JPH09195164A - Cotton fiber-containing fiber product - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a cotton-containing fiber product improved in handle, slight in reduction in tenacity and excellent in wrinkle resistance and washing resistance, shrinkage resistance and shape retention, by cross-linking a cotton- containing fiber structure. SOLUTION: A sliver-shaped cotton fiber is immersed in liquid ammonia, subjected to liquid ammonia removal, air-dried, neutralized with an aqueous solution of acetic acid, washed with water and dried so that a cotton single fiber has <50% cellulose I type crystal structure in the whole crystal and <=60 times/cm convolution to relax a strain in the fiber axis direction. The fiber is spun to give a woven fabric, which is desized, scoured, bleached and treated with liquid ammonia. The processed fabric is sewed into a shirt, etc., is subjected to cross-linking modifying process in >=0.6wt.% bonded formalin amount by a vapor-phase formalin processing method.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION Field of the Invention For clothing such as shirts, slacks, blouses, and hats, handkerchiefs, and other fiber miscellaneous goods.
The present invention relates to a suitable cellulosic fiber-containing fiber product, and more specifically, it suppresses the reduction in strength of the product and further improves shrink resistance, W & W (wash and wear) property, pleating property, puckering property, and shape retention property. The present invention relates to a cotton fiber-containing fiber product and a method for producing the same.

[0002]

2. Description of the Related Art Improvement of defects such as easy wrinkling and shrinkage of cellulosic fibers is a permanent problem. There is a strong demand for a puckering phenomenon (twitching phenomenon) caused by a difference in elasticity between sewing threads or fabric parts and an improvement in shape retention in a product shape.
In an attempt to solve this problem, there is an attempt to utilize a gas phase reaction with formalin in a product state. However, a new problem that cellulose fiber has a remarkable decrease in strength has been highlighted and a solution is desired.

[0003]

DISCLOSURE OF THE INVENTION The present invention has a good texture, is excellent in wrinkle resistance, and is excellent in puckering property after repeated washing, W & W property, shrink resistance and shape retention property, and at the same time vapor phase formalin. An object of the present invention is to provide a cotton fiber-containing fiber product in which strength reduction due to treatment or post-curing resin processing is suppressed as much as possible, and a manufacturing method excellent in industrial productivity.

[0004]

[Means for Solving the Problems] The inventors of the present invention have conducted extensive studies to solve the above-mentioned problems, and have paid attention to the fact that the strength of a cotton-containing fiber product becomes higher when the natural twist is removed by untwisting in water. As a result of repeated studies on how to untwist the monofilaments in the cotton fabric as an aggregate, the convolution (natural twist) of the cotton monofilaments was identified by changing the fine structure in the cotton monofilaments. The present invention has been found to be effective in alleviating distortion of the cotton fabric by reducing the number to less than or equal to a number, and thus suppressing the decrease in strength of the crosslinked modified cotton fiber product.

That is, the present invention is a fiber product in which a fiber structure containing cotton is cross-linked and modified, and the cellulose I type crystal structure of the cotton single fiber in the fiber structure is 50 in all crystals.
A cross-linked modified fiber product containing cotton in an amount of less than wt% and having an average convolution of cotton single fibers of 60 times / cm or less.

In a preferred embodiment, the modification method for cross-linking modification is a vapor phase formalin processing method, and the amount of bound formalin of the cotton in the cross-linking modified fiber structure is 0.6% by weight or more. It is a textile product containing.

Further, the amount of bound formalin after cross-linking modification is 0.6% by weight or more, and the crystal structure of cellulose type I is less than 50% by weight in all crystals.

[0008]

BEST MODE FOR CARRYING OUT THE INVENTION The fiber structure containing cotton fibers according to the present invention means not only 100% cotton but also other fibers,
For example, hemp, flax, pulp, natural cellulose fibers such as bacterial cellulose fibers, regenerated cellulose fibers such as viscose rayon (including polynosic), copper ammonia ray, solvent spinning rayon, polyester, polyamide, acrylic, polyethylene, polypropylene. Spun yarns, woven fabrics, knitted fabrics, non-woven fabrics and the like obtained by blending with synthetic fibers such as, for example, mixed spinning, mixed weaving, mixed twisting and the like. These structures may be exposed, dyed, dyed or printed. When used in combination with other fibers, the content of the cotton fibers is preferably 20% by weight or more, more preferably 30% by weight or more, and further preferably 50% by weight or more in order to bring out the effect of the present invention well.

The textile products referred to in the present invention include fabrics such as woven fabrics, knitted fabrics and non-woven fabrics using the above-mentioned cotton fibers and mixed fibers, and shirts, slacks, blouses, hats, handkerchiefs and the like obtained by using them. Means sewn products.

The cellulose type I having a crystal structure referred to in the present invention is obtained by an X-ray diffraction method. H.
Hermans & A. Weidinger: J. A
ppl. phys. , 19, 491-506 (194
8) and Hayashi et al., Hokkaido University Research Report, p. 83 (19
74).

The cellulose type I in the cotton single fiber in the present invention is less than 50% by weight in all the crystals. Preferably 40
It is less than 30% by weight, more preferably less than 30% by weight. If it is 50% by weight or more, the cross-linking of formaldehyde and cellulose becomes non-uniform, resulting in a marked decrease in strength, which is not preferable.

In the present invention, the average convolution of cotton single fibers measured by the method described in paragraph 0031 is 60 times / cm or less, preferably 30 times / cm.
It is the following, and more preferably 20 times / or less, a fiber product containing cotton fibers.

Crosslinking of cotton fibers with formaldehyde is usually carried out by the so-called gas-phase formalin processing method using formaldehyde vapor (gas) and sulfur dioxide gas. When the crystalline structure of cellulose type I is less than 50% by weight in the total crystal of the cotton fiber, formaldehyde vapor uniformly penetrates into the cotton fiber, and uniform crosslinking can be realized. Further, if the average convolution is 60 times / cm or less, it is advantageous for relaxing the stress concentration after cross-linking modification, and as a result, the strength retention can be improved.

In the present invention, the amount of bound formalin, which indicates the degree of cross-linking reaction between cellulose and the cross-linking agent in the gas-phase formalin processing, is 0.6% by weight or more, preferably 0.
It is 8% by weight or more. 0.6% by weight of bound formalin
If it is less than the above range, a sufficient modifying effect cannot be obtained. That is, the puckering property, W & W property, shape retention property, and pleating property are insufficient.

Due to the above vapor-phase formalin processing, it is excellent in wrinkle resistance, and has puckering property after repeated washing, W & W.
It is possible to manufacture a cellulosic fiber-containing fiber product that has excellent properties, shrink resistance, and shape retention properties, and at the same time minimizes the reduction in strength due to processing.

In the case of a woven fabric, the cotton fiber-containing fiber product of the present invention has a dry wrinkle degree of 270 degrees or more in accordance with the JIS L-1059B method (Monsanto method), and the total value of the moisture wrinkle degree is 550 degrees or more. Is preferable, and 570 degrees or more is more preferable. In particular, the higher the sum of the dry wrinkle degree and the moisture wrinkle degree, the higher the W & W property and the more excellent the puckering property and the shape retention property. Sewing articles containing cotton fibers modified to achieve these wrinkle resistance properties are AATCC 124
-W & W property in 1984 method is grade 3 or higher or JIS L
The puckering property in the AATCC method after 5 times of washing according to the method No. 103 of 0217 shows a shape retention of grade 4 or higher.

Agents capable of changing the crystal structure of cotton single fiber in the production method of the present invention include lithium hydroxide, sodium hydroxide, potassium hydroxide, ethylamine, liquid ammonia, alkali such as hydrazine, sulfuric acid,
Acids such as phosphoric acid and nitric acid, zinc chloride, calcium chloride, calcium sulfate, various rhodanate salts, salts such as potassium iodide,
And combinations thereof. Among these,
Sodium hydroxide and liquid ammonia are preferred, and a combination system of sodium hydroxide / liquid ammonia is more preferred from the viewpoints of improving dyeability and retaining the texture after washing.

However, the alkali treatment with sodium hydroxide transforms the crystal structure of cellulose from cellulose type I to cellulose type II. The efficiency of this crystal transformation depends on the sodium hydroxide concentration and the tension of the cellulose fibers during the alkaline treatment. It is greatly affected by the receiving method and alkali removal temperature.

On the other hand, the liquid ammonia treatment transforms the crystal structure from cellulose type I to cellulose type III. Regarding the crystal transformation efficiency in this case, considering the reduction of the water content in the cellulose, when the removal of ammonia is carried out by dry heat, the influence of the tension of the cotton fiber is relatively small and good.

Therefore, in order to reduce the crystal structure of cellulose type I to less than 50% by weight in all the crystals, it is necessary to consider the sodium hydroxide treatment at a relatively high concentration, to lower the tension and to lower the alkali removal temperature. The concentration of sodium hydroxide is 20 ° Be 'to 40 ° Be', and more preferably 23 ° Be 'to 35 ° Be'. The temperature at the time of removing the alkali is from 0 to 100 ° C, preferably 80 ° C or less. Further, in order to moderate the tension, it is also effective to previously apply a liquid or mechanical rubbing effect, such as a liquid jet dyeing machine, a washer, a tumbler, and a sunphorize, to remove the strain, and then to perform a mercerizing treatment to improve the crystal transformation efficiency.

On the other hand, when the tension is unavoidably increased, it can be achieved by using the liquid ammonia treatment together.
When treated with liquid ammonia, the cotton fiber-containing fabric is soaked in liquid ammonia for 2 to 20 seconds and then for 5 to 90 seconds.
Desirably, the deammonia treatment is performed by heat or steam at a timing of 5 to 20 seconds.

In the present invention, the alkali treatment with sodium hydroxide and / or the liquid ammonia treatment may be performed in any form of cotton raw cotton, sliver, spun yarn, and cloth. On the other hand, as a method of lowering the convolution, raw cotton with less convolution may be used. Also, sliver-like mercerizing or liquid ammonia treatment gives good results. Furthermore, it is also effective to apply a tension in the width direction during the mercerizing process and the liquid solution treatment.

The agent capable of cross-linking cellulose in the present invention may be any of gas, liquid, solid and aqueous solution, but it is one that can easily become vapor by heating and penetrate into the inside of cotton fiber, Formaldehyde is preferred.

In the case of formaldehyde vapor, MgC which can be used with usual resin finishing agents (eg DMDHEU)
Formaldehyde is present in cellulose by pretreating a latent acidic catalyst such as l ₂ .6H ₂ O, NH ₄ Cl, or a hydrochloride salt of an aliphatic amine in advance or by allowing a catalyst such as sulfur dioxide gas to coexist. It reacts with OH groups to form crosslinks between cellulose molecular chains. The treatment conditions for formaldehyde vapor are usually 80 to 160 ° C. in the presence of a catalyst.
It takes 1 to 60 minutes.

In the present invention, the cotton fiber is allowed to infiltrate the cotton fiber at least once inside the cotton fiber and as uniformly as possible before being contacted with vapor such as formaldehyde, etc. Then, vapor such as formaldehyde can easily penetrate into the inside of the cotton fiber and evenly.
Therefore, it is possible to prevent local cross-links from being formed in the cotton fiber or to prevent cross-linking that causes strain, and prevent the strength of the cotton fiber from being reduced.

The gas phase formaldehyde treatment is disclosed in Japanese Patent Laid-Open No.
No. 24597, Japanese Patent Publication No. 49-18517,
Japanese Examined Patent Publication No. 6-102865 and Japanese Patent Laid-Open No. 7-91776.
Although it is possible to carry out by any known method disclosed by the publication, etc., it is possible to process in both the state of the fabric and the state of the sewn product, but it is more problematic in the case of processing after making it into the sewn product. Since the shape of the sewn product is also effectively fixed, the puckering property and the shape retention property are remarkably enhanced, which is a preferred embodiment.

[0027]

EXAMPLES The present invention will be described below in more detail with reference to examples, but the present invention is not limited to these examples. The evaluation methods used in the examples are shown below. Tear strength: JIS L-1096 Pendulum method (horizontal direction, 2.5 cm width) Tensile strength retention ratio: The ratio after processing to the strength before processing is shown in percentage. W & W property: Judgment was made based on the AATCC 124-1984 5-step replica method. 5th grade (good)-1st grade (bad)

Puckering property: JIS L-0217
After 5 times of washing with 103 method, AATCC
It was evaluated by a 5-step replica of the seam according to the 88-B-1984 method. 5th grade (good)-1st grade (bad)

Shape-retaining property: Washing by the JIS L-1042 FII method and tumble drying (I-2 condition) were repeated 5 times, and then visually judged in 5 stages. 5 (grade): very good 4 〃: good 3 〃: normal 2 ：: slightly bad 1 〃: very bad

Cellulose type I crystal content (%): Cellulose monofilaments were taken out from the woven or knitted material and measured by the X-ray diffraction method. Cellulose I, Cellulose II, P. H. He
rmans & A. Weidinger: J. App
l. phys. , 19, 491-506 (1948) and Hayashi et al., Hokkaido University Research Report, p. 83 (1984)
According to the method.

The weft threads of the product were separated and cotton monofilaments were sampled from each. Then, the side surface of the fiber is photographed (500 times) by an optical microscope, and the photograph shows 1c
The convolution (natural twist) per m was counted. The number of measurements n was 30 or more for each sample.

Amount of bound formalin: Approximately 2 g of the treated cloth was treated in boiling water for 15 minutes, washed with water, precisely dried, and decomposed in 20% sulfuric acid by a steam distillation method to recover the produced formalin in an aqueous sodium hydrogen sulfite solution. Then, after oxidizing excess sodium bisulfite by an iodine titration method, the adduct was decomposed with an alkali, and the amount of formalin and added sodium bisulfite was determined, and the formalin per weight of the processed cloth was shown by weight%.

Example 1 Cotton (sliver-like) was dipped in liquid ammonia at -40 ° C. for 10 seconds, then deliquid ammonia and air dried. Further, it was neutralized with a 0.1% by weight aqueous acetic acid solution, washed with water and dried. The liquid ammonia treated cotton thus obtained was spun in a conventional manner and then woven (40 × 40/134 × 75,
A basis weight of 112 g / m ² ) was prepared and subjected to normal desizing, scouring and bleaching. Next, after soaking in liquid ammonia for 3 seconds, squeezing at a squeezing ratio of 70%, and after timing for 16 seconds, 1
It was dried at 60 ° C. for 15 seconds. A shirt was sewn using this processed cloth (A). This shirt was set in a known gas-phase reaction treatment tank and subjected to gas-phase formalin processing with a 37% formalin aqueous solution, steam and sulfur dioxide gas to obtain a shirt having the bound formalin amount shown in Table 1. Table 1 shows the evaluation results of the obtained shirts.

Example 2 Cotton fabric (80/2 × 80/2/134 × 76, basis weight 1
13 g / m ² ) of scouring and bleaching cloth was subjected to mercerizing treatment with 25 ° Be ′ sodium hydroxide by a conventional method, then immersed in liquid ammonia for 3 seconds, and then squeezed at a squeezing ratio of 70%,
After setting the timing for 15 seconds, it was dried at 90 ° C. for 1 minute. Using this processed cloth (B), a shirt was sewn and subjected to vapor phase treatment with formalin in the same manner as in Example 1.
Table 1 shows the evaluation results of the obtained shirts.

Example 3 Cotton fabric (80/2 × 80/2/134 × 76, basis weight 1
The scouring / bleaching cloth (13 g / m ² ) was subjected to the usual mercerizing treatment with 25 ° Be ′ sodium hydroxide twice, and then treated with liquid ammonia in the same manner as in Example 2 to obtain a processed cloth (C). . Using this processed cloth (C), a shirt was sewn and subjected to gas phase treatment with formalin in the same manner as in Example 1. Table 1 shows the evaluation results of the obtained shirts.

Example 4 In the mercerizing process, mercerizing was carried out using 32 ° Be'sodium hydroxide, and then liquid ammonia treatment was carried out in the same manner as in Example 2 to obtain a work cloth (D). Using this processed cloth (D), a shirt was sewn by a conventional method, and Example 1 was used.
The same gas phase treatment with formalin was performed. Table 1 shows the evaluation results of the obtained shirts.

Comparative Example 1 Cotton fabric (80/2 × 80/2/134 × 76, basis weight 1
A shirt was sewn using a scouring / bleaching cloth (E) of 13 g / m ² ) and subjected to a gas phase treatment with formalin in the same manner as in Example 1. The obtained results are shown in Table 1.

Comparative Example 2 Cotton fabric (80/2 × 80/2/134 × 76, basis weight 1
13 g / m ² ) of scouring and bleaching cloth was subjected to mercerizing treatment at 25 ° Be ′ sodium hydroxide by a conventional method. Using this processed cloth (F), a shirt was sewn and subjected to vapor phase treatment with formalin in the same manner as in Example 1. Table 1 shows the evaluation results of the obtained shirts.

Comparative Example 3 Cotton fabric (80/2 × 80/2/134 × 76, basis weight 1
13 g / m ² ) of scouring and bleaching cloth was mercerized with 32 ° Be ′ sodium hydroxide by a conventional method. Using this processed cloth (F), a shirt was sewn and subjected to vapor phase treatment with formalin in the same manner as in Example 1. Table 1 shows the evaluation results of the obtained shirts.

Comparative Example 4 A shirt was sewn using the work cloth (B) used in Example 2. This shirt was subjected to vapor-phase formalin processing in the same manner as in Example 1, and Table 1 shows the evaluation results of the shirt obtained.

The shirt of the present invention does not coarsely harden the texture and has a high wrinkle resistance, a small decrease in tensile strength, an excellent W / W property, and a remarkably excellent puckering property and shape retention property. It is difficult for the shirt according to the conventional method shown in the comparative example to satisfy all the above-mentioned characteristics, unlike the shirt according to the present invention.

[0042]

[Table 1]

[0043]

[Effects of the Invention] An agent that changes the crystal structure of cellulosic fibers such as sodium hydroxide and liquid ammonia significantly changes the original cellulose I type crystal structure to another crystal structure (cellulose type II, cellulose type III, etc.). By performing the crystal transformation, the convolution is reduced, the strain in the fiber axis direction is relaxed, and then the formaldehyde vapor is uniformly crosslinked. The fiber product containing the cotton fiber thus obtained has a good texture, little reduction in strength, high wrinkle resistance, and excellent W / W property, shrink resistance, and shape retention after repeated washing.

 ─────────────────────────────────────────────────── ─── Continuation of front page (72) Takeshi Doida, 1-1 1-1 Katata, Otsu City, Shiga Prefecture, Toyobo Co., Ltd. (72) Inventor Masaya Shinjo, 50 Inu, Daimon-cho, Imizu-gun, Toyama Prefecture Toyo Spinning Co., Ltd. Shogawa dyeing factory

Claims (3)

[Claims] 1. A fiber product obtained by cross-linking and modifying a fiber structure containing cotton, wherein the cotton single fiber in the fiber structure has a cellulose I type crystal structure of less than 50% by weight in all crystals.
And the convolution of cotton monofilament is 60 times / cm
The following are fiber products containing cotton fibers. 2. The cotton fiber-containing fiber product according to claim 1, wherein the cross-linking modification is carried out by a vapor-phase formalin processing method. 3. The cotton fiber-containing fiber product according to claim 1, wherein the amount of bound formalin is 0.6% by weight or more.