulsifier. The obtained emulsion was transferred to a four-necked flask, and 0.51 g of azobisisobutylamidine hydrochloride was added. After replacing the gas phase with nitrogen, copolymerization was carried out at 55 ° C. for 5 hours. The obtained emulsion was subjected to 229.
The mixture was diluted with 8 g to obtain a fluorine-containing copolymer emulsion having a solid content of 20%.

Structural formula a:

Embedded image (The molar ratio of n: 3, 4, 5, 6 is 5: 3: 2:
A mixture of 1)

Production Examples 2 to 4 (Preparation of Fluorine-Containing Copolymer) Fluorine-containing copolymers were produced in the same manner as in Production Example 1 by changing the types and the ratios of the non-fluorinated monomers and the acid group-containing monomers. A polymer emulsion was obtained. The composition is shown in Table 3.

[Table 3]

Preparation example of metal salt-treated test cloth 1 Nylon taffeta for dyeing test
It was immersed in a 30 ° C. aqueous solution (bath ratio: 10: 1) containing wt% basic chromium sulphate (trade name: Bichrome F, manufactured by Bayer AG) and used with a dyeing tester (manufactured by Tsujii Dyeing Machine Co., Ltd.). T
After rotation treatment for 0 minutes, sodium formate and sodium bicarbonate were each added by 0.2 wt% to the weight of the test cloth to neutralize. Next, the sample was further rotated at 40 ° C. for 20 minutes, drained, washed with water, and then dried at room temperature to obtain a sample.

[0037] Examples 1-4 have a solid content concentration fluorocopolymer emulsion respectively prepared in Production Example 1-4 was diluted with tap water to a 1%, further isopropyl alcohol 3% was added, the process I made a liquid. The test cloth prepared according to the metal salt-treated test cloth preparation example 1 was immersed in the treatment liquid, squeezed with a mangle to a wet pickup of 25%, dried at 110 ° C. for 3 minutes, and further heat-treated at 160 ° C. for 1 minute. Water repellency and oil repellency of the sample before and after washing 10 times were measured. Table 4 shows the results.
Shown in

Comparative Examples 1 to 4 The same treatments as in Examples 1 to 4 were carried out except that 6 nylon taffeta for a dyeing test which had not been treated with a metal salt was used. Water repellency and oil repellency of the sample before and after washing 10 times were measured. Table 4 shows the results.

[0039]

Table 4 Water and oil repellency Example 1 L0 100 + 6 L10 802 Example 2 L0 100 + 7 L10 100 3 Example 3 L0 100 6 L10 50 2 Example 4 L0 100 + 8 L10 100 3 Comparative Example 1 L0 50 5 L10 00 Comparative Example 2 L0 50 5 L10 00 Comparative Example 3 L0 00 L10 00 Comparative Example 4 L0 100 5 L10 50 0

Examples 5 to 6 Metal salt treated test cloth In Example 1, 6 nylon taffeta was subjected to the same process up to neutralization treatment, followed by drainage, and the emulsion of Production Example 1 or 2 (Example 5). Or 6) was immersed in 50 ° C. diluting water (bath ratio 10: 1) containing 15% by weight of the test cloth, and subjected to a rotation treatment for 60 minutes. After adding 3% of formic acid with respect to the weight of the test cloth in the same bath, a rotation treatment was further performed at 40 ° C. for 20 minutes. After draining, the body was washed with water, drained, dried at 110 ° C. for 3 minutes, and further heat-treated at 160 ° C. for 1 minute. The water repellency and oil repellency of the obtained sample before and after washing 10 times were measured. The results are shown in Table 5 as Examples 5 and 6.

Examples 7 and 8 Texguard TG-543, a fluorine-based water and oil repellent
1 (manufactured by Daikin Industries, Ltd.) with tap water so as to have a solid concentration of 1%.
% To add a processing solution. The test cloths obtained in Examples 5 and 6 were immersed therein, squeezed with a mangle to a wet pickup of 25%, dried at 110 ° C. for 3 minutes, and further heat-treated at 160 ° C. for 1 minute. The water repellency and oil repellency of the obtained sample before and after washing 10 times were measured. The results are shown in Table 5 as Examples 7 and 8.

Comparative Example 5 Texguard TG-543, a fluorine-based water and oil repellent
1 (manufactured by Daikin Industries, Ltd.) with tap water so as to have a solid concentration of 1%.
% To add a processing solution. Untreated 6 nylon taffeta for dyeing test is immersed in this, squeezed with a mangle to make the wet pickup 25%, dried at 110 ° C. for 3 minutes,
Further, heat treatment was performed at 160 ° C. for 1 minute. The water repellency and oil repellency of the obtained sample before and after washing 10 times were measured. Table 5 shows the results.

[0043]

Table 5 Water repellency / oil repellency Example 5 L0 100 + 6 L10 100 3 Example 6 L0 100+ 5 L10 100 2 Example 7 L0 100+ 6 L10 100 3 Example 8 L0 100+ 5 L10 100 2 Comparative example 5 L0 100 + 6 L10 800 Note) L0: not washed L10: after washing 10 times

Example 2 of preparation of test cloth for metal salt treatment Except for using basic zirconium sulfate (trade name: zirconium, manufactured by Rohm & Haas Co.) instead of basic chromium sulfate, the same as in preparation example 1 of test cloth for treatment with metal salt Was performed.

Example 9 The same procedure as in Example 1 was carried out except that the test cloth prepared in Preparation Example 2 for the metal salt-treated test cloth was used using the fluorinated copolymer emulsion prepared in Production Example 4 and the test cloth prepared in Preparation Example 2 for the metal salt treatment test cloth. Water repellency and oil repellency of the sample before and after washing 10 times were measured. Table 6 shows the results.

[0046]

Table 6 Water / oil repellency Example 9 L0 100+ 7 L10 90 3

[0047]

Industrial Applicability According to the present invention, excellent initial water and oil repellency is imparted to textiles, especially hydrophilic textiles, and durable water and oil repellency which withstands long-term use including washing and friction. Can be easily and stably provided.

────────────────────────────────────────────────── ─── Continuing on the front page (72) Inventor Motonobu Kubo 1-1, Nishiichitsuya, Settsu-shi, Osaka Daikin Industries, Ltd. Yodogawa Works (56) References JP-A-60-239568 (JP, A) JP-A-61-126193 (JP, A) JP-A-3-193975 (JP, A) JP-A-5-239770 (JP, A) JP-B-51-2433 (JP, B1) International Publication 94/13877 (WO , A1) (58) Fields investigated (Int. Cl. ⁷ , DB name) D06M 11/00-15/715

Claims (6)

(57) [Claims] 1. A method for treating a fiber product, comprising treating a fiber product with a salt of a divalent or higher-valent metal, and then treating the fiber product with a fluoropolymer containing a hydrophilic functional group capable of coordinating with the metal. . 2. The method according to claim 1, wherein the divalent or higher valent metal is selected from the group consisting of chromium, titanium, zirconium and aluminum. 3. The method according to claim 1, wherein the hydrophilic functional group is selected from the group consisting of a phosphoric acid group and a sulfonic acid group. 4. A fluorine-containing polymer comprising: (a) a repeating unit derived from a fluorine-containing vinyl monomer; and (b) a general formula: [Wherein, R ¹ is a hydrogen atom or a methyl group, and R ² is a carbon atom having 6 carbon atoms.
The following alkylene group or substituted alkylene group, or a divalent linking group obtained by linking them to an ether group, an ester group, an amide group, or the like, X is PO or SO ₂ , M is a hydrogen or alkali metal atom, X is PO Then, p is 1, n and m are 1 or 2, and n + m = 3,
When X is SO ₂ , p is 0 and n = m = 1. A repeating unit derived from an acid group-containing monomer represented by the formula: and (c) a repeating unit derived from a non-fluorine-based monomer containing neither a phosphate group nor a sulfonic acid group, if necessary. The method according to claim 1, wherein the copolymer is a unit consisting of units (however, the total amount of components (b) and (c) is 100 parts by weight or less based on 100 parts by weight of component (a)). 5. A textile product treated by the method according to claim 1. 6. The textile product according to claim 5, wherein the fibers of the textile product are polyamide or polyester.