JPH01260068A - Method of manufacturing antibacterial materials - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

Detailed Description of the Invention [Field of Industrial Application] The present invention relates to a method for producing fiber materials with excellent antibacterial properties, and more specifically, the present invention relates to a method for producing fiber materials with excellent antibacterial properties. This invention relates to a method for imparting to textile materials a sustainable antibacterial effect as well as functions such as water absorption, antistatic properties, moisture permeability, waterproofness, and windproof properties.

[Conventional technology]

In recent years, synthetic fibers and synthetic blended fibers have come to be increasingly used in blouses, shirts, underwear, etc., and there is an increasing need to treat these with antibacterial and deodorizing properties. Sweat absorbed by clothing promotes the growth of microorganisms, causing foul odors and adversely affecting dermatitis, athlete's foot, infectious diseases, etc. In order to prevent this, clothing fibers made by adsorbing quaternary ammonium salts (Japanese Unexamined Patent Publication No. 57-51874) and imidazole compounds (Japanese Unexamined Patent Publication No. 58-149) have been developed.
No. 375) is disclosed. However, the antibacterial substances applied to the fibers by the methods disclosed in these prior art techniques easily fall off or volatilize during washing, making it impossible to maintain the antibacterial effect for a long period of time.

[Problem to be solved by the invention]

Antibacterial processing to prevent harmful effects caused by microorganisms has the following properties: (1) High safety for the human body, (2) High antibacterial effect, (3) High sustainability of antibacterial effect, (4) Simple processing method. Therefore, low processing costs are required. However, there is no known material that satisfies all of these points.

Therefore, the purpose of the present invention is to easily process antibacterial inorganic powder such as antibacterial zeolite, which is extremely safe for the human body and has high antibacterial activity, into a fiber material to produce a durable antibacterial fiber material. It is about providing law.

[Means for Solving the Problems] The present invention provides a base fabric containing a resin composition containing an antibacterial inorganic powder, a resin, a high boiling point solvent with a boiling point of 100°C or higher, and a low boiling point solvent with a boiling point of 100°C or lower. and then curing the resin composition applied to the base fabric, and the difference between the boiling point of the high boiling point solvent and the boiling point of the low boiling point solvent is 50 ° C. or more ( (hereinafter referred to as method A).

Furthermore, the present invention provides an antibacterial inorganic powder, a resin, and a boiling point of 10
Forming a film from a resin composition containing a high boiling point solvent having a boiling point of 0°C or higher and a low boiling point solvent having a boiling point of 100°C or lower, and then coating a base fabric with the obtained film, and the boiling point of the high boiling point solvent. and the difference in boiling point of low boiling point solvent is 5℃
The present invention relates to a method for producing an antibacterial material (hereinafter referred to as method B) characterized by the above.

The present invention will be explained below (unless otherwise specified, the explanation is common to Method A and Method B).

In the present invention, examples of the "antibacterial inorganic powder" include powder of a substance having antibacterial properties and powder in which a substance having antibacterial properties is supported on an inorganic carrier. As the inorganic carrier, zeolite, amorphous aluminosilicate, silica gel, alumina, diatomaceous earth, etc. are preferably used.

In the present invention, antibacterial zeolite or amorphous aluminosilicate, for example, can be used as the antibacterial inorganic powder. In the present invention, as the antibacterial zeolite, for example, JP-A-59-133235, JP-A-60-181
No. 0023, No. 59-37956 and Patent Application No. 1986-3
Any zeolite described in No. 07355, etc., in which ion exchangeable ions in the zeolite are replaced with antibacterial metal ions and/or ammonium ions, can be used without limitation. Further, as the antibacterial amorphous aluminosilicate, for example, an amorphous aluminosilicate described in JP-A-61-174111 etc. in which ion-exchangeable ions are replaced with antibacterial metal ions and/or ammonium ions, etc. Shaped aluminosilicates can be used.

In the present invention, for example, antibacterial properties are obtained by replacing part or all of ion exchangeable ions in zeolite, such as sodium ions, calcium ions, potassium ions, magnesium ions, iron ions, etc., with ammonium ions and antibacterial metal ions. Zeolites can be used as antibacterial inorganic powders.

As the zeolite, both natural zeolite and synthetic zeolite can be used.

Zeolites are generally aluminosilicates with a three-dimensional skeletal structure, - as a form XM27nO'A j
! 20s4S+024H20te is displayed. ＋ ＋
TeM represents an ion that can be exchanged and is usually 1 or 2.
It is a valent metal ion. n is the valence of the (metal) ion. X and Y represent the respective metal oxide and silica coefficients, and Z represents the number of water of crystallization. Specific examples of zeolites include 8-type zeolide, X-type zeolide, Y-type zeolide, T-type zeolide, high silica zeolite, sodalite, mordenite, analcyme,
Examples include clinoptilolite, chabasite, and erionite. However, it is not limited to these. Is the ion exchange capacity of these exemplary zeolites an 8-type zeolide? meq/g% X-type zeolide 6
, 4 meQ/g, Y-type zeolide 5 meq/g.

T-type zeolide 3.4meQ/g, sodalite 11
．． 5 meq/g, clinoptilolite 2.6 meq/
g, chabasite 5 meq/g% erionite 3.
8 meq/g, and both have sufficient capacity for ion exchange with ammonium ions and silver ions.

Examples of antibacterial metal ions include silver, copper, zinc, mercury,
Mention may be made of ions of tin, lead, bismuth, cadmium, chromium or thallium, preferably silver, copper or zinc.

From the viewpoint of antibacterial properties, it is appropriate that the antibacterial metal ions are contained in the zeolite in an amount of 0.1 to 15%.

Silver ion 0.1-15% and copper ion or zinc ion 0
Antibacterial zeolite containing 61-8% is more preferred.

On the other hand, ammonium ions can be contained up to 20% in zeolite, but the content of ammonium ions in zeolite is 0.5 to 5%, preferably 0.5%.
From the viewpoint of effectively preventing discoloration of the zeolite, it is appropriate to set the content to 2%. In this specification, % refers to % by weight on a dry basis at 110°C.

The method for producing antibacterial zeolite will be explained below.

The antibacterial zeolite used in the present invention is produced by contacting the zeolite with a mixed aqueous solution containing ammonium ions and antibacterial metal ions such as silver ions, copper ions, zinc ions, etc. prepared in advance. The above ions are replaced. The contact temperature is 10-70℃,
Preferably at 40-60°C for 3-24 hours, preferably 1
It can be carried out by a batch method or a continuous method (for example, a column method) for 0 to 24 hours. The pH of the above mixed aqueous solution is 3.
It is appropriate to adjust it to 10 to 10, preferably 5 to 7. This adjustment is preferable because it can prevent silver oxides and the like from being deposited on the zeolite surface or into the pores. Further, each ion in the mixed aqueous solution is usually supplied as a salt.

For example, ammonium ions include ammonium nitrate, ammonium sulfate, ammonium acetate, ammonium perchlorate, ammonium thiosulfate, ammonium phosphate, etc. Silver ions include silver nitrate, silver sulfate, silver perchlorate, silver acetate, diammine silver nitrate, diammine silver sulfate, etc. Copper ions include copper nitrate (■), copper perchlorate, copper acetate, potassium tetracyanocuprate, copper sulfate, etc. Zinc ions include zinc nitrate (■), lead sulfate, zinc perchlorate, zinc thiocyanate, etc. Zinc acetate etc.
Mercury ions include mercury perchlorate, mercury nitrate, mercury acetate, etc.
Tin ions include tin sulfate, etc., lead ions include lead sulfate, lead nitrate, etc., bismuth ions include bismuth chloride, bismuth iodide, etc., and cadmium ions include cadmium perchlorate, cadmium sulfate, cadmium nitrate, cadmium acetate, etc. As the chromium ion, chromium perchlorate, chromium sulfate, ammonium chromium sulfate, chromium nitrate, etc. can be used, and as the thallium ion, thallium perchlorate, thallium sulfate, thallium nitrate, thallium acetate, etc. can be used.

The content of ammonium ions and the like in the zeolite can be appropriately controlled by adjusting the concentration of each ion (salt) in the mixed aqueous solution.

For example, when the antibacterial zeolite contains ammonium ions and silver ions, the amount of ammonium ions in the mixed aqueous solution is 0.2 M/j! ~2.5 M/l silver ion concentration to 0.002 M/j! ~0.15M/
1, an antibacterial zeolite having an ammonium ion content of 0.5 to 5% and a silver ion content of 0.1 to 5% can be obtained as appropriate. Further, when the antibacterial zeolite further contains copper ions and zinc ions, the copper ion concentration in the mixed aqueous solution is 0°IM/Il to 0.85.
M/1, zinc ion concentration is 0.15M#~1.2M
/ 1, the copper ion content can be adjusted to 0.1.
~8% and an antibacterial zeolite with a zinc ion content of 0.1 to 8%.

In addition to the mixed aqueous solution as described above, ion exchange can also be carried out by using an aqueous solution containing each ion individually and bringing each aqueous solution into contact with the zeolite sequentially. The concentration of each ion in each aqueous solution can be determined according to the concentration of each ion in the mixed aqueous solution.

After ion exchange, the zeolite is thoroughly washed with water and then dried. Drying is preferably carried out at 105°C to 115°C under normal pressure or 70°C to 90°C under reduced pressure (1 to 30 Torr).

Ion exchange of ions without suitable aqueous salts such as tin and bismuth or organic ions can be carried out using an organic solvent solution such as alcohol or acetone so that hardly soluble basic salts are precipitated.

In the present invention, antibacterial amorphous aluminosilicate (hereinafter referred to as AAS) in which part or all of the ion-exchangeable ions in the amorphous aluminosilicate are replaced with antibacterial metal ions is used.
) can be used as an antibacterial inorganic powder.

AAS (amorphous aluminosilicate) used as a raw material here is not particularly limited, and conventionally known ones can be used as they are. AAS generally has the composition formula x
M20.A 1 ,'L.ySi02.zH20, where M is generally an alkali metal element (eg, sodium, potassium, etc.). Moreover, xSySz indicates the molar ratio of metal oxide, silica, and crystal water, respectively. Unlike the crystalline aluminosilicate called zeolite, AAS is an amorphous substance that does not show a diffraction pattern even in X-ray diffraction analysis, and the synthesis process produces extremely fine zeolite crystals of several tens of amperes. and 5102 on its surface
- It is thought to have a structure in which an amorphous substance consisting of a complex combination of Al2O2, M2O, etc. is attached. AAS is generally produced by reacting an aluminum salt solution, a silicon compound solution, and an alkali metal salt solution at a predetermined concentration at a low temperature of 60° C. or lower, and washing with water before crystallization proceeds.

Examples of manufacturing methods include those described in Japanese Patent Publication No. 52-58099 and Japanese Patent Application Laid-Open No. 55-162418.

AAS obtained by the above method contains 10% or more of alkali metal oxide. The AAS can be used as it is for the production of antibacterial AAS, but it is recommended that the M, 0 content be 10% or less, preferably 8% or less, to avoid discoloration of the resin over time when added to the resin. This is particularly preferable from the viewpoint of effectively preventing. However, it is not limited to this range.

Furthermore, the AAS is ion-exchanged with antibacterial metal ions. Examples of antimicrobial metal ions include ions of silver, copper, zinc, mercury, tin, lead, bismuth, cadmium, chromium or thallium, preferably silver, copper or zinc.

Among the antibacterial metals, it is appropriate to add silver in an amount of 0.1 to 50%, preferably 0.5 to 5%, from the viewpoint of exhibiting excellent antibacterial activity. Furthermore, it is preferable to contain 0.1 to 10% of one or more of copper, zinc, mercury, tin, lead, bismuth, cadmium, chromium, and thallium.

Furthermore, the antibacterial AAS can also contain ammonium ions in addition to the above-mentioned antibacterial metals by ion exchange. Ammonium ions can be contained up to 15% in AAS, but the content of ammonium ions in AAS is 0.5 to 5%, preferably 0.5 to 2%. This is suitable from the viewpoint of effectively preventing discoloration.

The antibacterial AAS can be produced, for example, by the following methods (1) and (2).

Q) Contacting an amorphous aluminosilicate with an M,0 (M is an alkali metal) content of preferably 10% or less with antibacterial metal ions to produce ion-exchangeable ions in the amorphous aluminosilicate. Antibacterial AAS can be produced by exchanging antibacterial metal ions with antibacterial metal ions.

(2) The pH of the amorphous aluminosilicate slurry is preferably adjusted to 6 or less, and then the amorphous aluminosilicate in the slurry is brought into contact with antibacterial metal ions to exchange ions in the amorphous aluminosilicate. Antibacterial AAS can be produced by exchanging available ions with antibacterial ions.

In method (1), amorphous aluminosilicate (AAS)
) whose M20 content is preferably 10% or less. AAS obtained by conventional methods contains more than 10% M2O. Therefore, A obtained by the above method
For example, AS is suspended in water, and then an aqueous acid solution is added dropwise to the resulting slurry while stirring to neutralize the alkali metals and/or alkaline earth metals in AAS, thereby reducing the M20 content to 10% or less. can be adjusted to 0 as an acid aqueous solution. It is preferable to use a dilute acid aqueous solution having a concentration of IN or lower, and to carry out the dropwise addition at a rate of 100 m//30 minutes or less, although this will vary depending on the stirring conditions and reaction scale.

Furthermore, neutralization is performed until the pH of the slurry is 3 to 6, preferably 4.
It is preferable to set it in the range of 5 to 5. Examples of acids that can be used for neutralization include inorganic acids such as nitric acid, sulfuric acid, perchloric acid, phosphoric acid, and hydrochloric acid, and organic acids such as formic acid, acetic acid, citric acid, and citric acid.

AAS with an M,O content of 10% or less obtained by neutralization can be filtered, washed with water, and used as a slurry in the method (1) as it is, or it can be dried to obtain an M,O content of 10%. The following AAS may be used.

In the method (1), preferably M, 0 content is 10%
The following slurry of AAS and an aqueous solution containing antibacterial metal ions are mixed, and the AAS is brought into contact with the mixed aqueous solution containing antibacterial metal ions such as silver ions, copper ions, zinc ions, etc., so that the ions in AAS can be exchanged. The ion is replaced with the above ion. The contact is carried out at a temperature of 5-70°C, preferably 40-70°C.
It can be carried out at 60° C. for 1 to 24 hours, preferably for 10 to 24 hours, by a batch method or a continuous method (for example, a column method).

Each ion in the mixed aqueous solution is usually supplied as a salt. The salt used can be the same as the salt that can be used in the production of the antibacterial zeolite.

The content of ammonium ions, etc. in AAS can be adjusted by adjusting the degree of each ion (salt) in the mixed aqueous solution.
It can be controlled as appropriate. For example, when the antibacterial AAS contains silver ions, by setting the silver ion concentration in the mixed aqueous solution to 0.01 M/β to 0.30 M#,
Antibacterial AAS having a silver ion content of 0.5 to 6% can be obtained as appropriate. In addition, when the antibacterial AAS further contains copper ions and zinc ions, the copper ion concentration in the mixed aqueous solution is 0.05 M/β to 0.4 M/f, and the zinc ion concentration is 0.05 M/1 to 0. .4 M/f, it is possible to obtain an antibacterial AAS having an appropriate copper ion content of 1 to 8% and a zinc ion content of 1 to 8%.

In addition to the mixed aqueous solution as described above, ion exchange can also be carried out by using an aqueous solution containing each ion individually and bringing each aqueous solution into contact with AAS sequentially. The concentration of each ion in each aqueous solution can be determined according to the concentration of each ion in the mixed aqueous solution.

After ion exchange, the AAS is thoroughly washed with water and then dried. Drying is preferably carried out at 105°C to 115°C under normal pressure or at 70°C to 90°C under reduced pressure (1 to 30 Torr).

Ion exchange of ions without suitable water-soluble salts such as tin and bismuth or organic ions can be carried out using an organic solvent solution such as alcohol or acetone so that hardly soluble basic salts are precipitated.

On the other hand, in method (2), the pH of the AAS slurry obtained by a conventional method is adjusted to 6 or less, preferably 3 to 6, more preferably 4 to 5, and the M20 content in AAS is reduced to 10%.
It can be as follows. For adjusting the pH, the method exemplified in the method (1) above can be used similarly.

The pH-adjusted slurry can then be mixed with an antibacterial metal ion-containing solution to ion-exchange the AAS in the slurry. As the ion exchange method, a method similar to method (1) can be used as is.

The antibacterial inorganic powder used in the present invention has a moisture content of 0.
．． The content is preferably 5 to 20%, preferably 1 to 10%, from the viewpoint of obtaining good dispersibility. Furthermore, there is no particular restriction on the particle size of the antibacterial inorganic powder, but from the perspective of imparting high antibacterial activity to the dispersion with a smaller amount of powder,
Preferably, the particle size is relatively small. The particle size of the powder is, for example, 0.04 to 20 μm, preferably 0.1 to 10 μm.
It can be μm.

Examples of the "resin" used in the present invention include polyurethane resin, polyacrylic resin, silicone resin, epoxy resin, acetal resin, ketone resin, alkyl carbamate resin, urea resin, melamine resin, vinyl acetate resin, and vinyl chloride resin. , nylon resin, natural rubber, nitrile rubber (NBR), styrene butadiene rubber (SBR)
, chloroprene rubber (CR), and the like.

Among these, polyurethane resins, acrylic resins, silicone resins, or modified resins thereof are particularly preferred in the present invention because they simultaneously have moisture permeability and antistatic properties.

In the present invention, a high boiling point solvent having a boiling point of 100° C. or higher and a low boiling point solvent having a boiling point of 100° C. or lower are used as the solvent.

Examples of the above-mentioned high boiling point solvents include water (100°C), toluene (110.6°C), 0-xylene (144.4°C), m
-xylene (139,1℃), p-xylene (138,
4°C), butyl acetate (126.3°C), methyl isobutyl ketone (115.8°C), methyl cellosolve (124°C),
, 5°C), ethyl cellosolve (135, 1°C), ethyl cellosolve acetate (155°C), N,N-dimethylformamide (153°C), tetrachlorethylene (1°C),
21.2°C), cyclohexane (156°C), and mineral spirits (130 to 200°C), among which N,N-dimethylformamide is preferred (note that the boiling point is shown in parentheses).

Furthermore, as an example of the above-mentioned low boiling point solvent, ethyl acetate (79°C
), methyl ethyl ketone (79.6°C), isopropyl alcohol (82.3°C), dichloromethane (89.8°C)
℃), trichlorethylene (86.7℃), dichloroethane (83.5℃), trichloroethane (74.1℃)
, acetone (56.3°C) and water (100°C), among which trichloroethane is preferred (note that the boiling point is shown in parentheses).

In the present invention, one of the above solvents is used as the high boiling point solvent.
One or more of the above solvents can be used as the low boiling point solvent.

However, in the present invention, the combination is such that the difference between the boiling point of the high boiling point solvent and the boiling point of the low boiling point solvent is 5°C or more, preferably 9°C or more.

In the present invention, by using a high boiling point solvent and a low boiling point solvent together as described above, the low boiling point solvent evaporates at the beginning of the curing process and forms a coating film, and then when the high boiling point solvent gradually evaporates, the antibacterial effect is achieved. Because the surface of the inorganic powder is exposed, high antibacterial activity can be obtained.

In the present invention, a resin composition is prepared by mixing the antibacterial inorganic powder, resin, and two or more types of solvents, or by adsorbing a high boiling point solvent to the antibacterial inorganic powder in advance and then mixing them. do. In this mixing, the viscosity of the resin composition containing the antibacterial inorganic powder should be 1,000 to 200,000 cP, preferably 2,000 to 500,000 cP to facilitate coating with a knife coater or roll coater and to form a uniform resin composition. It is preferable from the viewpoint that it can be obtained in a relatively short time.

The content of the antibacterial inorganic powder in the resin composition containing the antibacterial inorganic powder, resin, high boiling point solvent, and low boiling point solvent used in the present invention is 0.1 to 30% based on the solid weight of the resin. , preferably 1 to 20%, from the viewpoint of exhibiting high antibacterial activity.

Furthermore, the weight ratio of the resin and the solvent (high boiling point solvent and low boiling point solvent) is, for example, 5 to 55:95 to 45 (resin: solvent).
This is preferable from the viewpoint of keeping the viscosity of the resin composition within the above range and exhibiting high antibacterial activity. In addition, the weight ratio of the high boiling point solvent and the low boiling point solvent is 5 to 80:80 to 5.
(high boiling point solvent: low boiling point solvent), preferably 15 to 70 nia 0 to 15. Higher antibacterial activity can be obtained by setting the weight ratio of the high boiling point solvent and the low boiling point solvent to the above range.

The resin composition used in the present invention can be manufactured using various mixers, such as a Pan Bali mixer with high sand dispersion power, a two-roll mill, and a three-roll mill with low sand dispersion power. Colloid mills, mixers, dispers, sand mills, ball mills, etc. can also be used.

The resin composition may also contain about 1 to 15% by weight of crosslinking agents, such as polyimine resins, butylated melamine resins, epoxy resins, and incyanates, and colorants and stabilizers as necessary. , a cell conditioner (surfactant), etc. may be included.

In the present invention, there are no particular limitations on the type, shape, etc. of the fiber material used as the base fabric, as long as it is not altered in quality by the manufacturing method of the present invention. For example, natural fibers such as cotton, wool, silk, and linen, cellulose fibers such as rayon and cupro, nylon 6, and nylon 6.
At least one type of fiber selected from polyamide fibers such as 6, polyester fibers such as polyethylene terephthalate fibers, acrylic fibers such as polyacrylonitrile fibers, water-insolubilized polyvinyl alcohol fibers, cellulose acetate fibers, etc. Examples include woven fabrics, knitted fabrics, nonwoven fabrics, nets, and composites thereof.

In the manufacturing method (method A) of the present invention, first of all, the resin composition is applied to a base fabric. There are no particular restrictions on the application method, and any method can be used as long as it does not cause decomposition or dissolution of the antibacterial inorganic powder. Application methods include spray coating (atomization), knife coating (square coating machine), gravure coating (same as gravure printing), and roll coating (
(adhering on a roller), impregnation coating (squeezing after dipping in liquid), etc.

The amount of the resin composition to be applied can be variously selected depending on the use etc., but for example, 5 to 600 g/m', preferably 10 to 400 g/m'.
g/m'' is appropriate.

Next, the applied resin composition is cured. Curing methods can include dry curing (eg, using a draft dryer) and steam curing (eg, using superheated steam). Furthermore, a crosslinking agent can be added to the resin composition, or a radiation polymerizable resin can be used as the resin and irradiated with radiation. Specifically, dry curing can be performed, for example, at 50 to 180°C for 30 seconds to 10 minutes.

Furthermore, the above-mentioned application and curing can be carried out simultaneously, and examples of such methods include, for example, a casting method (e.g., a method in which a solution is cast onto a rotating support), an extrusion method (e.g., a method in which a heated melted resin is passed through a T-shaped die) Examples include an extrusion method), a calendar method (for example, a method of rolling between two or more rolls), a stretching method (for example, a method of stretching with biaxial rolls, etc.).

Moreover, in the production method (Method B) of the present invention, a film is formed from the resin composition. The film can be formed by a known method (for example, an extrusion method, a roll knife method, a stretching method, etc.), and the resin composition can be cured in the same manner as in Method A above. The resulting film is then applied to a base fabric. The coating method is extrusion lamination (extrusion of molten film,
hot melt lamination method (heat applied), dry lamination method (adhesive is applied to the film by pressure after solidification), wet lamination (applyed with a water-soluble adhesive containing a solvent and then pressure bonded), etc. can be mentioned. In the present invention (method B), the formation of the film and the coating on the base fabric can be performed simultaneously.

The antibacterial material obtained by the present invention can be used as various textile products. For example, medical white coats, operating gowns (surgical gowns)
, uniforms such as meat processing work clothes, sports clothing, carpets, rugs such as back sizing, sleeping clothing such as sheets, pet covers, pillow cases, etc.
Kitchen utensils such as dishcloths, aprons, tablecloths,
Can be used for diaper covers, wallpaper, cloths, etc.

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

Reference example (preparation of antibacterial zeolite) A-type zeolide powder (Na2
Add water to 1 kg of 0・Al1(]+・1.9St02・xH2O: average particle size 1.5 μm) to make a slurry of 183β, then stir and degas, and then add an appropriate amount of 0
．． Adjust the pH to 5-7 by adding 5N nitric acid solution and water,
The entire slurry was made into a 1.81 slurry. Next, for ion exchange, 0.015N silver nitrate solution 31 was added and the entire volume was adjusted to 4.
8β, and this slurry liquid was maintained at 40 to 60°C and heated to 24°C.
The mixture was kept stirring for a period of time to reach an equilibrium state.

After the ion exchange was completed, the zeolite powder was filtered and washed with warm water until excess silver ions in the zeolite phase disappeared. Next, the sample was heated and dried at 110°C to obtain an antibacterial zeolite powder sample.

The resulting sample contained 2.5% silver.

Example 1 (Laminated film processing) As a base fabric, a jersey knitted fabric made of 50 denier, 32 filament 100% polyester filament yarn manufactured by Toshi Co., Ltd. was used. Apply the following resin composition 1 to a release paper with a thickness of 60 μm.
(wet 60g/m'') and dried with a dryer at 120-135℃ for 2 minutes to form a film.After applying 70g/m' of the following resin composition 2 on top of this, the above base fabric was placed. The cloth was laminated and dried in a dryer at 120 to 135° C. for 2 minutes to obtain a laminated cloth.

A laminate cloth containing no antibacterial inorganic powder was also produced under similar conditions.

(Resin composition 1) Toluene (bpllo, 6°C) 20 parts Antibacterial inorganic powder (Reference example) 3 parts (Resin composition 2
) Acetone (bp 56.3°C) 10 parts Toluene (bpllo, 6°C) 50 parts Example 2 (
Coating processing) Unitika's 100% cotton spun yarn fabric weaving structure, warp count 60, weft count 60, batting density, warp 112/2.54c
A 2.54 cm plain woven fabric was coated with the following resin composition 3 using a knife coater machine, and heated at 100° C. for 2 minutes as pre-drying. Thereafter, kinearing was performed at 140 to 150° C. for 1 minute to obtain a coated cloth. A coated cloth containing no antibacterial inorganic powder was also prepared under similar conditions.

(Resin composition 3) 1.1.1-trichloroethane 50 parts (b
p 86.7°C) Toluene (bpllo, 6°C) 35 parts Isocyanate 1 part (HL; Japan Polyurethane) Antibacterial inorganic powder (reference example) 3 parts Example 3 (
Printing Process) After printing the following resin composition 4 on a polyester palace (50 denier, 36 filaments), it was pre-dried at 110°C for 2 minutes and further heat-treated at 130-150°C for 5 minutes to obtain a printed cloth. A printed cloth containing no antibacterial inorganic powder was also produced under similar conditions.

(Resin composition 4) Dichloroethane (bp 83.5°C) 10 parts Toluene (bpHo, 6°C) 40! Antibacterial inorganic powder (reference example) 3 parts Example 4 (antibacterial activity test) The fabrics obtained in Examples 1 to 3 were washed 50 times (JIS-L-0217-103 method) with those immediately after processing. A comparative test was conducted on the antibacterial activity of these products.

15 mt' of Escherichia coli (105 cells/ml) fell on each city,
The cells were cultured at 37°C for 18 hours. The bacterial solution was washed away with physiological saline, and the number of E. coli present in this solution was measured. The results are shown in Table 1.

Comparative Example 1 A laminate cloth was obtained in the same manner as in Example 1, except that the following resin compositions 5 and 6 were used in place of resin compositions 1 and 2 in Example 1, respectively.

(Resin composition 5) Methyl ethyl ketone 45 parts Antibacterial inorganic powder (Reference example) 3 parts (Resin composition 6) Toluene 60 parts N,N-dimethylformamide 15 parts Antibacterial inorganic powder (Reference example) 3 parts Comparative example 2 A coated cloth was obtained in the same manner as in Example 2, except that Resin Composition 7 below was used instead of Resin Composition 3 in Example 2.

(Resin composition 7) 1.1.1-) Lichloroethane 80 parts Antibacterial inorganic powder (reference example) 3 parts Comparative example 3 The following resin composition 8 was used instead of resin composition 4 in Example 3.
A printed cloth was obtained in the same manner as in Example 3 except that the following was used.

(Resin composition 8) Butadiene latex 25 parts (Fixe
r45ON; Dainippon Ink) pigment
io part (white; Ryudye-to TA705
; Dainippon Ink) Emulsifying thickener
65 parts (Reducer 400: Dainippon Ink) Toluene 50 parts Antibacterial inorganic powder (reference example) 3 parts Comparative Example 4 A comparative test of the antibacterial activity of each city obtained in Comparative Examples 1 to 3 was conducted in Example 4.
I did it in the same way. The results are shown in Table 1.

Table 1 Example 5 Solvent (1,1,1-)'J of resin composition 3 of Example 2
Instead of chloroethane and toluene, 42.5 parts each of the two solvents shown in Table 2 were used (however, if a single solvent was used, the amount of solvent was 85 parts), and antibacterial inorganic powder was used. A coated cloth was prepared in the same manner as in Example 2, except that the amount was changed to 0.5 parts, and its antibacterial activity was tested in the same manner as in Example 4. The results are shown in Table 2.

Example 6 As a base fabric, jersey silk fabric made from Toshi's 50 denier, 32 filament 100% polyester filament yarn was used. The following resin composition 1 was spread on release paper to a thickness of 60 μm (
The base fabric was placed thereon and dried at 120 to 135°C for 2 minutes using a dryer to obtain a laminate fabric. Antibacterial test Example 4
The results are shown in Table 3.

Comparative Example 5.6 45 parts of methyl ethyl ketone (Comparative Example 5) or 30 parts of toluene and N,N- in place of the solvent (methyl ethyl coke, toluene and N,N-dimethylformamide) in Resin Composition 1 of Example 6. A laminate cloth was obtained in the same manner as in Example 6, except that 15 parts of dimethylformamide (Comparative Example 6) was used, and its antibacterial activity was determined (Table 3).

Example 7 A laminate cloth was obtained in the same manner as in Example 6 except that resin composition 2 was used instead of resin composition 1, and its antibacterial activity was determined (Table 3).

Comparative example 7.8 Solvent of resin composition 2 of Example 7 (toluene, N.

75 parts of dimethyl ketone (Comparative Example 7) or 60 parts of toluene instead of N-dimethylformamide and dimethyl ketone)
parts and 15 parts of N,N-dimethylformamide (Comparative Example 8
) was used in the same manner as in Example 7 to obtain a laminate cloth, and its antibacterial activity was determined (Table 3).

Comparative Example 9.10 Solvent (1,1,1-) of Resin Composition 3 of Example 2! J
85 parts of 1.1.1-)lichloroethane (Comparative Example 9) or 85 parts of toluene (1.1.1-) instead of chloroethane and toluene)
A coated cloth was obtained in the same manner as in Example 2, except that Comparative Example 10) was used, and its antibacterial activity was determined (Table 4).

Comparative Example 11.12 50 parts of dichloroethane instead of the solvent (toluene and dichloroethane) in Resin Composition 4 of Example 3 (Comparative Example 11)
Alternatively, a printed cloth was obtained in the same manner as in Example 3, except that 50 parts of toluene (Comparative Example 12) was used, and its antibacterial activity was determined (Table 4).

Example 8 (Lamination Processing Method) A 50 denier, 32 filament 100% polyester jersey knitted fabric manufactured by Toshi Co., Ltd. was used as the base fabric.

Resin compositions 9 to 11 shown in the table below were prepared, respectively.

The resin composition was applied onto a release paper using a three roll off theft gravure coater, and then dried at 70 to 100°C for 1 minute. The amount of resin composition applied was 50g/rn"
And so. Next, a base fabric was placed on the dried resin composition and laminated by applying pressure with a hot roll (120 to 140°C).

(Resin composition 9) Polyurethane resin 100 parts (Shiimine 140603; manufactured by Dainichiseika Chemical Industry Co., Ltd.) Toluene
35 parts Methyl ethyl ketone 35 parts Antibacterial inorganic powder 6 parts (Resin composition 10) Polyurethane resin 100 parts (Resamin [JD603; manufactured by Dainichiseika Chemical Industries, Ltd.) Toluene
70 parts Antibacterial inorganic powder 6 parts (Resin composition 11) Polyurethane resin 100 parts (Rezamin LID603; manufactured by Dainichiseika Industries) Methyl ethyl ketone 70 parts Antibacterial inorganic powder
Antibacterial activity was measured in the same manner as in Example 4 for laminate cloths obtained using 6 parts of each resin composition. (Number of E. coli)
Table 5 *Resin plasticity of (9) minus antibacterial component [Effects of the invention] According to the present invention, an antibacterial material that has high antibacterial power relatively easily and has excellent maintainability of antibacterial power can be provided.

Claims (4)

[Claims] (1) A resin composition containing an antibacterial inorganic powder, a resin, a high boiling point solvent with a boiling point of 100°C or higher, and a low boiling point solvent with a boiling point of 100°C or lower is applied to the base fabric, and then applied to the base fabric. A method for producing an antibacterial material, characterized by curing the resin composition and the difference between the boiling point of the high boiling point solvent and the boiling point of the low boiling point solvent being 5° C. or more. (2) The production method according to claim (1), wherein the antibacterial inorganic powder is an antibacterial zeolite or an antibacterial amorphous aluminosilicate. (3) A film is formed from a resin composition containing an antibacterial inorganic powder, a resin, a high boiling point solvent with a boiling point of 100°C or higher, and a low boiling point solvent with a boiling point of 100°C or lower, and then the obtained film is A method for producing an antibacterial material, characterized in that the antibacterial material is coated on a base fabric, and the difference between the boiling points of the high boiling point solvent and the low boiling point solvent is 5° C. or more. (4) The production method according to claim (3), wherein the antibacterial inorganic powder is an antibacterial zeolite or an antibacterial amorphous aluminosilicate.