JP2780745B2 - Cellulosic fiber-containing fiber product and method for producing the same - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a cellulosic fiber-containing fiber product suitable for clothing and clothing such as shirts, slacks and blouses. The present invention relates to a cellulosic fiber-containing fiber product having improved W (wash and wear) properties, pleating property, puckering property, and shape retention, 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 soft and resilient feel, is excellent in wrinkle resistance, and has a puckering property after repeated washing, W / W property, shrinkproof property, and mold retention. An object of the present invention is to provide a cellulosic fiber-containing fiber product which is excellent in the properties and at the same time suppresses the decrease in the strength due to the gas-phase formalin treatment as much as possible and a production method which is excellent in industrial productivity.

[0004]

Means for Solving the Problems The present inventors have made intensive studies to solve the above problems, and as a result, have reached the present invention. That is, the present invention contains a cellulose III type crystal structure in an amount of 5% by weight or more, is crosslinked by formaldehyde, and has the following change rate S (%) of a single fiber cross section due to water.
A cellulosic fiber-containing fiber product comprising a cellulosic fiber modified to be 0.4 or less.

S = (Aw-Ad) / Ad × 100 Aw: cross-sectional area after immersion in water at room temperature for 2 hours Ad: cross-sectional area after drying at 105 ° C. for 2 hours and

[0006] Cellulose fiber-containing woven or knitted fabric is treated with an agent capable of changing the crystal structure of cellulose,
After forming a cellulose III type crystal in the cellulosic fiber, a vapor of an agent capable of cross-linking cellulose is allowed to penetrate into the cellulosic fiber to cause a cross-linking reaction with the cellulose, thereby causing a simple reaction of the cellulosic fiber. A method for producing a cellulosic fiber-containing fiber product, wherein the rate of change S (%) according to claim 1 of the fiber cross section is 0.4 or less.

The cellulosic fibers in the present invention include natural cellulose fibers such as cotton, hemp, flax and pulp, regenerated cellulose fibers such as viscose rayon (including polynosic rayon), cuprammonium rayon, and solvent spinning rayon. And cellulose fibers such as bacterial cellulose fibers. Among these cellulosic fibers, cotton, hemp and viscose rayon are preferred. Further, among the cottons, those which are pretreated with a swelling agent and swell and have a short axis / major axis ratio of 0.70 to 0.80 in the cross section of the single fiber are preferable.

The term "cellulosic fiber" refers to 100% cellulosic fiber alone or mixed with other cellulosic fibers, or synthetic fiber such as polyester, polyamide, acryl, polyethylene, polypropylene or the like. Means a fiber when mixed by blending, blending, twisting and the like. In the case of a mixed product, the content of the cellulosic fiber is preferably 20% by weight or more, more preferably 30% by weight or more, in order to sufficiently exhibit the effects of the present invention.

The term "fiber product" as used in the present invention means a fabric such as a woven or knitted fabric using the above-mentioned cellulosic fiber or mixed fiber, and a sewn product such as a shirt, slacks or a blouse obtained using the same. I do.

The cellulose III having a crystal structure referred to in the present invention is obtained by X-ray diffraction.
y, B. G. FIG. : Acta. Chem. Scan
d. , 6 (1952), p. 116 and Hayashi et al., Hokkaido University Research Report, p. 83 (1974).

In the present invention, the content of the cellulose type III crystal in the cellulose fiber is at least 5% by weight. It is preferably at least 20% by weight, more preferably at least 40% by weight. If the amount is less than 5% by weight, the crosslinking of cellulose with formaldehyde becomes non-uniform, and the strength is greatly reduced, which is not preferable.

The crosslinking of cellulose fibers with formaldehyde is usually carried out by a so-called gas-phase formalin processing method using formaldehyde vapor (gas) and sulfur dioxide gas. If the cellulose fibers have a cellulose III type crystal structure of 5% by weight or more, formaldehyde vapor uniformly penetrates inside the cellulose fibers, and uniform crosslinking can be realized.

The cellulosic fiber containing the cellulose type III crystal and crosslinked with formaldehyde needs to have a small change in the cross-sectional area of the single fiber due to water.

That is, in the cross section of a single fiber of a cellulosic fiber, the cross section is determined from the cross sectional area Aw of a state immersed in water at room temperature for 2 hours and swelled sufficiently with water and the cross sectional area Ad obtained after drying at 105 ° C. for 2 hours. The following rate of change S (%)
0.4 % or less. S (%) = (Aw−Ad) / Ad × 100

The rate of change is 0.4% or less. If the rate of change exceeds 0.4 %, the shrinkage due to washing increases, and the shrink resistance is poor. The change rate is preferably as small as possible, and the smaller the change rate, the better the puckering property and the shape retention property.

The above-mentioned modified cellulosic fiber preferably contains at least 20% by weight, more preferably 30% by weight or more, in the fiber product. When the content of the modified cellulosic fiber is less than 20% by weight, the effect of the present invention is hardly exhibited.

In the case of a woven fabric, the cellulosic fiber-containing fiber product of the present invention has a wrinkle resistance of 250 ° or more according to JIS L-1059, and a total value of the wrinkle resistance and moisture resistance of 500 ° or more is preferable. 550 ° or more is more preferable. In particular, the higher the sum of the dryness and wetness wrinkles,
The W / W property is improved, and the puckering property and the shape retention property are also excellent. A sewn product containing a cellulosic fiber modified to achieve these wrinkle resistance is AATCC12.
Whether the W / W property in the 4-1984 method is 2.5 or higher or JI
The puckling property in the AATCC method after 5 washes of the SL-0217103 method is 4th grade or higher.

The agent capable of changing the crystal structure of cellulose in the production method of the present invention is an agent capable of forming cellulose type III crystals in cellulosic fibers, such as liquid ammonia, methylamine,
Primary amines such as ethylamine and hydrazine can be mentioned.

Of these agents, liquid ammonia is preferred because it can be treated uniformly, is easy to handle, and most efficiently forms cellulose III. In the case of treatment with liquid ammonia, the cellulosic fiber-containing woven or knitted fabric is subjected to deammonification treatment with heat or steam at a timing of 5 to 90 seconds, preferably 5 to 20 seconds after immersion in liquid ammonia for 2 to 20 seconds. .

It is preferable that 5 wt% or more of the cellulose III type crystal is formed in the cellulosic fiber by the above treatment. The content of crystals of cellulose type III is preferably at least 20% by weight, more preferably at least 40% by weight.

The cellulosic fibers in the cellulosic fiber-containing woven or knitted fabric used in the present invention are preferably pre-treated with a cellulose swelling agent before the treatment with liquid ammonia or the like.

Such swelling agents are those that change the crystal structure of cellulose, increase the amorphous region, or reduce the strain in fibers, and include lithium hydroxide, sodium hydroxide, potassium hydroxide, and ethylamine. , Liquid ammonia, alkali such as hydrazine, acid such as sulfuric acid, phosphoric acid, nitric acid, zinc chloride, calcium chloride, calcium sulfate,
Examples include various rhodan salts and salts such as potassium iodide.
When the cellulosic fiber is cotton, sodium hydroxide and liquid ammonia are preferable, and sodium hydroxide is more preferable in terms of improvement in dyeing properties and retention of feeling after washing.

The agent capable of crosslinking cellulose in the present invention may be any of a gas, a liquid, a solid, and an aqueous solution. Formaldehyde is preferred.

In the case of formaldehyde vapor, formaldehyde reacts with OH groups present in cellulose by causing a catalyst such as sulfur dioxide gas to coexist, and crosslinks between cellulose molecular chains are generated. The treatment conditions for formaldehyde vapor are usually at 80 to 140 ° C. for 10 to 60 minutes in the presence of a catalyst.

In the present invention, before contacting the cellulosic fiber with a vapor such as formaldehyde, an agent for changing the crystal structure of cellulose or a swelling agent for cellulose penetrates into the cellulose fiber at least once and as uniformly as possible. Then, the vapor of formaldehyde or the like can easily and uniformly penetrate into the cellulose fibers. Therefore, it is possible to prevent local crosslinks from being formed in the cellulose fibers or to avoid crosslinks that cause distortion, and to prevent a decrease in the strength of the cellulose fibers.

When viewed in cross section of a single fiber of the cellulosic fiber, there is no particular difference between the outside and the inside, and the crosslinking is performed uniformly.
Therefore, the shape of the cellulose single fiber is strongly fixed in the cross-sectional direction.

Therefore, the cross-sectional area of the cellulosic fibers treated according to the present invention is very little changed by water. That is, in the absolute dry state (105 ° C
× Drying for 2 hours) Rate of change S (%) determined from the cross-sectional area Ad and the cross-sectional area Aw in a state of being sufficiently swollen with water (room temperature × 2 hours immersion in water) = (Aw−Ad) / Ad × 100
Can be easily reduced to 1.0 or less.

As described above, since the change in the cross-sectional area of the cellulosic fiber due to water can be suppressed as much as possible, shrinkage due to washing can be reduced, and excellent W / W property,
Packing property and shape retention can be achieved.

The vapor-phase formaldehyde treatment can be performed in any of the state of the fabric and the state of the sewn product. However, the treatment after forming the sewn product has no problem in sewing and the shape of the sewn product is more effective. , So puckering,
This is a preferred embodiment because the shape retention is significantly increased.

[0030]

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 method used in the examples is shown below. Wrinkle resistance; wrinkle recovery angles when dry and wet according to JIS L-1059 B method (Monsanto method) (each D
CR and WCR). Tear strength; JIS L-1096 D method (Pendulum method) Flex wear strength; JIS L-1096 A-2 method (bending method) Strength retention rate: The ratio of strength after processing to strength before processing is shown in percentage. W / W properties: AATCC 124-1984 Judgment was made for every 0.5 class based on the 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)

Retainability: Washing and tumble drying (condition I-2) according to JIS L-1042 FII method were repeated 5 times, and visually judged in 5 steps. 5 (grade): very good 4 〃: good 3 〃: normal 2 ：: slightly bad 1 〃: very bad

Change rate (S%) of cross section of cellulose single fiber:
The cross-sectional area Ad of the single fiber after the treatment at 105 ° C. × 2 hours and the cross-sectional area Aw of the single fiber after the water immersion treatment at the room temperature × 2 hours were obtained from a microscope cross-sectional photograph, and S = (Aw−Ad) / Ad × 100.
I asked.

Cellulose type III crystal content (%): Cellulose single fiber was taken out of the woven or knitted fabric and measured by X-ray diffraction. The content of cellulose III was determined by Randy,
B. G: Acta. Chem. Scand. , 6 (19
52) p. 116 and Hayashi et al; Hokkaido University Research Report, p.
83 (1974).

No. 50 single yarn cotton broad cloth (50 ×
A cotton cloth (A cloth) obtained by scouring 50/144 × 81,110 g / m ² ) and treating with sodium hydroxide (25% NaOH aqueous solution for 60 seconds) is immersed in liquid ammonia for 2 seconds, and then squeezed by 70%. After squeezing at a rate of 10 seconds and drying at 90 ° C. for 1 minute (cloth B). This B cloth was sewn on a shirt by a conventional method. 25 kg of this shirt was set in a gas phase reaction treatment tank, and a 37% formalin aqueous solution 2 was added.
Is uniformly injected in the form of a mist together with steam.
00 g was injected. Thereafter, the temperature of the gas phase reaction tank was increased to 125
C. and kept at this temperature for 20 minutes. After a while
Deformalization treatment was performed with a small amount of aqueous ammonia and steam. Table 1 shows the evaluation results of the obtained shirts.

Comparative Example 1 The cloth A described in Example 1 was sewn on a shirt by a conventional method, and a gas phase reaction treatment of formalin was performed in the same manner as in Example 1. Table 1 shows the evaluation results of the obtained shirts.

Comparative Examples 2 and 3 The cloths A and B were immersed in the following processing agent bath composition (I) solution, squeezed so as to have a squeezing ratio of 70%, and intermediately dried at 110 ° C. for 3 minutes. Baking was performed at 150 ° C. for 3 minutes. (I) Bath composition: B425 (manufactured by Dainippon Ink and Chemicals, Inc., glyoxal resin) 4 parts Catalyst G (manufactured by Dainippon Ink and Chemicals, cross-linking catalyst) 0.5 part Finetex PEN (Dainippon Ink and Chemicals, Inc.) 2 parts Silicon Softener EP1010 (manufactured by Nikka Kagaku Kogyo Co., Ltd., silicon softener) 2 parts Water 91.5 parts The above-mentioned processing cloth (C cloth) of the A cloth and the above processing cloth (D cloth) of the B cloth ) Was used to sew a shirt in a conventional manner. Table 1 shows the evaluation results of the obtained shirts.

[0038]

[Table 1]

The shirt of the present invention has a high wrinkle resistance without rough hardening, a small reduction in tear strength and bending wear strength, excellent W / W properties, and remarkably excellent puckering properties and shape retention properties. . In the shirts according to the conventional methods shown in Comparative Examples 1 to 3, it is difficult to satisfy all the above-mentioned characteristics as in the shirt of the present invention.

[0040]

According to the present invention, an agent for changing the crystal structure of cellulosic fibers, such as liquid ammonia, swells uniformly in the cross-sectional direction of a single fiber so as to form cellulose III type crystals, and the swelling is uniform with formaldehyde vapor. The fiber products containing cellulose fibers, which are fixed by cross-linking and suppress the change of the cross-sectional area due to the water of the single fibers, have a good feeling, little strength reduction, high anti-wrinkling properties, even after repeated washing. It shows excellent W / W properties, shrinkage resistance, and shape retention.

 ──────────────────────────────────────────────────続 き Continuation of the front page (56) References JP-B-40-5556 (JP, B1) JP-B 48-314 (JP, B1)

Claims (2)

(57) [Claims] 1. A cellulose III type crystal structure comprising 5% by weight
A cellulosic fiber, characterized by containing a cellulosic fiber crosslinked by formaldehyde and modified so that the following change rate S (%) of the cross section of the single fiber with water is 0.4 or less. Contains textile products. S = (Aw−Ad) / Ad × 100 Aw: cross-sectional area after immersion in water at room temperature for 2 hours Ad: cross-sectional area after drying at 105 ° C. for 2 hours 2. A cellulose-containing fiber-containing woven or knitted fabric is treated with an agent capable of changing the crystal structure of cellulose to form cellulose III-type crystals in the cellulose-based fibers, and then the cellulose is crosslinked. 2. The rate of change S (%) according to claim 1 wherein the cross section of a single fiber of said cellulosic fiber is made to be 0.4 or less by infiltrating a vapor of a drug which can be permeated into said cellulosic fiber and causing a cross-linking reaction with cellulose. A method for producing a cellulosic fiber-containing fiber product, comprising: