JP2008202174A - Water- and oil-repellent animal hair textile product - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a water- and oil-repellent animal hair textile product capable of imparting excellent water- and oil-repellent performances to animal hair fibers such as wool and having excellent durability and shrinkage resistance to washing or dry cleaning and a touch feeling essentially possessed by the animal hair fibers in combination thereof. <P>SOLUTION: The water- and oil-repellent animal hair textile product has an intermediate coating layer in which at least a part of the animal hair fibers are present by covalent bonding with the animal hair fibers and at least a part of the intermediate coating layer is coated with a water-repellent material. <P>COPYRIGHT: (C)2008,JPO&INPIT

Description

  The present invention relates to animal hair fiber products having water and oil repellency and antifouling properties. More specifically, the present invention relates to an animal hair fiber product having excellent water resistance and oil repellency, which has excellent felt resistance and durability for washing and dry cleaning.

  The realization of clothing materials that do not get wet even when worn in the rain and do not stuffy and are highly breathable has been envied by many people, and many developments, improvements, and improvements have been made so far. As a general method for obtaining a material having these characteristics, a water / oil repellent treatment with a polysiloxane resin or a fluorine compound is known.

  Patent Document 1 describes a method of using a treatment agent in which a diepoxy compound and a polyamine are mixed as a fluorine-based water and oil repellent finishing agent. Patent Document 2 discloses a method using fluorinated polyethers. Furthermore, Patent Document 3 discloses a woven fabric having a coating film formed of a copolymer with a fluorine-containing acrylate compound on the surface and a treatment method thereof.

However, when water repellent treatment agent such as fluorine-containing acrylic polymer is directly processed on animal fiber or copolymerized on the fiber surface, the adhesive strength with animal hair fiber is weak, and washing and dry cleaning, etc. As a result, there is a problem that the water and oil repellency functions are rapidly dropped due to easy dropping from the fiber. In addition, when animal hair fibers are wetted, they become felt and the fibers tend to shrink. To avoid this, the amount of water and oil repellent increases, and the fibers become harder. There was a problem that the softness was lost and the texture was damaged.

On the other hand, in order to increase the adhesion between animal hair fibers and fluorine-containing water and oil repellents such as fluorine-containing acrylates, chemicals such as isocyanate compounds, epoxy compounds, and polyethers that can be bonded or cross-linked with animal hair fibers are used in the fluorine compounds. The method of introducing it automatically is also known. In these methods, since a compound having a functional group other than fluorine is mixed in the water / oil repellent, the ratio of fluorine atoms contained in the water / oil repellent is inevitably lowered, and sufficient water / oil repellent is obtained. There is a problem that oil performance cannot be obtained. In addition, such a treatment method has a problem that the water- and oil-repellent treatment film becomes hard and the natural texture of animal hair fibers cannot be obtained.
JP 2000-186130 A Special table 2004-536974 gazette Japanese Examined Patent Publication No. 63-014117

  The present invention has been made in view of such a current situation, and can impart excellent water and oil repellency performance that cannot be obtained by conventional techniques to animal hair fibers such as wool, for washing and dry cleaning. An object of the present invention is to provide a water- and oil-repellent animal hair fiber product that is excellent in durability and shrinkage resistance and has a texture inherent to animal hair fibers.

  The present inventors diligently studied methods for adding a water / oil repellent function to animal hair fiber products, a covalent bond structure between animal hair fibers and a water-repellent film, or causes of water repellency reduction due to dry cleaning, washing, etc. As a result, it was clarified that the decrease in the water and oil repellency of animal hair fibers was caused by the weak binding force between the animal hair fibers and the water and oil repellent treatment agent.

  From the above examination results, the present inventors repeated many experiments in order to improve the water and oil repellency characteristics and durability of animal hair fiber products, and the intermediate between the animal hair fibers and the water and oil repellency coating being firmly bonded. It has been found that excellent washing durability can be obtained by forming a layer, and the present invention has been completed.

  That is, in order to achieve the above-mentioned object, the water- and oil-repellent animal hair fiber product according to claim 1 has an intermediate coating layer in which at least a part of the animal hair fiber is covalently bonded to the animal hair fiber. The intermediate coating layer is at least partially covered with a water repellent material.

  The water / oil repellent animal hair fiber product described in claim 2 is characterized in that, in the invention described in claim 1, the intermediate coating layer is polyamide epichlorohydrin.

  The water / oil repellent animal hair fiber product of the present invention described in claim 3 is characterized in that, in the invention described in claim 1, the water repellent material is a fluorine-containing acrylate resin. .

  Next, the water- and oil-repellent animal hair fiber product of the present invention described in claim 4 is the invention described in any one of claims 1 to 3, wherein washing is performed 50 times according to method 103 of JIS L-0217. After repeating, the water repellency according to JIS L-1092 method is grade 3 or higher, and the oil repellency according to AATCC Test Method 118-1997 is grade 3 or higher.

  The water- and oil-repellent animal hair fiber product of the present invention has an intermediate coating layer in direct contact with the animal hair fiber, which is chemically bonded and firmly bonded to the animal hair fiber. The outermost water-repellent material is bonded, and the animal hair fibers, the intermediate coating layer, and the water-repellent material are firmly integrated by chemical bonding, so it has excellent durability for processing such as washing or dry cleaning. Have Furthermore, the water-repellent material of the outermost layer is excellent in water and oil repellency because it does not contain a mixture such as a binder that lowers the water repellency, and has a shrink-proof property because it is uniformly coated with a polyamide resin. The original soft texture of animal hair fibers can be obtained.

  Next, an embodiment of the present invention will be described. The water- and oil-repellent animal hair fiber product of the present invention includes an intermediate coating layer in which at least a part of animal hair fiber is covalently bonded to the animal hair fiber, and at least a part of the intermediate coating layer is water-repellent. It is coated with material and has a two-layer structure.

  The presence of the intermediate coating layer serves to chemically bond and integrate the outermost coating layers made of animal hair fibers and the water repellent material. Such a structure is a preferable structure because the water-repellent material does not fall off from the animal hair fibers and can improve durability against washing and dry cleaning. Furthermore, since the coating layer made of a water repellent material is coated only with a fluorine compound, it is difficult to wet even when immersed in a liquid having a low surface tension, and excellent water and oil repellency and antifouling properties can be obtained.

  For the water- and oil-repellent animal hair fiber product of the present invention, an animal hair fiber substrate such as wool, mohair, alpaca, cashmere, llama, bicurina, camel, angora and the like can be used. The animal hair fiber substrate includes a descaled one. Further, it may be a fiber in which animal hair fibers and other fibers such as polyester, acrylic, nylon, silk, cotton, and rayon are mixed. In order to exert the effect of the present invention more, it is preferable that the mixing ratio of the animal hair fiber base material is 50% or more. The water / oil repellent animal hair fiber product of the present invention refers to various types of fiber products such as a top material, a yarn, a woven fabric, a knitted fabric, and a non-woven fabric formed from an animal hair fiber substrate.

  Next, in this invention, it is preferable that the intermediate | middle coating layer which exists in direct covalent bond with an animal hair fiber is a polyamide epichlorohydrin. Polyamide epichlorohydrin is obtained by reacting an amine compound having at least two amino groups, a polyvalent carboxylic acid compound having at least two carboxylic acid groups, and epichlorohydrin. Polyamide epichlorohydrin has a cationic azetidinium ion and an epoxy group, and has water swellability. Examples of the polyamide epichlorohydrin having such an azetidinium cation and having water swellability include Hercoset 57 (Dick Hercules), Polaramine E-125, Polaramine 300XC, 305SW (Toho Chemical). It is done. The azetidinium cation and epoxy group present in these resins form a covalent bond and an ionic bond with the amino group, sulfonic acid group, carboxyl group, etc. on the surface of the wool, and therefore have excellent adhesion and high durability. A resin film can be formed.

  Next, in the present invention, the water repellent material is preferably a fluorine-containing acrylate resin. As the fluorine-containing acrylate resin, general fluorine-based water and oil repellents such as an acrylic copolymer containing a perfluoroalkyl group can be used. Of these, those having a functional group such as a hydroxyl group, a carboxyl group, an amino group, and a glycidyl group are more preferable. A perfluoroalkyl group having 3 or more carbon atoms is preferred because of its excellent water repellency. Unifluorine TG-470B (Daikin Kogyo Co., Ltd.), Quinnguard C-15 (Kotani Chemical Co., Ltd.), Asahi Guard AG310 (Asahi Glass Co., Ltd.), Fluorosurf FS-6010 (Fluoro Technology Co., Ltd.) ) Zonyl 6700 (Tefco Corporation) can be used.

Next, the water- and oil-repellent animal hair fiber product of the present invention has a water repellency according to JIS L-1092 method of 3 or more after repeated washing by JIS L-0217 method 103, and AATCC Test Method 118. The oil repellency according to -1997 is grade 3 or higher. That is, as a comparison of water repellency, the contact angle and wettability of pure water (surface tension 78 mN / m) are generally compared, but the water / oil repellency animal hair fiber product of the present invention is, for example, acetone (surface tension 23 .3 mN / m), ethyl alcohol (22.55 mN / m), and the like, it is difficult to get wet even when immersed in a liquid having a very strong osmotic force and has excellent oil repellency.

  Next, the method for producing the water- and oil-repellent animal hair fiber product of the present invention includes a first step of chlorinating animal hair fiber, and an intermediate coating layer using polyamide epichlorohydrin for the animal fiber after chlorination treatment. A second step of forming, and a third step of coating the surface of the animal hair fiber obtained in the second step with a water repellent material such as a fluorine-containing acrylate resin.

  The chlorination treatment includes a chlorine oxidation method using chlorine gas, sodium hypochlorite, sodium dichloroisocyanurate, and an oxygen oxidation method using potassium permanganate, persulfuric acid, potassium persulfate, and the like. Specifically, the chlorination treatment can be performed by immersing animal hair in an aqueous solution of chlorine or a chlorine donor to make it weakly acidic, and then neutralizing and washing with sulfurous acid.

  Chlorination treatment destroys the cystine and amide bonds on the surface of the wool fiber and generates ions, which increases the wettability of the wool surface and improves the sulfonic acid group and amino group on the scale surface. In order to increase the carboxylic acid group and the like, the animal hair fiber surface and the intermediate coating layer can be strongly covalently bonded, and the durability such as washability can be remarkably improved.

Further, the fluorine-containing acrylate resin substantially contains a functional group such as a hydroxyl group and a carboxyl group, and forms a covalent bond with the azetidinium cation and epoxy group contained in the polyamide epichlorohydrin, so that it has high durability. A water repellent resin film is formed. Furthermore, it is preferable that the fluorine-containing acrylate has a functional group such as an amino group or a glycidyl group because a stronger film can be obtained.
〔Example〕

Hereinafter, the present invention will be described more specifically with reference to examples. The characteristics in the following examples and comparative examples were measured using the following measuring instruments and inspection methods.
(1) Washing test Repeated washing test was performed according to method 103 of JIS L-0217.
(2) Evaluation of water repellency Water repellency was evaluated by the spray method of JIS L1092.
(2) Texture Test Using a texture measurement system (manufactured by Kato Tech Co., Ltd.), surface properties, compression properties, bending properties, shear properties, and tensile properties were measured and evaluated.
(4) Evaluation of oil repellency The oil repellency was evaluated according to AATCC (American Association of Textile Chemist and Colorists) Test Method 118-1997.

(1) Chlorination treatment 16 g of a wool woven fabric (weaving density by a double yarn of No. 74, length 87 / inch, width 84 / inch) was immersed in 480 ml of water. In advance, 0.4 g of sodium dichloroisocyanurate was dissolved in a small amount of water and added. Next, the pH was adjusted to 5 to 6 with acetic acid, and the chlorination treatment was performed by raising the temperature to 40 ° C. for 20 minutes at 25 ° C. and reacting for 10 minutes. Thereafter, 0.32 g of NA ₂ SO ₃ was previously dissolved in water and added, and the mixture was reacted for 10 minutes for neutralization. After the reaction, it was thoroughly washed with water and dried naturally.
(2) Polyamide epichlorohydrin treatment (intermediate coating layer treatment)
The dough subjected to the chlorination treatment was immersed in 470 ml of water, and the pH was adjusted to 5.5 with acetic acid. 1.072 g of polyamide epichlorohydrin resin (Polamin 305SW, manufactured by Toho Chemical Industry Co., Ltd.) was previously dissolved in 10 ml of water and added, and reacted at room temperature for 10 minutes. Thereafter, 0.32 g of sodium bicarbonate was dissolved in water in advance and added, and the pH was raised to 7.5 and reacted for 10 minutes. After the reaction, it was dried at 100 ° C. for 30 minutes. The adhesion amount of the polyamide epichlorohydrin resin after drying was 0.25% as a result of measurement from a change in the weight of the woven fabric.
(3) Fluorine water-repellent treatment The cloth after the intermediate coating layer treatment was immersed in 480 ml of a fluorine water-repellent material (Fluorosurf, manufactured by Fluoro Technology Co., Ltd.) diluted 30 times with water at room temperature for 20 minutes. Then, after taking out and squeezing, it was pre-dried at 100 ° C. for 20 minutes and heated in a constant temperature bath at 140 ° C. for 10 minutes. The adhesion amount of the fluorine water-repellent material measured after the heat treatment was 2.7% as a result of measuring from the change in the weight of the woven fabric.
(4) Evaluation of water repellency When the water repellency was evaluated by the JIS L1092 spray method using the water-repellent treated woven fabric of item (3), the initial water repellency was grade 5. Subsequently, the washing test (JIS L 0217 103 method) was repeated 50 times, and the water repellency was evaluated again. As a result, it was grade 5, and no decrease in water repellency was observed.
(5) Texture test Using a texture measurement system (manufactured by Kato Tech Co., Ltd.), surface properties, compression properties, bending properties, shear properties, and tensile properties are measured, and strain, slime, bulge values, and winter gentlemen. The overall texture as a fabric was determined. As a result of the evaluation, the total value was 3 or more as shown in Table 1, and the texture was preferable as a winter men's clothing fabric.

（６）撥油性評価
ＡＡＴＣＣ Ｔｅｓｔ Ｍｅｔｈｏｄ１１８−１９９７に準じて撥油性の評価を行った結果、撥油性は６級であり優れた撥油性を有する織り布が得られた。

(6) Evaluation of oil repellency As a result of evaluating oil repellency according to AATCC Test Method 118-1997, a woven fabric having oil repellency of grade 6 and excellent oil repellency was obtained.

(1) Chlorination treatment and polyamide epichlorohydrin treatment In the same manner as in Example 1, chlorination treatment and polyamide epichlorohydrin treatment were performed using the woven fabric of Example 1.
(2) Water repellent treatment Next, the fabric after polyamide epichlorohydrin treatment was immersed in 480 ml of a fluorine water repellent treatment agent (Unidyne TG470B, manufactured by Daikin Industries, Ltd.) diluted 30 times with water at room temperature for 20 minutes. After squeezing, it was pre-dried at 100 ° C. for 20 minutes, and heat-treated at 180 ° C. for 3 minutes.
(3) Measurement of adhesion amount When the adhesion amount was measured from a change in the weight of the woven fabric, the adhesion amount of the polyamide epichlorohydrin resin was 0.4%, and the adhesion amount of the water repellent material was 2.5%.
(4) Evaluation of water repellency Water repellency was evaluated in the same manner as in Example 1. As a result, the water repellency did not decrease even after the washing test was performed 50 times from the initial state.
(6) A woven fabric having excellent oil repellency was obtained with an oil repellency evaluation result of grade 6 by the same method as in Example 1 (6).
(Comparative Example 1)

(1) Water repellent treatment Fluorine water repellent treatment agent (Fluorosurf, manufactured by Fluoro Technology Co., Ltd.) obtained by diluting 16 g of the same wool woven fabric as in Example 1 with water without performing chlorination treatment and polyamide epichlorohydrin treatment. ) Soaked in 480 ml for 20 minutes. After squeezing, it was preliminarily dried at 100 ° C. for 20 minutes, and heat-treated for 10 minutes in a 140 ° C. constant temperature bath.
(2) Measurement of adhesion amount When the adhesion amount was measured from the change in the weight of the woven fabric, the adhesion amount of the fluorine water-repellent agent was 3.9%.
(3) Evaluation of water repellency When water repellency was evaluated in the same manner as in Example 1, the water repellency from the unwashed state to after 10 washings was grade 5, but 15 washings were performed. The water repellency decreased to the second grade.
(4) Further, the result of evaluating oil repellency by the same method as in Example 1 (6) was second grade, and sufficient oil repellency could not be obtained.
(Comparative Example 2)

(1) Chlorination treatment A chlorination treatment was carried out in the same manner as in Example 1 using 16 g of the same wool woven fabric as in Example 1.
(2) Water repellent treatment using a solution in which polyamide epichlorohydrin and a water repellent were mixed The chlorinated dough was immersed in 480 ml of water, and the pH was adjusted to 5.5 with acetic acid. A solution prepared by previously mixing 1.072 g of epichlorohydrin (Polamin 505 SW, manufactured by Toho Chemical Co., Ltd.) and 16 ml of a fluorine water repellent (Fluorosurf, manufactured by Fluoro Technology Co., Ltd.) is added to the solution in which the wool woven fabric is immersed. Then, it was immersed for 10 minutes at room temperature. Next, 0.32 g of sodium bicarbonate was previously dissolved in water and added, and reacted at pH 7.5 for 10 minutes. The woven fabric after the reaction was dried at 100 ° C. for 30 minutes, and heat-treated in a 140 ° C. constant temperature bath for 10 minutes.
(3) Amount of adhesion When the amount of adhesion was determined from the change in the weight of the woven fabric, it was 7.3%.
(4) Water repellency When the water repellency was evaluated in the same manner as in Example 1, it was grade 5 water repellency from the initial stage to 40 washing tests, but after 45 washing tests, it was graded to class 3 water repellency. Aqueousness decreased.
(5) Further, the evaluation result of oil repellency was second grade by the same method as in Example 1 (6), and sufficient oil repellency characteristics could not be obtained.

  As described above, as shown in the various characteristics of the examples, the water and oil repellent animal hair fiber product of the present invention has excellent water and oil repellency, and the characteristics may be deteriorated even by treatment such as washing and dry cleaning. And can be suitably used as a material for sports clothing, nursing clothing, rain gear, and the like.

Claims (4)

  An intermediate coating layer in which at least a part of animal hair fibers are covalently bonded to animal hair fibers, and at least a part of the intermediate coating layer is coated with a water-repellent material. Oil-repellent animal hair fiber products.   The water / oil repellent animal hair fiber product according to claim 1, wherein the intermediate coating layer is a polyamide epichlorohydrin resin.   The water- and oil-repellent animal hair fiber product according to claim 1, wherein the water-repellent material is a fluorine-containing acrylate resin.   The water repellency according to JIS L-1092 method is more than grade 3 and the oil repellency according to AATCC Test Method 118-1997 is more than grade 3 after washing according to method 103 of JIS L-0217 50 times. The water- and oil-repellent animal hair fiber product according to any one of claims 1 to 4.