JPH0411667B2 - - Google Patents

Description

[Detailed description of the invention]

[Industrial Application Field] The present invention relates to a wool product with a linen-like texture and a method for producing the same. [Prior Art] It is known that when silica particles are bonded to ordinary synthetic fibers or vegetable fibers, a dry feel similar to linen becomes stronger. However, if the silica particles are simply bonded together, the silica particles will fall off and the dry feeling will fade with repeated washing. Therefore, as a method of imparting washing durability to the dry feeling mentioned above, resins such as urethane-based, silicone-based, urea-formalin-based, glyoxal-based, acrylic-based, epoxy-based, acetal-based, etc. are added to the suspension containing silica particles. A method has been put into practical use in which silica particles are then reacted with fibers, and after dehydration and drying, the resin is crosslinked using a catalyst or heat to trap silica particles in a resin film. [Problems to be Solved by the Invention] Providing such a dry feel to wool fibers has been studied. However, wool fibers
Although it is naturally more hydrophilic than vegetable fibers, its surface is covered with a water-repellent epicuticle layer, so it has poor affinity for both hydrophilic and hydrophobic chemicals, so it cannot be used in water-based treatments as described above. At present, no resin has been found that forms a film on the wool surface. However, some resins have been found that do not form a film, but adhere to the wool surface in lumps and chemically bond with some of the wool fibers, making them durable against washing. These are applicable only to fabrics, and are applied to fibers and cured after drying to promote crosslinking between resins and form lumps.This lump resin bonds wool fibers, and It is used to prevent the movement of wool fibers and prevent felt shrinkage during washing. It was expected that mixing silica particles with such a resin would successfully impart a dry feel to wool fibers, but the above resin has poor affinity for both hydrophilic and hydrophobic chemicals. The affinity is given by a special structure that matches the special properties of wool fibers, so when silica particles are mixed in, the above affinity is lost and it no longer shows durable adhesion to wool fibers. . Therefore, it cannot be put to practical use. Further, it has been considered to modify the wool surface to make it hydrophilic and then apply a silica particle-containing aqueous resin to form a silica particle-containing resin film on the surface. However, since wool fibers are sensitive to alkalis and high temperatures, strong curing conditions cannot be set, resulting in insufficient crosslinking of the resin, resulting in only products with low washing resistance. The present invention was made in view of the above circumstances, and aims to provide a wool product that has a dry feel and exhibits excellent durability against washing, and a method for producing the same. be. [Means for Solving the Problems] In order to achieve the above object, the present invention provides cation-modified silica particles on the surface of wool fibers in which at least a portion of the cuticle layer on the surface has been removed and the number of anionic groups has increased. The first gist is a wool product in which the fiber is fixed in an ionic bond with an anion group on the fiber surface, and the outside is coated with a polyamide epichlorohydrin resin film that is covalently bonded to the wool fiber. a step of removing at least a part of the cuticle layer on the surface to increase anionic groups by oxidizing the wool with at least one of chlorine and oxygen; a step of treating the wool with a cation-modified silica particle suspension; The second gist is a method for producing a wool product, which comprises a step of treating the wool with a polyamide epichlorohydrin resin solution simultaneously with or after the treatment with a cation-modified silica particle suspension. [Function] In other words, the present inventors conducted research from various directions on methods of imparting a durable dry feel to wool fibers, and as a result, the present inventors discovered that the cuticle layer on the surface of wool fibers is damaged or removed to improve the surface of the fibers. By increasing the number of active anion groups, fixing cation-modified silica particles thereon by ionic bonding, and coating it with a polyamide epichlorohydrin resin that can be covalently bonded to wool fibers, the cation-modified silica particles will form on the fiber surface. Silica The present invention was achieved by discovering that the fine particles do not fall off the fiber surface and exhibit excellent washing resistance. Next, the present invention will be explained in detail. The wool products targeted by the present invention refer to fiber products in various forms such as slivers, loose wool, threads, and fabrics made of wool fibers. The wool product of the present invention is obtained by processing the fiber surface of the above-mentioned wool fiber product as follows, for example, to give it a dry feel. (1) Modification of the wool fiber surface Strong anionic groups are formed on the wool fiber surface by chlorine or oxygen oxidation, making it hydrophilic. That is, the epicuticle layer, which is the outermost layer of scales on the surface of wool fibers, is damaged or removed by elution to remove the water repellency of the wool fibers, and the intermediate layer, the exocuticle layer, is also damaged, resulting in the formation of the innermost layer, the endocuticle. Make it as hydrophilic as the layer. Normally, the exocuticle layer is less hydrophilic than the endocuticle layer, and due to the bimetallic action resulting from this difference, the cuticle layer rolls up in water and the fibers become entangled, resulting in a felting phenomenon. Therefore, when the hydrophilicities of both layers are made to be the same, the above-mentioned felting is eliminated and the wettability of the fiber surface is significantly improved. In addition, as a method for performing the above-mentioned chlorine or oxygen oxidation, for example, a method of chlorine oxidation (usually referred to as "chlorination") using a known chlorine processing machine can be mentioned. This method uses chlorine gas, hypochlorous acid (NaOCl), etc. to destroy cystine and peptide bonds on the surface scale of wool fibers to generate anionic groups, and is well-known as a shrink-proofing method for wool products. ing.
In the present invention, when performing the above-mentioned chlorine oxidation, it is preferable to set the effective chlorine amount to 1 to 6% owf (weight relative to fiber weight, same hereinafter). The chemical changes in wool fibers caused by such oxidation reactions will be explained below. Such modification treatment increases the number of anion groups that are highly reactive with cations on the wool fiber surface and improves wettability. (2) Bonding of cation-modified silica particles to the wool fiber surface Cation-modified silica particles are supplied to the wool modified as described above, and the cation-modified silica particles are ionically bonded to the anion groups on the wool fiber surface. . As a result, the cation-modified silica particles are directly and firmly fixed to the fiber surface. Moreover, since the silica particles are bonded in a uniformly dispersed state to the anion groups on the fiber surface, the distribution of the bonded silica particles is not biased. This is a major feature of the present invention. This binding reaction can be carried out, for example, by reacting a cationically modified silica particle suspension in the same manner as in the case of package dyeing of wool products such as slivers. Examples of the cation-modified silica particles include cation-modified colloidal silica (CLA-530, manufactured by Kyoei Yushi Kagaku Kogyo Co., Ltd.), which is commercially available as an aqueous colloidal solution. The above-mentioned cation-modified silica particles may be used alone or in combination of two or more. However, the particle size is 5 to 50m.
It is preferable to set it to approximately μ (millimicrons). In other words, if the particle size is smaller than 5 mμ, the resulting wool product will not have a sufficient dry feel, while if it is larger than 50 mμ, the rough and stiff feel will become stronger and the silica particles will tend to separate from the wool fiber surface more easily. This is because it will be done. In addition, the blending amount of silica particles is 0.3 to 2.0%.
It is preferable to set the owf to 0.6% to 1.5% owf. Within this range, a particularly desirable linen-like texture is obtained. (3) Filling and fixing of cation-modified silica particles with resin A polyamide epichlorohydrin resin capable of covalently bonding with hydrophilically modified wool fibers is supplied to the wool to which the cation-modified silica particles have been bonded as described above, and A resin film is formed to cover the wool fiber surface together with the silica particles, and the outside of the silica particles are covered and fixed to the wool fiber surface. Since the resin film is strongly integrated with the fiber surface through covalent bonds, the silica particles are firmly fixed. The thickness of the resin film to be formed is preferably 15 to 150 mμ (millimicrons), particularly around 100 mμ. In order to achieve the above thickness, the amount of polyamide epichlorohydrin resin used must be 0.3 to 3.0%.
It is preferable to set the owf to 0.6% to 1.5% owf. The above polyamide epichlorohydrin resin is
It has an azetidinium cation and is water-swellable. The azetidinium cation mentioned above is a quaternary ammonium cation as shown below, and has a structure that easily forms a covalent bond with an anion group. Having such an azetidinium cation,
Examples of polyamide epichlorohydrin resins that also have water-swelling properties include Hercoset 57.
(Manufactured by Deitsku Hercules, molecular weight 6000 ~
10000), Polamin E-125, Polamin
300XC (both manufactured by Toho Chemical Co., Ltd., molecular weight 8000~
11000) etc. The azetidinium cation present in the structure of these resins is the sulfonic acid group (-SO ₃ ) of the modified wool fiber,
Forms strong covalent bonds with carboxyl groups (-COO), etc. to form highly durable resin films. Therefore, since the silica particles are wrapped in this resin film, they do not easily fall off from the wool fiber surface, and their properties do not change even after repeated washing. Furthermore, since the resin itself is highly water-swellable, the resin absorbs water and swells during washing, making the wool fibers sufficiently flexible in aqueous systems. Therefore, no unreasonable load is applied to the fixed portion of the silica particles. Note that the supply of the cation-modified silica particles and the fixation of the silica particles with the resin may be performed in separate steps as described above, but there is no problem in performing them simultaneously. The wool products obtained in this way have a dry texture similar to linen due to the fixation of silica particles, and the dry feel and hard feel (shiny feel) are said to remain unchanged even after repeated washing. It has characteristics. Therefore, linen products and wool products were originally considered unsuitable for washing with water, but this wool product can be washed with water and is easy to handle. Next, examples will be described together with comparative examples. Example 1 First, a wool sliver was subjected to chlorine treatment under the following conditions. Available chlorine amount: 5% owf Processing machine: Kuroi processing machine Processing temperature: 10℃ The wool sliver obtained by the above treatment is
Its properties were improved as shown in Table 1 below compared to before treatment.

[Table] Next, the above wool sliver was spun into a 2/48 worsted yarn, which was then subjected to regular package dyeing. Then, using the package dyeing machine used for dyeing, cation-modified silica particles were bonded to the wool fiber surface under the following conditions, and at the same time a resin film was formed. Treatment liquid: Cation modified colloidal silica suspension (CLA
-530, manufactured by Kyoei Yushi Kagaku Kogyo Co., Ltd.) Solid content equivalent: 1.5
%owf Polyamide epichlorohydrin resin liquid (Hercoset 57, manufactured by Deik Hercules) 2.0%owf in terms of solid content Processing temperature: 20-25℃ Processing time: 20 minutes PH: Start at weak acidity (PH5.5-5.8), The final result is neutral to slightly alkaline (PH7.0 to 7.5).The wool worsted yarn obtained in this way, untreated wool yarn (wool count 2/48), hemp yarn (wool count 2/48) linen count 80/2), cotton yarn (cotton count 30/2, approximately equivalent to wool count 2/48)
Each was knitted into the same fabric using the same knitting machine. And Kawabata style texture test (KES)
According to the above, the values of bending properties, surface properties, and compression properties were measured. The results are shown in Table 2 below.

[Table] From the above results, although there is a tendency for the example products to remain slightly distorted when bent, the overall feel is similar to linen in terms of stiffness, surface properties, compression properties, etc. I understand. In addition, in order to examine the actual washing durability of the example products, untreated products, and other treated products, the following materials were prepared. <Materials prepared for comparison> Worsted yarn spun from untreated wool Worsted yarn spun from wool subjected to chlorine oxidation treatment (available chlorine amount 5% OWF) Chlorine oxidation treatment (available chlorine amount 2% OWF) and resin film formation Treatment (Hercoset resin 1.5% owf)
Worsted yarn spun from treated wool The above three types of materials were dyed and treated with silica and the following resin. <Resin used for treatment> a Hercoset resin (described above) 1.5% owf b Silicone resin (Superdyne 300, manufactured by Keihin Kasei Co., Ltd.) 5% soln c Polyurethane resin (Elastron BAP, Daiichi Kogyo Seiyaku) 1.5% owf d Polyether resin (Basolan SW, manufactured by BASF) 5% soln Each of the worsted yarns treated as above was knitted (flat knitted, circular knitted) and then subjected to actual washing, resulting in changes in shrinkage and texture before and after washing. was evaluated. The results are shown in Table 3 below.

〔Effect of the invention〕

As described above, in the wool product of the present invention, the cation-modified silica particles are bonded to the modified wool fiber surface through ionic bonds, and in this state are firmly integrated with the fibers through covalent bonds. Because it is coated with a special resin and fixed in place, it will not fall off when washed. Therefore, even after repeated washing, the linen-like dry feel derived from the silica particles is maintained for a long time, an effect that could not be achieved conventionally.

Claims (1)

[Scope of Claims] 1. Cation-modified silica particles are fixed in a state of ionic bonding with anion groups on the fiber surface on the wool fiber surface in which at least a part of the cuticle layer on the surface has been removed and anionic groups have increased, Moreover, the wool product is characterized in that the outside thereof is coated with a polyamide epichlorohydrin resin film covalently bonded to wool fibers. 2. A step of oxidizing the wool with at least one of chlorine and oxygen to remove at least a part of the cuticle layer on the surface to increase anionic groups, and a step of treating the wool with a cation-modified silica particle suspension. and a step of treating the wool with a polyamide epichlorohydrin resin solution simultaneously with or after the treatment with the cation-modified silica particle suspension.