JPH08296175A - Treatment of synthetic fiber product and its treated product - Google Patents

Abstract

PURPOSE: To obtain a product having water-repellent performance in a wet state even by repeatedly washing. CONSTITUTION: This treated material of a synthetic fiber product is obtained by providing a fiber product comprising a synthetic fiber with a treating solution composed of a perfluoroalkyl group-containing acrylic copolymer, an aminoplast resin, a polyfunctional block isocyanate group-containing urethane resin and ethylene carbonate in one bath and heat-treating the product. The treating solution comprising 0.01-10 pts.wt. of the perfluoroalkyl group-containing acrylic copolymer, 0.01-2 pts.wt. of the aminoplast resin, 0.01-4 pts.wt. of the polyfunctional block isocyanate group-containing urethane resin and 0.1-30 pts.wt. of the ethylene carbonate based on 100 pts.wt. of the synthetic fiber product is preferably used. Especially the product is preferably used as a cloth for clothing for outdoor sports.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a method for treating a synthetic fiber product and a method for treating a synthetic fiber product, which imparts water repellency excellent in abrasion resistance to a fiber product containing synthetic fibers (hereinafter referred to simply as synthetic fiber product). The obtained synthetic fiber product is related. More specifically, a water-repellent treatment method and a synthetic fiber having such a water-repellent property, which can impart a water-repellent property which is resistant to abrasion not only in a dry state but also in a wet state, and which is not deteriorated by washing, to the textile product. Regarding the product.

[0002]

2. Description of the Related Art Conventionally, as a means for imparting water-repellent performance to synthetic fiber products, a water-repellent agent containing a perfluoroalkyl group-containing acrylic copolymer as a main component (hereinafter simply referred to as a fluorine-based water-repellent agent) has been used. Water treatment was being done. However, fabrics that have been treated only with a fluorine-based water repellent are fir, thread,
There is a drawback that the water-repellent performance deteriorates due to abrasion such as me,
Especially, it is significantly reduced by washing.

In order to solve this problem, a method of treating in the presence of a fluorine-based water repellent, trimethylolmelamine and an organic amine; JP-A-54-133486 and JP-A-56-165072, Kaihei 5-27206
No. 0, etc., a method of treating in the presence of a fluorine-based water repellent and a polyfunctional blocked isocyanate urethane compound; a fluorine-based water repellent, an aminoplast resin, and a polyhydric agent described in JP-A-58-208473. A method of treating in the presence of a functionally blocked isocyanate urethane compound; Although the abrasion resistance of water repellency in a dry state is maintained by these methods even after washing, it cannot be said to be sufficient in a wet state. Therefore, a two-step processing method is employed in which after the water repellent treatment, the treatment is performed using a solvent-based fluorine or polysiloxane water repellent. However, the two-step processing has a large processing and time loss,
Depending on the type of solvent, there are problems in environmental aspects such as ozone destruction, and in safety aspects such as danger of ignition.

[0004]

In view of the above problems, the present invention provides a textile product with a water repellency which is excellent not only in the dry state but also in the wet state and has excellent wear durability, and which is not lost by washing. An object of the present invention is to provide a water-repellent treatment method that can be easily imparted, and a water-repellent fiber product that maintains the water-repellent performance with excellent abrasion durability even in a wet state even after washing.

[0005]

In order to solve the above-mentioned problems, the present invention provides 0.01 to 10 parts by weight of a perfluoroalkyl group-containing acrylic copolymer to 100 parts by weight of a fiber product containing synthetic fibers. And aminoplast resin to 0.
A treatment liquid containing 01 to 2 parts by weight, 0.01 to 4 parts by weight of a urethane resin containing a polyfunctional blocked isocyanate group, and 0.1 to 30 parts by weight of ethylene carbonate in one bath is applied to the textile product. The present invention provides a method for treating a synthetic fiber product, which is characterized by comprising heat treatment.

Further, according to the present invention, after a treatment liquid containing a perfluoroalkyl group-containing acrylic copolymer, an aminoplast resin, a polyfunctional blocked isocyanate group-containing urethane resin and ethylene carbonate is applied, it is heat treated. A characteristic synthetic fiber product is provided.

[0007]

[Operation and Example of Embodiment] When a textile product is treated with a fluorine-based water repellent, a water-repellent film is formed on the fiber in nanometer units. Most of the basic components of this water-repellent film remain without falling off from the fibers after several washings. However, when the film is cracked or cracked due to abrasion such as fir, thread, or oleum, moisture penetrates, and at the same time, the uniform molecular arrangement of the perfluoroalkyl groups forming the water-repellent film is disordered by tilting or collapse on the fiber. It is considered that the water repellency is deteriorated. This means that the content of perfluoroalkyl groups after washing hardly decreases compared to that before washing, and due to heat treatment such as abrasion or ironing after washing, the perfluoroalkyl groups on the fiber have the same uniform molecular arrangement as the original. It is also supported by the fact that the water repellent performance may be restored to a state close to. The present inventor, as a result of examining various compounds for the purpose of making the water-repellent coating stronger, as a result, using a perfluoroalkyl group-containing acrylic copolymer, an aminoplast resin, and a polyfunctional blocked isocyanate urethane resin, further ethylene carbonate It has been found that the combined use of the above is effective and the present invention has been achieved.

In the method for treating synthetic fiber products of the present invention, ethylene carbonate is adhered to fibers together with a fluorine-based water repellent, an aminoplast resin and a urethane resin containing a polyfunctional blocked isocyanate group, and heat treated.
By using ethylene carbonate together, the strength of the water-repellent coating is improved, and by extension, the abrasion resistance of the water-repellent performance when wet is improved. Simply adding an aminoplast resin and / or a polyfunctional blocked isocyanate-containing urethane resin to a fluorine-based water repellent agent provides water-repellent washing durability but insufficient abrasion durability, making it a practical film. You cannot get enough strength. Ethylene carbonate is a highly polar organic solvent, which undergoes ring-opening addition reaction and ring-opening condensation reaction for many compounds having active hydrogen.
The surface of the synthetic fiber is melted. This solubilization performance is not limited to fluorine-based water repellents, aminoplast resins and polyfunctional blocked isocyanate-containing urethane resins, and /
Alternatively, it is considered that these are incorporated into the surface of the synthetic fiber as a crosslinked product to further strengthen the backbone portion and the skeleton portion connecting the perfluoroalkyl groups to improve the strength of the water-repellent film. That is, by adding ethylene carbonate to the synthetic fiber, the surface of the synthetic fiber is soluble, the fluorine-based water repellent, aminoplast resin,
Further, it is considered that a stronger film is formed by reactive crosslinking with the polyfunctional blocked isocyanate group. Also, ethylene carbonate is commercially available,
It has a high melting point, is stable, and has no toxicity, so it is easy to use. The amount of ethylene carbonate used is 0.1 to 30 parts by weight, preferably 2 to 10 parts by weight, based on 100 parts by weight of the synthetic fiber product to be treated. If the amount of ethylene carbonate is too much, the synthetic fibers will be dissolved much, and the fiber product will become hard, which is not suitable for practical use. On the other hand, if the amount is too small, sufficient water repellency and abrasion resistance cannot be obtained.

The fluorine-based water repellent used in the method for treating a synthetic fiber product of the present invention is not particularly limited, but for example, C ₃
To C ₂₀ by homopolymerization of only a vinyl monomer having a perfluoroalkenyl group or perfluoroalkyl group, and the vinyl monomer and another vinyl monomer having no perfluoroalkenyl group or perfluoroalkyl group. The thing manufactured by copolymerization is mentioned. Examples of the vinyl monomer having a perfluoroalkenyl group or a perfluoroalkyl group include CH ₂ ═CHCOOCH ₂ C ₇ F ₁₅ CH ₂ ═C (CH ₃ ) COOCH ₂ C ₆ F ₁₂ CF ₃ (C
_{F 3) CH 2 = CHCOO (} CH 2) 2 N (C 3 H 7) SO 2
C ₈ F ₁₇ C ₆ F ₁₃ CH ₂ CH ₂ OH C ₈ F ₁₇ SO ₂ (C ₃ H ₇ ) CH ₂ CH ₂ OH C ₈ F ₁₇ SO ₂ (C ₃ H ₇ ) CH ₂ OOCNH (C
H _2), such as _{6 NH (CH 2 CH 2 O} ) 11 CH 3 can be used.

Examples of the other vinyl monomer having no perfluoroalkenyl group or perfluoroalkyl group are ethylene, vinyl chloride, vinylidene chloride, acrylamide, styrene, benzyl acrylate, vinyl alkyl ketone, maleic anhydride, isoprene and siloxane. And vinyl monomers of blocked isocyanate. Among them, a fluorine-based water repellent having a copolymer containing a vinyl monomer of blocked isocyanate as a main component is preferable. As the fluorine-based water repellent used, a perfluoroalkyl group-containing acrylic copolymer is 0.01 to 10% owf, particularly 0.03 to 5% owf, based on the synthetic fiber cloth.
Preferably, it is included.

Examples of the aminoplast resin include melamine resins such as trimethylol melamine and hexamethylol melamine; urea resins such as dimethylol propylene urea, dimethylol ethylene urea and dimethylol hydroxyurea; uron resins such as dimerol urone. Can be used. Among them, hexamethylolmelamine is preferable. The amount of the aminoplast resin is preferably 0.01 to 2 parts by weight, and more preferably 0.02 to 1 part by weight in terms of solid content, based on 100 parts by weight of the synthetic fiber product.

Further, a commonly used curing catalyst may be used together with the aminoplast resin. The curing catalyst is, for example, ammonium of an inorganic acid such as phosphoric acid, sulfuric acid or nitric acid,
Examples thereof include salts such as aluminum and zinc; salts of organic acids such as formic acid, acetic acid, acrylic acid and succinic acid.

The polyfunctional blocked isocyanate urethane resin is not particularly limited as long as it is an organic compound containing two or more blocked isocyanate functional groups in the molecule. Specific examples include tolylene diisocyanate, hexamethylene diisocyanate, diphenyl methane diisocyanate, hydrogenated diphenyl methane diisocyanate, triphenyl triisocyanate, xylidine isocyanate, dicyclohexyl methane diisocyanate, trimethylolpropane tolylene diisocyanate adduct, glyceryl tolylene diisocyanate. Phenol, malonic acid diethyl ester, methyl ethyl ketoxime, sodium bisulfite, ε-as a blocking compound capable of regenerating an active isocyanate group by dissociating into an adduct upon heating at 70 to 200 ° C.
A polyfunctional blocked isocyanate urethane resin obtained by reacting caprolactam or the like can be given. The polyfunctional blocked isocyanate urethane resin is preferably used as a water-dispersed liquid in which a small amount of a surfactant is mixed and forcibly emulsified. Among the above, an aqueous dispersion liquid of methylethylketoxime of diphenylmethane diisocyanate and methylethylketoxime of trimethylolpropane tolylene diisocyanate adduct is preferable. The amount of the polyfunctional blocked isocyanate urethane resin is preferably 0.01 to 4 parts by weight in terms of solid content based on 100 parts by weight of the synthetic fiber product, and the amount of the fluorinated water repellent used is a perfluoroalkyl group-containing acrylic resin. The amount of the copolymer is 0.01 to 10, preferably 0.03 to 1 part by weight based on the synthetic fiber cloth. Further, as the dissociation catalyst used for promoting the improvement of the thermal separation rate of the blocked isocyanate and the reduction of the thermal dissociation temperature, for example, dibutyltin dioleate, dibutyltin stearate, stearyl zinc, and an organic amine compound are preferable.

The method for treating synthetic fiber products according to the present invention is
It can be applied to textile products containing synthetic fibers. Examples of synthetic fibers include polyester fibers, polyamide fibers, polyurethane fibers, polyvinyl alcohol fibers,
Examples thereof include polyacrylonitrile fiber and polyvinyl chloride fiber. Synthetic fiber products may contain other fibers as long as they contain at least 50% synthetic fibers, for example polyester / cotton, polyester / rayon, polyester / hemp, polyamide / cotton, polyamide / rayon, polyurethane. It can be applied to synthetic fiber products consisting of mixed fibers of cotton / cotton.

The ethylene carbonate, the perfluoroalkyl group-containing acrylic copolymer, the aminoplast resin, and the polyfunctional blocked isocyanate group-containing urethane resin are diluted with water to prepare a one-bath treatment solution. This one-bath treatment liquid is uniformly applied to the synthetic fiber product by a pad method, a coating method, a spray method, etc.
After drying at around ℃, heat treatment as soon as possible.
The heat treatment is preferably performed at 140 to 180 ° C. for 5 to 10 minutes.

Further, in order to impart other performances to the synthetic fiber product according to the present invention, generally used treating agents such as polyamine type and guanidine type antistatic agents, amino and hydrogen polysiloxane type silicone softeners, Polyester, fluorine-based antifouling agent, ultraviolet absorber, heat stabilizer, ceramic, antibacterial agent, deodorant, and dye may be used in combination for treatment.

[0017]

EXAMPLES The present invention will be described in more detail by way of examples. In the examples and comparative examples, the water repellency performance was evaluated by the following method. (1) 10 times washing method Automatic reversal spiral electric washing machine (manufactured by Toshiba Corporation; VH-1)
(With the same performance as 150), 45 x 45 cm test cloth 8
00g and 40 ± 2 ℃ 0.2% slightly alkaline synthetic detergent (JIS K 3371 slightly alkaline, type 1) liquid 25
Then, it was washed under strong conditions for 25 minutes. Then, after dehydration for about 30 seconds with a centrifugal dehydrator, rinsing was performed for 10 minutes while allowing room temperature water to overflow. Then, it was dehydrated again for about 30 seconds and rinsed for 10 minutes under the same conditions. The above method was repeated twice, resulting in 10 washes. After washing 10 times,
After being dried, the water repellency was measured by JIS L-1092 rain test (shower method).

(2) Wet abrasion method Abrasion table (manufactured by Custom Co .; Appearance Ret)
Ention Tester (hereinafter referred to as ART),
A test cloth with a diameter of 17.5 cm is set, and a test cloth with a diameter of 10 cm (Kanakin 3 for dyeing fastness test is stacked on it.
No.) was immersed in distilled water and set in a wet state of 200%. It was rubbed 50 times with a pressure of 400 g. Immediately after that, JIS
The water repellency was measured by L-1092 rain test (shower method).

Examples 1 and 2, Comparative Examples 1 to 4 First, a fluorine-based water repellent agent and a urethane resin containing a polyfunctional floc isocyanate group were produced as follows. Production of Fluorine-Based Water Repellent A rotary vane stirrer, a condenser, a thermometer, and a reaction vessel with a cooling function were charged with the compounds in the amounts shown below and distilled water, and stirred for 20 minutes while blowing nitrogen gas. Then, the temperature was raised to 70 ° C., and the copolymerization reaction was carried out for 20 hours to obtain a copolymer (hereinafter referred to as EC-400). The obtained copolymer was a slightly yellowish milky white emulsion and had a concentration of 30%. C _4-12 F _9-25 (CH ₂ ) ₂ OCOCH = CH ₂ 88 g CH ₃ (C ₂ H ₅ ) C ONCH (C ₆ H ₄ ) CH ₂ (C ₆ H ₄ ) NHCOO (CH ₂ ) ₂ CH = CH ₂ 1 g Stearyl acrylate 9 g Vinyl chloride 4 g Stearyl methyl ammonium chloride 2 g C ₁₂ H ₂₅ O (C ₂ H ₄ O) ₁₂ H 2.4 g Acetone 60 g Distilled water 415 g Amine catalyst 0.8 g Polyfunctional block isocyanate group-containing urethane resin In the same reactor used in the production, 120 g (1 mol) of trimethylolpropane was charged and heated to 60 ° C. to dissolve it, and then 423 g of a mixture of 2.6- and 2.4-tolylene diisocyanate (2.3. 7 mol) and trimethyldiamine catalyst are added, the reaction is carried out at 60 ° C. with stirring, and a part of the reaction product is taken out on the way. The residual isocyanate group content was measured and allowed to react until the amount is 18.78 wt%. Then, to the reaction product, ethyl acetate 15
86 g of methyl ethyl ketoxime in 6 g (2.6 mo
The mixed solution in which l) was dissolved was added dropwise over 2 hours in the range where the internal temperature did not exceed 50 ° C. Then stir for 2 hours,
It was confirmed that the amount of residual isocyanate groups in the reaction product was 0% by weight. The obtained reaction product was a pale yellow transparent viscous liquid and had a concentration of 81%.

The composition of the obtained reaction product was analyzed by gel permeation chromatography. As a result, 72% by weight of the reaction product in which the molar ratio of trimethylolpropane / tolylene diisocyanate / methylethylketoxime was 1/3/3 was 1%. / 2/2 of the reaction product is 14% by weight and 1 or more /
12% by weight of the reaction product of 3 or more / 3 or more and 2% by weight of others were contained. 313 g of the above reaction product was placed in another homomixer stirrer, distillation apparatus, and reaction container with cooling function.
And 30 g of C ₁₈ H ₃₇ O (C ₂ H ₄ O) ₁₆ H, and C ₁₂ H
₂₅ O (C ₂ H ₄ O) ₄₀ SO ₃ Na was charged with 5 g, and while maintaining the internal temperature at 60 ° C., the homomixer stirrer was rotated at 3500 rpm, and 735 g of hot water at 50 ° C. was gradually added over 4 hours. I put it in. After that, set the rotation speed to 1
It was dropped to 500 rpm and stirred for 6 hours. 82 g of a mixed liquid of ethyl acetate and water produced during the reaction was removed by a distillation apparatus to obtain a compound (hereinafter referred to as JB-7200). The obtained compound was a milky white emulsion and had a concentration of 30%.

Using the EC-400 and JB-7200 produced in the above steps 1 and 2, the treatment solutions of Examples 1 and 2 and Comparative Examples 1, 2, 3 and 4 were prepared in the formulations shown in Table 1. The fiber product containing synthetic fibers, the polyamide Oxford 220 g / m ² at 120 denier warp weft both (No. F-1330), in a generally used method, scoured, dyed with acid dyes, washed with water, syntans A cloth which was fixed, washed with water, and dried was used. Each of the prepared treatment liquids was padded on the cloth, squeezed with a pickup of 60%, dried at 120 ° C. for 3 minutes, and then heat-treated for 45 seconds to obtain synthetic fiber cloths of the present invention and comparative examples.

The water repellency of the obtained fabric was maintained at 70 points or more in the dry state in the 10 times washing method. Moreover, the wet abrasion method also showed 70 or more points. This is when treated without using ethylene carbonate (Comparative Example 1), when using no aminoplast resin (Comparative Example 2), when not using a polyfunctional blocked isocyanate base-containing urethane resin (Comparative Example 3), and fluorine. When using only a water-based water repellent and a urethane resin containing a polyfunctional blocked isocyanate group (Comparative Example 4), when using only a fluorine water repellent and an aminoplast resin (Comparative Example 5), and when using only a fluorine water repellent The value was higher than any of the cases (Comparative Example 6).

[0023]

[Table 1] The treating agents shown in Table 1 are EC-400, JB-7200, Catalyst WL-2 (manufactured by Kyoshin Kasei Co., Ltd.), Sumitex Resin M6 (manufactured by Sumitomo Chemical Co., Ltd.), Sumitex Accelerator ACX (Sumitomo Chemical Co., Ltd.). Manufactured by Toa Gosei Chemical Industry Co., Ltd.).

[0024]

The synthetic fiber product treated by the method for treating a synthetic fiber product according to the present invention is not only dried,
It has water repellency with excellent abrasion durability even in a wet state after washing and drying. In particular, it is suitable for use in fabrics for outdoor sports such as skiing, skating, and golf.

─────────────────────────────────────────────────── ───

[Procedure amendment]

[Submission date] July 26, 1996

[Procedure Amendment 1]

[Document name to be amended] Statement

[Correction target item name] 0013

[Correction method] Change

[Correction content]

The polyfunctional blocked isocyanate urethane resin is not particularly limited as long as it is an organic compound containing two or more blocked isocyanate functional groups in the molecule. Specific examples include tolylene diisocyanate, hexamethylene diisocyanate, diphenyl methane diisocyanate, hydrogenated diphenyl methane diisocyanate, triphenyl triisocyanate, xylidine isocyanate, dicyclohexyl methane diisocyanate, trimethylolpropane tolylene diisocyanate adduct, glyceryl tolylene diisocyanate. Phenol, malonic acid diethyl ester, methyl ethyl ketoxime, sodium bisulfite, ε-as a blocking compound capable of regenerating an active isocyanate group by dissociating in an adduct upon heating at 70 to 200 ° C.
A polyfunctional blocked isocyanate urethane resin obtained by reacting caprolactam or the like can be given. The polyfunctional blocked isocyanate urethane resin is preferably used as a water-dispersed liquid in which a small amount of a surfactant is mixed and forcibly emulsified. Among the above, an aqueous dispersion liquid of methylethylketoxime of diphenylmethane diisocyanate and methylethylketoxime of trimethylolpropane tolylene diisocyanate adduct is preferable. The amount of the polyfunctional blocked isocyanate urethane resin, to synthetic textiles 100 parts by weight, 0.01 to 4 parts by weight is preferable in terms of solid content, is good Mashiku a further 0.
It is from 03 to 1 part by weight. Further, as the dissociation catalyst used for promoting the improvement of the thermal separation rate of the blocked isocyanate and the reduction of the thermal dissociation temperature, for example, dibutyltin dioleate, dibutyltin stearate, stearyl zinc, and an organic amine compound are preferable.

 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Shogo Hiraiwa 1-1-1, Sonoyama, Otsu City, Shiga Toray Co., Ltd. Shiga Plant (72) Inventor Terusaka Sakai 19th Omiyajiri-cho, Karahashi, Minami-ku, Kyoto-shi, Kyoto Prefecture 7-share company Kyokinkasei

Claims (2)

[Claims] 1. A perfluoroalkyl group-containing acrylic copolymer in an amount of 0.01 to 10 parts by weight and an aminoplast resin in an amount of 0.0 to 100 parts by weight of a fiber product containing synthetic fibers.
A treatment liquid containing 1 to 2 parts by weight, 0.01 to 4 parts by weight of a polyfunctional blocked isocyanate group-containing urethane resin, and 0.1 to 30 parts by weight of ethylene carbonate in one bath,
A method for treating a synthetic fiber product, which comprises applying heat to the fiber product and then heat-treating it. 2. A synthesis characterized in that a treatment liquid containing a perfluoroalkyl group-containing acrylic copolymer, an aminoplast resin, a polyfunctional blocked isocyanate group-containing urethane resin and ethylene carbonate is applied and then heat-treated. Fiber products.