JPH04289274A - Deodorizing textile product - Google Patents

Abstract

PURPOSE:To obtain the title product causing no discoloration having excellent deodorizing function by incorporating copper at a specified level or higher in the polymer grafted onto the surface of a textile. CONSTITUTION:A textile product such as of synthetic fibers, regenerated fibers or natural fibers is impregnated with (A) a monomer containing or reactive with copper (e.g. a vinyl monomer having carboxyl or sulfonic group) and (B) a vinyl monomer as comonomer to be used in copolymerization followed by graft polymerization and then reaction in a copper sulfate solution, thus giving at a low cost the objective freely dyeable product containing >=100ppm of copper, causing no discoloration and having excellent deodorizing function.

Description

[Detailed description of the invention]

0001

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to textile products such as bedding, interior goods, and clothing that are required to have deodorizing functions, as well as their raw material fibers.

0002

[Prior Art] As a method for imparting a deodorizing function to textile products, a method using ascorbic acid and a divalent iron compound is described in JP-A-61-296111. It has an adsorption effect and is not very effective against mercaptan odor.

[0003] Furthermore, a method for processing fibers with a phthalocyanine copper compound in a manner similar to dyeing is disclosed in Japanese Patent Application Laid-Open No. 62-6978.
It is stated in the No. There are also methods of processing copper sulfide into acrylic fibers and methods of coordinating copper to hydrolyzed acrylic fibers, but each method has the serious drawback that the fibers are colored green or brown. Ta. All textile products are colorfully decorated with fashion. It is not possible to freely dye fibers that are colored green or brown.

[0004] Further, as a deodorant, a deodorizing ingredient extracted from natural Camellia family plants is described in JP-A-56-100060. There is a method of processing this deodorizing ingredient into textile products. However, the deodorizing effect of natural extracts from Camellia family plants is an inclusion effect, and odor components are incorporated into this extract, but compared to the catalytic action of the copper compounds mentioned above, the deodorizing effect is inferior and it is expensive. There is a drawback.

[0005]

[Problems to be Solved by the Invention] An object of the present invention is to provide an inexpensive deodorant fiber product that has an excellent deodorizing function, is hardly colored, and can be freely colored by dyeing, and its raw material fiber. .

[0006]

[Means for Solving the Problems] The present inventors have discovered that the deodorizing function of textile products is caused by copper ions on the surface of the textile products exerting a catalytic action, and that the copper ions inside the textiles are not substantially involved. Focusing on this, they researched a method for stably attaching copper ions to the surface of textile products, leading to the completion of the present invention.

That is, the deodorizing fiber product of the present invention is characterized by containing 100 ppm or more of copper in the graft polymerized portion on the fiber surface.

[0008] In order to attach copper ions to the surface of textile products, coating a copper compound with a resin is the easiest and cheapest method, but the resin layer becomes thick and the copper ion content is low. There is a problem that the deodorizing effect is low. There is also the problem that the deodorizing effect cannot be effectively exhibited unless it is uniformly dispersed in the resin, and there is also the problem that the texture of textile products becomes hard and changes significantly due to resin processing.

Graft polymerization is a method for uniformly and thinly attaching a resin layer to fibers, and in the present invention, a thin resin layer copolymerized with a vinyl comonomer having a carboxylic acid or sulfonic acid group is formed on the fiber surface by this graft polymerization. . These carboxylic or sulfonic acid groups can easily form copper salts. Furthermore, a vinyl comonomer in which the carboxylic acid or sulfonic acid group is a copper salt may be copolymerized. Furthermore, a vinyl comonomer in which the carboxylic acid or sulfonic acid group is a sodium salt may be copolymerized. The sodium salts of the carboxylic acid or sulfonic acid groups of the above sodium salt comonomers can readily form copper salts.

Methods for forming radicals in graft polymerization of vinyl monomers include methods using electron beam irradiation, radiation irradiation, and radical initiators. The present invention can use all of these methods, but the methods of electron beam irradiation and radiation irradiation lack versatility because the irradiation equipment is expensive. On the other hand, these methods have the advantage that radicals are easily generated in the fibers themselves, so that the fibers and the graft polymer layer can be bonded more firmly.

Radical initiators include azo initiators such as azobisisobutyronitrile and azobisvaleronitrile, organic peroxide initiators such as benzoyl peroxide, and potassium persulfate and sodium persulfate. , inorganic persulfate initiators such as ammonium persulfate. Peroxide initiators are not so preferred because they require special care in handling because they can explode. It is preferable to use an inorganic persulfate as an initiator because it is easy to handle and inexpensive. When a persulfate is used as an initiator, it is preferable to use a reducing agent such as sodium bicarbonate or sodium carbonate as is commonly used. The reducing agent may be used in an amount approximately five times that of the initiator, as is commonly used.

[0012] The initiator may be attached to the fibers together with the monomer, but if the initiator is attached to the fibers in advance,
It is preferred that the initiator be at or near the fiber surface.

The graft polymer layer of the present invention exhibits its deodorizing function even if it is as thin as a monomolecular layer. The graft polymerization layer may be thin as long as it has a sufficient copper content. For example, a copper acrylate homopolymer with a molecular weight of 135.5 has a copper content of about 47%, so in order for the graft polymer layer of a copper acrylate homopolymer to contain 100 ppm of copper, it is necessary to On the other hand, 0.02% by weight of a homopolymer of acrylic acid copper salt is sufficient, but since it is difficult to graft-polymerize a homopolymer, in reality, the amount of the graft polymerized layer is 0.05% by weight or more based on the fiber weight. to form. From the viewpoint of the coating strength of the graft polymer layer, it is preferable to form the graft polymer layer in an amount of 0.1% by weight or more based on the weight of the fiber. If the graft polymerization layer is too thick, the texture may change due to adhesion between fibers and dyeing may be hindered, which is not preferable. Moreover, if the graft polymerization layer is thicker than necessary, the deodorizing function will not be improved and the processing cost will increase, which is not preferable.

[0014] The coating strength of the graft polymerization layer depends on the reactivity or affinity with the fiber itself, so it is preferable to select a monomer that has a strong affinity with the fiber. In addition, the higher the molecular weight of the graft polymerization layer, the stronger the film strength, but in order to increase the molecular weight, it is necessary to reduce the amount of initiator and increase the molecular weight, which requires a longer reaction time. Should.

The main monomer used in the graft polymerization of the present invention is a monomer containing copper or reacting with copper. That is, vinyl monomers having carboxylic acid or sulfonic acid groups and salts thereof. The comonomer used in the copolymerization may be a common vinyl monomer. As the vinyl monomer having a carboxylic acid group, for example, acrylic acid, methacrylic acid, maleic acid, etc. can be used. Further, potassium salts, sodium salts, copper salts, etc. of these salts can also be used. Examples of the vinyl comonomer having a sulfonic acid group include allyl sulfonic acid (hereinafter abbreviated as "AS"),
Examples include meta-allylsulfonic acid (hereinafter abbreviated as "MAS"), styrene sulfonic acid, and 2,2-acrylamidomethylpropylsulfonic acid (hereinafter abbreviated as "AMS"). Further, potassium salts, sodium salts, copper salts, etc. of these salts can also be used.

Examples of common vinyl monomers include acrylonitrile, methylacrylonitrile, acrylic methylate, acrylic ethylate, acrylic butyrate,
Methacryl methylate, methacryl ethylate, methacryl butyrate, styrene, vinyl acetate, vinylidene chloride, etc. can be used. Furthermore, in order to improve the film strength of the graft polymerization layer, dienes such as tripropylene glycol diacrylate (hereinafter abbreviated as "TGA") or 2-propenoic acid (2-
Ethyl 2-((2-((1-oxo-2-propenyl)
Crosslinking can also be carried out using a triene such as (oxy)propoxy)methyl)-1,3-propanedyl)bis(oxy(1-methyl-2,1-ethanedyl))ether (hereinafter abbreviated as "TTA"). can.

Regarding the copolymerization ratio of the monomer containing or reacting with copper and the general vinyl monomer, the higher the ratio of the monomer containing or reacting with copper, the better the deodorizing function. However, it should be selected appropriately in consideration of the polymerization yield and the coating strength of the graft polymerization layer. Especially vinyl comonomers with sulfonic acid groups, such as allyl sulfonic acid, methacrylic acid, styrene sulfonic acid, 2,2-
When using acrylamide methylpropylsulfonic acid, their sodium salts, and copper salts as copper-containing or reactive monomers, it is better to copolymerize them with common vinyl monomers rather than homopolymers. Good polymerization yield. It is preferable to copolymerize at least 5% by weight of a common vinyl monomer.

[0018] Furthermore, during graft polymerization, a monomer diluted with a solvent may be attached to the fibers and polymerized, but the graft polymerization yield generally decreases. However, in the present invention, since the weight of the graft polymerization layer is low relative to the weight of the fiber, it is often difficult in practice to uniformly attach the monomer to the fiber using only the monomer. In order to uniformly attach the monomer to the fibers, it is often diluted with a solvent, but when diluting, take into account the effect of the solvent on polymerization, and take care to fine-tune the polymerization reaction conditions and ensure that the initiator does not decrease during dehydration. Should.

For example, in the case of a hydrophilic initiator, it is preferable to dilute the monomer with a lipophilic solvent so that the initiator does not decrease from the fiber surface.

[0020] A commonly used dipping method may be used to attach the monomer to the fibers. Since the spray method tends to cause spots, the dipping method should be used whenever possible. Excessive liquid can be removed using a commonly used mangle squeezer or centrifugal dehydrator.

During graft polymerization, oxygen in the air acts as an inhibitor, so it is better to seal with nitrogen.

[0022] The fiber material used in the present invention is not particularly limited. Synthetic fibers such as nylon, acrylic, polyester, polyethylene, polypropylene, vinylon, etc., and recycled fibers such as rayon, acetate, etc. can be used if the monomer or diluting solvent is appropriately selected during graft polymerization. Also natural fibers such as cotton, ramie,
Linen, wool, silk, etc. can also be used.

[0023] In the deodorizing process of the present invention, the form of the textile product to be processed is not particularly limited. In other words, whether the textile product is tow, cotton, spun yarn, filament, fabric, raised product, sweater, or other product, as long as there are no problems such as being attacked by solvents or monomers during processing, or dimensional deformation due to heat, etc. Can be processed at any stage.

To evaluate the deodorizing properties of textile products, add 30 ml of ethyl mercaptan to a 100 ml sample bottle containing 1 gram of sample.
Ethyl mercaptan in the sample head was measured by gas chromatography after 30 minutes and 60 minutes had elapsed after 0 ppm was added, and the amount was determined from the weight loss.

[0025] The amount of copper in the textile product was determined using a Shimadzu Green solid sample atomic absorption spectroscopy system SM-30. The copper content of the graft polymerized portion was determined from the difference between the measured copper value of the entire processed fiber and the measured copper value of the untreated fiber. Among the untreated fibers subjected to measurement, those that reacted or adsorbed with copper were measured on those that had previously reacted or adsorbed with copper, and the results were subtracted as the copper content inside the fibers.

[0026]

[Effects of the present invention] The deodorizing fiber product of the present invention has an excellent deodorizing function and is hardly colored, and even after having the deodorizing function, it can be freely colored by dyeing. Moreover, the deodorizing function can be imparted regardless of the fiber material, and the deodorizing function can be imparted at low cost regardless of the form of the textile product.

[0027]

[Example] Details will be explained below in Examples. In the examples, "%" means "% by weight" unless otherwise specified.

Example 1 20/2 cotton, 2/3 regular acrylic
4th, nylon filament bright 70/24D
A knitted fabric made by knitting three types of five-strand fabric yarns using a 16-gauge circular knitting machine was scoured, dried, and degreased using a standard method to prepare a sample fabric. These knitted fabrics were immersed in a 1% aqueous solution of potassium persulfate, and after dehydration in a centrifugal dehydrator until the adhesion amount was 35%,
It was dried with hot air at 50°C for 2 hours. Next, after being immersed in a solution with the monomer composition shown in Table 1, it was centrifuged to remove the liquid, and the amount of liquid attached was 32%.
The sample cloth was placed in an autoclave, and after the atmosphere was purged with nitrogen, graft polymerization was carried out at 80° C. for 2 hours. Next, after washing with water at 60°C for 10 minutes, it was reacted in a 1% aqueous copper sulfate solution at 95°C for 10 minutes, followed by washing again with water and drying.

The whiteness of the knitted fabric after treatment was the same as before and after treatment. The deodorizing properties and copper content of three types of graft-polymerized knitted fabrics were measured and shown in Tables 2, 3, and 4.

Example 2 Regular Acrylic Bright 3d 51 mm cotton was coated with No. 1 in Table 1 in the same manner as in Example 1. Cotton processed under conditions 2 to 4 was prepared. Then, the deodorizing properties and copper content were measured, and the results are shown in Table 5.

Example 3 Table 1 No. created in Example 1. A regular acrylic knitted fabric processed under conditions 2 to 4 was adjusted to pH 3.5 with cationic dye (malachite green) OWF 1% and acetic acid, and placed in a dyeing solution containing a slow dyeing agent at a bath ratio of 1:50. As a result of dyeing at 95°C according to a standard method, the dyeing property was not much different from that of the undeodorized product. Next, the deodorizing properties and copper content were measured, and the results are shown in Table 6.

[0032]

[Table 1]

[0033]

[Table 2]

[0034]

[Table 3]

[0035]

[Table 4]

[0036]

[Table 5]

[0037]

[Table 6]

Claims (1)

[Claims] 1. A textile product characterized by containing 100 ppm or more of copper in a graft polymerized portion on the fiber surface.