JPH07268774A - Processing of cellulose-based fiber - Google Patents

Abstract

PURPOSE:To apply a resin treatment to a cellulose-based fiber from a fiber stage while reducing deterioration of strength of the treated fiber and keeping a high productivity. CONSTITUTION:This method includs the following five processes; (A) impregnating a cellulose-based fiber with a cellulose cross-linking agent and a cross-linking catalyst (B) reacting a cellulose cross-linking agent while keeping the water content of the fiber to 5 to 80wt.% after the process (A) and then washing it with water (C) weaving or knitting the fiber to make a fabric after the process (B) or the process (D) described below (D) adding a cross-linking catalyst again after the process (B) or the process (C) (E) applying a heat treatment in a state in which the second addition of the cross-linking catalyst is carried out and completing the reaction of the cellulose cross-linking agent. The method can produce a product excellent in shrink resistance, crease resistance and wash and wear properties, having a gentle finished touch and low in content of free formaldehyde without causing end breakage during the course of weaving or knitting.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for resin-processing a cellulosic fiber from the yarn stage. More specifically, it relates to an improved processing method from the yarn stage for imparting shrink resistance, wrinkle resistance, wash and wear property (hereinafter referred to as W & W property), etc. to a cellulosic fiber cloth or product. Is.

[0002]

BACKGROUND ART Processing for imparting shrinkage resistance, wrinkle resistance, and W & W property to cellulosic fibers is carried out by using cellulosic fiber cloths, or fiber products made of such cloths, as cellulose cross-linking agents, cross-linking catalysts, etc. The method of applying is conventionally performed. However, in processing into fabrics, etc., the cured cellulose cross-linking agent tends to be unevenly distributed at contact points such as knot points and cross points between threads, so that the texture becomes coarsely rigid and the strength decreases. There is a limit. Therefore, processing at the yarn stage has been attempted conventionally.

The conventional processing at the yarn stage is
Cellulose fiber yarn, cellulose crosslinking agent, crosslinking catalyst,
Basically, the reaction of the cellulose cross-linking agent is completed by a heat treatment after adding other components and pre-drying if necessary, and then weaving or knitting to form a fabric, and further a fiber product. The cellulosic fiber cloth or product obtained by such a method is less likely to coarsely stiffen the texture or reduce the strength, as compared with the one processed at the stage of the cloth or fiber product, and has a preferable quality. However, such processing at the yarn stage reduces the tensile strength and elongation of the cellulosic fiber threads after processing with the cellulose cross-linking agent, and thread breakage easily occurs during weaving / knitting. Was extremely difficult and the productivity was low.

[0004]

DISCLOSURE OF THE INVENTION The present inventors have accomplished the present invention as a result of earnest research in view of the present situation. Therefore, an object of the present invention is to process a cellulosic fiber from the yarn stage, which has features such as less coarse stiffness of texture and less strength reduction, with less reduction in tensile strength and elongation during weaving / knitting. And to implement without reducing productivity.

[0005]

In order to solve such a problem, the present invention provides a method for processing a cellulosic fiber including the following steps (A) to (E).

(A) Cellulosic fiber yarn contains a cellulose crosslinking agent and a crosslinking catalyst, and (B) the water content of the cellulosic fiber yarn containing the cellulose crosslinking agent and the crosslinking catalyst is adjusted to 5 to 80% by weight. Keeping the cellulose cross-linking agent to react and then washing with water, (C) the cellulose-based fiber yarn after reacting the cellulose cross-linking agent,
Weaving or knitting to form a fabric, (D) reacting the cellulose crosslinking agent in step (B), washing with water, before step (C), or after weaving or knitting in step (C), Reapplying the cross-linking catalyst, and (E) completing the reaction of the cellulose cross-linking agent by heat treatment with the second cross-linking catalyst applied.

FIG. 1 is a flow chart schematically showing one embodiment of the method of the present invention, and the present invention will be described in detail with reference to this figure as well.

The term "cellulosic fiber" as used in the present invention means cotton,
Those composed of natural cellulose fibers such as hemp or regenerated cellulose fibers such as viscose rayon, cupra and polynosic, mixed products thereof, and mixed products with other fibers such as synthetic fibers containing 10% by weight or more of these cellulose fibers. means. The cellulosic fiber yarn means a yarn made of such a cellulosic fiber, and the cellulosic fiber cloth means a woven fabric or a knitted fabric using such a cellulosic fiber. Further, the cellulosic fiber product means a molded or sewn product obtained by cutting such cellulosic fiber cloth and then performing steps such as sewing and / or pressing.

The cellulose cross-linking agent applied to the cellulosic fiber yarn in the present invention is preferably one having excellent stability and durability. For example, formaldehyde, tetraoxane, dimethylol dihydroxyethylene urea resin,
Dimethylol alkyl carbamate resin, tetramethylol acetylene diurea resin, dimethylol-4-
Examples thereof include methoxy-5,5-dimethylpropylene urea-based resin. Among them, dimethyloldihydroxyethyleneurea resins and dimethyloldihydroxyethyleneurea resins such as alkyl etherified modified products thereof are industrially preferably used.

The crosslinking catalyst used in the present invention is hydrochloric acid,
Free acids such as acetic acid, oxalic acid, maleic acid, citric acid, magnesium chloride, zinc chloride, aluminum chloride,
Metal salts such as magnesium sulfate, zinc sulfate, aluminum sulfate, magnesium nitrate, zinc nitrate, magnesium borofluoride, zinc borofluoride, ammonium salts such as ammonium chloride, ammonium sulfate, ammonium phosphate, monoethanolamine hydrochloride Such organic amine salts and the like can be mentioned. These are either alone or 2
A combination of two or more species can be used.

In the step (A), the cellulosic fiber yarn contains the cellulose crosslinking agent and the crosslinking catalyst as described above. In the present invention, a processing liquid obtained by diluting and blending a cellulose crosslinking agent and a crosslinking catalyst with water to an appropriate concentration is usually used. There is no particular restriction on the method of including the cellulose crosslinking agent and the crosslinking catalyst in the cellulosic fiber yarn, for example, cheese, corn, a method of including the processing liquid in the state of ridges, a method of centrifugal dehydration, or a continuous thread A method of immersing in a processing liquid and squeezing the liquid with a means such as mangle can be applied.

The step (B) is to react the cellulose crosslinking agent contained in the cellulosic fiber yarn in the step (A). The cellulosic fiber yarn containing the cellulose cross-linking agent and the cross-linking catalyst is dried at room temperature to about 120 ° C. for about 10 seconds to about 1 hour, if necessary, to adjust the water content to the range of 5 to 80% by weight. . If the proper moisture content is achieved by dehydration or squeezing, it may be used as it is. The water content as used herein means a value measured according to JIS L 1096-90, item 6.9.

If the water content here is less than 5% by weight,
If the moisture content here exceeds 80% by weight, the final product is difficult to exhibit sufficient shrink resistance, wrinkle resistance and W & W property when weaving / knitting. Therefore, by adjusting the water content of the cellulosic fiber yarn containing the cellulosic crosslinking agent and the crosslinking catalyst in the range of 5 to 80% by weight and reacting the crosslinking agent, the cellulosic fiber cloth targeted by the present invention or You can get the product. Preferably, the water content here is adjusted to the range of 5 to 70% by weight, more preferably 5 to 60% by weight.

The cellulosic fiber yarn whose moisture content has been adjusted in this manner is subjected to a treatment for reacting a cellulose crosslinking agent. This treatment is for reacting the cellulose cross-linking agent contained in the cellulosic fiber yarn with cellulose, and the conditions thereof are not particularly limited, but for example, any of the following methods can be adopted.

The first method is 5 to 50 ° C., preferably 1
The reaction is carried out at a temperature of 0 to 30 ° C. for 1 to 50 hours. When the reaction temperature is lower than 5 ° C., the reaction time becomes extremely long, which is industrially disadvantageous. On the other hand, if the reaction temperature exceeds 50 ° C., it becomes difficult to control the reaction. There are no particular restrictions on other reaction conditions or operations, and the reaction may be performed under the above-mentioned predetermined conditions while avoiding a large change in the water content of the cellulosic fiber yarn. The second method is to react for 15 seconds to 10 minutes under moist heat. The moist heat in this case is 100 to 150.
Saturated steam at about ℃ is preferable.

After completion of the reaction, the product is washed with water. The water may be washed with water only, but it is preferable to wash with water after neutralizing with 0.5 to 5 g / L of an aqueous solution of soda ash. The neutralization treatment and washing with water are generally performed at a temperature of 5 to 80 ° C.

After washing with water, it is subjected to a step (C) of weaving or knitting cellulosic fiber yarns into a cloth and a step (D) of adding a crosslinking catalyst again. These steps (C) and (D) The order of) is arbitrary. Therefore, the following two methods can be used for the step after washing with water. The first is
Weaving or knitting the dried threads after washing with water to form a cloth,
In this method, the cross-linking catalyst is added to the cloth again. There is no particular restriction on the method of applying the catalyst, and it can be carried out by a spray method, a coating method, a padding method, an immersion / centrifugal dehydration method, or the like. The second is a method in which after washing with water, if necessary, it is dried, the crosslinking catalyst is added again, and the cloth is dried. The method of applying the catalyst in this case is also arbitrary, and for example, the same method as that described above for applying the processing liquid composed of the cellulose crosslinking agent and the crosslinking catalyst can be adopted.

The cross-linking catalyst used here can also be those exemplified above, and any one kind or two or more kinds thereof is used in an appropriate amount. The crosslinking catalyst applied here may be the same as or different from the crosslinking catalyst previously applied together with the cellulose crosslinking agent. For example, it is effective that the cross-linking catalyst applied first with the cellulose cross-linking agent has a relatively high acidity, and the cross-linking catalyst applied the second time has a relatively low acidity.

Also in this case, a working fluid obtained by diluting the crosslinking catalyst with water to an appropriate concentration is usually used. At this time, the processing liquid contains a strength reduction preventing agent, a softening agent, an oil agent, a hardening agent, a sizing agent, a repulsion elasticity imparting agent, an optical brightening agent, a bluing agent, a dye fixing agent,
Any one kind or two or more kinds of a water repellent, an oil repellent, an antifouling agent, a formaldehyde scavenger, a moisturizer and the like can be blended as necessary. Further, as moisturizers, polyols such as ethylene glycol, diethylene glycol, polyethylene glycol, polypropylene glycol polyethylene glycol ether, and glycerin are effective in reducing the amount of residual formaldehyde, improving W & W property, and suppressing reduction in strength. Particularly preferably used.

After adding a catalyst or other chemicals, if necessary, it is dried. This drying is preferably carried out at a temperature of 50 to 150 ° C., more preferably 80 to 120 ° C., and controlled conditions are desired so that the reaction of the cellulose cross-linking agent practically does not proceed.

In the step (E), heat treatment is performed in the state where the second crosslinking catalyst is applied as described above to complete the reaction of the cellulose crosslinking agent. The cloth in the state where the crosslinking catalyst is applied through the steps (C) and (D) is
It is heat-treated as it is to complete the reaction of the cellulose cross-linking agent, or this fabric is molded and / or sewn into a fiber product by a usual method and then heat-treated to complete the reaction of the cellulose cross-linking agent. For the reaction at the fabric stage,
For example, a tenter type curing machine, a roller baking machine, or the like is used, while a sewn product curing machine or the like is used for the reaction after forming a fiber product.

The heat treatment here is for completing the reaction of the cellulose cross-linking agent previously applied, and is usually carried out at a temperature of 130 to 180 ° C. for about 30 seconds to 15 minutes. In this way, the textile product by the improved processing method aimed at by the present invention can be obtained.

[0023]

The present invention will be described in more detail with reference to the following examples, but the present invention is not limited thereto. In the examples,% and proportions representing the content or the addition amount are based on weight unless otherwise specified.

Example 1 100% twirled yarn of 100% cotton, which had been mercerized, was adjusted to pH with hydrochloric acid.
It was immersed in a 100 g / L aqueous solution of Sumitex Resin NS-19 (Dimethyloldihydroxyethylene urea resin manufactured by Sumitomo Chemical Co., Ltd.) adjusted to 1 and centrifugally dehydrated and squeezed to a wet pickup of 45%. This thread was sealed with a polyethylene film, reacted at 20 ° C for 24 hours, then immersed in a 1 g / L soda ash aqueous solution for 5 seconds, washed with water at 45 ° C, and dried in an oven at 80 ° C. Was applied.

[0025] The yarn thus treated is added to the Sumitex Acceler
It was immersed in a 30 g / L aqueous solution of ator X-110 (composite metal salt crosslinking catalyst manufactured by Sumitomo Chemical Co., Ltd.), centrifugally dehydrated, squeezed to 45% wet pickup, and then dried in an oven at 80 ° C. . The treated yarn after drying is JIS L 1095-7
According to the method of 7.5 of 9 above, the tensile strength and the elongation rate were tested by a constant speed tension type, and the tensile strength was 560 g and the elongation rate was 5.4%.

Further, the treated yarn after drying was knitted by a knitting machine. At that time, no thread break was observed. The obtained knitted fabric was heat-treated in an oven at 150 ° C. for 4 minutes and then subjected to the following measurement test, and the results shown in Table 1 were obtained.

1) Wrinkle resistance when dried: JIS L 1018-90
Based on the B method described in 6.23, the same as in 6.23.2 (2)
(a) It was measured by a method without pretreatment. 2) Shrinkage rate: Based on the G method described in 6.30 of JIS L 1018-90, the method of washing was carried out by the 103 method of JIS L 0217 and screen-dried. 3) Wrinkles after washing: The wrinkles were evaluated by the method A described in item 6.31 of JIS L 1018-90. The drying method is tumble drying. 4) Bursting strength: Measured by method A described in JIS L 1018-90, item 6.17. 5) Free formaldehyde amount (abbreviated as FF amount): J
It was measured by the B method described in 5.3.1 (2) (b) of ISL 1041-83. 6) Finishing feeling: It was judged by the following criteria by observing the feeling of touch. ○ There is no rough feeling at all, and a favorable texture. △ There is a slightly rough feeling. × Rough and unfavorable texture.

Comparative Example 1 (resin processing completed at the yarn stage) 100 g of Sumitex Resin NS-19 and 1 liter of
The same 100% cotton No. 40 yarn as used in Example 1 was dipped in an aqueous solution containing 30 g of Sumitex Accelerator X-110, centrifugally dehydrated and squeezed to a wet pickup of 45%, and then in an oven at 80 ° C. Dried. Then 15
Heat treatment was performed for 4 minutes in an oven at 0 ° C. When the treated yarn was tested for tensile strength and elongation in the same manner as in Example 1, the tensile strength was 365 g and the elongation was 2.7%.

Further, when this treated yarn was treated by a knitting machine to form a knit, yarn breakage frequently occurred and the knit could not be obtained.

Example 2 Sumitex adjusted to pH 1 with hydrochloric acid as in Example 1.
Immerse 100% cotton thread in 10% aqueous solution of Resin NS-19,
It was centrifugally dehydrated and squeezed to a wet pickup of 45%.
The yarn was dried in an oven at 70 ° C. and adjusted to have a water content of 10%. Then, after reacting with saturated steam at 103 ° C. for 5 minutes, it was immersed in a 1 g / L soda ash aqueous solution for 5 seconds, further washed with water at 45 ° C., and dried in an oven at 80 ° C.

The dried treated yarn was tested for tensile strength and elongation in the same manner as in Example 1, and the tensile strength was 57.
It was 5 g and the elongation rate was 5.8%.

Further, the dried treated yarn was knitted by a knitting machine. At that time, no thread break was observed. The obtained knit is Sumitex Accelerator X-110.
20 g / L aqueous solution, squeezed to a wet pickup of 68% with a mangle, dried with a pin tenter type dryer at 110 ° C. for 2 minutes, and further heat-treated at 150 ° C. for 3 minutes. The knitted fabric thus treated was subjected to the same measurement test as in Example 1, and the results shown in Table 1 were obtained.

Example 3 In the same steps as in Example 1, neutralization (treatment with an aqueous solution of soda ash), washing with water and drying treatment were carried out. The yarn thus provided with the cross-linking agent and the catalyst was reacted with 30 g of Sumitex Accelerator X-110 in 1 liter of Sumi.
40 g of tex Softener L (softener for textile processing made by Sumitomo Chemical Co., Ltd.) and 30 g of diethylene glycol
It was immersed in an aqueous solution containing water, centrifugally dehydrated, squeezed to a wet pickup of 45%, and then dried in an oven at 80 ° C.

When the treated yarn after drying was tested for tensile strength and elongation in the same manner as in Example 1, a tensile strength of 62 was obtained.
It was 6 g and the elongation was 6.1%.

Further, the dried treated yarn was knitted by a knitting machine. At that time, no thread break was observed. The obtained knitted fabric was heat-treated in an oven at 150 ° C. for 4 minutes, and then subjected to the same measurement test as in Example 1,
The results shown in Table 1 were obtained.

Comparative Example 2 (Excessive Moisture Content during Reaction) As in Example 1, Sumitex adjusted to pH 1 with hydrochloric acid.
Immerse 100% cotton thread in 10% aqueous solution of Resin NS-19,
Liquid was squeezed to 100% wet pickup by a centrifugal dehydrator. This thread is sealed with polyethylene film and kept at 20 ℃
After reacting for 24 hours in 1 hour, it was immersed in a 1 g / L soda ash aqueous solution for 5 seconds, further washed with water at 45 ° C., and dried in an oven at 80 ° C.

The yarn treated in this way is passed through Sumitex Accelera
It was immersed in a 30 g / L aqueous solution of tor X-110, centrifugally dehydrated, squeezed to 90% wet pickup, and then dried in an oven at 80 ° C. When the treated yarn after drying was tested for tensile strength and elongation in the same manner as in Example 1, the tensile strength was 591 g and the elongation was 6.1%.

Further, the dried treated yarn was knitted by a knitting machine. The knitted fabric thus obtained was heat-treated in an oven at 150 ° C. for 4 minutes and then subjected to the same measurement test as in Example 1 to obtain the results shown in Table 1.

Comparative Example 3 (Insufficient Moisture Content during Reaction) As in Example 1, Sumitex adjusted to pH 1 with hydrochloric acid.
Immerse 100% cotton thread in 10% aqueous solution of Resin NS-19,
It was squeezed to a wet pickup of 45% with a centrifugal dehydrator. Next, it was dried in an oven at 50 ° C. to a moisture content of 3%. This thread is sealed with polyethylene film and kept at 20 ℃
After reacting for 24 hours in 1 hour, it was immersed in a 1 g / L soda ash aqueous solution for 5 seconds, further washed with water at 45 ° C., and dried in an oven at 80 ° C.

The yarn treated in this way is treated with Sumitex Accelera
It was immersed in a 30 g / L aqueous solution of tor X-110, centrifugally dehydrated, squeezed to a wet pickup of 45%, and then dried in an oven at 80 ° C. When the treated yarn after drying was subjected to a tensile strength and elongation test in the same manner as in Example 1, the tensile strength was 385 g and the elongation was 2.8%.

Furthermore, when the treated yarn after drying was treated by a knitting machine to be knitted, yarn breakage frequently occurred and the knitting could not be obtained.

Comparative Example 4 (without wet cure) 100 g of Sumitex Resin NS-19 and 1 liter of
The same thread as used in Example 1 was dipped in an aqueous solution containing 30 g of Sumitex Accelerator X-110, centrifugally dehydrated, squeezed to a wet pickup of 45%, and then dried in an oven at 80 ° C. When the dried yarn was tested for tensile strength and elongation in the same manner as in Example 1, the tensile strength was 569 g and the elongation was 5.6%.

Furthermore, the treated yarn after drying was knitted by a knitting machine. At that time, no thread break was observed. The knitted fabric thus obtained was heat-treated in an oven at 150 ° C. for 4 minutes and then subjected to the same measurement test as in Example 1 to obtain the results shown in Table 1.

Comparative Example 5 (resin processing at the fabric stage) The same yarn as used in Example 1 was knitted on a knitting machine, and then 100 liters of Sumitex Resin NS-19 was added in 1 liter.
g and Sumitex Accelerator X-110 in an aqueous solution containing 30 g and wet picking 75% with mangle
Squeezed into Furthermore, at a pin tenter type dryer, 105 ℃
After drying for 3 minutes at 150 ° C., heat treatment was performed at 150 ° C. for 3 minutes. The knitted fabric thus treated was subjected to the same measurement test as in Example 1, and the results shown in Table 1 were obtained.

Comparative Example 6 (without resin processing) The same yarn as that used in Example 1 was knitted on a knitting machine and then subjected to the same measurement test as in Example 1 to obtain the results shown in Table 1. .

[0046]

[Table 1]

[0047]

EFFECTS OF THE INVENTION According to the method of the present invention, since the yarn strength and elongation are not lowered during weaving and knitting, the productivity is not lowered. Also, the final product obtained has useful characteristics such as no roughening of the texture, little reduction in strength, and a significantly small amount of free formaldehyde. Therefore, this method is excellent as a wrinkle-proof, shrink-proof and W & W process for cellulosic fiber products.

[Brief description of drawings]

FIG. 1 is a flow chart schematically showing one embodiment of the method of the present invention.

Claims (9)

[Claims] 1. A cellulose fiber yarn comprising (A) a cellulose cross-linking agent and a cross-linking catalyst, and (B) a cellulose fiber yarn containing the cellulose cross-linking agent and the cross-linking catalyst having a water content of 5 to 80% by weight. %, The cellulose cross-linking agent is reacted, and then washed with water, (C) the cellulosic fiber yarn after reacting with the cellulose cross-linking agent is woven or knitted into a fabric, (D) step After the cellulose cross-linking agent is reacted in (B), after washing with water, before the step (C), or after weaving or knitting in the step (C), the cross-linking catalyst is added again, and (E) thus 2 A method for processing a cellulosic fiber, comprising the steps of heat-treating in a state where the crosslinking catalyst is applied for the second time to complete the reaction of the cellulose crosslinking agent. 2. The method according to claim 1, wherein the cellulose cross-linking agent is a dimethylol dihydroxyethylene urea resin. 3. The method according to claim 1, wherein the reaction of the cellulose cross-linking agent in step (B) is carried out at a temperature of 5 to 50 ° C. for 1 to 50 hours. 4. The method according to claim 1 or 2, wherein the reaction of the cellulose cross-linking agent in the step (B) is carried out by wet heat treatment for 15 seconds to 10 minutes. 5. A step (C) of reacting a cellulose cross-linking agent and washing with water, followed by a step of drying and then weaving or knitting to form a cloth (C), and then applying a cross-linking catalyst again (D). ) Is applied, the method according to any one of claims 1 to 4. 6. A step (B) of reacting a cellulose cross-linking agent and washing with water, followed by a step (D) of adding a cross-linking catalyst again, and then drying the obtained cellulosic fiber yarn, followed by weaving or knitting. The method according to any one of claims 1 to 4, wherein the step (C) of forming a cloth with a cloth is performed. 7. After applying a crosslinking catalyst in step (D), 5
The method according to any one of claims 1 to 6, wherein the drying is carried out at a temperature of 0 to 150 ° C under the condition that the reaction of the cellulose crosslinking agent does not substantially proceed. 8. The method according to claim 1, wherein step (E) further comprises the step of forming the cellulose fiber cloth into a fiber product before heat treatment. 9. The heat treatment in the step (E) is performed in the range of 130 to 180.
The method according to any one of claims 1 to 8, which is carried out at a temperature of ° C for 30 seconds to 15 minutes.