JPH03287874A - Worsted outerwear product and production thereof - Google Patents

Abstract

PURPOSE:To obtain the title evenly dense-colored product with high fastness by dyeing under specified conditions a knit fabric composed of worsted yarns produced by oxidation treatment of wool surface followed by shrink proofing with a specific resin. CONSTITUTION:Firstly, wool slivers are put to oxidative treatment with chlorine or oxygen, etc., to remove part of the cuticular layer on the surface and expose the hydrophilic inside layer, thus obtaining modified worsted yarns. Second, the yarns are put to shrink proofing with a polyamide epichlorohydrin resin to produce slivers, which are then spun into worsted yarns. Using the yarns, a knit with fabric is formed and then dyed in a boiling state in an alkaline dyeing solution containing such a compound as to gradually degrade in a boiling state and generate an acid (for the dye, acidic mordant, metal-contg., acidic super-milling dye, etc., is used), thus obtaining the objective evenly densecolored outerwear product with high fastness.

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. covered with the epidermis. Therefore, when water is absorbed, the inner exocuticle layer 2 and the endocuticle layer 3 expand, and the endocuticle layer 3 expands more than the exocuticle layer 2, causing the epidermis to warp outward as shown in FIG. 3 due to the bimetallic effect. These parts of the fibers intertwine and shrink (felt).

Therefore, when a wool product made by forming a knitted fabric from worsted yarn is dyed (product dyeing) by ordinary dip dyeing, felting occurs. Therefore, in order to obtain washable worsted outer clothing products, the wool surface is generally modified by chlorination or oxygen oxidation at the wool raw material stage, and then a shrink-proofing treatment is applied by applying polyamide epichlorohydrin resin. The raw wool material is spun, dyed, and then knitted.

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)
721, dated June 8, 1986 II.

[Problems to be Solved by the Invention] However, when the method of the above application is applied to the dyeing of commercially available knitted fabrics made of worsted yarns that have been preshrunk-treated with a resin, it is found that Due to the action of the resin, the dyeing process becomes faster, so the dye may not spread evenly and cause spots, or the dye solution may not penetrate into overlapping areas of the knitted fabric, leaving those areas extremely light-colored. The reality was that it was not possible to obtain high-quality dark-dyed products.

The present invention has been made in view of the above circumstances, and provides a worsted outer garment product made by dyeing a knitted fabric made of worsted yarn that has been preshrunk with a resin and dyed in a high-quality dark color, and a method for manufacturing the same. purpose.

[Means to solve the problem]

In order to achieve the above object, the present invention provides that a worsted yarn made of wool fibers in which at least a part of the cuticle layer on the surface has been removed to expose the inner part of the cuticle layer is
After being preshrunk with hydrin resin, it is formed into a knitted fabric.
The first aspect is a worsted outer garment product that is dyed in a deep color in that state, and the wool is oxidized with at least one of chlorine and oxygen to remove at least a part of the cuticle layer on the surface and to remove the inner part of the wool. a step of exposing the wool, a step of treating the wool with a polyamide epichlorohydrin resin, a step of forming a knitted fabric using the wool, and a compound that gradually decomposes the knitted fabric in a boiling state to generate an acid. The second gist is a method for manufacturing a worsted outer garment product, which comprises a step of dyeing with an alkaline dye solution in a boiling state.

[Effect]

That is, the present inventors conducted a series of studies on a method for dyeing a knitted fabric, which has been preshrink-proofed by resin processing, in a deep color. As a result, even with preshrunk knitted fabrics, if dyed in boiling conditions with an alkaline dye solution that contains compounds that gradually decompose under boiling conditions and generate acids, robust dyes such as reactive dyes will be removed. The present invention was achieved by discovering that high-quality dyed products can be obtained without causing uneven dyeing even when used.

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 and optimizing worsted yarns made of wool fibers to give them a predetermined color and shape.

Outer clothing refers to underwear when distinguishing clothing, and refers to knit products such as sweaters, polo shirts, training suits, women's dresses, and shorts. 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 has, for example, the following (1) to (5).
It can be obtained through the process of

(1) Modification of the wool fiber surface Anion or cation or both are generated on the wool fiber surface by chlorine or oxygen oxidation 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. , generates cations and makes its surface 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.

In addition, as a method for performing the above chlorine or oxygen oxidation,
For example, a method of oxidizing chlorine (usually referred to as "chlorination") using a known chlorine processing machine can be cited.

This method uses chlorine gas, hypochlorous acid (NaOCl), etc. to destroy cystine and polypeptide bonds on the surface scale of wool fibers to generate ions, and is well known as a shrink-proofing method for wool products. ing. In the present invention, when performing the above chlorine oxidation, the effective chlorine amount is 1 to 6%.
owf (weight relative to fiber weight, hereinafter the same) is suitable. The chemical changes on the wool fiber surface caused by such an oxidation reaction are as follows.

■ Cystine oxidation I R-NO-C-R R-NH3 (El + 0OOC-R) Anionic and cationic groups are generated, increasing the ionic binding capacity and improving the wettability. Critical surface tension is 40-45 dyne/c
s, but the critical surface tension was reduced to 55dy by the above modification.
It is possible to increase ne/Cm or more.

Therefore, if a resin having a critical surface tension below the above value is used when forming a resin film, which will be described later, the resin will easily diffuse onto the wool surface, making it possible to form a uniform and strong resin film.

This modification process is applied to sliver and loose hair.

This is done on worsted yarn raw materials such as tops.

(2) Resin processing A resin capable of covalently bonding with the wool fiber whose hydrophilicity has been modified is supplied to the worsted yarn raw material modified as described above to form a resin film covering the surface of the wool fiber. Prevents felting caused by entanglement of fibers. The thickness of the resin film formed on the wool fiber surface is preferably 15 to 150 mμ (millimicrons), particularly around 100 mμ.

In order to achieve the above thickness, the blending amount of the resin used must be
0, 3-3. O%oivf, especially 0.6-1.5%o
It is preferable to set it to wf.

As the above-mentioned resin, a resin having an azetidinium cation and water-swelling property is most suitable.

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.

(Margin) Examples of resins that have such an azetidinium cation and have water-swellability include Hercocet 57 (manufactured by Dick Vercules, molecular weight 6,000 to 10,000), which is a polyamide epichlorohydrin resin, Boramin E-125, Bo, Ramin 30,0XC (both manufactured by Toho Chemical Co., Ltd., molecular weight 8°OO to 11000), and the like. The critical surface tension of these resins is 50-54 dyne
/cm, and has good stain resistance with the modified wool fibers (critical surface tension of 55 dyne/cm or more).The azetidinium cations present in the structure of these resins are The sulfonic acid groups (-so, -'') and carboxyl groups (-Co.

) etc. to form a highly durable resin film by forming strong covalent bonds.

(3) Spinning The worsted yarn raw material that has been modified as described above and subjected to line-proofing treatment with a resin film is spun according to a conventional method to obtain a worsted yarn. There are various methods for spinning worsted yarn, such as the English method and the French method, and the method is appropriately selected depending on the type of worsted yarn to be obtained.

(4) Optimization of knitting of worsted yarn The worsted yarn obtained by the above spinning is knitted into a knitted fabric 4 as shown in FIG. 1(a).
) Cut and saw into the product shape as shown.

(5) Dyeing The knitted fabric 4 formed into the above product shape is dyed using a paddle dyeing machine.
The product is dyed using a product riding dyeing machine such as a drum dyeing machine.

At this time, as an auxiliary agent, a compound that gradually decomposes under boiling to generate acid is used, and a strong acidic mordant dye,
By dyeing with a metal-containing dye, acidic super milling dye 1 back-reactive dye, etc. in a boiling state, it is possible to achieve uniform and high-quality deep color dyeing. This is because the system is kept alkaline at the beginning due to the presence of the special auxiliary agent mentioned above.
This is thought to be due to the fact that it can be gradually made acidic and the transferability of the dye can be ensured. Examples of compounds that gradually decompose in the boiling state to generate acid include Belacid K (manufactured by Daiwa Chemical Co., Ltd.), which is a combination of halogen-containing organic compounds and the like. In addition to auxiliary agents such as the above-mentioned Belacid, auxiliary agents consisting of phosphonic acid compounds, such as Belleveler P4, may also be used.
(manufactured by Mihejima Kagaku Kogyo Co., Ltd.) is preferable because it further improves level dyeing properties and completely eliminates microscopic dyeing unevenness (skittering) and irritation.

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.

The fact that worsted outer garment products can be easily dyed means that uncolored intermediate products can be stored and sequentially dyed to suit the changing needs of fashions before being released on the market. This means that the present invention makes it possible to develop a wide variety of products.

Moreover, since the worsted material that makes up the knitted fabric has been surface-modified and pre-shrink-proofed with resin, it will not become felt even after repeated washing in a washing machine.

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.

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: 2%owf Processing machine: Kuroi processing machine Processing temperature = 10°C Processing time ~10 seconds Next, resin processing was performed under the following conditions.

Polyamide epichlorohydrin resin liquid (half set 5, manufactured by Fick Vercules): 1.5% o
wf PH sub-adjustment: 7. O ~ 7.5 (adjusted with NaHCO3) Processing temperature: 30°C Processing time: 10 seconds The above wool sliver is spun into a 2/48 worsted yarn, then knitted into a knitted fabric, and then patterned. A molded article in the shape of a women's sweater was obtained by cutting into a predetermined shape and sewing according to the procedure.

The above-mentioned molded article was dyed using a Badle dyeing machine under the following conditions.

·dye: Lanasol Yellow 4R (Made by Ciba Geigy) Lanasol Red 6G (manufactured by Ciba Geigy) Lanasol Blue 3G (manufactured by Ciba Geigy) 1.911%owf 0.542 1.183 Auxiliary: N8gSO410%owf Belacid K (manufactured by Daiwa Chemical Co., Ltd.) 2 g/l Albegar LS (manufactured by Ciba Geigy) 2% owf Bell Leveler P4 (manufactured by Ihejima Chemical Industry Co., Ltd.) 2% owf Ammonia p Adjusted to H9.5 Bath ratio: 1:50 Temperature: Boiling (98°C) Time: Bring pH to 9.0 after 10 minutes in boiling state.

And 41g # of Bel Acid! of Add in proportions and continue boiling for another 50 minutes. The pH is adjusted to 5.9 at the end of staining.

At the end of the above staining, the system was cooled to 80°C and NFi, O
0.5% owf of B was injected and ammonia treatment was performed at pH 8 for 15 minutes to remove unreacted dye, followed by washing with water.

Next, 0.5% OHF of acetic acid was injected to perform acid treatment, followed by dehydration and drying.

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

[Example 2] Bell Leveler P4 was not used during staining.

Other than that, a women's sweater was obtained in the same manner as in Example 1 above.

[Comparative Example 1] Staining was carried out according to the following staining conditions without using Beracid or Berle Leveler P4. Other than that, a women's sweater was obtained in the same manner as in Example 1 above.

Dye: Lanasol Yellow 4R (manufactured by Ciba Geigy) 1.911%owfLan
asol Red 6G (manufactured by Ciba Geigy) 0.542 Lanasol
Blue 3G (manufactured by Ciba Geigy) 1.183 Auxiliary agent: NazSOa 10%owf (NH4) x
sOa 5 〃NH40)1 2 N Bath ratio: 1:50 Temperature: 95°C Time: 30 minutes PH: Initial dyeing pH 8,0 → Before dyeing completion pH 6,5
[Comparative Example 2] Belacid K was not used during dyeing, but instead the pH of the system was adjusted to 9.5 at the initial stage, and after 10 minutes of boiling,
Acetic acid was gradually added to adjust the pH to 5.9 after 60 minutes of boiling. Other than that, a women's sweater was obtained in the same manner as in Example 1 above.

The four types of wool sweaters for women thus obtained were visually evaluated for dyeing condition (presence or absence of uneven dyeing, degree of penetration of dye into seams, and irritation of knitted fabrics).

These results are shown in the table below.

(Hereinafter, blank spaces) From the above results, it can be seen that the products of Examples 1 and 2 have no uneven dyeing or irritation in appearance, and are products of good quality.

In particular, the product of Example 1, in which Bel Acid and Bel Leveler P4 were used in combination, showed excellent dyeability. In contrast, Comparative Example 1, which was dyed by a conventional method that did not use Bel Acid and Bel Leveler P4, had a poor dyeing state and was not practical. On the other hand, Bell Leveler P4. The two comparative examples, in which dyeing was carried out while adjusting the pH of the system with acetic acid over time, have a certain level of dyeing property, but are not practical as pH adjustment requires a great deal of effort. .

〔Effect of the invention〕

As described above, the worsted outer garment product of the present invention is dyed under special dyeing conditions on a knitted fabric made of worsted yarn whose surface has been modified in advance and which has been preshrunk treated with resin. It is possible to achieve strong and uniform deep color dyeing without shrinking the knitted fabric during dyeing. Therefore, according to the present invention, the preshrunk worsted yarn can be stored undyed and cut and sewn, and then 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, etc., and is machine washable and very convenient to handle, so it has high commercial value.

[Brief explanation of drawings]

FIGS. 1(a) and (b) are explanatory diagrams showing the process of forming the bottom shape of a knitted fabric according to the present invention, and FIGS. 2 and 3 are explanatory diagrams showing the structure of the wool fiber surface. 4...Knitted fabric (a) Figure 1 (b)

Claims (4)

[Claims] (1) Worsted yarn made of wool fibers from which at least a portion of the cuticle layer on the surface has been removed to expose the inner part is preshrunk treated with polyamide epichlorohydrin resin and then formed into a knitted fabric, which is dark colored in that state. A worsted outer garment product characterized by being dyed. (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 and exposing the inner part; and a step of treating the wool with a polyamide epichlorohydrin resin;
forming a knitted fabric using the wool; and dyeing the knitted fabric in a boiling state with an alkaline dye solution containing a compound that gradually decomposes in a boiling state to generate an acid. Characteristic manufacturing method for worsted outer garment products. (3) A method for producing a worsted outer garment product, characterized in that in the step of dyeing the knitted fabric, an auxiliary agent consisting of a phosphoric acid compound is included in the alkaline dye solution. (4) The dye used in the dyeing process is an acid mordant dye. The method for producing a worsted outer garment product according to claim 2 or 3, wherein the dye is at least one selected from the group consisting of metal-containing dyes, acidic supermilling dyes, and reactive dyes.