JPH0482960A - Worsted outer garment product and production thereof - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Field of Application] The present invention relates to a washable, darkly dyed worsted outer garment product and a method for producing the same.

[Conventional technology]

As shown in FIG. 2, wool has a scaly surface consisting of a hydrophobic evicuticle layer 1, a hydrophilic exocuticle layer 2, and an endocuticle layer 3 that is even more hydrophilic than the exocuticle layer 2. epidermis (cuticle N)
When water is absorbed, the inner exocuticle layer 2 and the endocuticle layer 3 expand, and since the endocuticle layer 3 expands more than the exocuticle layer 2, the bimetallic effect causes the epidermis to expand as shown in Figure 3. The fibers curve outward, and these parts of the fibers intertwine and contract (felt).

Therefore, it is not possible to dye (product dyeing) wool products made by forming worsted yarns into knitted fabrics by ordinary dip dyeing (product dyeing).In general, in order to obtain washable worsted outer garment products,
At the wool raw material stage, the surface of the wool is modified by chlorination or oxygen oxidation, and then a polyamide epichlorohydrin resin is added to make it pre-shrunk, and this pre-shrunk wool raw material is spun, dyed and then knitted. There is.

In contrast, the present applicant has modified the wool surface and
They discovered that if worsted yarn is made as is without resin processing, and knitted fabric is formed from this worsted yarn and dyed, the knitted fabric can be dyed in a deep color with a strong dye without shrinking, and has already filed an application. (Special application 1986-140)
No. 721, filed on June 8, 1986).

[Problem to be solved by the invention]

However, in the above method, the wool surface must be modified before being kneaded and dyed after being kneaded, so the above-mentioned modifying treatment and dyeing treatment must be carried out in one treatment tank. It cannot be performed continuously within the same period. Therefore, by not performing any treatment before knitting, but by applying some kind of chemical treatment after knitting, the treatment and dyeing can be carried out continuously to create a worsted outer garment product that can be washed with water. Although it is desired to establish a method for obtaining it, the reality is that one of sufficient quality has not yet been obtained. For example, attempts have been made to sequentially apply chlorination treatment, dyeing, and resin treatment for shrink-proofing to knitted fabrics, but although this method achieves a certain degree of washing resistance, the surface of the knitted fabrics There is a problem that pilling occurs and the quality deteriorates. Alternatively, methods have been proposed, such as an oxidation method using monopersulfuric acid, a method in which silicone elastomer is applied after neutralization treatment with sulfurous acid, and a method in which solvent-based silicone is supplied in a solvent finishing machine by a spray method and then dried, etc. However, it is not widely used due to problems such as washing resistance.

The present invention has been made in view of these circumstances, and is made by applying specific chemical treatments and dyeing to knitted fabrics, which exhibit excellent properties in terms of anti-pilling properties, dyeability, and washing resistance. Its purpose is to provide worsted outer garment products and methods for producing the same.

[Means to solve the problem]

In order to achieve the above object, the present invention provides a dyed knitted fabric knitted using worsted wool yarn, in which the cell membrane complex of the wool fibers constituting the knitted fabric is formed by hydroxyalkylphosphine or a derivative thereof. The first aspect is a worsted outer garment product that has been altered in quality and in which at least a part of the cuticle layer of the wool fiber has been removed by oxidation treatment and its inner part is exposed, and is a dyed product of the same knitted fabric as above, The second aspect is a worsted outer garment product in which the cell membrane complex of the wool fibers constituting the knitted fabric is modified with hydroxyalkyl phosphine or its derivative, and the wool fiber surface is coated with polyamide epichlorohydrin resin. a step of knitting the knitted fabric onto a fabric; a process of treating the knitted fabric with hydroxyalkylphosphine or a derivative thereof to alter the cell membrane complex of the wool fibers constituting the knitted fabric; and oxidizing the knitted fabric with at least one of chlorine and oxygen. A third method for producing a worsted outer garment product comprising a step of removing at least a part of the cuticle layer of the wool fibers constituting the knitted fabric to expose the inner part thereof by treatment, and a step of dyeing the knitted fabric. The process of knitting a worsted wool system into a knitted fabric, the process of treating the above knitted fabric with hydroxyalkylphosphine or its derivative to alter the cell membrane complex of the wool fibers constituting the knitted fabric, and polyamide epichlorohydrin. The fourth aspect is a method for manufacturing a worsted outer garment product, which includes a step of coating the surface of the wool fibers constituting the knitted fabric with a resin, and a step of dyeing the knitted fabric.

[Effect]

In other words, the present inventors applied a special chemical treatment to the knitted fabric (product or semi-finished product) before and after dyeing to improve the washing resistance, pilling resistance, and deep color dyeing property of the knitted fabric. We conducted a series of studies on how to give. As a result, knitted fabrics made from worsted wool yarn are treated with hydroxyalkyl phosphine or its derivatives, and oxidized with at least one of chlorine and oxygen, or treated with a polyamide epichlorohydrin resin. It was discovered that the intended purpose could be achieved by carrying out this method, and the present invention was achieved.

Next, the present invention will be explained in detail.

The worsted outer garment product that is the object of the present invention refers to an outer garment product obtained by knitting worsted yarn made of wool fibers and giving it a predetermined color and shape.

Outer clothing refers to underwear, and refers to knitted products such as sweaters, polo shirts, training suits, women's dresses, and suits. In addition, in the present invention, outer clothing products include hats, socks, mufflers, and other accessories using knitted fabrics.

The worsted outer garment product of the present invention, for example, has the following (1) to (4).
It can be obtained through the process of

(1) Making worsted yarn into a knitted fabric After knitting the worsted wool yarn into a knitted fabric 4 as shown in Figure 1(a), it is formed into a product shape by cutting and sawing as shown in Figure 1(b). do.

(2) Modification of wool fibers by oxidation treatment By oxidation treatment of at least one of chlorine and oxygen, anions or cations or both are generated on the surface of the wool fibers to impart hydrophilicity. That is, the water repellency on the surface of the wool fiber is removed by damaging or dissolving the outermost layer of the surface scale of the wool fiber, and the intermediate layer, the exocuticle layer, is also damaged and anions are deposited on the surface of the wool fiber. , give rise to cations,
The surface is made to be as hydrophilic as the innermost layer, the endocuticle layer. When the hydrophilicities of both layers are made to be the same as described above, the so-called felting phenomenon described above is eliminated and the wettability of the fiber surface is significantly improved. Note that the above oxidation treatment is performed using a dyeing machine such as a paddle dyeing machine, and using a treatment liquid containing a predetermined chlorinating agent or oxidizing agent instead of a dyeing liquid. For example, when performing chlorine oxidation, it is preferable to set the effective chlorine amount to 1 to 6% owf (weight relative to fiber weight, the same applies hereinafter). The chemical changes on the wool fiber surface caused by such an oxidation reaction are as follows.

■ Cleavage of peptide bond R-NH-C-R--→ R-NH3■+○0OC-R
(2) Cystine decomposition by sulfite c=o C=OC=0 The above decomposition reaction generates anionic and cationic groups on the wool fiber surface, increasing the ionic binding ability and improving the wettability. Incidentally, the visual surface tension of normal wool fibers is 40 to 45 dyne/cm, but the above modification can increase the critical surface tension to 55 dyne/cm or more.

(3) Dyeing The knitted fabric 4 that has been subjected to the above oxidation treatment is continued to be dyed while being placed in the paddle dyeing machine that has undergone the above treatment. Staining is performed, for example, as follows. That is,
First, it is pretreated with alkaline water, and then dyed using a strong acidic super milling dye 2 attack dye, etc., starting with weak alkaline water and under conditions such that the pH becomes acidic at the time of boiling. In this way, it is possible to realize uniform and high quality deep color dyeing.

(4) Anti-pilling treatment with hydroxyalkyl phosphines While the knitted fabric 4 dyed above is placed in the paddle dyeing machine that has undergone the above treatment, hydroxyalkyl phosphine or its derivatives are continuously supplied to the knitted fabric. 4
Provides anti-pilling properties. The above-mentioned hydroxyalkylphosphine is represented by the following general formula, and its derivatives include those to which alkylene oxide such as ethylene oxide and propion oxide is added.

R2-P-R3 It's okay.

As such hydroxyalkylphosphines,
For example, dimethylhydroxymethylphosphine, dimethylhydroxyethylphosphine, diethylhydroxypropylphosphine, ethylhis(hydroxyethyl)phosphine, ethylhis(hydroxypropyl)phosphine, 1-lishydroxymethylphosphine, trishydroxyethylphosphine, trishydroxypropylphosphine, l-lis Examples include hydroxybutylphosphine, trishydroxypentylphosphine, trishydroxyhexylphosphine, trishydroxyoctylphosphine, and the like.

The above hydroxyalkyl phosphine or its derivative (
When a material (hereinafter abbreviated as "hydroxyalkylphosphines") is provided to the knitted fabric 4, excellent anti-pilling properties can be obtained, and the secondary effect of improving the shrink-proofing effect can also be obtained. Although the mechanism of this action is not yet well understood, the above-mentioned hydroxyalkylphosphines dissolve or dissolve the cell membrane complexes that play a role in adhering the cortex cells and cuticle cells that make up wool fibers and these cells. This series of changes is collectively referred to as "alteration of the cell membrane complex" in the present invention), and as a result, the fiber strength decreases and anti-pilling performance appears. . In addition, the main cause of felting is that the endocuticle swells more than the exocuticle when absorbing water, resulting in bimetallic scale formation, but the above-mentioned hydroxyalkylphosphines cause Because a space is formed by elution, the cuticle cell itself no longer causes a bimetallic rise phenomenon even if the endocuticle swells. ■Hydroxyalkyl phosphines have the effect of preferentially decomposing disulfide bonds, The exocuticle with a high content of disulfide bonds was preferentially affected and became hydrophilic, and there was no big difference in behavior during water absorption compared to the exocuticle.
The cuticle cells themselves do not rise; the outermost lipid layer of the cuticle cells disappears through treatment, the frictional resistance increases, and the anisotropy of the frictional resistance, which is unique to wool fibers, decreases as a result. It is thought that the overall effect is that it exhibits shrink-proofing and anti-felting properties.

Note that the above hydroxyalkyl phosphines are phosphorus (
P) as O, OO2~5. The percentage of Oowf, more preferably 0. txh at a rate of OO5~3.0%owf
It is preferable to supply it to the ground 4.

The worsted outer garment product obtained in this way is dyed darkly and uniformly with a strong dye, and the fiber itself is modified and shrink-proofed, so it can be washed with water or machine washed, and is used as a product. Has excellent quality.

In this way, the ability to easily bundle knitted fabrics means that intermediate products can be stored in an uncolored, untreated state, and then the series of treatments mentioned above can be sequentially applied to meet the changing needs of fashions. This means that the present invention can be put on the market, and the present invention makes it possible to develop a variety of products.

In addition, in the above manufacturing method, dyeing is performed after the knitted fabric 4 is formed into a product shape by cutting and sawing.
It may be dyed at the stage of knitting, or at the stage of cutting at the front or back, and then shaped. Therefore, the term "knitted fabric" in the present invention is intended to include knitted fabrics in various forms, such as knitted fabrics for so-called garments, as well as knitted fabrics formed into product shapes by cutting and sawing. be.

Further, in the above manufacturing method, dyeing is performed by machine dyeing, but if a special texture or color is desired, hand dyeing may be performed.

In the present invention, the order of the oxidation treatment, dyeing treatment, and anti-pilling treatment on the knitted fabric is not limited to the above example, but may be performed in any order shown below. However, if dyeing is performed before oxidation treatment, the dye will be decomposed by the oxidizing agent such as chlorine used in oxidation treatment, and phenomena such as poor dye fastness and discoloration will appear, so it is not practical, so such cases should be excluded. There is.

Furthermore, in the present invention, instead of the oxidation treatment described above, coating treatment with polyamide epichlorohydrin resin may be combined with anti-pilling treatment. The coating treatment with the polyamide epichlorohydrin resin is preferably performed on the knitted fabric that has been subjected to the anti-pilling treatment using the hydroxyalkyl phosphine, or to the knitted fabric that has been subjected to the anti-pilling treatment and dyeing treatment described above. The polyamide epichlorohydrin resin has a quaternary ammonium cation (acetinium cation) as shown below, has a structure that easily forms a covalent bond with an anion group, and exhibits water-swellability.

(Margin) Therefore, when the above-mentioned polyamide epichlorohydrin resin is supplied to the knitted fabric 4, a resin coating film is formed that is firmly bonded to the wool fiber surface by covalent bonds, thereby preventing felting caused by entanglement of the fibers. The thickness of the resin coating film is 15 to 150 mμ (millimicrons), especially 100 mμ
It is preferable to set the thickness to approximately mμ, and in order to achieve a thickness within this range, the blending amount of the resin used should be 0.3 to 3.0
It is suitable to set it to %owf, especially 0.6 to 1.5oiyf.

In addition, as the polyamide epichlorohydrin resin, Hercocet 57 (manufactured by Dick Vercules, molecular weight 6,000 to 10,000), Boramin E-125,
Boramin 300XC (both manufactured by Toho Chemical Co., Ltd., Molecule II
8,000 to 11,000), etc.

The resin treatment, dyeing treatment, and anti-pilling treatment can be performed in any of the following orders. However, the compatibility with the resin improves only after the water repellency of the wool fiber surface is lost by the anti-pilling treatment.
Resin treatment must be performed after anti-pilling treatment.

<Resin treatment> <Dyeing treatment> <Anti-pilling treatment> Next, examples will be described together with comparative examples.

[Example 1] First, worsted wool yarn was knitted into a jersey fabric with a cover factor of 0.41, and then cut into a predetermined shape and sewn to obtain a molded article in the shape of a women's sweater.

This is passed through a paddle dyeing machine, ■Oxidation treatment→■Dyeing treatment→
■ Anti-pilling treatment was applied sequentially. Each processing condition is as follows.

■Oxidation treatment After treatment at 25°C for 60 minutes in the above treatment bath, Na)I
2g/! of SO3! After processing at 60° C. for 5 minutes, it was washed with hot water and then with water.

(2) Staining treatment In the above treatment bath, treatment was carried out at 95° C. for 60 minutes while adjusting the pH to 8.0 at the initial stage of staining and 6.3 before the end of staining. After dyeing, the system was cooled to 80°C, and NH and OH were added to adjust the system to pH.
After processing at 7.5 for 15 minutes, it was washed with water. Then,
Acid treatment was performed by injecting acetic acid at a rate of 0.5% owf.

■Anti-pilling treatment In the above treatment bath, treatment was performed at 75°C for 20 minutes.

The thus obtained dyed product was embroidered and buttoned, and then shaped using a steam setter to obtain a women's sweater.

[Example 2] In the same manner as in Example 1 above, ■Oxidation treatment→■Dyeing treatment→
■Anti-pilling treatment was performed in the order of anti-pilling treatment to obtain a women's sweater. However, in the above anti-pilling treatment, the amount of virgon pp-40 in the treatment bath was set to 10%.

[Example 3] In the same manner as in Example 1 above, ■Oxidation treatment→■Dyeing treatment→
■Anti-pilling treatment was performed in the order of anti-pilling treatment to obtain a women's sweater. However, in the above anti-pilling treatment, the amount of Pirbon pp-4O in the treatment bath was 5% owf.

[Example 4] Under the same conditions as in Example 1 above, treatments were carried out in the order of (1) oxidation treatment, (2) anti-pilling treatment, and (2) dyeing treatment to obtain a women's sweater.

[Example 5] Under the same conditions as in Example 1 above, treatments were carried out in the order of (1) anti-pilling treatment, (2) oxidation treatment, and (2) dyeing treatment to obtain a women's sweater.

[Example 6] ■Anti-pilling treatment→■Resin treatment→■Dyeing treatment was performed to obtain a women's sweater. However, anti-pilling treatment and dyeing treatment were performed in the same manner as in Example 1, and resin treatment was performed as follows.

■Resin treatment pHgJl adjustment '7-0~1-5 (NaHCO
3T: ii) Treatment was performed at 30°C for 20 minutes in the above treatment bath.

[Example 7] Under the same conditions as in Example 5 above, 1 anti-pilling treatment, 2 dyeing treatment, and 2 resin treatment were performed to obtain a women's sweater.

[Example 8] A women's sweater was obtained under the same conditions as in Example 5 above, by carrying out (1) dyeing treatment, (2) anti-pilling treatment, and (2) resin treatment.

[Comparative Example 1] A women's sweater was obtained by performing only oxidation treatment under the same conditions as in Example 1 above.

[Comparative Example 2] Only anti-pilling treatment was applied under the same conditions as in Example 1 above,
I got a women's sweater.

[Comparative Example 3''J Under the same conditions as in Example 5 above, (1) dyeing treatment → (2) resin treatment was performed to obtain a women's sweater.

[Comparative Example 4] Under the same conditions as in Examples 1 and 5 above, a women's sweater was obtained by carrying out (oxidation treatment) → (dying treatment) → (resin treatment).

[Comparative Example 5] At the raw material sliver stage, using a chromium processing machine, ① oxidation treatment → ③ resin treatment was performed under the following conditions.

Then, the fabric was spun and knitted in the same manner as in Example 1, and then dyed in the same manner as in Example 1 using a badle dyeing machine to obtain a women's sweater.

■Oxidation treatment It was treated at 30°C for 30 seconds under the above conditions.

The various wool sweaters for women thus obtained were tested in the IWS Washer Pull Washing Test (TM31.
The felt before the test and the appearance after the test were observed, and the felt shrinkage rate after the test was measured. In addition, a pilling test was conducted according to JISL-1076, 6, IA method to evaluate anti-pilling properties.

These results are shown in the table below.

(Margin below) It was treated at 10° C. for 10 seconds under the above conditions.

■Resin treatment - polyamide epichlorohydrin resin liquid Based on the above results, the height measurements performed generally showed wash resistance.

It can be seen that it has excellent anti-pilling properties and has an excellent texture after washing. However, in the product of Example 3 in which the amount of hydroxyalkylphosphines supplied during anti-pilling processing was small, the felt shrinkability and anti-pilling performance were slightly inferior. On the other hand, all comparative height measurements have high felt shrinkage rates or poor anti-pilling performance, and are not suitable for practical use.

〔Effect of the invention〕

As described above, the present invention improves anti-pilling properties and washing resistance by knitting wool worsted yarn and then subjecting it to a combination of dyeing treatment, anti-pilling treatment with hydroxyalkylphosphines, oxidation treatment, or resin treatment. To obtain a worsted outer garment product with excellent quality. Therefore, according to the present invention, undyed cut and saw intermediate products that are not subjected to any chemical treatment can be stored at that stage and sequentially dyed in trendy colors according to market needs and shipped. , it is possible to develop a wide variety of products. The worsted outer garment product thus obtained is of high quality with no uneven dyeing, and can be machine washed.
Because it is very convenient to handle, it has a high commercial value.

[Brief explanation of drawings]

FIGS. 1(a) and (b) are explanatory views showing the process of forming a knitted fabric in the present invention, and FIGS. 2 and 3 are explanatory views showing the structure of the wool fiber surface. 4...Knitted fabric

Claims (4)

[Claims] (1) A dyed product of a knitted fabric knitted using worsted wool yarn, in which the cell membrane complex of the wool fibers constituting the knitted fabric has been altered by hydroxyalkyl phosphine or its derivative, and A worsted outer garment product characterized in that at least a part of the cuticle layer is removed by oxidation treatment to expose the inner part of the cuticle layer. (2) A dyed product of a knitted fabric according to claim (1), wherein the cell membrane complex of the wool fiber constituting the knitted fabric is modified by hydroxyalkylphosphine or a derivative thereof, and the wool fiber surface is made of polyamide epichlorohydrin. A worsted outer garment product characterized by being coated with resin. (3) a step of knitting the wool worsted yarn into a knitted fabric; a step of treating the knitted fabric with hydroxyalkylphosphine or its derivative to alter the cell membrane complex of the wool fibers constituting the knitted fabric; The method comprises the steps of removing at least a part of the cuticle layer of the wool fibers constituting the knitted fabric by oxidizing with at least one of chlorine and oxygen to expose the inner part thereof, and dyeing the knitted fabric. A method for manufacturing a worsted outer garment product characterized by the following. (4) a step of knitting a worsted wool yarn into a knitted fabric; a step of treating the knitted fabric with hydroxyalkylphosphine or a derivative thereof to alter the cell membrane complex of the wool fibers constituting the knitted fabric; and a polyamide epichlorohydrin resin. A method for producing a worsted outer garment product, comprising the steps of: coating the surface of the wool fibers constituting the knitted fabric; and dyeing the knitted fabric.