JP4081578B2 - Method for removing amine odor from cellulosic fiber structure - Google Patents

Description

The present invention relates to a method for removing an amine odor from a cellulosic fiber structure processed with a resin. More specifically , the present invention is free from the generation of free formaldehyde, and has a high form stability level that suppresses the generation of odor of resin and the change in whiteness of the fabric. The present invention relates to a method for removing an amine odor from a form-stable cellulosic fiber structure capable of providing an antifungal effect.

  Conventionally, various resin processing agents and resin processing methods have been studied in order to impart form-stabilizing performance such as anti-molding or shrink-proofing properties to cellulosic fiber structures.

  By the way, the cause of wrinkles or shrinkage of the cellulosic fiber fabric is that hydrogen bonds in the amorphous region of cellulose are broken and deformed by the action of external force or water, and hydrogen bonds are generated again in that state. It will occur.

  The imparting of antifungal or shrinkage resistance by resin processing of the dough is based on the fact that cross-linking is generated between cellulose molecules by a resin processing agent, and the introduction of this cross-linking makes the hydrogen bond difficult to break by the action of external force or water. In this case, as the resin processing agent, a method using a so-called fiber-reactive resin such as urea formaldehyde resin, glyoxal resin, or melamine resin is generally used.

  In addition, a method for forming a film using a polyurethane resin or the like and restraining the movement of fibers is also known in order to perform a fender-proofing process on the fabric.

  However, according to the processing method using the fibrin-reactive resin, a certain degree of antifungal properties can be obtained, but the strength decreases with an increase in the amount of resin added. There are problems such as occurrence. Moreover, although the method using a polyurethane resin does not generate free formaldehyde, the obtained antifungal property is very low, and the antifogging property at the form stable level cannot be obtained.

  In some cases, formaldehyde itself is used for anti-mold processing, but high concentration of formaldehyde is said to adversely affect the human body. Therefore, the cellulose resin cross-linking agent has been improved to have a lower generation amount of free formaldehyde, and at present, a low-formaldehyde resin cross-linking agent has been put into practical use. On the other hand, a non-formaldehyde resin processing method in which free formaldehyde is not generated has been proposed, but sufficient antifungal property and whiteness cannot be obtained, and the present state is that it has not been put into practical use as a form-stable processing.

  Processing methods using non-formaldehyde resin processing agents that do not generate free formaldehyde include (a) glyoxal-based non-formaldehyde resin, (b) BHES (bishydroxyethylsulfone), (c) epoxy resin, and (d) prevention with polycarboxylic acid. In the case of (i), there is a defect that an abnormal odor such as an amine odor due to decomposition and modification of the resin occurs from the processed fabric. In the cases of (b) and (c), the whiteness changes. In the case of (d), since the texture is remarkably hard, the product having a high resin concentration used for form stabilization processing has a large influence of the problem, and none of them has been put into practical use.

In addition, as a well-known document relevant to this invention, there exist the following.
Japanese Patent Laid-Open No. 10-168741

The present invention has been made in view of the above circumstances, and is a form-stable cellulosic fiber structure capable of imparting high anti-mold properties with a high form-stable level excellent in washing durability without generating free formaldehyde. to provide the amine odor removal how.

As a result of intensive studies to achieve the above object, the present inventor has applied a treatment liquid containing a glyoxal-based non-formaldehyde resin processing agent and a specific amount of a resin processing catalyst to a cellulosic fiber structure, followed by heat treatment. to upon the resin finishing agent and cellulose and resin finish a certain amount by reacting Ru is adhered to the fiber structure, pretreated in advance impart photocatalyst before granting resin finish or resin finish after heat treatment to impart and to impart photocatalytic worked up by Rukoto depositing a specific amount of the photocatalyst relative to the fiber structure, to prevent the occurrence of odor due to decomposition of the resin, the whiteness It is possible to suppress changes, and to impart high antifungal properties to the fiber structure without generating free formaldehyde, and it has a low W & W (wash and wear) property. It found that sex cellulosic fiber structure is obtained, leading to completion of the present invention.

  That is, as described above, the fibrin-reactive resin that does not generate free formaldehyde is (i) glyoxal non-formaldehyde resin, (b) BHES (bishydroxyethylsulfone), (c) epoxy resin, (d) poly. There are carboxylic acids, but (a) Glyoxal-based non-formaldehyde resins have the problem of generating amine odors due to decomposition and modification of the resin. (B) BHES is extremely yellowed and cannot be bleached or processed white. Epoxy resin turns the fluorescent whitening agent for cellulose green, so it cannot be processed white. (D) Polycarboxylic acid needs to form an anhydride once, and a high temperature is required at that time. And (b), (c), and (d) are all difficult to form-stabilize, which has high fouling resistance. Not suitable from.

  In addition, (b) a catalyst that prevents degradation and modification of the resin has also been proposed for the glyoxal-based non-formaldehyde resin, but in order to obtain a high form-stable antifungal property with a non-formaldehyde resin that is poorly reactive with fibrin. In order to improve the reactivity, it is necessary to increase the resin concentration and to select a catalyst having a higher reactivity, which is insufficient. In addition to these problems, there is a problem that even if these catalysts are used, an odor is generated when irradiated with light such as sunlight. The present invention can solve these problems of the prior art and can impart a high degree of form-stable performance to the cellulosic fiber structure.

Therefore, the present invention
(1) from glyoxal based cellulosic fiber structure with a resin processed by non-formaldehyde resin finish to a method of removing amine odor generated by decomposition and denaturation of the resin finish, the cellulose-based fiber structure, glyoxal A non-formaldehyde resin processing agent and a treatment liquid containing 1 to 6% by mass of a resin processing catalyst to the resin processing agent, followed by heat treatment to cause the resin processing agent and cellulose to react to form a fiber structure respect upon the resin finish Ru is deposited 10 to 30 mass%, after applying before or heat treatment of the treatment solution, 0.1 to 5% by weight of the photocatalyst was treated with an agent containing a photocatalyst relative to the fiber structure by adhering the resin by glyoxal-based non-formaldehyde resin processing agent characterized that you decomposed and removed by the photocatalyst of the amine odor Amine odor removal method of engineering cellulosic fibrous structure,
(2) The method according to (1) , wherein the treatment liquid is dried at 80 to 130 ° C. and the heat treatment is performed at 140 to 170 ° C.
To provide.

According to how the present invention, since no free formaldehyde generated high safety and little generation of amine odor due grayed Riokizaru based non-formaldehyde resins, moreover the washing durability while suppressing a decrease and lowering of strength whiteness Excellent advanced antifungal properties and high W & W properties can be imparted to the cellulosic fiber structure.

  The processing method of the present invention is a form-stable cellulosic fiber in which a treatment liquid containing a non-formaldehyde resin processing agent and a catalyst is applied to a cellulosic fiber structure and then heat treated to react the resin processing agent with cellulose. It is a processing method of a structure, which is treated with a chemical containing a photocatalyst before application of the treatment liquid or after heat treatment.

  Here, examples of the cellulosic fiber structure of the present invention include woven fabric, knitted fabric, and non-woven fabric. Cellulosic fibers constituting these fiber structures include natural cellulose fibers such as cotton and hemp, viscose rayon, copper ammonia rayon (cupra), tencel (purified cellulose), regenerated cellulose fibers such as polynosic, acetate, etc. Semi-regenerated cellulose fibers are mentioned. Among these, in particular, it is preferable to contain 30% by mass or more, particularly 50% by mass or more of cotton fiber from the viewpoint of water absorption, hygroscopicity, texture, etc. Can be used.

  These cellulosic fiber structures can be subjected in advance to known treatments such as hair burning, desizing, scouring, bleaching, mercerizing and the like, if necessary. The fabric may be dyed or printed.

  In the processing method of this invention, the said fiber structure is processed with the chemical | medical agent containing a photocatalyst, and a photocatalyst is made to adhere to a fiber structure. In this case, the treatment with the chemical containing the photocatalyst is performed before or after the heat treatment. By using a photocatalyst, it is possible to prevent odorous components such as amine odor generated from fiber structures when processed with non-formaldehyde resins, especially glyoxal-based non-formaldehyde resins, and to improve comfort be able to.

  When processing (pretreatment) with a chemical containing a photocatalyst before applying a resin processing agent, first, after applying a chemical containing a photocatalyst (aqueous dispersion) to the fiber structure, the photocatalyst is dried. Adhere to fiber structure.

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

  In the present invention, among these, titanium oxide and silicon dioxide-containing composite titanium oxide are preferably used from the viewpoints of ease of use and effects. Examples of the crystal type of titanium oxide include an anatase type, a rutile type, a brookite type, and the like. Any crystal type can be suitably used as long as it has photocatalytic performance.

  The amount of the photocatalyst used is preferably 0.1 to 5% by mass, particularly preferably 0.5 to 4% by mass in terms of solid content based on the mass of the fiber structure (untreated). If the amount of the photocatalyst attached is too small, the deodorizing effect may not be exhibited. If the amount is too large, the texture may be cured, and the fabric strength may be reduced and the color may be whitened.

  The method for attaching the photocatalyst to the fiber structure may be any method as long as the above chemical can be applied to the fiber structure, and known methods such as a pad-dry method, a coating method, a spray method, and a bath method. Can be adopted. Among these, it is particularly preferable to use the pad / dry method from the viewpoint of excellent workability and economy.

  The treatment by the pad / dry method is performed by immersing the fiber structure in a chemical containing a photocatalyst, and squeezing at a drawing ratio of, for example, 50 to 70% so that the amount of the photocatalyst attached to the fiber structure is within the above-described range Treatment is performed at 90 to 170 ° C., particularly 100 to 150 ° C. for 1 to 3 minutes, particularly 1 to 2 minutes, to attach the drug to the fiber structure. Here, if the dry temperature is too low, the drying time may be long and workability may be reduced.

  Next, a treatment liquid (aqueous dispersion) containing a non-formaldehyde resin processing agent and a catalyst is applied to the fiber structure so that the fiber structure is impregnated with the treatment liquid.

  In the present invention, a non-formaldehyde resin processing agent that does not release formaldehyde from the processed fiber structure is used as the resin processing agent. Non-formaldehyde resins include glyoxal non-formaldehyde resins such as N, N'-dimethyldihydroxyethylene urea, polycarboxylic acid non-formaldehyde resins such as citric acid, butanetetracarboxylic acid, maleic acid, succinic acid, and adipic acid, ethylene glycol Examples thereof include epoxy non-formaldehyde resins such as diglycidyl ether, diethylene glycol diglycidyl ether, and propylene glycol diglycidyl ether, and sulfone non-formaldehyde resins such as BHES (bisβ-hydroxyethyl sulfone). Of these, N, N′-dimethyldihydroxyethyleneurea, which is a glyoxal-based resin with less whiteness reduction, discoloration, and texture hardening, is preferable.

  The amount of the resin processing agent attached to the cellulosic fiber structure is preferably 10 to 30% by mass, more preferably 15 to 20% by mass as the solid content, based on the mass of the cellulosic fiber structure (untreated) to be processed. %. If the adhesion amount is too small, the effect of resin processing may not be sufficiently exhibited, and if it is too large, the strength of the fiber structure and the generation of a strange odor accompanying resin processing may be significant. In order to obtain shape stability, it is desirable to give the highest concentration that can maintain the practical strength of the resin.

  A catalyst is added to the treatment liquid used in the present invention in order to increase the reaction activity between the resin processing agent and cellulose and to perform resin processing quickly. The catalyst is not particularly limited as long as it is a catalyst usually used for resin processing. For example, boron fluoride such as ammonium borofluoride, sodium borofluoride, potassium borofluoride, zinc borofluoride, magnesium borofluoride, and the like. Compounds, inorganic metal salt catalysts such as magnesium chloride, magnesium sulfate and magnesium nitrate, and inorganic acids such as phosphoric acid, hydrochloric acid, sulfuric acid, sulfurous acid, hyposulfite and boric acid. These catalysts can be used in combination with organic acids such as citric acid, tartaric acid, apple acid and maleic acid as a co-catalyst, if necessary.

  1-6 mass% is preferable with respect to the resin processing agent, and, as for the usage-amount of the said catalyst, 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 it is too large, the fabric may be deteriorated. In order to obtain shape stability, it is desirable to give the highest concentration that can maintain the practical strength of the catalyst.

  Moreover, the auxiliary | assistant for advancing reaction with a cellulose and a resin processing agent smoothly can be added to a process liquid as needed. That is, the auxiliary agent has an action as a reaction solvent that promotes the reaction between the resin processing agent and cellulose, or promotes the reaction even in the cross-linking reaction, and further has an action of swelling cellulose.

  Examples of the auxiliary agent 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 glycol monobutyl ether. Nitrogen-containing solvents such as ether alcohols, dimethylformamide, morpholine, 2-pyrrolidone, dimethylacetamide, N-methylpyrrolidone, ethyl acetate, isopropyl acetate, butyl acetate, amyl acetate, ethylene glycol monomethyl ether, ethylene glycol monoethyl acetate Examples thereof include esters such as ether and γ-butyrolactone.

  In addition to the above-described components, a texture adjusting softener, a surfactant as a penetrating agent, and the like can be added to the treatment liquid of the present invention as necessary.

  The method for applying the treatment liquid to the cellulosic fiber structure is not particularly limited, and a known method such as a normal pad / dry method, a coating method, a spray method, or a bath method can be employed. Among these, the pad dry method using a tenter can be preferably used because it is excellent in workability and economy.

  In the pad-dry method, after immersing the fiber structure in a treatment liquid containing a resin processing agent and a catalyst, the resin processing agent and the catalyst have an adhesion amount in the above-described range with respect to the fiber structure, for example, 50 to It is desirable to squeeze at a squeezing ratio of 120%, dry the water under conditions of a dry temperature of 80 to 130 ° C., particularly preferably 90 to 110 ° C., a treatment time of 1 to 10 minutes, particularly preferably 1 to 3 minutes. The drying temperature is preferably as low as possible, but if it is less than 90 ° C., a long drying time is required, and if it exceeds 130 ° C., migration of the resin processing agent occurs, causing inconveniences such as uneven distribution of the resin processing agent. In some cases, the morphological stability may not be obtained.

  Heat treatment (baking) is necessary to crosslink the resin and cellulose after pad drying, but the conditions are 140-170 ° C., preferably 150-160 ° C., 2-10 minutes, preferably 2-6. For minutes. The baking machine for the heat treatment is not particularly limited, and a tenter can be used. However, 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 the reaction proceeds slowly when the heat treatment temperature is less than 140 ° C, and the dough turns yellow when the heat treatment temperature exceeds 170 ° C. Inconveniences such as this may occur.

  It is preferable to adjust the pH of the fiber structure obtained by the heat treatment by washing away the unfixed resin processing agent by washing with water and neutralizing and washing with sodium carbonate or the like.

  It is possible to sew once after the pad and dry, and then heat treatment, but in that case, the heat treatment conditions may be almost the same, but it is difficult to wash after sewing and heat treatment or to apply a photocatalyst, so pretreatment It is preferable to apply a photocatalyst in advance and perform resin processing.

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

  The drug used in the present invention may contain, in addition to the above components, a softening agent for adjusting the texture, a deodorant, a hard finish, a functional drug, and the like as necessary.

  Finally, if necessary, dyeing, raising, soft finishing and the like can be performed.

  According to the processing method of the present invention, high antifungal properties can be imparted to the cellulosic fiber structure while maintaining sufficient whiteness while being non-formaldehyde. In addition, as will be described later, the cellulose fiber structure obtained by the method of the present invention is excellent in washing durability, can achieve high W & W properties, and has little generation of amine odor due to glyoxal non-formaldehyde resin. It can be said that the value is extremely high.

  EXAMPLES Hereinafter, although an Example and a comparative example are shown and this invention is demonstrated more concretely, this invention is not restrict | limited to the following Example.

[Example 1]
100% cotton warp 50 × 40 weft plain fabric (warp density 148 / inch, weft density 70 / inch) is bleached in a conventional manner, impregnated with liquid ammonia at −34 ° C. for 10 seconds, and then heated with liquid ammonia Removed by evaporation.
A non-formaldehyde resin treatment liquid having the formulation shown in Table 1 was applied to this woven fabric by a pad-dry method (100 ° C. × 120 seconds) with a multistage tenter, followed by baking at 160 ° C. for 2 minutes with a multistage tenter, washed with water, Antibacterial finishing was performed by post-treatment using the chemicals shown in Table 2 by the pad-dry method (120 ° C. × 1 minute).
The amount of resin adhered to the fabric was 18% by mass, and the amount of photocatalyst adhered was 1.5% by mass.

＊二酸化ケイ素含有複合酸化チタンスラリー

* Composite titanium oxide slurry containing silicon dioxide

About the obtained textile fabric, W & W property and antifungal property were evaluated by the following method, and the odor sensory test was done. The results are shown in Table 4.
W & W property evaluation method: JIS L 1096
Washing / drying method: JIS L 217 103 method / tumble drying Tensile strength: JIS L 1096 Tensile strength and elongation A method (labeled strip)
Tear: JIS L 1096 Tear Strength Measured by Method D (Pendulum Method) Odor Sensory Test Method: 10 g of dough placed in a 200 ml flask, sealed and exposed to sunlight
For 48 hours.
<Evaluation criteria> ○: Substantially odorless
Δ: Slight odor
×: Strong odor

[Example 2]
The treatment was performed in the same manner as in Example 1 except that the drying was performed at 130 ° C. for 60 seconds and the baking was performed at 160 ° C. for 2 minutes. The results are shown in Table 4.

[Example 3]
The treatment was performed in the same manner as in Example 1 except that baking was performed at 145 ° C. for 4 minutes, and evaluation was performed in the same manner. The results are shown in Table 4.

[Comparative Example 1]
It processed similarly to Example 1 except not putting a photocatalyst in a post-processing prescription, and evaluated similarly. The results are shown in Table 4.

[Comparative Example 2]
The same treatment as in Example 1 was conducted except that a natural deodorant (Fresh Shiramatsu FS-500M (manufactured by Matsuo Pharmaceutical Co., Ltd.)) was added instead of the photocatalyst in the post-treatment formulation shown in Table 3 below, and evaluation was performed in the same manner. The results are shown in Table 4.

[Example 4]
100% cotton warp 50 × 40 weft plain fabric (warp density 148 / inch, weft density 70 / inch) is bleached in a conventional manner, impregnated with liquid ammonia at −34 ° C. for 10 seconds, and then heated with liquid ammonia Removed by evaporation.
The pretreatment agent shown in Table 5 was applied to this woven fabric by a pad-dry method (120 ° C. × 60 seconds) using a multistage tenter, and then the non-formaldehyde resin treatment solution shown in Table 6 was applied using a pad-dry method (100 ° C x 120 seconds). Then, after cutting and sewing, anti-mold processing was performed by baking (150 ° C. × 6 minutes) with a trolley conveyor type baking apparatus.
The amount of resin adhered to the fabric was 18% by mass, and the amount of photocatalyst adhered was 1.5% by mass.

  About the obtained textile fabric, W & W property and antifungal property were evaluated by the same method as Example 1, and the odor sensory test was done. The results are shown in Table 9.

[Comparative Example 3]
The treatment was the same as in Example 4 except that no pretreatment was performed, and the same evaluation was performed. The results are shown in Table 9.

[Comparative Example 4]
It processed similarly to Example 4 except having set it as the pretreatment agent shown in Table 7, and evaluated similarly. The results are shown in Table 9.

[Comparative Example 5]
The sample was treated in the same manner as in Example 4 except that there was no pretreatment and the resin treatment solution shown in Table 8 was evaluated in the same manner. The results are shown in Table 9.

Claims (2)

Cellulosic fiber structure with a resin processed by glyoxal-based non-formaldehyde resin finish to a method of removing amine odor generated by decomposition and denaturation of the resin finish, the cellulose-based fiber structure, glyoxal-based non-formaldehyde After the treatment liquid containing 1 to 6% by mass of a resin processing catalyst is applied to the resin processing agent and the resin processing agent, the resin processing agent and cellulose are reacted by heat treatment to the fiber structure. upon the resin finish Ru is deposited 10 to 30 mass%, after applying before or heat treatment of the process liquid, depositing a photocatalyst 0.1 to 5 mass% with respect to treatment with a drug containing a photocatalyst fiber structure in, the amine odor to the resin processed by glyoxal-based non-formaldehyde resin processing agent characterized that you decomposed and removed by the photocatalyst Amine odor removal method of cellulosic fiber structure. Dried after the treatment liquid application at 80 to 130 ° C., Method person according claim 1, characterized in that heat treatment at 140 to 170 ° C..