KR20060119750A - Method for processing of shape-stable cellulose-based fiber structural product and shape-stable cellulose-based fiber structural product - Google Patents

Abstract

A shape-stable cellulose-based fiber structural product and a processing method thereof are provided to inhibit lowering of the whiteness. The treating solution containing the non formaldehyde resin working agents and the resin working catalyst is provided with the cellulose base fiber structure. Thereafter the cellulose base fiber structure is treated by heat so that the resin working agent and the cellulose are reacted with each other. After or before the heat treatment, the cellulose based fiber structure is treated by medicine containing the optical catalyst. After providing the treatment solution, the cellulose base fiber structure is dried at 80-130 degrees in centigrade and the heat treatment is performed at 140-170 degrees in centigrade.

Description

TECHNICAL PROCESSING OF SHAPE-STABLE CELLULOSE-BASED FIBER STRUCTURAL PRODUCT AND SHAPE-STABLE CELLULOSE-BASED FIBER STRUCTURAL PRODUCT

Technical Field

The present invention relates to a processing method of a cellulose-based fiber structure, which will be described in more detail. There is no generation of free formaldehyde, and a high anti-wrinkling effect with a high level of shape stability that suppresses the occurrence of odor of resin and the change of whiteness of fabric is provided. It relates to a processing method of a shape stable cellulosic fiber structure obtained and a shape stable cellulosic fiber structure obtained by this method.

Background

Background Art Various resin processing agents and resin processing methods have been studied in order to impart morphological stability performance such as wrinkle prevention or shrinkage property to cellulose fiber structures.

By the way, the cause of wrinkles or shrinkage in the fabric of the cellulose-based fiber is caused by the hydrogen bond in the amorphous region of the cellulose is broken and deformed due to the action of external force or water, and the hydrogen bond is generated again in that state.

The prevention of wrinkles or preshrinkage by resin processing of the original fabric is used to create crosslinks between the cellulose molecules by the resin processing agent, and the hydrogen bonds are not easily destroyed by the action of external force or water by the crosslinking introduction. In this case, as the resin processing agent, a method using a so-called fibrin-reactive resin such as urea formaldehyde resin, glyoxal resin or melamine resin is generally used.

Moreover, in order to give wrinkle prevention processing to a fabric, the method of forming a film using a polyurethane resin and restraining the movement of a fiber is also known.

However, according to the processing method using the fibrin-reactive resin, although some degree of anti-wrinkle resistance can be obtained surely, a strong decrease occurs as the amount of resin added increases, and free formaldehyde is generated by hydrolysis of the resin. There is a problem. In addition, the method using a polyurethane resin does not generate | occur | produce glass formaldehyde, but the wrinkle prevention property obtained is very low, and the wrinkle prevention property of the shape stability level cannot be obtained.

Although formaldehyde itself may be used for wrinkle prevention processing, high concentration of formaldehyde is said to have an adverse effect on a human body. Therefore, the resin crosslinking agent of cellulose is being improved by lower generation | occurrence | production amount of free formaldehyde, and the low formaldehyde type resin crosslinking agent is put into practical use now. On the other hand, a non-formaldehyde resin processing method in which free formaldehyde does not occur at all has been proposed. However, sufficient anti-wrinkle properties and whiteness have not been obtained, which is not currently used as a form stability processing.

As a processing method by the non-formaldehyde resin processing agent which does not generate free formaldehyde, (A) glyoxal type non-formaldehyde resin, (B) BHES (bishydroxyethyl sulfone), (C) epoxy resin, ( D) Anti-wrinkling treatment with polycarboxylic acid has been proposed. However, in the case of (A), there is a drawback that an abnormal smell such as an amine odor due to decomposition modification of resin is generated from the processed fabric. In the case of (B) and (C), the change in whiteness is large, and in the case of (D), the texture becomes hard. All have not been put to practical use.

On the other hand, the following are well-known documents concerning this invention.

[Patent Document 1] Japanese Patent Application Laid-Open No. 10-168741

The present invention provides a method for processing a morphologically stable cellulose-based fiber structure which can impart high wrinkle resistance without having to generate free formaldehyde and having excellent washing durability, and a cellulose-based excellent morphological stability obtained by the method. Provide a fiber structure.

Means to solve the problem

As a result of intensive studies to achieve the above object, the present inventors give a cellulose fiber structure a treatment liquid containing a non-formaldehyde resin processing agent and a resin processing catalyst, and then heat-treat the reaction to react the resin processing agent with cellulose. In the method for processing a morphologically stable cellulose-based fiber structure, before the resin processing agent is applied to the cellulose fiber structure, the photocatalyst is pretreated with a photocatalyst, or after the heat treatment is performed with the resin processing agent, the photocatalyst is added after the heat treatment. By treating, it is possible to prevent the generation of odors due to decomposition of the resin, to suppress the change in whiteness, and to impart high wrinkle resistance to the fiber structure without generating free formaldehyde, and to prevent W & W (washing). And wear) excellent shape stability cellulose fiber structure And it came to realize the present invention found.

That is, as described above, the fibrin-reactive resin in which no free formaldehyde is generated may be (a) glyoxal non formaldehyde resin, (b) BHES (bishydroxyethylsulfone), (c) epoxy resin, ( D) polycarboxylic acids. However, (a) glyoxal-based non-formaldehyde resins have a problem in that amine odor due to decomposition modification of the resin is generated. (B) BHES cannot be bleached and white processed because of its yellowing. (C) Epoxy resins cannot be white processed because they fluoresce the fluorescent whitening agents for cellulose. (D) The polycarboxylic acid needs to form anhydride once, and there is a problem that discoloration and texture become hard due to the need for high temperature at that time. (B), (C) and (D) are not suitable for the shape stability processing which has a high wrinkle prevention property since it lacks wrinkle prevention property.

In addition, (a) glyoxal-based non-formaldehyde resins have been proposed catalysts to prevent decomposition modification of resins, but non-formaldehyde resins that lack reactivity with fibrin have high reactivity to obtain wrinkle resistance. In order to improve, the resin concentration needs to be high, and the catalyst is also insufficient because it is necessary to select a more reactive one. In addition to these problems, there is a problem in that even if these catalysts are used, odor is generated when irradiated with light such as sunlight. The present invention solves these problems of the prior art, and can impart a high form stability performance to the cellulosic fiber structure.

Therefore, the present invention,

(1) A processing method of a morphologically stable cellulose fiber structure in which a treatment liquid containing a non-formaldehyde resin processing agent and a resin processing catalyst is given to a cellulose fiber structure, followed by heat treatment to react the resin processing agent with cellulose.

Before or after the heat treatment of the treatment solution, processing method of the morphologically stable cellulose-based fiber structure, characterized in that the cellulose-based fiber structure is treated with a medicament containing a photocatalyst,

(2) The processing method according to (1), wherein the treatment solution is dried at 80 to 130 ° C. and heat treatment is performed at 140 to 170 ° C.,

(3) The processing method according to (1) or (2), wherein the non-formaldehyde resin processing agent is a glyoxal non-formaldehyde resin,

(4) The processing method according to (1), (2) or (3), wherein the adhesion amount of the non-formaldehyde resin processing agent to the fiber structure is 10 to 30% by mass,

(5) The processing method according to any one of (1) to (4), wherein the catalyst for resin processing is selected from a boron fluoride compound, an inorganic metal salt, and an inorganic acid,

(6) The processing method according to any one of (1) to (5), wherein the amount of the catalyst for resin processing is 1 to 6% by mass relative to the resin processing agent,

(7) The photocatalyst according to any one of (1) to (6), wherein the photocatalyst is titanium oxide, ferric oxide, zinc oxide, tungsten trioxide, bismuth trioxide, strontium titanate, cadmium oxide, cesium oxide, silicon dioxide A processing method, characterized in that it is selected from containing complex titanium oxide,

(8) The processing method according to any one of (1) to (7), wherein the adhesion amount of the photocatalyst to the fiber structure is 0.1 to 5% by mass,

(9) Form stable cellulosic fiber structure obtained by the processing method in any one of (1)-(8).

To provide.

Effects of the Invention

According to the processing method of the present invention, since high free formaldehyde does not occur, safety is high, and there is little generation of amine odor caused by glyoxal non-formaldehyde resins, and high wrinkles excellent in washing durability while suppressing the decrease in whiteness Preventive property and high W & W property can be provided to a cellulose fiber structure.

To practice the invention  for Best  shape

The processing method of the present invention provides a processing solution containing a non-formaldehyde resin processing agent and a resin processing catalyst to a cellulose fiber structure, and then heat-processes to react the resin processing agent with cellulose. For example, the cellulose fiber structure is treated with a medicament including a photocatalyst before or after heat treatment.

Here, the cellulose fiber structure of the present invention may include woven fabrics, knitted fabrics, nonwoven fabrics, and the like. Examples of the cellulose fibers constituting these fiber structures include cotton, natural cellulose fibers such as hemp, viscose rayon, copper ammonia rayon (cupra), regenerated cellulose fibers such as tencel (purified cellulose), polynostic, and the like. And regenerated cellulose fibers. Among these, it is preferable to contain 30 mass% or more, especially 50 mass% or more of cotton fiber especially from a viewpoint of water absorption, hygroscopicity, a touch, etc., Especially the fiber structure of 100 mass% of cotton fiber can be used suitably.

These cellulosic fiber structures can be subjected to known treatments such as fine hair removal, pull-out, refining, bleaching, and squeegee processing, if necessary. In addition, this fabric may be dyed or printed.

In the processing method of the present invention, the fiber structure is treated with a medicament including a photocatalyst to attach the photocatalyst to the fiber structure. In this case, the treatment with the medicament containing the photocatalyst is carried out before imparting the resin processing agent or after the heat treatment. By the use of a photocatalyst, an unpleasant odor component such as an amine odor generated from a fibrous structure when processed into a non-formaldehyde resin, particularly a glyoxal non-formaldehyde resin, can be prevented by the photocatalyst, thereby improving comfort. have.

In the case of treatment (pretreatment) with a medicament including a photocatalyst before the resin processing agent is applied, a medicament containing a photocatalyst (water dispersion) is first applied to the fiber structure, followed by drying to attach the photocatalyst to the fiber structure.

Here, examples of the photocatalyst used in the present invention include titanium oxide, ferric oxide, zinc oxide, tungsten trioxide, bismuth trioxide, strontium titanate, cadmium oxide, cesium oxide, and silicon dioxide-containing composite titanium oxide. They may be freely used in the form of a slurry dispersed in water, alcohol, or the like, or in the form of a paste and a powder.

In the present invention, among these, titanium oxide and silicon dioxide-containing composite titanium oxide are suitably used in view of ease of use and effect. Examples of the crystal form of titanium oxide include an anatase type, rutile type, brookite type, and the like, and any type of crystal can be suitably used as long as it has photocatalytic performance.

As for the usage-amount of a photocatalyst, 0.1-5 mass%, especially 0.5-4 mass% are preferable at solid content concentration with respect to the mass of a fiber structure (untreated). If the amount of the photocatalyst is too small, the deodorizing effect may not be exhibited. If the amount is too large, the texture becomes hard, and the strength of the original fabric may decrease, and the color whitening may occur.

The method of attaching the photocatalyst to the fiber structure may be any method as long as the agent can be applied to the fiber structure, and a known method such as a pad drying method, a coating method, a spray method, a bath method, or the like can be adopted. Among these, it is preferable to use the pad drying method from the point which is excellent in workability and economic efficiency especially.

The treatment by the pad drying method is to immerse the fiber structure in a drug containing a photocatalyst, to hold the photocatalyst to the above-described fiber structure so that the amount of adhesion of the photocatalyst to the above-mentioned range is e.g. The agent is attached to the fibrous structure by treatment at 170 ° C., in particular 100-150 ° C., for 1-3 minutes, in particular 1-2 minutes. Here, when dry temperature is too low, drying time may become long and workability may fall.

Next, a treatment liquid (water dispersion) containing a non-formaldehyde resin processing agent and a catalyst for resin processing is applied to the fiber structure to impregnate the treatment liquid in the fiber structure.

The present invention is characterized by using a non-formaldehyde resin processing agent which does not favor formaldehyde from the fiber structure after processing as a resin processing agent. As non-formaldehyde resin, Glyoxal non-formaldehyde resins, such as N, N'- dimethyl dihydroxy ethylene urea, Polycarboxylic-acid ratio, such as citric acid, butane tetracarboxylic acid, maleic acid, oxalic acid, adipic acid, etc. Sulfur, such as formaldehyde resin, ethylene glycol diglycidyl ether, diethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, such as epoxy-type non-aldehyde resin, BHES (bis (beta) -hydroxyethyl sulfone) And von non formaldehyde resins. Among them, N, N'-dimethyldihydroxyethylene urea of glyoxal-based resins having less whiteness, discoloration, and hardening of the texture is preferable.

The amount of adhesion of the resin processing agent to the cellulose fiber structure is preferably 10 to 30% by mass, more preferably 15 to 20% by mass, as a solid content with respect to the mass of the cellulose fiber structure (untreated) to be processed. When there is too little adhesion amount, the effect of resin processing may not fully be exhibited, and when too much, the strong fall of the fiber structure resulting from resin processing and occurrence of an abnormal smell may become remarkable. In order to obtain morphological stability, it is preferable that the concentration of the resin be given the highest concentration that can maintain the practical strength.

In the treatment liquid used in the present invention, a catalyst for resin processing is added to increase the reaction activity between the resin processing agent and cellulose and to perform the resin processing quickly. Such catalyst is not particularly limited as long as it is a catalyst generally used for resin processing, and examples thereof include boron fluoride compounds such as ammonium borohydride, sodium borohydride, potassium borofluoride, zinc borofluoride and magnesium borohydride, magnesium chloride and magnesium sulfate. And inorganic metal salt catalysts such as magnesium nitrate, phosphoric acid, hydrochloric acid, sulfuric acid, sulfurous acid, hyposulfuric acid, and boric acid. In these catalysts, organic acids, such as citric acid, tartaric acid, malic acid, and maleic acid, can also be used together as a promoter as needed.

As for the usage-amount of the said catalyst for resin processing, 1-6 mass% is preferable with respect to a resin processing agent, More preferably, it is 1-2 mass%. If the amount of the catalyst used is too small, the crosslinking reaction may not proceed, and if the amount is too large, deterioration of the original fabric may occur. In order to obtain morphological stability, the concentration of the catalyst is preferably to give the highest concentration that can maintain the practical strength.

In addition, to the treatment liquid, a preparation for smoothly advancing the reaction between the cellulose and the resin processing agent can be added. That is, the preparation has the effect of promoting the reaction between the resin processing agent and the cellulose, or even the crosslinking reaction, as a reaction solvent for evenly advancing the reaction, furthermore, swelling the cellulose.

Examples of the preparation include polyhydric alcohols such as glycerin, ethylene glycol, polyethylene glycol, and polypropylene glycol, ethylene glycol monoethyl ether, diethylene glycol monoethyl ether, ethylene glycol monomethyl ether, diethylene glycol monomethyl ether, and diethylene. Ether alcohols such as glycol monobutyl ether, nitrogen-containing solvents such as dimethylformamide, morpholine, 2-pyrrolidone, dimethylacetamide, N-methylpyrrolidone, ethyl acetate, isopropyl acetate, butyl acetate, Ester, such as amyl acetate, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether acetate, (gamma) -butyrolactone, etc. are mentioned.

In addition to the above-described components, a softening agent for adjusting the feel, a surfactant as a penetrating agent, and the like may be added to the treatment liquid of the present invention as necessary.

The method for imparting the treatment liquid to the cellulosic fiber structure is not particularly limited, and known methods such as a general pad drying method, a coating method, a spray method, and a bath method can be adopted. Among these, the pad drying method using a tenter can be used preferably from the point which is excellent in workability and economy.

In the pad drying method, the fiber structure is immersed in the treatment liquid containing the resin processing agent and the catalyst, and then the resin processing agent and the catalyst are attached to the fiber structure in a range of 50 to 120%, for example, so as to have an adhesion amount in the above-described range. It is preferable to dry moisture under conditions of 80 to 130 degreeC of drying, especially preferably 90 to 110 degreeC, and processing time for 1 to 10 minutes, especially preferably 1 to 3 minutes. The drying temperature is preferably as low as possible, but when it is below 90 ° C, a long drying time is required, and when it exceeds 130 ° C, problems such as migration of the resin processing agent and uneven distribution of the resin processing agent occur. This may not be obtained.

Heat treatment (baking) is required to crosslink the resin and cellulose after the pad drying, and the conditions are 2 to 10 minutes at a temperature of 140 to 170 ° C, preferably 150 to 160 ° C, and preferably 2 to 6 minutes. The baking machine for the heat treatment is also not particularly limited, and a tenter can be used, but from the viewpoint of workability and cost, it is preferable to continue the heat treatment with the tenter after drying. The heat treatment temperature and time depend on the type of resin, the amount of resin used, the type of catalyst, the amount of catalyst added, etc., but when the heat treatment temperature is lower than 140 ° C, the reaction progresses slowly, and when the temperature exceeds 170 ° C, yellowing of the fabric occurs. There is a case.

It is preferable that the fiber structure obtained by heat processing wash | cleans an unfixed resin processing agent etc. by water washing, and adjusts pH by neutralizing and washing using a soda carbonate etc.

Although it may be sewn once after the pad drying and heat treatment thereafter, the heat treatment conditions may be almost the same, but since it is difficult to wash after sewing and heat treatment or to impart a photocatalyst, the photocatalyst is attached in advance by pretreatment and the resin It is good to perform processing.

In the present invention, in addition to the above-described method, a treatment (post-treatment) with a drug including a photocatalyst may be performed after the heat treatment, and the treatment conditions in this case can be the same as above.

On the other hand, the drug used in the present invention may contain, in addition to the above components, a softening agent, a deodorant, a hardening agent, a functional drug, and the like, for adjusting the feel, if necessary.

Finally, dyeing, brushing, soft finishing, etc. may be performed as needed.

According to the processing method of the present invention, high wrinkle resistance can be imparted to the cellulosic fiber structure while maintaining sufficient whiteness while being non-formaldehyde. In addition, as described below, the cellulose fiber structure obtained by the method of the present invention is excellent in washing durability, can achieve high W & W properties, and is practical because it hardly generates amine odor due to glyoxal non-formaldehyde resin. The value is very high.

(Example)

Hereinafter, although an Example and a comparative example are given and this invention is demonstrated further more concretely, this invention is not limited to the following Example.

Example 1

100% cotton 50% weft 40 plain fabric (bent density 148 / inch, weft density 70 / inch) was bleached according to the conventional method, and liquid ammonia impregnated at 134 ° C for 10 seconds, and then liquid ammonia was Superheat evaporated off.

The non-formaldehyde resin treatment liquid of the prescription shown in Table 1 was applied to the fabric by a pad drying method (100 ° C. × 120 seconds) with a multistage tenter, and then baked at 160 ° C. × 2 minutes with a multistage tenter, followed by washing with water. The post-treatment was performed by the pad drying method (120 degreeC x 1 minute) using the chemical | medical agent of the prescription shown in 2, and anti-wrinkling process was performed.

The resin adhesion amount to the fabric was 18 mass%, and the adhesion amount of the photocatalyst was 1.5 mass%.

The obtained fabric was evaluated for W & W properties and anti-wrinkle properties by the following method, and an odor sensory test was performed. The results are shown in Table 4.

W & W evaluation method: JIS L 1096

Washing and drying method: JIS L 217 103 method / tumble drying

Length: measured by JIS L 1096 tensile strength and elongation A method (labeled strip method)

Tear: Measured by JIS L1096 Tear Strength D Method

Odor sensory test method: 10 g of fabric was placed in a 200 ml flask, sealed, and subjected to daylight irradiation for 48 hours.

<Evaluation criteria> 0: Almost odorless

            △: slightly smelly

            ×: Severe smell

Example 2

The same process as in Example 1 was conducted except that the drying was changed to a condition of 130 ° C. × 60 seconds and baking to 160 ° C. × 2 minutes, and the evaluation was performed in the same manner. The results are shown in Table 4.

Example 3

Except having changed baking to the conditions of 145 degreeC * 4 minutes, it processed by the method similar to Example 1, and evaluated by the same method. The results are shown in Table 4.

Comparative Example 1

The same procedure as in Example 1 was conducted except that no photocatalyst was added to the post-treatment formulation, and the evaluation was performed in the same manner. The results are shown in Table 4.

Comparative Example 2

It was treated in the same manner as in Example 1 except that a natural deodorant (Fresh Raimatsu FS-500M (Matsuo Pharmaceutical Co., Ltd.)) was added to the post-treatment formulation of Table 3 below, and evaluated in the same manner. The results are shown in Table 4.

Example 4

100% cotton 50% weft 40 plain fabric (bent density 148 / inch, weft density 70 / inch) was bleached according to the conventional method, and liquid ammonia impregnated at 134 ° C for 10 seconds, and then liquid ammonia was Superheat evaporated off.

The pretreatment agent shown in Table 5 was given to this fabric by the pad drying method (120 degreeC * 60 second) by the multistage tenter, and the non-formaldehyde resin process liquid of Table 6 was padded by the multistage tenter (100 degreeC *). 120 seconds). Then, after cutting and sewing, the anti-wrinkling process was performed by baking (150 degreeCx 6 minutes) with the trolley conveyor type baking apparatus.

The resin adhesion amount to the fabric was 18 mass%, and the adhesion amount of the photocatalyst was 1.5 mass%.

About the obtained fabric, W & W property and wrinkle prevention were evaluated in the same manner as Example 1, and the smell sensory test was done. The results are shown in Table 9.

Comparative Example 3

Except not performing pretreatment, it processed by the same method as Example 4, and evaluated in the same method. The results are shown in Table 9.

[Comparative Example 4]

Except having changed into the pretreatment agent shown in Table 7, it processed by the same method as Example 4, and evaluated by the same method. The results are shown in Table 9.

[Comparative Example 5]

The same process as in Example 4 was carried out except that no pretreatment was carried out and the resin treatment liquid of Table 8 was evaluated. The results are shown in Table 9.

According to the processing method of the present invention, since the free formaldehyde does not occur, the safety is high, there is little generation of amine odor by the glyoxal non-formaldehyde resin, and while suppressing the decrease in whiteness, The wrinkle prevention property and high W & W property can be given to a cellulose fiber structure.

Claims (9)

As a processing method of the morphologically stable cellulose fiber structure which gives a process liquid containing a non-formaldehyde resin processing agent and a resin processing catalyst to a cellulose fiber structure, and heat-processes and makes a resin process agent react with cellulose, A method for processing a morphologically stable cellulose fiber structure, characterized in that the cellulose fiber structure is treated with a medicament containing a photocatalyst before or after the treatment solution is applied. The processing method according to claim 1, wherein the drying is performed at 80 to 130 ° C after the treatment liquid is applied, and the heat treatment is performed at 140 to 170 ° C. The processing method according to claim 1, wherein the non-formaldehyde resin processing agent is a glyoxal non-formaldehyde resin. The processing method of Claim 1 whose adhesion amount of a non-formaldehyde resin processing agent with respect to a fiber structure is 10-30 mass%. The processing method according to claim 1, wherein the catalyst for resin processing is selected from a boron fluoride compound, an inorganic metal salt, and an inorganic acid. The processing method of Claim 1 whose usage-amount of the catalyst for resin processing is 1-6 mass% with respect to a resin processing agent. The photocatalyst according to claim 1, wherein the photocatalyst is selected from titanium oxide, ferric oxide, zinc oxide, tungsten trioxide, bismuth trioxide, strontium titanate, cadmium oxide, cesium oxide, and silicon dioxide-containing composite titanium oxide. Processing method. The processing method according to claim 1, wherein the adhesion amount of the photocatalyst to the fiber structure is 0.1 to 5% by mass. It is obtained by the processing method of Claim 1, The shape stable cellulose fiber structure characterized by the above-mentioned.