JPH02288804A - Deodorizing, antimicrobial and antifungal composition and deodorizing, antimicrobial and antifungal processing - Google Patents

Abstract

PURPOSE:To obtain a deodorizing, antimicrobial and antifungal composition capable of removing both nitrogen-based bad-smelling substances and sulfur- based bad amelling substances, comprising a carboxyl group-containing polymer and an aqueous solution or water dispersion of polyvalent metallic salt. CONSTITUTION:A composition comprising (A) a water-soluble or waterdispersible polymer composed of a polymer containing >=30mol% monomer unit of carboxyl group and/or metallic salt of carboxyl group or a copolymer composed of 5-98mol% carboxyl groupcontaining monomer, 1-50mol% ionic monomer and 1-50mol% monomer copolymerizable with these monomers and (C) an aqueous solution or water dispersion of a metallic compound selected from Zn, Ag, Cu, Al, Ti and Zr having 0.1-10 equivalent ratio of metallic ion based on the carboxyl group contained in the component A. The composition or the component A thereof is attached to a porous sheet substrate, then the component B and/or a quaternary ammonium salt shown by the formula (R is 12-18C) is bonded to the substrate so that the substrate is provided with deodorizing, antimicrobial and antifungal properties.

Description

Detailed Description of the Invention [Field of Industrial Application] The present invention provides a deodorizing agent with antibacterial and anti-fungal properties that can remove both nitrogen-based malodorous substances and sulfur-based malodorous substances, and paper, woven fabric, and non-woven fabric. A colorless to white polymeric deodorizing ingredient that is insoluble in water and has antibacterial and antifungal properties is produced on a porous sheet substrate such as leather. The present invention relates to a method of imparting a fungal function, and in particular to a deodorizing and antibacterial/anti-fungal processing method suitable for textile processing.

[Problems to be solved by conventional techniques and inventions] Conventionally,
In the field of deodorants, ferrous glyoxanope sulfate, green tea ingredients, camellia extracts, organic carboxylic acid compounds such as ascorbic acid, malic acid, fumaric acid, maleic acid, oxalic acid, and activated carbon are used as substances with deodorizing effects. Zinc compounds etc. are used. However, these deodorants themselves have drawbacks in color tone and water resistance, have poor deodorizing, antibacterial, and antifungal properties in aqueous systems, and have unsatisfactory texture as porous sheet base materials.

[Means to solve the problem]

The present invention is directed to a polymer containing 30 mol% or more of a monomer unit of a carboxyl group and/or a metal salt of a carboxyl group in the polymer chain (x + acid component or monomer unit of a carboxyl group and/or a metal salt of a carboxyl group). 5 to 98 mol% of the body,
A water-soluble or water-dispersible polymer consisting of a copolymer (x2 components) containing 1.0 to 50 mol% of an ionic monomer and 1.0 to 50 mol% of a monomer copolymerizable with them. (component x) and a metal compound selected from the group consisting of zinc, silver, copper, aluminum, titanium, and zirconium, in which the equivalent ratio of metal ions to the carboxyl group contained in component X is 0.1 to 1.0. One or more types of (x
A deodorizing and antibacterial/antifungal composition characterized by comprising an aqueous solution or aqueous dispersion of component), and after fixing the above composition or its X component to a porous sheet substrate, further
A component and/or a quaternary ammonium salt whose general formula is (in the formula, R represents an alkyl group having 12 to 18 carbon atoms) at an equivalent ratio of 0.1 to 1.0 to the carboxyl group contained in the X component. Relating to a deodorizing and antibacterial/antifungal processing method characterized by forming a water-insoluble deodorizing, antibacterial, and antifungal component in the porous sheet base material by contacting the porous sheet base material at a certain ratio. It is something.

The present invention will be explained in detail below.

A polymer containing 30 mol% or more of a carboxyl group and/or a metal salt monomer unit of a carboxyl group in the polymer chain used in the present invention (x+acid component is a homopolymer of acrylic acid, methacrylic acid, or a copolymer thereof). Copolymers of polymerizable itaconic acid, maleic acid, maleic anhydride, and unsaturated hydrocarbon monomers such as acrylic acid ester, ethenope methacrylate, methyl vinyl ether, styrene, and ethylene, which are copolymerizable with these. and their Na, K, AI, Cu, Ag, Zn,
Mg, Co.

Examples include salts of Ca, Ti, and Ba.

In addition, as a copolymer (x2 component) containing a carboxyl group and/or a metal salt monomer of a carboxyl group, an ionic monomer, and a monomer copolymerizable with them, x
In addition to the monomer compounds mentioned above for one component, compounds containing the following ionic monomers can be mentioned. That is, the anion types include vinyl sulfonic acid, vinylbenzenesulfonic acid, vinyl-α-methylbenzenesulfonic acid, vinyl phosphoric acid, and their salts, and the cation types include vinylpyridinium, vinyltrimethylammonium, allyltrimethylammonium, and oxyethyl-1-methylene. Trimethylammonium, vinylbenzyltrimethylammonium, N-methylvinylpyridinium, N-
Vinyl-2,3-dimethylimidazolium, N-methyl-2-vinylimidazolium, oxyethyl-1-methylenepyridinium, 2hydroxy-3-acryloxypropyltrimethylammonium, N-acrylamidopropyl-3-trimethylammonium, N , N-dimethyl-3,5-methylenepiperidinium, 2-acryloxydimethylsulfonium, glycidyldimethylsulfonium, glycidyltributylphosphonium, and other chlorides.

The degree of polymerization of these polymers is preferably 10 or more,
Those having a degree of polymerization of less than 10 are not preferred because they have low water resistance and are eluted from the porous sheet substrate when washed or the like.

Preferred metal compound components (y component) used in the present invention are zinc compounds, such as zinc sulfate, zinc chloride, zinc phosphate, zinc hydroxide, zinc oxalate, zinc citrate,
Examples include zinc fumarate and zinc white. Other metal compounds include AI, Cu, Ag, Ti,
A metal compound selected from Zr is used, but it is necessary to use a metal compound that does not cause coloration by forming metal crosslinks with the polymer.

Components X and x2 used in the present invention must contain 30 mol% or more of carboxyl groups and/or Although it is necessary to contain a metal salt unit of a carboxyl group, if the metal salt unit of a carboxyl group is 30 mol% or more, X l +
It becomes difficult to maintain the water solubility of the two components. Also X
In order to improve the adhesion of l and X2, it is usually 1.0 to 1
Requires 0 mole % carboxyl groups.

Furthermore, in order to impart antibacterial and antifungal properties to component x2, it is necessary to copolymerize 1 to 50 mol% of the ionic monomer component.

In order to increase the water resistance of the xl+X2 component, the polyvalent metal salt that is the y component should be added in an amount of 0.1 to 1% relative to the carboxyl group contained in the XX2 component. It is preferable to react at an equivalent ratio of θ, preferably 0.5 to 1.0. If it is less than 0.1, water resistance decreases slightly.

Furthermore, in order to further enhance the antibacterial and antifungal properties of the xl and X2 components, it is possible to enhance the antibacterial and antifungal properties by reacting a mixed component of the above-mentioned y component and a quaternary ammonium salt.

In the present invention, in order to perform deodorization and antibacterial/antifungal processing on a porous sheet substrate, the above-mentioned xl and/or After drying, the above-mentioned y component or a mixed component of this and a quaternary ammonium salt is further added in an amount of 0.1 to 1 per carboxyl group contained in X and/or x2 component = 7. Deodorizing and antibacterial effects are applied to the porous sheet base material by coating, impregnating, spraying, etc. on the porous sheet base again at an equivalent ratio of 0.0, preferably 0.5 to 1.0.・Can be treated with anti-mold treatment. The amount carried as a deodorizing and antibacterial/antifungal ingredient is 0.1
~15.0 g/m2 is suitable. If the amount is too small, the effect will be low, and if it is too large, the texture, physical properties, etc. will be affected, and there is a risk of slight coloring.

The porous sheet substrate used in the method of the present invention is not particularly limited, and paper, woven fabric, nonwoven fabric, leather, etc. can be used.

In carrying out the present invention, Xl+X2+ may be used as necessary.
Other optional components such as surfactants, binders, humectants, protective colloids, fragrances, and solvents may be added to component V within a qualitative and quantitative range that does not impair the objectives and effects of the present invention.

〔Example〕

EXAMPLES The present invention will be specifically explained below with reference to Examples, but the present invention is not limited to these Examples. Parts and percentages in the examples are based on weight unless otherwise specified.

In addition, prior to the examples, evaluation methods of deodorizing performance, antibacterial performance, anti-mold performance, and washing resistance adopted in the examples will be explained.

Ammonia, deodorizing performance evaluation method> 6. 28% ammonia water was added to a desiccator with a 51-capacity cock using a microsyringe to an initial concentration of 400 ppm.
After that, the evaluation sample (0.5 g or 10 x 20 cm2) was added, the inside of the desiccator was stirred with a magnetic stirrer, and the change in ammonia gas concentration over time was measured using a gas detection tube. The deodorizing effect is expressed as a ratio to the initial concentration.

Hydrogen sulfide deodorizing performance evaluation method> Hydrogen sulfide was used instead of ammonia, and the initial concentration was set to 40
The method for evaluating ammonia deodorizing performance is the same as described above, except that the value is ppm.

Methyl mercaptan deodorizing performance evaluation method〉Methyl mercaptan was used instead of ammonia, and the initial concentration was 20p.
The method for evaluating the ammonia deodorizing performance was the same as described above, except that it was set to pm.

<Trimethylamine deodorizing performance evaluation method> Trimethylamine was used instead of ammonia, and the initial concentration was 20 ppm.
The method for evaluating the ammonia deodorizing performance was the same as described above, except for the following.

<Antibacterial performance evaluation method> Evaluate Staphylococcus aureus according to the shake flask method.

<Mold-resistant performance evaluation method> Black mold is evaluated according to JIS Z 2911.

<Washing resistance performance evaluation method> JIS L-0 50 x 25 cm deodorizing and antibacterial treated fabric
217, the ratio of the weight after washing 10 times to the weight before washing is expressed as a percentage.

<Solubility in water> Dried sample 2. 200ml of pure water at 40℃! to 2
．． After stirring for 0 hours, the undissolved matter is collected and weighed, the amount dissolved is determined, and the amount dissolved is converted to the amount per 100 rd of water.

Example 1-1 Nippon Shokubai ◇ Aqualic MP made by Kiku as an alkali salt of high molecular weight polycarboxylic acid (carboxyl group-containing polymer)
-30 (sodium polyacrylate, degree of polymerization 400, solid content concentration (NV) 30.0%) 500g is 5I! The mixture was poured into a container and diluted with 2000 g of pure water to prepare a 6.0% sodium polyacrylate solution.

Separately, dry zinc sulfate (ZnS) manufactured by Shinyo ■ is used as a zinc compound.
A solution obtained by dissolving 142.8 g (Oi purity: 89%, Zn content: 36%) in 1000 g of pure water was added to the above sodium polyacrylate solution and stirred for 30 minutes to form a water solution of high molecular weight polycarboxylic acid zinc salt. A dispersion (pH 5,6) was formed.

Next, it was washed and purified three times with 2000 g of pure water by the decantation method, and the solid concentration was 14.5% and the pH was 6.0.
A dispersion of a high molecular weight polycarboxylic acid zinc salt was obtained. This dispersion was dried at 120°C for 3.0 hours and then dried at 20°C and 55% R.
After adjusting the temperature to H, the deodorizing performance against ammonia and hydrogen sulfide was evaluated according to the above-mentioned evaluation method, and the results showed that it had excellent performance as shown in Table 1-1.

In addition, the water resistance was 0.05 g/100- as a result of evaluating the solubility in water under the above-mentioned conditions.

Example 1-2 Polyacrylic acid (degree of polymerization 400, NV 27.0%) 555 was used instead of sodium polyacrylate used in Example 1-1.
Put 2000 g of pure water into a 51 container, add 2000 g of pure water, and
．． A 0% polyacrylic acid solution was prepared.

Separately, a dispersion of 84.2 g of zinc springs dispersed in 1000 g of pure water was stirred and added to the above polyacrylic acid solution, and stirred for 30 minutes to form a dispersion of high-molecular polycarboxylic acid zinc salt. A dispersion of polycarboxylic acid zinc salt having a concentration of 16.7% and a pH of 6.5 was obtained.

The deodorizing performance of this zinc salt dispersion was evaluated under the same conditions as in Example 1-1, and the results were as shown in Table 1-1. Also, the solubility in water is 0.03g/100ml! Met.

Example 1-3 Instead of the sodium polyacrylate used in Example 1-1, 500 g of Aron A-30SL (manufactured by Toagosei ■) (ammonium polyacrylate, NV 40%) was charged into a container No. 51, and 2000 g of pure water was added. was added to prepare an aqueous ammonium polyacrylate solution with a concentration of 6.0%.

Separately, as a zinc compound, 189g of zinc chloride was added to 100g of pure water.
The aqueous solution dissolved in 0 g was stirred and added to the above aqueous ammonium polyacrylate solution to form a dispersion of a high molecular weight polycarboxylic acid zinc salt (pf 16.5). Next, the dispersion was washed three times with 2000 g of pure water by a decantation method to obtain a dispersion of polycarboxylic acid zinc salt having a solid content concentration of 17.2% and a pH of 7.0.

The deodorizing performance of this polymeric polycarboxylic acid zinc salt dispersion was evaluated under the same conditions as in Example 1-1. The results are shown in Table 1-
It was as shown in 1. Also, the solubility in water is 0.02
g/100mff.

Example 1-4 70 g of ethyl acrylate and 25.8 g of methacrylic acid (
Mix 0.1 g of benzoyl peroxide and 0.01 g of dodecyl mercaptan with a monomer mixture with a molar ratio of 7o/30), and add lauryl sulfate to 143.7 g of pure water in a 3-meter flask equipped with a reflux condenser and a dropping funnel. 2.9g soda
was added, heated and stirred at 68°C under nitrogen gas aeration, polymerized dropwise over 1.0 hours, heated to 80°C and aged for 1.0 hours to obtain carboxyl with a solid content concentration of 38.5% and pH of 2.7. A group-containing acrylic copolymer dispersion was obtained.

For 100g of this dispersion, 5.7g of zinc white and 11g of pure water
6.2 g was added to make the solid content concentration 16.5%, pH 6,
A purified polymeric polycarboxylic acid zinc salt dispersion of No. 2 was obtained.

The deodorizing performance of this polymeric polycarboxylic acid zinc salt dispersion was evaluated under the same conditions as in Example 1-1. The results are shown in Table 1-
It was as shown in 1. Also, the solubility in water is 0.0:3
g/100mf.

Example 1-5 0.1 g of benzoyl peroxide and 0.01 g of dodecyl mercaptan were mixed with a monomer mixture of 65 g of ethyl acrylate, 5 g of polyethylene, and 51.6 g of methacrylic acid (molar ratio 65/5150), and 143.7 g of pure water was added. , placed in a 1β autoclave with 2.9 g of sodium lauryl sulfate,
Under nitrogen gas atmosphere, pressurized to 5.0 kg/cm2, 68
After heating and stirring at .degree. C. for 1 hour, the temperature was raised to 80.degree. C., and the mixture was further heated and stirred for 1 hour to obtain a carboxyl group-containing ethylene acrylic copolymer dispersion having a solid content of 48.5% and a pH of 2.7.

For 100g of this dispersion, 5.7g of zinc white and 11g of pure water
00g was added to obtain a polymeric polycarboxylic acid zinc salt dispersion having a solid content concentration of 14.1% and a pH of 6.3.

The deodorizing performance of this polymeric polycarboxylic acid zinc salt dispersion was evaluated under the same conditions as in Example 1-1. The results are shown in Table 1-
It was as shown in 1. Also, the solubility in water is 0.02
g/100m1! Met.

Comparative Example 1-1 150 g of fumaric acid, which is a low molecular weight polycarboxylic acid, was charged in a 5β container in place of the high molecular weight polycarboxylic acid.
g of pure water was added to prepare a dispersion liquid with a concentration of 6.0%.

Separately, add 146g of basic zinc carbonate as a zinc compound to 11g of pure water.
000 g of the dispersion was stirred and added to the above fu-15-maric acid dispersion to form an aqueous dispersion of zinc carboxylic acid salt. Next, by the decantation method, 2
Washed 3 times with 000 g of pure water to a solid concentration of 15.5%.
, +11 (6,5) to obtain a dispersion of carboxylic acid zinc salt.

The deodorizing performance of this carboxylic acid zinc salt dispersion was evaluated under the same conditions as in Example 1-1. The results are shown in Table 1-1. The ammonia deodorizing performance was excellent, but the hydrogen sulfide deodorizing performance was excellent. Performance is low and solubility in water is 1.55 g/
100m1! It had insufficient water resistance and was unsuitable for textile processing.

Comparative Example 1-2 The monomer mixing molar ratio of Example 1-4 was changed to ethyl acrylate/methacrylic acid = 75/25 (feeding ratio 75g/21
．． Polymerization was carried out in the same manner as in Example 1-4 instead of 5 g), and reacted with zinc white in the same manner to obtain a solid concentration of 16.2%,
A dispersion of polymeric polycarboxylic acid zinc of p) 16.2 was obtained.

Example 1 about this polymeric polycarboxylic acid zinc dispersion
Table 1-1 shows the results of evaluating deodorizing performance under the same conditions as 1-1.
However, the deodorizing performance of ammonia and hydrogen sulfide was low. Moreover, the solubility in water was 0.03 g/100-.

Processing Example 100 g of a dispersion in which the 14.5% polymeric polycarboxylic acid zinc salt dispersion obtained in Example 1-1 was dispersed in a sand mill to a particle diameter of 5 μm or less, Sumikaflex manufactured by Sumikagaku Kogyo ■. 900 (binder resin, EVA copolymer emulsion, solid content 50% N7.2g, pure water 1
11.8 g and 0.08 g of Nopco NXZ (antifoaming agent) manufactured by San Nopco Co., Ltd. were mixed to prepare a deodorizing impregnating solution with a concentration of 10%, and a dry basis weight of 1 was applied to a cotton cloth of 100 g/m2.
After being impregnated to a concentration of 0 g/m', it was dried at 130°C for 60 seconds, and then heat set at 160°C for 150 seconds to obtain an impregnated cotton fabric.

The deodorizing performance of this impregnated cloth was evaluated.

In addition, this impregnated cloth was washed 10 times using the washing method using an electric washing machine as shown in the JIS L-0217-103 standard, dried, and stored in a room at 55% RH for 24 hours to control the humidity, and then deodorized. Performance was evaluated. In addition, the residual rate of basis weight after washing 10 times was also determined.

The results are shown in Table 1-2. As is clear from Table 1-2, the deodorizing performance was maintained even after thorough washing.

Comparative Processing Example An impregnated cloth was obtained in the same manner as in the Processing Example, using Anico KM201■ (ferric sulfate-based deodorizer manufactured by Minato Sangyo ■) in place of the polymeric polycarboxylic acid zinc salt dispersion used in the Processing Example. The deodorizing performance was evaluated, and the residual rate of basis weight after washing 10 times was also determined. As a result, the treated fabric remained brown even after washing, and its deodorizing performance was also insufficient as shown in Table 1-2.

Example 2-1 Aqualic ■MP- manufactured by Nippon Shokubai ■ as an alkali salt of high molecular weight polycarboxylic acid (carboxyl group-containing polymer)
30 (sodium polyacrylate, degree of polymerization 400, non-volatile content 30.0% N6.7g, pure water 80.2g, ethanol 3
．． A 5.0% mixture of 0g and 0.1g of Emulgen A60 (nonionic surfactant made by Kao) was impregnated into 200g/+n2 cotton cloth to a dryness of 5.0g/m2, and after air drying. , further 5.0 g of zinc sulfate,
91.9 g of pure water, 3.0 g of ethanol.

Impregnated with a 5.0% mixture of 600.1 g of Emulgen A to a dry area weight of 4.8 g/m'.
A treated cotton fabric was prepared by drying at ℃ for 30 minutes. This processed cotton cloth was washed 10 times using the washing method using an electric washing machine as shown in the JIS L-0217-103 standard, and after drying,
After storing in a room with 5% R)I for 24 hours and adjusting the humidity, the deodorizing performance was evaluated.

The results are shown in Table 2-1.

As is clear from Table 2-1, an excellent deodorizing function could be imparted. In addition, as a result of evaluating the solubility in water under the above conditions, it was 0.
．． 01 g/100d.

Example 2-2 Instead of Aqualic MP-30 used in Example 2-1, an acid type of MP-30 (polyacrylic acid, degree of polymerization 40) was used.
0, non-volatile content 30.0%) 16.7g, pure water 80.2
g, ethanol 3.0 g, Emulgen A-600
, 1g was processed in the same manner as in Example 2-1, and then 3 containing 3.0g of zinc white, 93.9g of pure water, 3.0g of ethanol, and 1g of Emulgen A-600.
．． A cotton cloth was prepared which was further impregnated with the 0% mixed dispersion.

This processed cotton fabric was evaluated in the same manner as in Example 2-1, and the results are shown in Table 2-1.

As is clear from Table 2-1, an excellent deodorizing function could be imparted.

Example 2-3 In place of MP-30 used in Example 2-1, a copolymer with a carboxyl group content of 30 mol% and a copolymerization molar ratio of ethyl acrylate/acrylic acid of 70/30 (degree of polymerization 120) was used. , non-volatile content 30%) 16.7g, pure water 80.2
g, ethanol 3.0 g, Emulgen A-600
A processed cotton fabric was prepared in the same manner as in Example 2-2 using a 5.0% mixed solution containing 1 g of . This processed cotton cloth was used in Example 2-1.
Table 2-1 shows the results of the same evaluation.

As is clear from Table 2-1, the deodorizing function could be imparted.

Comparative Example 2-1 5.0% containing 5.0 g of fumaric acid, 91.9 g of pure water, 3.0 g of ethanol, and 1 g of Emulgen A-600
After impregnating and air drying the mixed processing liquid in the same manner as in Example 2-1, 5.0 g of basic zinc carbonate and 91.9 g of pure water were added.
g, ethanol 3.0 g, Emulgen A-600
, 1 g of a 5.0% mixed processing solution was similarly impregnated to prepare a processed cotton fabric. This processed cotton fabric was evaluated in the same manner as in Example 2-1, and the results are shown in Table 2-1.

As shown in Table 2-1, this treated cotton fabric was unable to maintain its deodorizing function. Also, the solubility in water is 1.55.
g/100m1! Comparative Example 2-2 7.5 g of fumaric acid, 7.5 g of basic zinc carbonate dispersed to a particle size of 5 μm, 100 g of a dispersion solution, Sumikaflex 900 (for binder) manufactured by Sumitomo Chemical Co., Ltd. resin, EVA copolymer emulsion, solid content 50%) 17
．． 2 g of pure water, 111.8 g of pure water, and 0.08 g of Nopco NXZ (antifoaming agent) manufactured by San Nopco Co., Ltd. were mixed to prepare a deodorizing impregnating solution with a concentration of 10%, and a dry basis weight was applied to a cotton cloth of 200 g/m2. After impregnating it to 10g/m2, 13
It was dried at 0°C for 60 seconds and then heat set at 160°C for 150 seconds to obtain an impregnated cotton fabric, but the dispersion particles did not penetrate into the inside of the fibers and most of them were attached to the weave, so the texture was a little poor. It was bad.

As a result of performing the same evaluation as in Example 2-1, the deodorizing function was insufficient as shown in Table 2-1.

Comparative Example 3-1 As a polymer containing a polymeric carboxylate salt, 6.7 g of aqueous solution H of Nippon Shokubai's Aqualic MP-30 (partially neutralized sodium polyacrylate, degree of polymerization 400, purity 30%) was purified. 100% aqueous solution of polymer dissolved in 83.3 g of water
I got g. This aqueous solution is calculated to contain 0.0532 gram equivalent of carboxyl groups in the polymer.

On the other hand, 100 g of a 5% aqueous solution of zinc sulfate monohydrate and 100 g of a 5% aqueous solution of copper sulfate were prepared. The metal ions in each aqueous solution were 0.0013 gram equivalent and 0.005 gram equivalent.
6 grams equivalent. Mix these three to pH 7.5
112 g of the aqueous partially reacted polymer solution was impregnated into 100 g of cotton cloth (fabric weight: 100 g/m2), air-dried as it was, and further dried with hot air at 70° C. for 30 minutes. The processed area weight was 5.6 g/m2.

Example 3-1 The processed cotton fabric (105.6 g/m2) obtained in Comparative Example 3-1 was further impregnated with 80 g of a 5% aqueous solution of zinc sulfate monohydrate. The zinc ion in the impregnating solution is 0.0447 gram equivalent. The treated cotton fabric was air-dried and then dried at 70°C for 30 minutes. The total processed area weight was 10.1 g/m2.

Example 3-2 As a high-molecular carboxylic acid-containing polymer, Nippon Shokubai's Aqualic PS-AL37 (partially neutralized acrylic acid maleic anhydride copolymer, degree of polymerization 4000, purity 36%)
3.9 g of the aqueous solution N was dissolved in 86.1 g of pure water to obtain 100 g of a 5% aqueous solution of the polymer.

This aqueous solution was mixed with 100 g of a 5% aqueous solution of zinc sulfate monohydrate to obtain a partially reacted polymer aqueous solution of p) 17.5, and 115 g of this aqueous solution was mixed with 10 g of the same cotton cloth as used in Comparative Example 3-1.
It was impregnated with 0 g. After air-drying and drying, it was again impregnated with 80 g of a 5% aqueous solution of zinc sulfate, and air-dried.

Table 3-1 and Table 3- show the results of examining deodorizing performance and antibacterial properties.
Shown in 2. Example 3-1 and Comparative Example 3-1 having copper ions and zinc ions were excellent in antibacterial properties, and Example 3-1 and Example 3-2 were excellent in deodorizing performance and washing resistance. .

Example 4-1 As a carboxyl group-containing polymer, 16.7 g of Aqualic MP-30 manufactured by Nippon Shokubai Co., Ltd. (neutralized sodium polyacrylate, aqueous solution purity 30.0% with a degree of polymerization of 400) was mixed with pure water. 83.3 g of a 5.0% aqueous solution of the polymer 10
Prepare 0g. It is calculated that the carboxyl group of the polymer in this aqueous solution is contained in an amount of 0.05319 gram equivalent. On the other hand, 5.0% aqueous solution of zinc sulfate heptahydrate 30.5
g (0,01064 gram equivalent) was prepared in advance, and 5
．． A 100 g/m2 cotton fabric was impregnated with 100 g of a 20% partially zinc crosslinked polymer aqueous solution (PT (7,6, viscosity 13 cps, concentration 5.0%) by adding and mixing with a 0% aqueous polymer solution, and after air drying, ℃ for 30 minutes with hot air, and then separately prepared Sanizol B50 (quaternary ammonium salt manufactured by Kao,
50% concentration) 3.0 g and zinc sulfate heptahydrate 5.5 g (gram equivalent ratio: quaternary ammonium salt/zinc sulfate heptahydrate =
0.11/100) was mixed and dissolved in 91.5 g of pure water and impregnated again with 100 g of a mixed solution, air-dried, and then dried with hot air at 70°C for 30 minutes to obtain a polymer metal salt with a quaternary ammonium salt added. A treated wire fabric with a loading amount of 10.2 g/m2 was prepared, and after evaluating its washing resistance, the deodorizing performance and antibacterial/antifungal properties were evaluated.The results are shown in Table 4-1 and Table 4-2. It is.

Example 4-2 As a carboxyl group-containing polymer, 12.5 g of Aqualic DL-40 manufactured by Nippon Shokubai Co., Ltd. (neutralized sodium polyacrylate, 40% aqueous solution with a molecular weight of 4000) was added to 87.7 g of pure water.
5 g to prepare 100 g of a 5.0% aqueous polymer solution. This aqueous solution contains 0.0531 carboxyl groups.
It contains 9 gram equivalents. To this aqueous solution was added 26.6 g of a 5.0% aqueous solution of copper sulfate pentahydrate (0,
01064 gram equivalent) was added to prepare a 20% aqueous copper crosslinked polymer solution (pH 8.0, viscosity 5 cps).

After impregnating 100 g of Sanizol B50 (concentration 5.0%) into cotton cloth in the same manner as in Example 4-1,
Kao quaternary ammonium salt, 50% concentration) 5.0g and zinc sulfate heptahydrate 5. Og (gram equivalent ratio quaternary ammonium salt/zinc sulfate heptahydrate = 0.20/100) in pure water 9
100 g of the mixed solution mixed and dissolved in 0.0 g = 31- was impregnated again, air-dried, and then hot-air dried at 70°C for 30 minutes.
A processed cotton cloth carrying 10.4 g/m2 of a high molecular weight metal salt added with a quaternary ammonium salt was prepared and evaluated in the same manner as in Example 4-1. The results are shown in Table 4-1 and Table 4-
The performance was as shown in 2.

Example 4-3 Acrylic acid 10 mol% (7.1 g), maleic acid 20
Mol% (23.2g), ethyl acrylate 20mol%
(20.0 g), acrylic acid/Na 30 mol% (2
8,3g>, 20 mol% of 2hydroxy-3-acryyloxypropyltrimethylammonium chloride (4
123.4 g of a mixture of 4.8 g) and 0 potassium persulfate.
．． 1 g of the mixture was mixed, 287.9 g of pure water was added to an IL flask equipped with a reflux condenser, and the mixture was stirred and heated to 70°C under nitrogen gas aeration to carry out a polymerization reaction for 1.0 hours, resulting in a solid content of 29.9 g.
An 8% aqueous copolymer solution with a pH of 6.5 was obtained. After diluting this copolymer aqueous solution to 5.0%, it was impregnated into cotton fabric in the same manner as in Example 4-2, and after air-drying and heat-drying, the zinc white 3
2.4g (0.8g equivalent), caustic soda 10.0
A processed fabric with a basis weight of 10.4 g/m2 was prepared by impregnating it with a 5% mixed aqueous solution of g (0.25 g equivalent) and drying, and after evaluating its washing resistance, it was evaluated for deodorizing performance, antibacterial and anti-mold properties. evaluated. The results are shown in Table 4-1.4-2.

Comparative Example 4-1 26.6 g of a 5.0% aqueous solution of copper sulfate pentahydrate (0,
A 20% copper crosslinked polymer aqueous solution (pH 8.2, viscosity 11 cps, concentration 5
．． 0%) 10(lg) was impregnated in the same manner as in Example 4-1, and then impregnated again with 100 g of a 6.1% zinc sulfate aqueous solution, and evaluated in the same manner as in Example 4-1.The results are as follows. Table 4
-1, the performance shown in Table 4-2, and the mold resistance is slightly inferior.

Table 4-1 Deodorizing performance and washing resistance Table 4-2 Antibacterial/antifungal performance [Effects of the invention] As mentioned above, a porous sheet material is impregnated with a polymer solution containing a carboxyl group, and then a polyvalent metal When the aqueous salt solution is brought into contact with the porous sheet material, a water-insoluble polymeric polyvalent metal salt is produced in the porous sheet material. If an appropriate metal is used, a polymeric polyvalent metal salt having deodorizing and antibacterial properties can be obtained, so the porous sheet material supporting this salt will have deodorizing and antibacterial properties.

However, since the reaction rate between a polymer containing a carboxyl group and a polyvalent metal salt is quite fast, the reaction occurs on the surface of the sheet material, so if the sheet is thick, the subsequent penetration of the polyvalent metal salt will be This may result in non-uniform reaction and loading conditions, and insufficient washing resistance.

In this case, if a polymer containing carboxyl groups is impregnated with a polyvalent metal salt that has been partially reacted with the polyvalent metal salt, the reaction rate when it comes into contact with the polyvalent metal salt aqueous solution is relatively slow, and the latter is completely reacted. The reaction is completed after penetrating into the sheet. Therefore, the supported state and degree of crosslinking become uniform and complete, and processing with excellent washing resistance can be obtained. In addition, this method can easily be used in combination with antibacterial agents such as polyvalent metal salts and quaternary ammonium salts, making it possible to obtain a process that has both excellent deodorizing and antibacterial performance.

Claims (1)

[Scope of Claims] 1. A polymer (x_1 component) containing 30 mol% or more of a monomer unit of a carboxyl group and/or a metal salt of a carboxyl group in the polymer chain, or a carboxyl group and/or a metal salt of a carboxyl group. A water-soluble copolymer (x_2 components) containing 5 to 98 mol% of monomers, 1 to 50 mol% of ionic monomers, and 1 to 50 mol% of monomers copolymerizable with these monomers. water-dispersible polymer (x component)
and one metal compound selected from the group consisting of zinc, silver, copper, aluminum, titanium, and zirconium, in which the equivalent ratio of metal ions to the carboxyl group contained in component x is 0.1 to 1.0, or A deodorizing, antibacterial and antifungal composition comprising an aqueous solution or dispersion of two or more (y components). 2. The composition of claim 1 or its x component is fixed on a porous sheet substrate, and then the y component and/or general formula is ▲a numerical formula, a chemical formula, a table, etc.▼ (in the formula, R is a carbon number of 12 to 18 (representing an alkyl group) is brought into contact with the porous sheet substrate at an equivalent ratio of 0.1 to 1.0 to the carboxyl group contained in the component A deodorizing, antibacterial, and antifungal processing method characterized by forming water-insoluble deodorizing, antibacterial, and antifungal components in wood.