JPH0559662A - Antimicrobial fiber product - Google Patents

Abstract

PURPOSE:To obtain an antimicrobial fiber product having excellent washing resistance by providing a base material fiber product with a neutralized acidic group-containing acidic polymer, a crosslinking agent and a germicidal metal compound. CONSTITUTION:A base material fiber product is provided with (A) 0.01-10wt.%, preferably 0.05-5wt.% based on the base material fiber product of a neutralized acidic group-containing acidic polymer such as of styrene-maleic anhydride copolymer sodium salt or ethylene-maleic anhydride copolymer sodium salt, (B) a water-soluble crosslinking agent such as polyfunctional epoxy compound in an amount to give 0.05-50mol%, preferably 0.5-30mol% functional group in the crosslinking agent based on 1mol of the acidic group and the neutralized acidic group of the neutralized acidic group-containing acidic polymer and (C) 0.0005-1.3mol, preferably 0.01-0.5mol water-soluble germicidal metal compound selected from copper salts and silver salts such as copper sulfate and silver sulfate by immersion method, spray method or coating method.

Description

Detailed Description of the Invention

[0001]

The present invention relates to an antibacterial textile product,
More specifically, it relates to an antibacterial fiber product having excellent antibacterial performance even after washing.

[0002]

2. Description of the Related Art In recent years, a comfortable living space has been demanded, and molds and various bacteria have become a problem in many cases. Propagation of these bacteria and fungi causes generation of ammonia and lower fatty acids to give offensive odors, and also causes diseases such as asthma and dermatitis.

Therefore, attempts have been made so far to give various products the ability to suppress the growth of bacteria and mold (hereinafter referred to as antibacterial ability). Among them, textile products provided with antibacterial ability are futon cotton. It is used for beddings, sanitary materials, carpets, curtains and various filters, etc., and has been attracting attention because of its wide range of applications.

There have been several reports on fiber products having antibacterial properties, for example, acrylonitrile fiber products containing a copper compound (JP-A-54).
No. 147220) or a fiber product obtained by binding copper ions to a fiber product having an ion exchange ability (Japanese Patent Laid-Open No. 55-
No. 137210) is known.

However, the textile products described in these publications are extremely colored, the antibacterial performance is deteriorated due to dyeing or resin processing, and the antibacterial performance is significantly deteriorated after washing. I have a problem.

[0006]

The inventors of the present invention have been earnestly researching antibacterial agents, but by adhering specific components to a base fiber product, the antibacterial properties without the above-mentioned drawbacks can be obtained. Found that textile products can be obtained,
The present invention has been completed based on this finding.

[0007]

According to the present invention, there is thus provided an antibacterial fiber product comprising a neutralized acidic group-containing acidic polymer, a crosslinking agent and a bactericidal metal compound. ..

(Neutralized acidic group-containing acidic polymer) The neutralized acidic group-containing acidic polymer used in the present invention is an acidic polymer having a neutralized acidic group.

Here, the acidic polymer is a polymer having an acidic group in its molecule. The acidic group may be a functional group that releases hydrogen ions or an anhydride or ester of a functional group that releases hydrogen ions, and examples thereof include a sulfonic acid group, a carboxylic acid group, an acid anhydride group, a phenolic hydroxyl group, and a sulfate ester group. , Phosphoric acid ester groups and the like.

The acidic polymer is not particularly limited depending on its production method, for example, one obtained by a method of homopolymerizing, copolymerizing or copolymerizing another monomer having an acidic group with another monomer. Is mentioned.

The monomer having an acidic group may be any monomer containing an acidic group and a polymerizable unsaturated bond, and examples thereof include unsaturated carboxylic acid monomers such as acrylic acid, methacrylic acid and itaconic acid. Maleic anhydride, itaconic anhydride,
Α, β-Unsaturated dicarboxylic acid anhydride monomers such as citraconic anhydride; unsaturated carboxylic acid ester monomers such as ethyl acrylate and methyl methacrylate; vinyl carboxylic acid monomers such as vinyl acetate; polyvalent Examples thereof include vinyl ether ester monomers of carboxylic acid; monomers such as unsaturated sulfonic acid monomers such as vinyl sulfonic acid and p-styrene sulfonic acid. In particular, α, β-unsaturated dicarboxylic acid anhydride monomers such as maleic anhydride, itaconic anhydride, and citraconic anhydride are preferred.

Other monomers copolymerizable with the monomer having an acidic group include nitrile group-containing olefins such as acrylonitrile and methacrylonitrile; ethylene, propylene, isobutene, butene, pentene, methylbutene,
Aliphatic monoolefins such as hexene, dodecene, trimethylpentene, decene, octadecene; Cyclic monoolefins such as cyclopentene, cyclohexene, cyclooctene; Aliphatic diolefins such as butadiene, isoprene, piperylene; Styrene, vinyltoluene, Examples include monomers such as aromatic monoolefins such as alkyl styrene; vinyl halides such as vinyl chloride; vinyl ethers such as methyl vinyl ether.

The neutralized acidic group-containing acidic polymer can usually be obtained by neutralizing the acidic polymer with a basic substance. Neutralization may be carried out by an ordinary method, for example, a method of dispersing or dissolving the acidic polymer in water, adding a basic substance and stirring.

The basic substance may be any substance having a property of accepting hydrogen ions. Specific examples of the basic substance include alkali metals such as sodium hydroxide, potassium hydroxide and calcium hydroxide or alkaline earth. Hydroxides of group metals; ammonia and salts thereof; amines such as methylamine, ethylmethylamine, dimethylamine, aniline and the like, among which hydroxides of alkali metals are preferable.

The neutralized acidic group-containing acidic polymer used in the present invention is obtained by homopolymerization or copolymerization of a salt of a monomer having an acidic group, or copolymerization with another monomer. It may be a polymer.

The proportion of the neutralizing acidic groups in the neutralizing acidic group-containing acidic polymer used in the present invention is 2 mol% or more, preferably 8 mol, in terms of monomer units having neutralizing acidic groups. %
The above is more preferably 15 mol% or more. If the proportion of neutralized acidic groups is low, sufficient antibacterial performance cannot be obtained.

In the present invention, the neutralized acidic group-containing acidic polymer may be used alone or in combination of two or more kinds. A water-soluble acidic polymer containing a neutralized acidic group is preferably used. Even when the neutralized acidic group-containing acidic polymer is not water-soluble, it can be used if an appropriate organic solvent or the like is selected in consideration of the influence on the base fiber product.

In the present invention, the amount of the neutralized acidic group-containing acidic polymer adhered to the base fiber product is 0.
It is from 01 to 10%, preferably from 0.05 to 5%. If this adhesion amount is too small, antibacterial performance cannot be imparted. Conversely, if it is too large, the texture of the antibacterial fiber product is impaired, the strength of the antibacterial fiber product is reduced, or the antibacterial fiber product is colored. The problem arises.

(Crosslinking Agent) The crosslinking agent used in the present invention may be any crosslinking agent capable of reacting with an acidic group and / or a neutralizing acidic group, and examples thereof include a hydroxyl group, an epoxy group, a methylol group and an amino group. Examples thereof include those having a plurality of functional groups or polyvalent metal salts.

Specific examples of the crosslinking agent used in the present invention include polyhydric alcohol compounds such as ethylene glycol, glycerin and polyvinyl alcohol; glycerin diglycidyl ether, ethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether and glycerin triglycidyl. Polyhydric epoxy compounds such as ethers; Polyhydric amine compounds such as polyethyleneimine, ethylenediamine, diethylenetriamine, triethylenetetramine, melamine; Polymethylol compounds such as trimethylolmelamine; Calcium salts, barium salts, aluminum salts, copper salts, etc. Examples thereof include polyvalent metal salts, and among them, polyvalent epoxy compounds are preferred.

The cross-linking agent used in the present invention is preferably a water-soluble one in consideration of the operability when adhering to the base fiber product and the influence of the solvent on the base fiber product.

In the present invention, the amount of the cross-linking agent attached is usually such that the amount of the functional group in the cross-linking agent is 0.05 to 1 mol with respect to 1 mol of the acidic group and the neutralizing acidic group in the neutralizing acidic group-containing acidic polymer. Fifty
The amount is a mol%, preferably 0.5 to 30 mol%. However, in the case of an acid anhydride group, 1 mol thereof is converted to 2 mol of an acidic group. If the adhered amount is too small, the antibacterial performance after washing is deteriorated. On the contrary, if the adhered amount is too large, the texture of the antibacterial fiber product is impaired and it is not economical.

(Bactericidal Metal Compound) Examples of the bactericidal metal compound used in the present invention include tin, silver, and
Examples thereof include compounds of elements such as lead, copper, arsenic, zinc and chromium. The form of the compound may be any of an inorganic acid salt, a sulfide, an organic acid salt, a complex, a hydroxide and an oxide,
For example, inorganic salts such as copper sulfate, silver sulfate, zinc sulfate, silver nitrate, chromic nitrate, zinc nitrate, copper nitrate, copper phosphate, zinc phosphate, copper carbonate; stannous chloride, copper chloride, zinc chloride , Copper bromide, copper iodide and other halides; lead acetate, copper malate, copper glyoxylate, copper citrate and other organic acid salts; phthalocyanine copper and other complexes; copper oxide, silver oxide and other oxides Can be mentioned. Particularly, in consideration of antibacterial effect, light resistance, economy, operability, etc., it is preferable to use a water-soluble copper salt or silver salt.

In the present invention, the amount of the bactericidal metal compound attached is usually 0.0005 to 1.3 mol, relative to 1 mol of the acidic group and neutralizing acidic group in the neutralized acidic group-containing acidic polymer.
It is preferably 0.01 to 0.5 mol. However, in the case of an acid anhydride group, 1 mol thereof is converted to 2 mol of an acidic group.
If the adhered amount is too small, the antibacterial performance of the antibacterial fiber product is not sufficient, and if it is too large, problems such as coloring and strength reduction occur.

(Base fiber product) The base fiber product used in the present invention is not particularly limited, and examples thereof include natural fiber products such as cotton, silk, and hemp; polyamide fibers,
Chemical fiber products such as polyvinyl chloride fiber, cellulose fiber, polyester fiber, polyvinyl alcohol fiber, polyvinylidene chloride fiber, polyacrylonitrile fiber, polyolefin fiber, polyurethane fiber, carbon fiber, glass fiber, etc. be able to. The shape is not limited, and staples, filaments, processed threads, woven fabrics,
Any of non-woven fabric may be used.

(Antibacterial Fiber Product) The antibacterial fiber product of the present invention can be obtained by attaching a neutralizing acidic group-containing acidic polymer, a crosslinking agent and a bactericidal metal compound to a base fiber product.

When the components of the neutralized acidic group-containing acidic polymer, the cross-linking agent and the bactericidal metal compound are attached to the base fiber product, they may be attached to each component, or any combination of a plurality of components may be attached. You may. Also, the order of deposition is not limited. In addition, the form in which each component is adhered may be an aqueous solution or an organic solvent solution, or may be adhered in a solid form or a liquid form which is a usual form of each component.

Next, the method for attaching each component to the base fiber product is not particularly limited, but for example, a solution of each component,
A method of immersing the base fiber product in the dispersion liquid, a method of spraying or applying a solution or dispersion of each component to the base fiber product, and the like can be shown.

When the neutralized acidic group-containing acidic polymer, the cross-linking agent and the bactericidal metal compound are used as an aqueous solution, the concentration of each of these components is not particularly limited, but is usually 0.1 respectively. -20% by weight, 0.01-10% by weight, 0.1-10% by weight. If the concentration is too low at this time, the amount of each component adhered to the base fiber product may be small and sufficient antibacterial performance may not be obtained. Conversely, if the concentration is too high, the solution viscosity will be high and the processability will decrease. Or, the amount of adhesion may increase and the texture of the antibacterial textile product may be deteriorated.

After depositing the above components on the base fiber product,
The antimicrobial textile can be dried if desired.
The drying method is not particularly limited as long as it can remove water, and the drying temperature is preferably 70 to 200 ° C. If the drying temperature is low, it takes a long time to dry and the efficiency is lowered. On the contrary, if the drying temperature is excessively high, the performance of the base fiber product itself or the antibacterial performance may be lowered.

Further, in the base fiber product, in addition to the neutralized acidic group-containing acidic polymer, the crosslinking agent and the bactericidal metal compound,
A fiber treatment agent such as a dyeing agent, a flame retardant, a softening agent, an antifouling agent, and a moisture absorbent can be attached, and even when these fiber treatment agents are attached, the antibacterial performance does not deteriorate. In particular, an antibacterial textile product to which a phosphorus-based flame retardant is attached is preferable because not only the flame retardant performance is imparted but also the antibacterial performance is further improved.

[0032]

As described above, according to the present invention, it is possible to obtain an antibacterial textile product which has excellent antibacterial performance and can retain the antibacterial performance even after washing.

[0033]

EXAMPLES The present invention will be described in more detail with reference to the following examples. The parts and% in the examples and comparative examples are based on weight unless otherwise specified.

Example 1 Styrene-maleic anhydride copolymer (copolymerization molar ratio 1 /
1. Arco Chemical Company) sodium salt (proportion of monomer units having neutralizing acidic groups = 45 mol%)
Polyethylene glycol diglycidyl ether (Kyoeisha Yushiki Kagaku Kogyo Co., Ltd., Epolite 400E) was added to 100 parts of a 1% aqueous solution of 5 mol% in terms of epoxy group with respect to the acid anhydride group and its sodium salt in the copolymer, A uniform aqueous solution (A) was obtained. An undyed (white) cotton fabric (weight per unit area: 200 g / m ² ) is dipped in this aqueous solution (A), and the aqueous solution (A) is thoroughly permeated into the aqueous solution (A).
Then, the dough was uniformly squeezed with a roll. The amount of the aqueous solution (A) attached was 100 g / m ² (the amount of the copolymer attached was about 1 g / m ² fiber product). Then, the cotton fabric to which the aqueous solution (A) was adhered was dried in an oven at 150 ° C. for 3 minutes and then dipped in a 1% aqueous solution of copper sulfate pentahydrate to allow the copper sulfate pentahydrate aqueous solution to penetrate the entire fabric. After that, rinse with fresh water at a liquid temperature of 20 ° C. twice, then take out the dough, squeeze it with a roll, and dry it in an oven at 130 ° C. for 3 minutes to obtain a light blue antibacterial cotton fabric (a). Obtained.

Example 2 Ethylene-maleic anhydride copolymer (copolymerization molar ratio 1 /
1, 1% of sodium salt (manufactured by Monsanto Company) (ratio of monomer units having a neutralizing acidic group = 40 mol%)
Polyethylene glycol diglycidyl ether was added to 100 parts of the aqueous solution (Epolite 400 manufactured by Kyoeisha Yushi Kagaku Kogyo Co., Ltd.).
E) was added to the acid anhydride group of the copolymer and its sodium salt in an amount of 10 mol% in terms of epoxy group to prepare a uniform aqueous solution (B). An undyed (white) polyester fabric (weight per unit area: 200 g / m ² ) is dipped in this aqueous solution (B) to thoroughly permeate the aqueous solution (B), and then the aqueous solution (B)
Then, the dough was uniformly squeezed with a roll. The amount of the aqueous solution (B) deposited was 100 g / m ² (the amount of the copolymer deposited was about 1 g / m ² fiber product). Then, the polyester fabric to which the aqueous solution (B) is adhered is dried in an oven at 170 ° C. for 3 minutes, then immersed in a 0.5% aqueous solution of silver nitrate to allow the aqueous solution of silver nitrate to permeate the entire fabric, and then fresh water having a liquid temperature of 20 ° C. Rinse twice using the product, then take out the dough, squeeze it with a roll, and dry it in an oven at 130 ° C. for 3 minutes to obtain a white antibacterial polyester fabric (b).

Comparative Example 1 A light blue cotton fabric (C) was prepared in the same manner as in Example 1 except that polyethylene glycol diglycidyl ether was not used.
Got

Comparative Example 2 An ethylene-maleic anhydride copolymer (copolymerization molar ratio) was used instead of the sodium salt of ethylene-maleic anhydride copolymer (ratio of monomer units having neutralizing acidic groups = 40 mol%). 1/1, manufactured by Monsanto Company, Ltd. (ratio of monomer units having a neutralizing acidic group = 0 mol%) was used to obtain a white polyester fabric (d) in the same manner as in Example 2. ..

Example 3 Staphylococcus aureus (IFO1273, Staphylococcus aureus, before and after washing of the doughs (a) to (d) obtained in Examples 1 to 2 and Comparative Examples 1 to 2 before and after washing
2)) was subjected to an antibacterial test. The results of the antibacterial test are shown in Table 1. The antibacterial test and the washing method were performed according to the following methods.

(Antibacterial property test) The antibacterial property test is carried out by the method of measuring the number of bacteria, the test method of the Textile Products Hygiene Processing Council (Reference: Osamu Yuge, "Antibacterial Deodorant", 182-183 (1989),
Textile company). The smaller the number of viable cells after culturing and the larger the difference in increase / decrease value, the better the antibacterial performance.

(Washing method) The washing method is "JIS L
0217 103 method ”.

[0041]

[Table 1]

From the results shown in Table 1, when the cross-linking agent was not used (fabric (c)), the antibacterial performance after washing decreased.
It is also understood that the antibacterial performance cannot be obtained when the neutralized acidic group-containing acidic polymer is not used (fabric (d)). On the other hand, according to the present invention, when using a neutralizing acidic group-containing acidic polymer and a crosslinking agent, it has excellent antibacterial performance,
It can be seen that this performance is sufficiently retained even after washing.

Example 4 An antibacterial test was conducted in the same manner as in Example 3 except that Klebsiella pneumoniae (Klebsiella pneumoniae, [IFO 13277]) was used instead of S. aureus. The results are shown in Table 2.

[0044]

[Table 2]

From the results shown in Table 2, it can be seen that the antibacterial fiber product of the present invention has antibacterial performance against different kinds of bacteria.

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Claims (1)

[Claims] 1. An antibacterial fiber product comprising a neutralized acidic group-containing acidic polymer, a cross-linking agent and a bactericidal metal compound.