JPH03269173A - Deodorizing textile product - Google Patents

Abstract

PURPOSE:To obtain the title textile product having deodorizing performances with excellent washing durability, by sticking a polymer containing an acid anhydride group and a crosslinking agent to a textile product. CONSTITUTION:Natural yarn, synthetic yarn, etc., is immersed in a solution of deodorizing composition comprising a polymer containing an acid anhydride group, such as a polymer comprising an alpha, beta - unsaturated dicarboxylic acid anhydride monomer (preferably maleic anhydride monomer) or a styrene maleic anhydride copolymer comprising maleic anhydride and a monomer copolymerizable with the monomer and glycerin diglycidyl ether as a crosslinking agent and 0.01-10%wt. of the polymer is attached to the yarn to give a deodorizing textile product. The product is further immersed in a solution of copper sulfate or cupric chloride and cupric salt is stuck to the yarn to give a deodorizing textile product having excellently deodorizing characteristics against various offensive smells with excellent washing resistance.

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a deodorizing textile product, and more particularly to a deodorizing textile product that has excellent deodorizing performance even after washing.

[Conventional technology]

In recent years, various bad odors in daily life have become a problem, and the main components of these bad odors are said to be ammonia, amines, hydrogen sulfide, mercaptans, etc. Various methods have been proposed to remove bad odors. On the other hand, attempts have been made to add deodorizing functions to various products, but among them, textile products with deodorizing functions have been used for bedding such as futon cotton, sanitary materials, sanitary materials, etc.
It is used in carpets, curtains, and various filters, and is attracting attention because of its wide range of applications.

So far, there have been several reports on fibers with deodorizing functions, examples of which include:

Fibers containing deodorizing functional components during fiber production (deodorizing polyester fibers containing iron compounds = JP-A-62-223)
No. 318, acrylic fibers containing unsaturated carboxylic acids = JP-A-62-179464 ICE), fibers with deodorizing properties added through post-processing (metal phthalocyanine compounds supported on cellulose fibers, polyamide fibers, etc.) Deodorizing fiber = JP-A-61-125353, JP-A-61-258077
(Japanese Unexamined Patent Publication No. 61-258078).

However, the methods described in these publications.

The types of bad odors that can be targeted are limited, the deodorant component is colored and foams during processing, the applicable fibers are limited, the coloration due to the deodorant component is severe, and the deodorizing performance is low because the amount of the deodorizing component cannot be increased. However, the deodorizing function is significantly reduced after washing.

[Problem to be solved by the invention]

The present inventors have been conducting intensive research on deodorizing agents, and have found that deodorizing textile products without the above-mentioned drawbacks can be obtained by attaching a deodorizing composition consisting of specific ingredients to textile products. Based on this knowledge, the present invention was completed.

[Means to solve the problem]

Thus, according to the present invention, there is provided a deodorizing textile product and a polymer having an acid anhydride group, characterized in that a deodorizing composition containing a polymer having an acid anhydride group and a crosslinking agent is attached to the textile product. A deodorizing textile product is provided, which is characterized in that a deodorizing composition containing a crosslinking agent and a cupric salt is attached to the textile product.

(Polymer having acid anhydride group) Used in the present invention. The polymer having an acid anhydride group (hereinafter simply referred to as an acid anhydride group-containing polymer) may be any polymer having an acid anhydride group in its molecule, and is not limited by its synthesis method.

A specific example of the synthesis method includes a method of polymerizing an α,β-unsaturated dicarboxylic acid anhydride monomer alone or together with a monomer copolymerizable therewith. Alternatively, it may be obtained by introducing an acid anhydride group into any polymer by a known polymer reaction.

The content of monomer units containing an acid anhydride group in these polymers is not particularly limited, but is preferably 30 mol% or more. When this amount is too small, it is necessary to use a large amount of the polymer to impart deodorizing performance, which adversely affects the texture and strength of the textile product.

The molecular weight of these polymers is not particularly limited, but usually
500-1,000. OoO1 preferably 1.000~
300. It is OoO. If the molecular weight is too small,
The deodorizing performance of the resulting deodorizing textile products after washing is significantly reduced, and if the molecular weight is excessively large, problems may occur during processing due to decreased water solubility and increased solution viscosity. .

The α,β-unsaturated dicarboxylic acid anhydride monomer used in the synthesis of the acid anhydride group-containing polymer is not particularly limited, but examples thereof include maleic anhydride, itaconic anhydride, citraconic anhydride, and the like. Among them, from the economic point of view,
Maleic anhydride is preferred.

Specific examples of monomers copolymerizable with the α,β-unsaturated dicarboxylic acid anhydride monomer include aromatic monoolefins such as styrene, α-methylstyrene, vinyltoluene, etc.; ethylene, propylene, etc. , isobutyne, butene-
1, butene-2, pentene-1, pentene-2,2-methylbutene-1,2-methylbutene-2, hexene-1
,2,2,4-trimethylpentene-1,2,2,4-
Trimethylpentene-2, decene-1, octadecene-
Aliphatic monoolefins such as 1; cyclopentene ~
Cyclic monoolefins such as cyclohexene, cyclooctene, etc.Aliphatic diolefins such as butadiene, isoprene, piperylene, etc.;Unsaturated carboxylic acids such as acrylic acid, methacrylic acid, etc.Unsaturated such as ethyl niacrylate, methyl methacrylate, etc. Carboxylic acid esters;
Unsaturated nitriles such as acrylonitrile and methacrylonitrile; vinyl halides such as vinyl chloride;
Examples include vinyl carboxylates such as vinyl acetate; vinyl ethers such as methyl vinyl ether; unsaturated sulfonic acids such as vinylsulfonic acid and p-styrenesulfonic acid.

In the present invention, one type of acid anhydride group-containing polymer may be used alone or two or more types may be used in combination.

In the present invention, acid anhydride group-containing polymers that are water-soluble are preferably used. Acid anhydride group-containing polymers can generally be made water-soluble by neutralizing the acid anhydride groups with a base, but low molecular weight and water-soluble polymers do not need to be neutralized.

Note that polymers that are not water-soluble can also be used if an appropriate organic solvent or the like is selected in consideration of the influence on the fibers.

The acid anhydride group-containing polymer may be neutralized by a known method, whereby the acid anhydride group becomes a carboxylic acid salt. Specific examples of such salts include alkali metal salts such as sodium salts and potassium salts; ammonium salts; amine salts; among these, alkali metal salts are preferred.

The degree of neutralization of the acid anhydride group is not particularly limited, but
Preferably it is 0.8 or less. If the degree of neutralization is low, high molecular weight polymers may not be water-solubilized, and if the degree of neutralization is too high, the deodorizing performance after washing may be reduced.

In the present invention, the amount of the acid anhydride group-containing polymer deposited on the textile product is 0.01 to 10%, preferably 0.05 to 5% of the weight of the textile product. If the amount of this adhesion is too small, sufficient deodorizing performance cannot be imparted, and if it is too large, the texture of the textile product may be impaired, the strength of the textile product may be reduced,
or.

This may cause problems such as coloring of textile products.

(Crosslinking agent) The crosslinking agent used in the present invention may have a plurality of groups capable of reacting with a carboxyl group or an acid anhydride group, but it may be difficult to use a solvent for the textile product due to the operability when attaching it to the textile product. Considering the influence of water, etc., water-soluble ones are preferable.

Specific examples of such water-soluble crosslinking agents include polyvalent epoxy compounds such as glycerin diglycidyl ether, ethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, and glycerin triglycidyl ether; polyethylene imine, ethylene diamine,
Polyvalent amine compounds such as diethylenetriamine, triethylenetetraamine, and melamine; polyhydric alcohol compounds such as ethylene glycol, glycerin, and polyvinyl alcohol, and polyvalent methylol compounds such as trimethylolmelamine; calcium salts, barium salts, aluminum salts, and copper salts. Examples include polyvalent metal salts such as, among others, polyvalent epoxy compounds.

In the present invention, the amount of the crosslinking agent used is 1. Usually, the acid anhydride group (in the case of a carboxyl group) in the acid anhydride group-containing polymer is
The 2 moles are converted into 1 mole of acid anhydride group. ) The amount of the group capable of reacting with a carboxyl group or an acid anhydride group is 0.1 to 100 mol, preferably 1 to 60 mol, per 1 mol. If this amount is too small, the deodorizing performance after washing will deteriorate, and if it is too large, it will remain in the textile product, impairing the feel of the product, and is not economical.

(Copper salt) In the present invention, in the acid anhydride group-containing polymer and the crosslinking agent,
Furthermore, by using a cupric salt in combination, a textile product with even better deodorizing performance can be obtained.

The cupric salt used in the present invention is not particularly limited, but water-soluble salts are preferred for the same reasons as in the case of the crosslinking agent.

Specific examples thereof include copper sulfate, cupric chloride, cupric nitrate, cupric hydroxide, and the like.

In the present invention, the amount of the cupric salt deposited is usually 0.001 per mole of acid anhydride group in the acid anhydride group-containing polymer.
-2.5 mol, preferably 0.02-1 mol. If this amount is too small, the deodorizing performance against sulfur-based malodors from textile products will not be sufficient, while if it is too large, problems such as coloring and reduced strength of the textile products will occur.

(Jfi' textile products) The fibers W and products used in the present invention are not particularly limited by the type of fiber, and include natural fibers such as cotton, ship, hemp, etc.; cellulose fibers, polyester fibers, and polyvinyl alcohol fibers. , polyamide fibers, polyvinyl chloride fibers, polyvinylidene chloride fibers, polyacrylonitrile fibers, polyolefin R fibers, polyurethane fibers, and other synthetic fibers. In addition, the shape of textile products is not limited; stable, filament, processed yarn,
Any of fiber fabrics, non-woven fabrics, etc. may be used.

(Deodorizing textile product) The deodorizing textile product of the present invention can be obtained by attaching an acid anhydride group-containing polymer and a crosslinking agent (and, if desired, a cupric salt) to a textile product, and then drying the product. can get.

When these three components are attached to a textile product, they may be used individually or in any combination of a plurality of components. Furthermore, the order of attachment is not limited. Further, each component may be used in an aqueous solution or an organic solvent solution, or may be used in its usual solid or liquid form. Next, as a method for attaching each component to textile products,
Examples include a method of spraying, dipping, or coating a solution or dispersion of each component, and a method of coating or scattering each component as it is, but methods other than these may also be used.

Among the above methods, from the viewpoint of operability and deodorizing performance of the obtained deodorizing textile product, it is preferable to use each component as a solution, and a method using an aqueous solution is more preferable.

When the acid anhydride group-containing polymer, the crosslinking agent, and the cupric salt are used as an aqueous solution, the concentrations of each of these components are not particularly limited, but are usually 0.1 to 20% each.
% by weight, 0.01 to 10% by weight, and 0.1 to 10% by weight. If the concentration is too low, the amount of active ingredients attached to the textile product may be small and sufficient deodorizing performance may not be obtained. If the amount increases, it may deteriorate the texture of textile products.

The drying method after adhering each of the above components to the textile product is not particularly limited as long as it can remove moisture, but preferably heat drying at 70 to 200°C. If this drying temperature is low, drying time will be required and efficiency will be reduced, whereas if it is too high, the performance of the textile product itself and deodorizing performance may be reduced.

〔Effect of the invention〕

Thus, according to the present invention, it has excellent ability to remove various bad odors such as ammonia, amines, hydrogen sulfide, mercaptans, etc.
It is possible to obtain a deodorizing textile product that can maintain its deodorizing performance even after washing.

〔Example〕

The present invention will be explained in more detail with reference to Examples below.

Note that parts and percentages in Examples and Comparative Examples are based on weight unless otherwise specified.

(Production of deodorizing fiber products) Example 1 Styrene-maleic anhydride copolymer (copolymerization molar ratio 1/
1. Manufactured by Arco Chemical Company, 5MA1000
A) 1% aqueous solution of sodium salt (degree of neutralization 0.1) 100
20 mol% of polyethylene glycol diglycidyl ether (manufactured by Kyoeisha Yushi Kagaku Kogyo Co., Ltd., Evolite 400E) in terms of epoxy groups based on the acid anhydride groups of the polymer was added to the mixture and mixed uniformly to obtain a deodorizing composition dipping liquid. . An undyed (white) polyester fabric (240g/rrr) is soaked in this to allow the dipping liquid to penetrate the entire fabric, and then squeezed with a roll to deposit 100g/rrr of the dipping liquid (a. The amount is approximately 1 g/rr?fiber product.

) and then dried in an oven at 170° C. for 3 minutes to obtain a white deodorizing polyester fabric (a).

Example 2 In place of the styrene-maleic anhydride copolymer sodium salt, isobutyne-maleic anhydride copolymer (copolymerization molar ratio 1/1, manufactured by Kuraray Isoprene Chemical Co., Ltd., Isopan-04) sodium salt (medium) was used. 0.3) and 40 mol% of polyethylene glycol diglycidyl ether.
A white deodorizing polyester fabric (b) was obtained in the same manner as in Example 1 except for the addition.

Example 3 Styrene-maleic anhydride copolymer (copolymerization molar ratio 1/
1. Manufactured by Arco Chemical Company, 5MA100
0A) A deodorizing polyester fabric obtained in the same manner as in Example 1 except that the degree of neutralization of the sodium salt was adjusted to 0.2 was soaked in a 5% aqueous solution of copper sulfate pentahydrate, and the copper sulfate aqueous solution was soaked. After soaking it into the entire fabric, rinse it twice in fresh room temperature water.Then, take out the fabric, squeeze it with a roll, and dry it for 3 minutes in an oven kept at 130℃ to remove the slightly blue color. Deodorizing polyester fabric (c)
I got it. The amount of copper salt deposited is 0.74 mmol/r
It was rf.

Example 4 Ethylene-maleic anhydride copolymer (copolymerization molar ratio 1
/1, manufactured by Monsanto Company, EMA-21) sodium salt (neutralization degree o, 3) was placed on copper sulfate, cupric chloride was used, and the amount of polyethylene glycol diglycidyl ether was adjusted to 30 mol%. A pale blue deodorizing polyester fabric (d) was obtained in the same manner as in Example 3. The amount of copper salt deposited was 1.78 mmol/bo.

Example 5 Isobutyne-maleic anhydride copolymer (manufactured by Kuraray Isoprene Chemical Co., Ltd., Isopan-04) sodium salt (neutralization degree 0.5) was used in place of the styrene-maleic anhydride copolymer sodium salt. A pale blue deodorizing polyester fabric (e) was obtained in the same manner as in Example 3, except that cupric chloride was used instead of copper sulfate and the amount of polyethylene glycol diglycidyl ether was 50 mol%. The amount of copper salt deposited was 2.44 mmol/bo.

Example 6 Ethylene diamine (manufactured by Wako Pure Chemical Industries, Ltd., reagent special grade) 6 in place of 20 mol% of ethylene glycol diglycidyl ether
A pale blue deodorizing polyester fabric was obtained in the same manner as in Example 3, except that 0 mol % was used and copper sulfate was not used.

Example 7 Using isobutyne-maleic anhydride copolymer (manufactured by Kuraray Isoprene Chemical Co., Ltd., Isopan-04) sodium salt (degree of neutralization 0.3) in place of styrene-maleic anhydride copolymer sodium salt, Instead of 20 mol% of ethylene glycol diglycidyl ether, 100 mol% of polyvinyl alcohol (manufactured by Kuraray Co., Ltd., PVA217) (5
% solution. ) was used, but in the same manner as in Example 3, a pale blue deodorizing polyester fabric (G) was obtained.

The amount of copper salt deposited was 1.95 mmol/bo.

Comparative Example 1 A white polyester fabric (H) was obtained in the same manner as in Example 1 except that polyethylene glycol diglycidyl ether was not used.

Comparative Example 2 Polyacrylic acid (manufactured by Nippon Pure Chemical Industries, Ltd., Jurimer AC-1) was used instead of styrene-maleic anhydride copolymer sodium salt.
A white polyester fabric was obtained in the same manner as in Example 1, except that 0P) was used.

Example 8 (Deodorizing performance test) The deodorizing performance of the deodorizing textile products obtained in Examples 1 to 7 and Comparative Examples 1 to 2 above was evaluated before and after washing.

The results are shown in Table 1.

The deodorizing performance test method and washing method are as follows.

``Deodorizing performance test'': Sample fabrics from 50 countries and 2 contentsff
15. Place the primary bottle in a 1150 ml glass ampoule with a cap and seal it. OOOppm ammonia gas, 10,000ppm hydrogen sulfide gas, ooo
After replacing the inside of the ampoule with air containing methyl mercaptan gas of PPm, the gas concentration inside the ampoule was measured by gas chromatography after 24 hours and the amount of deodorization was calculated.

"Washing": Water at 40° C. was placed in a washing tank, and powdered detergent (weakly alkaline type 1) was added and dissolved at a ratio of 2 g to 1 liter of water to obtain a washing liquid. A sample and, if necessary, a load cloth were added to the washing liquid so that the bath ratio (the weight ratio of the sample to the washing liquid) was 1:30, and then the water flow was made into a strong swirl and the operation was carried out for 50 minutes. . The sample was taken out, placed in a dehydration tank, and dehydrated for 1 minute. Next, the washing liquid was drained, and fresh water (bath ratio 1:30) with a liquid temperature of 40°C was added, and the sample was rinsed in this water for 5 minutes. The rinsing solution was drained from the washing tank, and while injecting new water at room temperature, rinsing was performed for 10 minutes using the overflow method.
Next, the sample was taken out again, placed in a dehydration tank, dehydrated for 1 minute, and then placed in an oven and dried at 70°C for 30 minutes.

From the results in Table 1, it can be seen that the deodorizing fiber products of the present invention have excellent deodorizing performance against various bad odors, and this performance is sufficiently maintained even after washing.

Claims (1)

[Scope of Claims] 1) A deodorizing textile product, characterized in that a deodorizing composition containing a polymer having an acid anhydride group and a crosslinking agent is attached to the textile product. 2) A deodorizing textile product, characterized in that a deodorizing composition containing a polymer having an acid anhydride group, a crosslinking agent, and a cupric salt is attached to the textile product.