JPWO1993015254A1 - Textile product treatment agent, textile product treatment method, and treated textile products - Google Patents

Abstract

(57) [Abstract] This publication contains application data prior to electronic filing, so abstract data is not recorded.

Description

[Detailed Description of the Invention] Textile Treatment Agent, Textile Treatment Method, and Treated Textile Products Background of the Invention Industrial Application Field The present invention relates to a textile treatment agent, a textile treatment method, and treated textile products.

PRIOR ART It has been previously known, as disclosed in Japanese Patent Publications 43-4503 and 48-4770, that fluorine-containing phosphate esters and fluorine-containing phosphonic acids exhibit oil repellency toward textiles, fabrics, and paper. However, when these fluorine-containing phosphate esters or fluorine-containing phosphonic acids are used alone, the treatment results in a deterioration of feel, texture, color, and flexibility, and the initial water and oil repellency is insufficient. Furthermore, these properties are significantly reduced by washing, friction, and other factors.

Japanese Patent Publication No. 2-215900 discloses a method for treating leather with a fluorine-containing phosphate compound and a cationic compound, but does not mention fiber treatment, which emphasizes texture, color, and flexibility. U.S. Patent Specification No. 2,662,835 also discloses a method for treating fibers with a chromium complex salt of a fluorine-containing carboxylic acid. However, this method only mentions water and oil repellency, and even at high concentrations, the effect is insufficient, and the fibers are significantly discolored.

U.S. Patent Specification No. 3,096,207 discloses a method for treating leather or textiles with a fluorine-containing phosphate compound or its metal salt, but because the treating agent and method differ from those of the present invention, the effect is not as sufficient and the durability is not as good.

On the other hand, treatment with conventionally widely used polymer-based fluorine-containing compounds, such as acrylic polymer-based compounds containing fluoroalkyl groups, has the drawback of causing the treated textile to lose its original feel, texture, and flexibility. Furthermore, these properties, as well as the resulting water and oil repellency, are significantly reduced by washing and friction. Furthermore, initial repellency is also very poor for highly hydrophilic materials such as nylon. It is known that, after light washing, heat treatment such as ironing can restore repellency to some extent, but this process is extremely cumbersome.

In recent years, in an attempt to improve durability, additives have been used in conjunction with fluoroalkyl-containing acrylic polymers during processing. Examples include melamine-based resins and urea-based resins. However, the use of these resins tends to further impair the texture of the fibers compared to when the polymer is used alone. Therefore, durability and flexibility are in a tradeoff when using fluorine-containing polymers.

Furthermore, acrylic polymers containing fluoroalkyl groups have a low glass transition temperature (Tg). Therefore, above Tg, the arrangement of the fluoroalkyl groups that cause water and oil repellency becomes disordered, resulting in a significant decrease in water and oil repellency. This makes them highly susceptible to boiling water, making them difficult to dispose of in hot water.

As described above, all of the treatment agents and methods used to date have impaired the inherent properties of natural and synthetic fibers, and the imparted water and oil repellency has also deteriorated due to washing and other processes.

Summary of the Invention Problem to be Solved by the Invention The object of the present invention is to maintain the original feel, texture, color (vividness), and flexibility of textiles after processing, and to maintain these properties even after prolonged use, including washing, while also imparting weather resistance and durable water/oil repellency and stain resistance.

Means for Solving the Problem In one aspect, the present invention relates to a textile treatment agent represented by the general formula: [wherein R and R are the same or different and are a hydrogen atom or R,-(CH),- (where R is a saturated or unsaturated, linear or branched, fluorine-containing aliphatic group having 4 to 20 carbon atoms, which may have an oxygen atom, nitrogen atom, sulfonyl group, or aromatic ring interposed between the carbon-carbon bond; m is 1 or 2) (provided that R and R are not simultaneously hydrogen atoms), A is an oxygen atom, sulfur atom, or direct bond, and n is 1 or 2.], and the agent is a combination of a modifier comprising a fluorine-containing phosphoric acid derivative or salt thereof having a molecular weight of 2.000 or less and a fixing agent comprising a metal salt compound.

According to a second aspect, the present invention relates to a method for treating textile products with the above-mentioned treating agent.

According to a third aspect, the present invention relates to a textile product treated with the above-mentioned treatment agent.

In a fourth aspect, the present invention relates to a method for treating textile products, which comprises a two-stage treatment in which textile products are treated with the textile product treating agent and then treated with a fluorine-containing water/oil repellent or fluorine-containing stain-resistant agent.

Detailed Description of the Invention In the present invention, a textile product may be treated with a fixative and then with a modifier. Alternatively, a textile product may be treated with a modifier and then with a fixative. In the present invention, the combined use of a modifier and a fixative allows the fiber's original feel, texture, color, and flexibility to be maintained for a long period of time. Furthermore, the bond between the fiber and the fluorine-containing phosphate derivative is strengthened, preventing the fluorine-containing phosphate derivative from peeling from the fiber.

In the present invention, the modifier is a fluorine-containing phosphonic acid derivative represented by the general formula (1) or a salt thereof. The fluorine-containing phosphonic acid derivative is a compound containing a P-OH bond and a fluorine-containing organic group. The fluorine-containing organic group is typically a fluorine-containing aliphatic group, which is a saturated or unsaturated, linear or branched fluorine-containing aliphatic group, but also includes those in which an oxygen atom, a nitrogen atom, a sulfonyl group, or an aromatic ring is interposed between the carbon-carbon bond. Examples of salts of the fluorine-containing phosphonic acid derivative include monovalent metal salts such as sodium salts, potassium salts, and lithium salts; organic amine salts such as diethanolamine salts, triethylamine salts, propylamine salts, and morpholine salts; and ammonium salts. These compounds have water and oil repellency.

Specific examples of fluorine-containing phosphate derivatives are listed below, but the invention is not limited to these.

In the present invention, the metal in the metal salt compound used as the fixing agent may be a divalent or higher metal that ionically bonds with the hydroxyl group bonded to the phosphorus atom, and typically, chromium, zirconium, titanium, aluminum, etc. are preferred. From the viewpoint of color, zirconium, titanium, aluminum, etc. are more preferred. The metal salt compound is preferably water-soluble, and examples thereof include chlorides, nitrates, sulfates, and hydroxides.

In the present invention, the textile products provided include not only fibers themselves but also threads, woven fabrics, knitted fabrics, nonwoven fabrics, and the like formed from fibers. The fibers may be natural fibers such as cotton, wool, or silk, or chemical fibers, including synthetic fibers such as acrylic, nylon, cellulose, and polyester. However, this method is particularly effective for protein fibers such as nylon and silk, and polyamide fibers. Furthermore, threads, woven fabrics, knitted fabrics, and nonwoven fabrics made from ultrafine fibers, which have seen remarkable development in recent years, are particularly suitable for this invention, as their texture and feel are important. Ultrafine fibers are typically 1 denier or less, preferably 1 to 0.0001 denier, and more preferably 0.1 to 0.001 denier.

One example of a textile product suitable for the present invention is a carpet. The carpet may be formed from yarn and then treated according to the present invention. Alternatively, the yarn may be treated according to the present invention and then formed into a carpet.

The carpets used in the present invention are not limited to any particular material, including polyamides such as nylon, polyesters, and acrylics. However, the present invention is particularly effective for nylon carpets, which are typically used under extreme conditions. Furthermore, there are no restrictions on carpet structure, weave type, pile length, etc.

In the method of the present invention, textiles are treated with the textile treatment agent described above. The order of use of the modifier and fixative is not critical, as shown below. Treatment methods using the modifier and fixative include methods (1), (2), and (5) shown below.

(i) A method of first treating with a fixative and then with a modifier will be described. The textile is immersed in a fixative solution, removed from the bath, and drained. Next, the textile is immersed in a modifier solution, and an acid solution is added to the bath to adjust the pH to 1 to 5, preferably 3 to 4. The textile is then left to stand, drained, thoroughly rinsed, drained, and dried. Alternatively, the textile can be immersed in a modifier solution, drained, then immersed in an acid solution, drained, thoroughly rinsed, drained, and dried.

(ii) The order of immersion in the fixative solution and the modifier solution may be reversed. First, the textile is immersed in the modifier solution, and then the textile is removed from the bath and drained.

Next, the textile is immersed in a fixative solution, and then an acid solution is added to the bath to adjust the pH to 1 to 5, preferably 3 to 4, and the textile is left to stand, drained, thoroughly rinsed, drained, and dried. Alternatively, the textile is immersed in a fixative solution, drained, then immersed in an acid solution, drained, thoroughly rinsed, drained, and dried.

(Shin) Furthermore, these series of treatments can be carried out in the same bath. For example, after immersing the textile in a fixative solution, a modifier is added to the bath and the textile is immersed. An acid solution is then added to adjust the pH to 1 to 5, preferably 3 to 4, and the textile is left to stand, drained, and then thoroughly rinsed with water. The textile is then drained and dried. Alternatively, the fixative solution may be added after immersion in the modifier solution.

In the above methods (D), (Il), and (V), the fixative solution is typically an aqueous solution containing 0.001 to 20 wt %, preferably 0.01 to 10 wt %, of the fixative based on the weight of the textile to be treated. The temperature of the fixative solution is typically 20 to 70°C. The modifier solution is typically an aqueous or alcoholic solution containing 0.01 to 50 wt %, preferably 0.1 to 2 wt %, of the modifier based on the weight of the textile to be treated. The temperature of the modifier solution is typically 5 to 90°C, preferably 20 to 70°C. The acid solution used for immersion or pH adjustment is a solution containing a mineral acid such as hydrochloric acid or sulfuric acid, or an organic acid such as formic acid, acetic acid, or propionic acid, preferably an aqueous solution. The concentration of the acid solution is not limited. The concentration is usually 0.05 to 30% by weight, preferably 0.1 to 5% by weight. The temperature of the acid solution is usually 5 to 90°C, preferably 20 to 70°C. The immersion time in each of the fixative solution, modifier solution, and acid solution is usually 10 seconds or more, preferably 1 to 120 minutes, and more preferably 1 to 30 minutes. The standing time in a solution adjusted to a pH of 1 to 5 is usually 10 seconds or more, preferably 1 to 30 minutes. The drying temperature is usually 10 to 70°C, preferably room temperature. The drying time varies depending on the drying conditions (especially the drying temperature), but is usually within 24 hours, preferably 0.1 to 10 hours. When using the same bath, the weight ratio of the fixative to the modifier in the bath is 0.1 + 1 to 10.1.

In the present invention, other modifiers or treatments may be used in combination, if necessary. For example, treatment with a conventional fluorine-containing water- and oil-repellent agent, softening finishes such as silicone, or resin finishes may be used in combination. A fluorine-containing stain-resistant finish may also be used in combination. It is particularly preferable to use a fluorine-containing water- and oil-repellent agent or, depending on the application, a fluorine-containing stain-resistant finish in combination.

In the present invention, other treatment agents and additives, such as a stain release (SR) agent, an antistatic agent, a flame retardant, an antibacterial agent, a shrinkage preventer, and the like, may also be used in combination.

In the present invention, the fluorine-containing water and oil repellent used in the second treatment step is typically a fluorine-containing polymer having a perfluoroalkyl group in the side chain, and a wide range of conventionally known fluorine-containing polymers can be used. For example, polymers and copolymers of the following monomers are commonly used:

is an integer from 5 to 21. Furthermore, in the present invention, the fluorine-containing stain-resistant finishing agent used in the second-stage treatment includes a polyfluoroalkyl-containing urethane compound, a polyfluoroalkyl-containing ester compound, etc. Representative examples are shown below, but the present invention is not limited to these. For example, the compounds listed as fluorine-containing water and oil repellents can also be used as fluorine-containing stain-resistant finishing agents. Silicone-based stain-resistant finishing agents can also be used instead of fluorine-containing stain-resistant finishing agents.

These fluorine-containing stain-resistant finishes may be used in combination with various co-agents, such as melamine resins, urea resins, blocked isocyanates, and glyoxal.

After the first treatment, the textile product is treated in the second stage with a fluorine-containing water- and oil-repellent agent or a fluorine-containing stain-resistant agent. The second stage treatment can be carried out by a conventional method, such as spraying, foaming, dipping, impregnation, padding, or coating, followed by drying.

In this case, a co-agent such as a melamine resin or a urea resin may be used in combination.

If necessary, further heat treatment or calendering may be carried out. In addition, a treatment agent other than the fluorine-containing compound, for example, a silicon-based compound, may also be used in combination.

The fluorine-containing water- and oil-repellent agent and fluorine-containing stain-resistant agent may be used in the form of an emulsion or a solution in an organic solvent. In the case of an emulsion, adding 0.1 to 10 wt. % of a water-soluble lower alcohol or ketone (isopropyl alcohol is particularly preferred) to the emulsion, more preferably 1 to 5 wt. %, is preferred for penetration of the fluorine-containing water- and oil-repellent agent.

The two-stage treatment can be performed on any textile product. For example, the two-stage treatment can be performed on a finished carpet. Alternatively, the two-stage treatment can be performed on the raw yarn and wool used in the carpet, and the treated raw yarn and wool can be used to make a carpet. Furthermore, the first stage of treatment can be performed on the raw yarn or wool, and the second stage of treatment can be performed on the finished carpet.

By forming a complex between a metal fixed or coordinated to a fiber bundle and a fluorine-containing phosphate derivative, the original feel, texture, color (vividness), and flexibility of the fiber are preserved, while the aforementioned properties are maintained for a long period of time and durable water and oil repellency, which are not possible with conventional textile treatments. Furthermore, since the fluorine-containing phosphate derivative penetrates into the fiber bundle and then fixes itself, the present invention avoids the drawback of only achieving water and oil repellency on the surface of a woven fabric, and can maintain its effectiveness deep into even thick fabrics. The same effect can be obtained with various forms of textile products, including fibers, yarns, woven fabrics, knitted fabrics, and nonwoven fabrics.

Furthermore, when textiles are treated with a textile treatment agent and then with a fluororesin-containing water- and oil-repellent agent, the loss of original texture and flexibility previously seen with fluororesin-containing water- and oil-repellent treatment alone is dramatically improved. Even when the fluororesin-containing water- and oil-repellent agent is used in combination with other agents such as melamine resin or blocked isocyanate, the texture remains unchanged from that of untreated textiles, a completely unexpected effect. Furthermore, the durability of the water- and oil-repellent agent is further enhanced.

Because the textile products of the present invention have the above-mentioned excellent characteristics, they can be used in applications where water- and oil-repellent properties and stain resistance are particularly important, such as applications exposed to outdoor rainwater. Examples of applications exposed to outdoor wind and rain include tent covers, automobile covers, motorcycle covers, truck bed covers, construction covering sheets, umbrellas, and clothing [especially rainwear (e.g., raincoats, jackets, etc.)]. Furthermore, they can be used in hats, footwear (e.g., shoes, slippers, bags, pouches), textile products used as coverings for seats (e.g., car seats, seats, sofas), curtains, rugs, interior walls and ceilings of buildings and vehicles (e.g., automobiles, trains, airplanes, ships, etc.), and various displays. Among the above applications, they are preferably used for textile products that are difficult to clean, easily soiled, or cannot be washed multiple times.

PREFERRED EMBODIMENTS OF THE INVENTION The present invention will be described in detail below with reference to the following examples and comparative examples. In the following examples, percentages are by weight unless otherwise specified.

The water repellency shown in Examples 1-18 and Comparative Examples 1-10 was measured in accordance with JIS-L-1092-1977 and is expressed as a number as shown in Table 1. The water repellency shown in Examples 19-23 and Comparative Examples 11-14 was measured by gently placing a small droplet of an isopropyl alcohol/water mixture of the composition shown in Table 2 on the sample surface. The maximum isopropyl alcohol content among the droplets that retained their shape after 3 minutes was expressed as the water repellency. Oil repellency was measured according to AATTC™-118-1975. Oils with different surface tensions shown in Table 3 were dropped onto the sample. The highest number of the oil that showed no penetration after 30 seconds was used as the oil repellency index.

Washing durability was measured according to J15-L-0217-103 and shown as water and oil repellency before and after 20 washes.

The water repellency was measured using hot water at 75°C in accordance with JI 5-L-1092-1977 and expressed in the same manner as for the water repellency.

In addition, a cross next to the water repellency and water drainage properties indicates that the performance is slightly better, and a - indicates that the performance is slightly worse.

To evaluate the stain resistance of the DryFill, the sample was soiled 50 times with DryFill of the composition shown in Table 4 in accordance with J 15-L-1021-1979. Afterwards, excess soiling was removed from the sample with a vacuum cleaner, and the brightness of the sample surface was measured with a colorimeter. The soiling rate was calculated using the following formula to evaluate the stain resistance of the DryFill.

Contamination rate (%) - [(Lo - L)/Lo] x 100 (where Lo represents the brightness of the sample before contamination, and L represents the brightness of the sample after contamination). Friction durability was evaluated by rubbing the sample 3,000 times under a 5.00 g (m) weight using the Gakushin friction tester described in J15-L-0823-1971, and examining the water and oil repellency of the rubbed area.

The texture was judged by touch according to the criteria in Table 5.

Example 1 Each textile sample (6-nylon taffeta, silk habutae, and acrylic muslin, size: 20 cm square) was immersed in a 0.1% aqueous solution of chromium sulfate (trade name: Bayer Biochrome F) (bath ratio: 50:1) at 40°C for 10 minutes. After draining, the sample was immersed in a 0.125% aqueous solution of Compound 11 (a fluorine-containing phosphoric acid derivative) shown in Table 6 (bath ratio: 40:1) at 40°C for 10 minutes. The bath was adjusted to pH 3 by adding 0.1% formic acid, and the sample was left for 10 minutes. The sample was then drained, washed with water at 40°C, and dried at room temperature. The feel, texture, and flexibility of each textile sample were compared before and after treatment, and all were found to be equivalent. These properties were unchanged before and after washing. Furthermore, the water and oil repellency of each textile sample were measured before and after washing. The results are shown in Table 7.

Example 2 The same procedure as in Example 1 was repeated, except that a 0.61% aqueous solution of zirconium sulfate (trade name: Blanccolor ZB33, manufactured by Bayer) was used instead of the aqueous solution of chromium sulfate. The results are shown in Table 7.

Example 3 The same procedure as in Example 1 was repeated, except that a 0.1% aqueous solution of aluminum chloride (product name: Niltan FS, manufactured by BASF) was used instead of the aqueous solution of chromium sulfate. The results are shown in Table 7.

Example 4 The same procedure as in Example 1 was repeated, except that compound 12 shown in Table 6 was used as the fluorine-containing phosphate derivative. The results are shown in Table 7.

Example 5 The same procedure as in Example 2 was repeated, except that compound 12 shown in Table 6 was used as the fluorine-containing phosphate derivative. The results are shown in Table 7.

Example 6 The same procedure as in Example 3 was repeated, except that compound 12 shown in Table 6 was used as the fluorine-containing phosphate derivative. The results are shown in Table 7.

Example 7 The same procedure as in Example 1 was carried out, except that the order of the chromium sulfate aqueous solution treatment and the fluorine-containing phosphate derivative aqueous solution treatment was reversed. The results are shown in Table 7.

Example 8 The same procedure as in Example 2 was carried out, except that the order of the zirconium sulfate aqueous solution treatment and the fluorine-containing phosphate derivative aqueous solution treatment was reversed. The results are shown in Table 7.

Example 9 The same procedure as in Example 3 was carried out, except that the order of the aluminum chloride aqueous solution treatment and the fluorine-containing phosphate derivative aqueous solution treatment was reversed. The results are shown in Table 7.

Example 10 The same procedure as in Example 4 was carried out, except that the order of the chromium sulfate aqueous solution treatment and the fluorine-containing phosphate derivative aqueous solution treatment was reversed. The results are shown in Table 7.

Example 11 The same procedure as in Example 5 was carried out, except that the order of the zirconium sulfate aqueous solution treatment and the fluorine-containing phosphate derivative aqueous solution treatment was reversed. The results are shown in Table 7.

Example 12 The same procedure as in Example 6 was carried out, except that the order of the aluminum chloride aqueous solution treatment and the fluorine-containing phosphate derivative aqueous solution treatment was reversed. The results are shown in Table 7.

Comparative Example 1: The same procedure as in Example 1 was repeated except that the chromium sulfate aqueous solution was not used. The results are shown in Table 7.

Comparative Example 2: A textile sample similar to that used in Example 1 was treated with TG-230 (a polymeric fluorine-containing compound manufactured by Daikin Industries, Ltd.) at 25°C for 10 minutes at a solids concentration of 0.125% (bath ratio of 40:1). It was then dried at 80°C for 3 minutes and cured at 130°C for 3 minutes.

The water and oil repellency of each textile sample was measured before and after washing. The results are shown in Table 7.

Comparative Example 3 Textile samples similar to those used in Example 1 were treated with Scotchgard 2 33A (a fluorine-containing chromium carboxylate complex salt manufactured by 3M) at 25°C for 10 minutes at a solids concentration of 0.125% (bath ratio of 40:1). The samples were then dried at 80°C for 3 minutes and cured at 130°C for 3 minutes. The water and oil repellency of each textile sample was measured before and after washing. The results are shown in Table 7.

Comparative Example 4 The same procedure as in Comparative Example 3 was carried out, except that the solids concentration was 1.5%. The results are shown in Table 7.

In all of the above Comparative Examples 1 to 4, the feel, texture, and softness of the fibers were inferior to those before treatment. These properties were not improved by washing.

Test Example 1 The color difference ΔEab of the unwashed nylon 6 taffeta samples of Examples 1 to 6 and Comparative Examples 3 and 4 was measured using a color difference meter R-200 (Minolta) with untreated nylon 6 taffeta as a control. The results are shown in Table 8.

Example 13 First-Step Treatment Each textile sample (polyester tropical for dyeing tests, nylon taffeta for dyeing tests) was immersed in a 0.5% aqueous solution of chromium sulfate (product name: Bayer Biochrome F) (bath ratio: 10:1) at 30°C and tumbled for 30 minutes using a dyeing tester (Tsujii Senki Kogyo Co., Ltd.). After draining, the sample was immersed in a 0.5% aqueous solution of Compound 21 (fluorine-containing phosphoric acid derivative) shown in Table 9 (bath ratio: 10:1) at 50°C and tumbled for 30 minutes. The bath was adjusted to pH 3 by adding 0.3% formic acid, and the sample was tumbled for 30 minutes, drained, washed with water at 40°C, and then dried at room temperature.

Second-stage treatment (Method A): Fluorine-containing water and oil repellents Texcard TG-5431 and TG-5120 (Daikin Industries, Ltd.) and Asahiguard LS-317 (Asahi Glass Co., Ltd.) were diluted with tap water to a solids concentration of 1%, and 3% isopropyl alcohol was added to prepare a treatment solution. Test cloths that had undergone the first-stage treatment were immersed in this solution and squeezed with a mangle to make a wet pickup of 40% polyester cloth and 25% nylon cloth. The cloths were then dried at 110°C for 3 minutes and then heat-treated at 160°C for 1 minute.

The water repellency, oil repellency, and texture of each textile sample were measured before and after washing. The results are shown in Table 10. The initial weathering properties were also measured. The results are shown in Table 11.

Example 14 First-stage treatment The same procedure as in Example 13 was repeated.

Second-Stage Treatment (Method B) The same procedure as in Example 13 was repeated, except that 2% Elastron BN-69 (a blocked isocyanate manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd.) and 2% Elastron Catalyst (a catalyst manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd.) were also used in the treatment bath.

The same evaluation as in Example 13 was carried out, and the results are shown in Tables 10 and 11.

Example 15 First Stage Treatment The same procedure as in Example 13 was repeated.

Second-Stage Treatment (Method C) The same procedure as in Example 13 was repeated, except that 0.3% Sumitex Resin M-3 (a methylol melamine from Sumitomo Chemical Co., Ltd.) and 0.3% Sumitex Accelerator (a catalyst from Sumitomo Chemical Co., Ltd.) were used in the treatment bath.

The evaluation was carried out in the same manner as in Example 13. The results are shown in Tables 10 and 11.

Comparative Example 5 Second-stage Treatment (Method A) Only The same textile product samples as those used in Example 13 were subjected to only the same second-stage treatment (Method A) as in Example 13. Evaluations were performed in the same manner as in Example 13. The results are shown in Tables 10 and 11.

Comparative Example 6 Second-Stage Treatment (Method B) Only The same textile product samples as those used in Example 13 were subjected to only the same second-stage treatment (Method B) as in Example 14. Evaluations were performed in the same manner as in Example 13.

The results are shown in Tables 10 and 11.

Comparative Example 7 Second-Stage Treatment (Method C) Only The same textile product samples as those used in Example 13 were subjected to only the same second-stage treatment (Method C) as in Example 15. Evaluations were performed in the same manner as in Example 13.

The results are shown in Tables 10 and 11.

Example 16 First-Stage Treatment The same procedure as in Example 13 was repeated, except that each textile product sample (Ecsaine (Toshiko Co., Ltd.), a suede-like artificial leather) and Sofri Nanyar (Kuraray Co., Ltd., a nubuck-like artificial leather) were used.

Second-Stage Treatment (Method A): Texguard TG-5431 (Daikin Industries, Ltd.), a fluorine-containing water and oil repellent, was diluted with tap water to a solids concentration of 1%, and 3% isopropyl alcohol was added to create a treatment solution. The test fabrics that had been treated in the first stage were immersed in this solution and squeezed with a mangle to achieve a wet pickup of 50% for both Ecsaine and Sofinacial. The fabrics were then dried at 110°C for 3 minutes and then heat-treated at 160°C for 1 minute.

The water repellency, oil repellency, and texture of each textile sample were measured before and after washing. The results are shown in Table 12.

Example 17 First-Stage Treatment The same procedure as in Example 12 for the first-stage treatment was repeated, except that the same textile samples as used in Example 16 were used.

Second-Stage Treatment (Method B) The same procedure as in Example 16 was repeated, except that 2% Elastron BN-69 (a blocked isocyanate manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd.) and 0.2% Elastron Catalyst (a catalyst manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd.) were also used in the treatment bath.

The water repellency, oil repellency, and texture of each textile sample were measured before and after washing. The results are shown in Table 12.

Example 18 First-stage treatment The same procedure as in Example 16 was repeated.

Second-Stage Treatment (Method C) The same procedure as in Example 16 was repeated, except that 0.3% Sumitex Resin M-3 (Sumitomo Chemical Co., Ltd., methylol melamine) and 0.3% Sumitex Accelerator (Sumitomo Chemical Co., Ltd., Ii! Catalyst) were also used in the treatment bath.

The water repellency, oil repellency, and texture of each textile sample were measured before and after washing. The results are shown in Table 12.

Comparative Example 8 Second-Stage Treatment (Method A) Only The same textile samples as those used in Example 16 were subjected to only the second-stage treatment (Method A) of Example 16. The water repellency, oil repellency, and texture of each textile sample were measured before and after washing. The results are shown in Table 12.

Comparative Example 9 Second-Stage Treatment (Method B) Only The same textile samples as used in Example 16 were subjected to only the second-stage treatment (Method B) of Example 17. The water repellency, oil repellency, and texture of each textile sample were measured before and after washing. The results are shown in Table 12.

Comparative Example 10 Second-Stage Treatment (Method C) Only The same textile samples as used in Example 16 were subjected to only the same second-stage treatment (Method C) as in Example 18. The water repellency, oil repellency, and texture of each textile sample were measured before and after washing. The results are shown in Table 12.

Table 9 Compound 21 j/ Tritylamine salt H of CF3CF2(CF2CF2)nC)12CE120-P [Mixture where n is 3, 4, 5, 6 (respective ratios are 5, 3, 21)] Example 19 A nylon loop pile carpet sample was immersed in a 0.5% aqueous solution of chromium sulfate (product name: Bayer AG) (bath ratio 10:1) at 30°C and tumbled for 30 minutes using a dyeing tester (Tsujii Senki Kogyo Co., Ltd.). After draining, it was immersed in a 0.5% aqueous solution of 5000 of Compound 21 (a fluorine-containing phosphoric acid derivative) shown in Table 9 (bath ratio 10:1) and tumbled for 30 minutes. The bath was adjusted to pH 3 by adding 0.3% formic acid, tumbled for 30 minutes, drained, washed with water at 40°C, and then dried at room temperature.

The treated samples were evaluated for dry-fill stain resistance, texture before and after rubbing, water repellency, and oil repellency. The results are shown in Table 13.

Example 20 Fluorine-containing water and oil repellent TG-950 (Daikin Industries, Ltd., solids concentration 30%) was diluted 10-fold with tap water and spray-applied to the carpet sample treated in Example 19 to a treatment amount of 75 g/m², then dried at 130°C for 3 minutes. Evaluations were performed in the same manner as in Example 19. The results are shown in Table 13.

Example 21 A fluorine-containing water and oil repellent agent TG-950 (manufactured by Daikin Industries, Ltd., solids concentration 30%) was diluted 10-fold with tap water, and the diluted solution was sprayed onto the carpet sample treated in Example 19 to a treatment amount of 75 g/m², followed by drying at 130°C for 3 minutes. Evaluations were performed in the same manner as in Example 19. The results are shown in Table 13.

Example 22: A solution of fluorine-containing water- and oil-repellent AG-800 (Asahi Glass Co., Ltd., solids concentration 30%) diluted 10-fold with tap water was sprayed onto the carpet sample treated in Example 19 to a treatment amount of 75 g/m², and the sample was dried at 130°C for 3 minutes.

Evaluation was carried out in the same manner as in Example 19. The results are shown in Table 13.

Example 23 A solution of the silicone stain-resistant agent Byguard AS (Bayer, 6% solids concentration) diluted 10 times with tap water was sprayed onto the carpet sample treated in Example 19 to a treatment amount of 75 g/m², and then dried at 130°C for 3 minutes.

Evaluation was carried out in the same manner as in Example 19. The results are shown in Table 13.

Comparative Example 11 A 10-fold diluted solution of TG-950 was sprayed onto the same nylon loop (Dolphin Pet) sample as used in Example 19 to a treatment amount of 75 g/m², and then dried at 130°C for 3 minutes. Evaluation was performed in the same manner as in Example 19. The results are shown in Table 13.

Comparative Example 12 A 10-fold diluted solution of TG-951 was sprayed onto a nylon loop pile carpet sample similar to that used in Example 19 to a treatment amount of 75 g/m², and the sample was dried at 130°C for 3 minutes. Evaluations were carried out in the same manner as in Example 19. The results are shown in Table 13.

Comparative Example 13 A 10-fold diluted solution of AG-800 was spray-coated onto a nylon loop nylon carbide sample similar to that used in Example 19 to a treatment amount of 75 g/ml, and the sample was dried at 130°C for 3 minutes. Evaluation was performed in the same manner as in Example 19. The results are shown in Table 13.

Comparative Example 14 A 10-fold diluted solution of Viguard AS was sprayed onto a nylon Lubebyl Carbe throat sample similar to that used in Example 19 to a treatment amount of 75 g/m², and then dried at 130°C for 3 minutes. Evaluation was performed in the same manner as in Example 19. The results are shown in Table 13.

Reference Example 1 (Test Fabric Preparation Example) Wool muslin for dyeing tests was immersed in a 25°C hydrochloric acid solution (3000% water, 6% 35% concentrated hydrochloric acid relative to the sample) and tumbled for 10 minutes using a dyeing tester (Tsujii Senki Kogyo Co., Ltd.). After tumbled for an additional 30 minutes, a sodium hypochlorite solution was added to the sample to achieve a 1% active chlorine concentration. After cooling, a 25°C sodium carbonate solution (3000% water, 4% sodium carbonate relative to the sample) was added and the muslin was immersed. Sodium sulfite was added to the sample to achieve a 4% active chlorine concentration, and the muslin was tumbled for 10 minutes. After cooling and rinsing, the muslin was air-dried to obtain a descaled wool test fabric.

Example 24 Each textile sample (descaled wool test cloth obtained in Reference Example 1, nylon 6 for dyeing test) was immersed in a 5% aqueous solution of chromium sulfate (trade name: Bayer Bichrome F) (bath ratio: 10:1) at 30°C and tumbled for 30 minutes using a dyeing tester (Tsujii Senki Kogyo Co., Ltd.). After draining, the sample was immersed in a 0.5% aqueous solution of Compound 31 (fluorine-containing phosphoric acid derivative) shown in Table 14 (bath ratio: 10:1) at 50°C and tumbled for 30 minutes. A 0.3% aqueous solution of formic acid was added to the bath to adjust the pH to 3, and the sample was tumbled for 30 minutes, drained, washed with water at 40°C, and then dried at room temperature.

The water repellency, oil repellency, and handle of each textile sample were measured before and after washing. The results are shown in Table 15.

Example 25 First Stage Treatment The same procedure as in Example 24 was repeated.

Second-stage treatment (Method A): Texcard TG-5431 (Daikin Industries, Ltd.), a fluorine-containing water and oil repellent, was diluted with tap water to a solids concentration of 1%, and 3% isopropyl alcohol was added to create a treatment solution. The test cloths that had been treated in the first stage were immersed in this solution and squeezed with a mangle to make a wet-pickup wool cloth solution of 65% and nylon cloth solution of 25%. The cloths were then dried at 110°C for 3 minutes and then heat-treated at 160°C for 1 minute.

The same evaluation as in Example 24 was carried out, and the results are shown in Table 15.

Example 26 First Stage Treatment The same procedure as in Example 24 was repeated.

Second-Stage Treatment (Method B) The same procedure as in Example 25 was repeated, except that 2% Elastron BN-69 (Dai-ichi Kogyo Seiyaku Co., Ltd., pro-tacky isocyanate) and 0.2% Elastron Catalyst (Dai-ichi Kogyo Seiyaku Co., Ltd., catalyst) were used in the treatment bath.

The same evaluation as in Example 24 was carried out, and the results are shown in Table 15.

Example 27 First Stage Treatment The same procedure as in Example 24 was repeated.

Second-Stage Treatment (Method C) The same procedure as in Example 25 was repeated, except that 0.3% Sumitex Resin M-3 (methylol melamine, manufactured by Sumitomo Chemical Co., Ltd.) and 0.3% Sumitex Accelerator (catalyst, manufactured by Sumitomo Chemical Co., Ltd.) were also used in the treatment bath.

The same evaluation as in Example 24 was carried out, and the results are shown in Table 15.

Example 28 The same procedure as in Example 24 was repeated, except that compound 32 shown in Table 14 was used as the fluorine-containing phosphate derivative. The results are shown in Table 15.

Example 29 The same procedure as in Example 25 was repeated, except that compound 32 was used as the fluorine-containing phosphate derivative. The results are shown in Table 15.

Example 30 The same procedure as in Example 26 was repeated, except that compound 32 was used as the fluorine-containing phosphate derivative. The results are shown in Table 15.

Example 31 The same procedure as in Example 27 was repeated, except that compound 32 was used as the fluorine-containing phosphate derivative. The results are shown in Table 15.

Comparative Example 15 Second-stage Treatment (Method A) Only The same textile product samples as those used in Example 24 were subjected to only the same second-stage treatment (Method A) as in Example 25, and the same evaluations were performed as in Example 24. The results are shown in Table 15.

Comparative Example 16 Second-stage Treatment (Method B) Only The same textile product samples as those used in Example 24 were subjected to only the same second-stage treatment (Method B) as in Example 26, and the same evaluations were performed as in Example 24. The results are shown in Table 15.

Comparative Example 17 Second-Stage Treatment (Method C) Only The same textile product samples as those used in Example 24 were subjected to only the same second-stage treatment (Method C) as in Example 27, and the same evaluations as in Example 24 were conducted. Effect of the Invention The present invention allows textile products to retain their original feel, texture, color, and flexibility even after treatment, and maintains these properties even after long-term use, including washing and friction. It also provides durable water and oil repellency and stain resistance.

Claims (16)

[Claims] 1. General Formula: ▲Mathematical formula, chemical formula, table, etc.▼ (I) [wherein Rl and R2 are the same or different and are a hydrogen atom or Rf-(CH2)m- (where Rf is a saturated or unsaturated, linear or branched, fluorinated aliphatic group having 4 to 20 carbon atoms, which may have an oxygen atom, nitrogen atom, sulfonyl group, or aromatic ring interposed between the carbon-carbon bonds; m is 1 or 2) (provided that Rl and R2 are not both hydrogen atoms), A is an oxygen atom, sulfur atom, or direct bond, and n is 1 or 2.] A textile treatment agent is represented by the formula: [wherein Rl and R2 are the same or different and are a hydrogen atom or Rf-(CH2)m- (wherein Rf is a saturated or unsaturated, linear or branched, fluorinated aliphatic group having 4 to 20 carbon atoms, which may have an oxygen atom, nitrogen atom, sulfonyl group, or aromatic ring interposed between the carbon-carbon bonds; m is 1 or 2) (provided that Rl and R2 are not both hydrogen atoms), A is an oxygen atom, sulfur atom, or direct bond, and n is 1 or 2.] The textile treatment agent is represented by the formula: [wherein Rl and R2 are the same or different and are a hydrogen atom, 2. The textile treatment of claim 1, wherein the metal salt compound is selected from the group consisting of chlorides, nitrates, sulfates, and hydroxides of Cr, Zr, Ti, and Al. 3. A method for treating textile products with the textile product treating agent according to claim 1. 4. The method of claim 3, wherein the textile is treated with the fixative and then with the modifier. 5. The method of claim 3, wherein the textile is treated with a fixative after being treated with a modifier. 6. A textile product treated by the method of claim 3. 7. Protein fiber products and polyamide fiber products treated by the method of claim 3. 8. A method for treating textile products comprising a two-stage treatment comprising treating the textile product with the textile product treating agent according to claim 1 and then treating the textile product with a fluorine-containing water-repellent oil agent. 9. A method of treating the surface by the method of claim 4 or 5, and then further treating the surface with a fluorine-containing water- and oil-repellent agent. 10. A textile product treated by the method of claim 8 or 9. 11. A method of treating carpet with the textile treatment of claim 1. 12. A method for treating carpets comprising a two-stage treatment comprising treating the carpets by the method of claim 11 and then further treating the carpets with a fluorine-containing stain-resistant agent. 13. A carpet treated by the method of claim 11 or 12. 14. A method for producing carpets using yarn treated by the method of claim 3 or claim 8. 15. A durable stain resistant carpet made by the method of claim 14. 16. The textile product according to claim 6 or 10, which is used for umbrellas, clothing, footwear, bags, pouches, textile products for seats, and interior fittings for buildings and vehicles.