JPH07279042A - Production of fiber product containing cellulose-based fiber - Google Patents

Abstract

PURPOSE:To obtain a fiber product containing a cellulose-based fiber, small in lowering of strength, excellent in crease resistance, keeping high wash and wear properties, puckering resistance and shape-holding property even after repeatedly washed and free from browning. CONSTITUTION:This method for producing a fiber product containing a cellulose- based fiber comprises previously uniformly providing a latent acidic catalyst to a fiber product containing a cellulose-based fiber in which a cellulose I type crystal structure is contained in a ratio of <50wt.% based on total crystals, and then, crosslinking the cellulose-based fiber with formaldehyde vapor.

Description

Detailed Description of the Invention

[0001]

[Field of Industrial Application] The present invention relates to a cellulosic fiber-containing fiber product which is suitable for clothing such as shirts, slacks, blouses, and the like. The present invention relates to a method for producing a cellulosic fiber-containing fiber product having improved W (wash and wear) property, pleating property, puckering property, and shape retention property.

[0002]

2. Description of the Related Art Improving defects such as wrinkles and shrinkage of cellulosic fibers has been a permanent problem, and in the case of sewn products, it has been more difficult than conventional to fabricate cellulosic fibers containing textile products by repeated washing. It is strongly desired to improve the puckering phenomenon (tightening phenomenon) caused by the difference in elasticity between the sewing thread and the fabric portion and the shape retention in the product shape.
In order to improve this problem, there is an attempt to utilize the gas phase reaction between formalin and sulfur dioxide in the product state, but in addition to the significant decrease in strength of cellulose fiber, a new problem of rust contamination is closed. It has been uploaded and the 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 (EN) It is intended to provide a cellulose fiber-containing fiber product that suppresses rust contamination as much as possible while suppressing the strength reduction due to a phase formalin treatment, and a manufacturing method excellent in industrial productivity.

[0004]

The present inventors have arrived at the present invention as a result of intensive studies for solving the above-mentioned problems.

Cellulosic fiber-containing fiber products which have been treated with an agent capable of changing the crystal structure of cellulose, and as a result, have a crystal structure of cellulose type I of less than 50% by weight based on the total crystals, have a latent acidity in advance. A method for producing a cellulosic fiber-containing fiber product, characterized in that a vapor of a chemical capable of imparting a catalyst and then crosslinking cellulose is permeated into the inside of the cellulosic fiber to cause a crosslinking reaction with the cellulosic fiber.

The cellulosic fibers in the present invention are natural cellulosic fibers such as cotton, hemp, flax, pulp and the like, and crystalline structure of bacterial cellulosic fibers such as cellulose I.
It shows the type. Among these cellulosic fibers,
Cotton, hemp and flax are preferred.

Furthermore, among cotton, it is pretreated with a swelling agent and swells, and the short axis / long axis ratio in the cross section of the single fiber is 0.7.
It is preferably 0 or more.

The cellulosic fibers include the above-mentioned cellulosic fibers alone or mixed with other cellulosic fibers containing regenerated cellulose such as viscose rayon (including polynosic), copper ammonia ray and solvent spinning rayon. It means 100% of cellulosic fibers or fibers obtained by blending the cellulosic fibers with synthetic fibers such as polyester, polyamide, acrylic, polyethylene, polypropylene by mixed spinning, mixed weaving, or twisting. In the case of a mixed product, the content of the cellulosic fibers is preferably 20% by weight or more, and more preferably 30% 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 and knitted fabrics using the above-mentioned cellulosic fibers and mixed fibers, and shirts, slacks, blouses, hats, handkerchiefs and the like obtained using the same. 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, and is described in P. H.
Hermans & A. Weidinger: J. A
ppl. phys. 19 491-506 (1948)
And Hayashi et al., Hokkaido University Research Report, p. 83 (197
4).

Cellulose type I in the cellulosic fibers in the present invention is less than 50% by weight based on all crystals. It is preferably less than 40% by weight, more preferably less than 30% by weight. If it is 50% by weight or more, the cross-linking of cellulose by formaldehyde becomes non-uniform, and the strength is significantly reduced, which is not preferable.

On the other hand, the cross-linking of cellulose fibers with formaldehyde is usually carried out by a so-called vapor-phase formalin processing method using formaldehyde vapor (gas) and sulfur dioxide gas. In this method, puckering after repeated washing is carried out. It has excellent heat resistance, W / W property, shrinkage resistance, and shape retention, but heavy metal deposits centering on iron elements mainly generated from sewing process and gas phase reaction tank are corroded and browned by strong acid generated from sulfur dioxide. Alternatively, there is a browning due to oxidative decomposition of cellulose due to the strong acid itself, and there is a drawback that the appearance is remarkably deteriorated.

Therefore, in the present invention, after the latent acidic catalyst is uniformly applied to the woven / knitted fabric of the cellulosic fibers,
By the gas phase formalin processing method using formaldehyde vapor, puckering property after repeated washing, W / W property,
It was excellent in shrink resistance and shape retention, suppressed the decrease in strength as much as possible, and succeeded in solving the browning problem of the woven fabric.

In the case of a woven fabric, the cellulosic fiber-containing fiber product of the present invention has a dry wrinkle degree of 270 ° or more according to the JIS L-1059 method, and the total value with the moisture wrinkle degree is preferably 500 ° or more, More preferably, it is 550 ° or more. Especially, the higher the sum of dry wrinkle and moisture wrinkle,
The W / W property is high, and the puckering property and the shape retention property are excellent. Sewing articles containing cellulosic fibers modified to achieve these wrinkle resistance properties are AATCC 12
The W / W property in 4-1984 method is 3rd grade or higher or JISL
The puckering property in the AATCC method after 5 times of washing of the No. 103 method of No. 0217 shows a shape retention of grade 4 or higher.

Agents capable of changing the crystal structure of cellulose 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. When the cellulosic fiber is cotton, sodium hydroxide and liquid ammonia are preferred, and a combined sodium hydroxide / liquid ammonia system is more preferred from the viewpoints of improving the dyeability and maintaining 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. The crystal transformation efficiency at this time is good because the effect of the tension of the cellulose fiber is relatively small when ammonia is removed by dry heat in consideration of reducing the water content in the cellulose.

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 sodium hydroxide removal temperature. is necessary. The concentration of sodium hydroxide is 20 ° Be 'to 35 ° Be', and more preferably 23 ° Be 'to 28 ° Be'. The water temperature at the time of removing sodium hydroxide is 0 to 100 ° C, preferably 80 ° C or less. In addition, in order to loosen the tension of the woven or knitted fabric, the physical and mechanical rubbing effects such as jet dyeing machine, washer, tumbler, and sanforize can be applied in advance to remove the strain, and then the mercerizing treatment can improve the crystal transformation efficiency. Useful for.

When treated with liquid ammonia, the cellulosic fiber-containing woven / knitted fabric contains 2-20 liquid ammonia.
After soaking for 2 seconds, deammonification treatment is performed by heat or steam at a timing of 5 to 90 seconds, preferably 5 to 20 seconds.

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 which can easily become vapor by heating and penetrate into the inside of cellulose fiber, Formaldehyde is preferred. In the case of formaldehyde vapor, the latent acidic catalyst is evenly applied to the cellulosic fiber-containing woven / knitted fabric in advance, so that the formaldehyde reacts with the OH groups present in the cellulose without using sulfur dioxide gas, and the cellulose molecule Crosslinks between chains form.

The latent acidic catalyst that can be used in the present invention includes
Typical examples are NH ₄ Cl, NH ₄ Br,
(NH ₄ ) ₂ HPO ₄ , NH ₄ H ₂ PO ₄ (NH ₄ ) ₂
Ammonium salts of strong inorganic acids such as SO ₄ and NH ₄ NO ₃ , ammonium salts of organic acids such as ammonium formate, ammonium acetate, and ammonium oxalate, ZnCl ₂ , Zn (N
O ₃ ) ₂ , Zn (BF ₄ ) ₂ , MgCl ₂ , MgHPO
₄ , AlCl ₃ , Al (NO ₃ ) ₃ , Al ₂ (SO ₄ )
₃ , strong acid salts of metals such as CaCl ₂ , 2-amino-2
-Alkanolamine hydrochlorides such as methyl propanol hydrochloride and mixed catalyst systems thereof.

H ₂ SO ₄ , HNO ₃ , H
It is possible to use strong acids such as Cl, formic acid, and oxalic acid. Preferred are ammonium salts of strong inorganic acids, strong acid salts of metals, and alkanolamine salts.

In the present invention, the cellulosic fiber, before being contacted with vapor such as formaldehyde, penetrates into the cellulosic fiber at least once with the agent for changing the crystal structure of cellulose and the swelling agent for cellulose, and as uniformly as possible. Then, the vapor such as formaldehyde can easily penetrate into the inside of the cellulose fiber and evenly. Therefore, it is possible to form local cross-links in the cellulose fibers and avoid cross-links that cause strain, and it is possible to prevent the strength of the cellulose fibers from decreasing.

The gas phase formaldehyde treatment can be carried out either in the condition of the cloth or the condition of the sewn product, but it is more effective in treating the shape of the sewn product by treating it after making it into a sewn product. Since it is fixed to, the puckering method,
The shape retention property is remarkably enhanced, which is a preferred embodiment.

[0025]

EXAMPLES The present invention will now be described in 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. Wrinkle prevention method; Wrinkle recovery angle (each D in JIS L-1059 B method (Monsanto method))
CR and WCD). Tensile strength; JIS L-1096 Grab method (horizontal direction) Tensile strength retention rate: 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. Grade 5 (good) to Grade 1 (bad)

Puckering property: JIS L-0217
After repeating washing by method 103 five times, AATCC
The evaluation was made by a 5-step seam replica of the 88-B-1984 method. Grade 5 (good) to Grade 1 (bad)

Shape retention: 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 (class): Very good 4 〃: Good 3 〃: Normal 2 〃: Slightly bad 1 〃: Very bad

Browning degree: It was visually judged in 5 stages. 5 (class): 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, Cellulose II
The content of I is P. H. Hermans & A. We
idinger: J. Appl. phys. 19 49
1-506 (1948) and Hayashi et al., Hokkaido University Research Report, p. 83 (1974).

Example 1 Cotton (sliver-like) was immersed in 25 ° Be ′ sodium hydroxide at room temperature for 20 minutes, then thoroughly washed with water at 20 ° C., neutralized with a 1% by weight acetic acid aqueous solution, and then washed with water. And dried. The mercerized cotton thus obtained was spun by a conventional method and then woven (50 × 50/145 × 75, 112 g /
m ² ) was prepared and subjected to normal desizing, scouring and bleaching. Next, it was dipped in an aqueous solution of 0.2% by weight ammonium chloride, squeezed to a squeezing ratio of 75%, and dried at 120 ° C. for 3 minutes to obtain a cloth (A). A shirt was sewn using this cloth (A). 10 kg of this shirt was set in a gas phase reaction treatment tank, and 5 liters of a 37% formalin aqueous solution was uniformly injected in a mist state together with steam. Then, the temperature of the gas phase reaction tank is increased to 15
The temperature was raised to 0 ° C. and kept at this temperature for 2 minutes. After that, the water was subjected to a formalin treatment. The evaluation results of the obtained shirts are shown in Table 1.

Example 2 Cotton fabric (90/2 × 90/2/142 × 76, 111
g / m ² ) of scouring and bleaching cloth was repeated twice with 25 ° Be ′ sodium hydroxide by a conventional method of mercerizing, then immersed in liquid ammonia for 2 seconds and squeezed with a squeezing ratio of 70% to obtain 10 After setting the timing of seconds, it was dried at 90 ° C. for 1 minute. Then, soak in a 0.25 wt% ammonium chloride aqueous solution, squeeze so that the squeezing rate is 75%, and 120 ° C x
It was dried for 3 minutes to obtain a cloth (B). Using this cloth (B), a shirt was sewn and subjected to a vapor phase treatment with formalin as in Example 1. The evaluation results of the obtained shirts are shown in Table 1.

Example 3 Cotton fabric (90/2 × 90/2/142 × 76, 111
g / m ² ) after scouring / bleaching was mercerized with 32 ° Be ′ sodium hydroxide, and then Example 2
Liquid ammonia treatment was performed in the same manner as in. Further, it was dipped in an aqueous solution of 0.2% by weight ammonium chloride, squeezed so that the squeezing ratio was 75%, and then dried at 120 ° C. for 3 minutes to obtain a cloth (C). Using this cloth (C), a shirt was sewn and subjected to a vapor phase treatment with formalin in the same manner as in Example 1. Table 1 shows the evaluation results of the obtained shirts.

Example 4 Cotton fabric (90/2 × 90/2/142 × 76, 111
(g / m ² ), scouring and bleaching were performed with the same liquid ammonia treatment as in Example 2, and then 1% by weight of MgCl ₂ was added.
・ Immerse in 6H ₂ O and 0.5 wt% NH ₄ H ₂ PO ₄ aqueous solution, squeeze to obtain a squeezing ratio of 70%, and 120 ° C.
It was dried for 3 minutes to obtain a cloth (D). Using this cloth (D), a shirt was sewn and subjected to the same vapor phase treatment with formalin as in Example 1. The results obtained are shown in Table 1.

Comparative Example 1 Cotton fabric (90/2 × 90/2/142 × 76, 111
The scouring and bleaching (g / m ² ) was usually mercerized with 25 ° Be ′ sodium hydroxide to obtain a fabric (E). A shirt was sewn using this cloth (E). 10 kg of this shirt was set in a gas phase reaction treatment tank, 5 liters of 37% formalin aqueous solution was uniformly injected in a mist state together with steam, and then 200 g of sulfur dioxide gas was injected. Then, the temperature of the gas phase reaction tank was raised to 128 ° C. and kept at this temperature for 2 minutes. After that, a formalin treatment was performed with aqueous ammonia and steam. Table 1 shows the results obtained.
It was shown to.

[0035]

[Comparative Example 2] Cotton fabric (90/2 × 90/2/142 ×
76,111 g / m ² ) of scouring and bleaching at 32 ° B
e'Serkette processed with sodium hydroxide, then dipped in 0.2 wt% ammonium chloride aqueous solution to squeeze
And squeezing so as to obtain a fabric (F). Using this cloth (F), a shirt was sewn and subjected to a vapor phase treatment with formalin in the same manner as in Example 1. The results obtained are shown in Table 1.

Comparative Example 3 The fabric (E) used in Comparative Example 1 was dipped in the processing composition (I) solution, squeezed to a squeezing ratio of 72%, and 120 ° C. for 2.
After intermediate drying for 5 minutes, it was cured at 150 ° C. for 3 minutes. Using this processed cloth, a shirt was sewn by a conventional method. Table 1 shows the evaluation results of the obtained shirts. (I) Bath composition: Beckamine B425 (manufactured by Dainippon Ink and Chemicals, Inc., Glyoxal resin) 5 parts Catalyst G (manufactured by Dainippon Ink and Chemicals, Inc., crosslinking catalyst) 0.6 parts Finetex PEN (Dainippon Ink and Chemicals) 2 parts Silicone Softener EP1010 (manufactured by Nika Kagaku Kogyo Co., Ltd., Silicone Softener) 2 parts Water 90.4 parts

Comparative Example 4 Cotton fabric (90/2 × 90/2/142 × 76, 111
The scouring / bleaching (g / m ² ) was repeated twice with 25 ° Be ′ sodium hydroxide as in Example 2, and then liquid ammonia treatment was performed to obtain a fabric (B ′). Using this cloth (B '), a shirt was sewn and then subjected to a vapor phase treatment with formalin as in Comparative Example 1. The results obtained are shown in Table 1.

[0038]

[Table 1] INDUSTRIAL APPLICABILITY 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, a remarkably excellent puckering property and a good shape-retaining property, and a heavy metal oxide such as iron rust. No browning due to application or oxidative decomposition of cellulose.

[0039]

[Effects of the Invention] An agent that changes the crystal structure of a cellulosic fiber such as sodium hydroxide or liquid ammonia is used to drastically transform the crystal structure of the original cellulose type I into another crystal structure. After uniformly swelling, and then uniformly applying a latent acidic catalyst in advance, and then uniformly cross-linking with formaldehyde vapor and fixing, a fiber product containing cellulosic fibers in which the generation of strain due to cross-linking is suppressed as much as possible Good, little decrease in strength, high wrinkle resistance, and excellent W / W even after repeated washing.
It exhibits excellent properties, shrink resistance, and shape retention, and is free from browning due to the addition of heavy metal oxides such as iron rust and the oxidative decomposition of cellulose.

Front page continuation (72) Inventor Masaya Shinjo 1-1-1, Katata, Otsu, Shiga Prefecture, Toyobo Research Co., Ltd. (72) Inventor Tetsunori Nagara 2-1-1, Katata, Otsu, Shiga Prefecture Toyobo (2) Inventor Isao Iwata 2-2-8 Dojimahama, Kita-ku, Osaka Toyobo Co., Ltd.

Claims (1)

[Claims] 1. A fiber product containing a cellulosic fiber, which has been pretreated with an agent capable of changing the crystal structure of cellulose and has a crystal structure of cellulose type I in an amount of less than 50% by weight based on all the crystals. A method for producing a cellulosic fiber-containing fiber product, characterized in that a vapor of a chemical capable of cross-linking cellulose is applied to the inside of the cellulosic fiber to cause a cross-linking reaction with the cellulosic fiber.