JP2810942B2 - Manufacturing method of towels having antibacterial properties and water absorbency and repeatedly washing - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Application Field] The present invention relates to a cloth used in a wet state after washing, such as a cloth (a cloth, a cloth, a towel, etc.) having antibacterial properties and water absorbency and used repeatedly. Is referred to as a towel for repeated washing in the present specification.) More specifically, an antibacterial property characterized by applying a resin composition containing an antibacterial powder to a base fabric. And a method of manufacturing a towel having water absorbency and being repeatedly washed.

[Conventional technology]

In recent years, with respect to clothing, there have been problems in that absorbed sweat promotes the growth of microorganisms, causing odor, and adverse effects such as dermatitis, athlete's foot, and infectious diseases. For this reason, various antibacterial and deodorizing treatments are applied to socks and bedding products. These treatments include those that adsorb quaternary ammonium salts (JP-A-57-51874) and those that adsorb imidazole compounds (JP-A-58-14937).
5) is disclosed. However, these methods have problems such as the safety of the antibacterial agent itself, and the problem that the antibacterial agent hardly persists due to falling off or volatilization due to repeated washing. In addition, for textiles such as towels, cloths, towels and the like which are repeatedly used in the kitchen, yarns obtained by kneading particles of antibacterial amorphous aluminosilicate into polyamide filaments (Japanese Patent Application No. 62-49535) ) Is disclosed. However, since the environment of use in the kitchen is harsh such as high temperature and humidity and rich in nutrients, it is difficult for a material kneaded in the yarn itself to exhibit sufficient antibacterial and deodorant curing.

[Problems to be solved by the invention]

The antibacterial processing required to prevent the harmful effects of microorganisms on the fiber materials used in the kitchen is necessary for (1) high safety for the human body, (2) large antibacterial effect, and (3) sustainability of the antibacterial effect. (4) good water absorption, (5) repetitive washing use, (6) simple processing method and low processing cost are required. However, those satisfying the above points are not disclosed.

Therefore, an object of the present invention is extremely safe for a human body. Processes antibacterial powder such as antibacterial zeolite into a fiber material that can be used repeatedly for easy washing, and has a sustained antibacterial effect without impairing the absorption and drainage of the base fabric during washing. An object of the present invention is to provide a method for producing an antibacterial fiber material.

[Means for solving the problem]

The present invention uses a means for adhering a resin composition containing an antibacterial powder and a resin only to the surface of the base cloth without penetrating into the fibers of the base cloth for printing or the like with respect to a base cloth having water absorption. Then, by attaching to the surface of the base cloth so that water absorption inside the base cloth and drainage can be obtained at intervals of 0.2 to 4 cm,
This is a method for producing a towel having antibacterial properties and water absorption.

 Hereinafter, the present invention will be described.

In the present invention, examples of the antibacterial powder include a powder of a substance having an antibacterial property and a powder in which a substance having an antibacterial property is supported on an inorganic carrier. As the above-mentioned inorganic carrier, it is preferable to use zeolite, amorphous aluminosilicate, silica gel, alumina, and diatomaceous earth which easily adsorb a solvent.

In the present invention, examples of the antibacterial powder include antibacterial zeolite or antibacterial amorphous aluminosilicate (hereinafter AA).
S) can be used.

That is, the present invention relates to a zeolite holding an antibacterial metal ion (hereinafter, referred to as an antibacterial zeolite), preferably a part or all of ion-exchangeable ions in the zeolite is replaced with an ammonium ion and an antibacterial metal ion. The present invention provides a method for producing a towel by applying a resin composition containing an antibacterial zeolite substituted with a base cloth to a cloth.

In the present invention, as the “zeolite”, both natural zeolites and synthetic zeolites can be used. Zeolite is generally an aluminosilicate having a three-dimensional skeleton structure, and has a general formula of XM _{2 / n} O.Al ₂ O _3.
Displayed as YSiO ₂ · ZH ₂ O. Here, M represents an ion-exchangeable ion and is usually a monovalent or divalent metal ion. n is the valence of the (metal) ion. X and Y indicate the respective metal oxides and silica coefficients, and Z indicates the number of crystal waters. Specific examples of zeolite include, for example, A-
Type zeolite, X-type zeolite, Y-type zeolite,
T-type zeolites, high silica zeolites, sodalite, mordenite, analcyme, clinoptilolite, chabazite, erionite and the like can be mentioned. However, it is not limited to these. The ion exchange capacity of these exemplified zeolites is 7 m of A-type zeolite.
eq / g, X-type zeolite 6.4meq / g, Y-type zeolite 5m
eq / g, T-type zeolite 3.4meq / g, sodalite 11.5me
q / g, mordenite 2.6meq / g, analcyme 5meq / g, clinoptilolite 2.6meq / g, chabazite 5meq / g, erionite 3.8meq / g, all of which are ion-exchanged with antibacterial metal ions. It has enough capacity.

The antibacterial zeolite used in the present invention is an ion-exchangeable ion in the zeolite, for example, a part or all of sodium ions, calcium ions, potassium ions, magnesium ions, iron ions, etc., is an antibacterial metal ion, preferably ammonium. Ion and antibacterial metal ion. Examples of antibacterial metal ions include silver, copper, zinc, mercury, tin, lead, bismuth, cadmium, chromium or thallium ions, preferably silver, copper or zinc ions.

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%.
0.1 to 15% of silver ion and 0.1 to 0.1% of copper ion or zinc ion
Antibacterial zeolites containing 8% are more preferred. On the other hand, ammonium ions can be contained in the zeolite up to 20%, but the content of ammonium ions in the zeolite is preferably 0.5 to 5%, preferably 0.5 to 2%, so that the discoloration of the zeolite can be effectively reduced. It is appropriate from the viewpoint of prevention. In addition, in this specification,% means weight% of 110 degreeC dry basis.

Hereinafter, a method for producing the antibacterial zeolite used in the present invention will be described. For example, the antibacterial zeolite used in the present invention is prepared by bringing the zeolite into contact with a mixed aqueous solution containing antibacterial metal ions such as silver ions, copper ions, and zinc ions, and preferably further containing ammonium ions, and performing ion exchange in the zeolite. The possible ions are replaced by the above ions. Contact is performed at 10-70 ° C, preferably at 40-60 ° C for 3 hours.
It can be carried out by a batch system or a continuous system (for example, a column method) for up to 24 hours, preferably 10 to 24 hours. The pH of the mixed aqueous solution is suitably adjusted to 3 to 10, preferably 5 to 7. This adjustment is preferable because precipitation of silver oxide or the like on the zeolite surface or in pores can be prevented. 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, and ammonium phosphate. Silver ions include silver nitrate, silver sulfate, silver perchlorate, silver acetate, silver diammine nitrate, and silver diammine acid. Copper ions such as salts are copper (II) sulfate, copper perchlorate, copper acetate, potassium tetracyanocuprate, copper sulfate, etc. Zinc ions are zinc nitrate (II), zinc sulfate, zinc perchlorate, zinc thiocyanate, Mercury ions, such as zinc acetate, mercury perchlorate, mercury nitrate, mercury acetate, etc., tin ions, tin sulfate, etc., and lead ions,
Bismuth ions such as lead sulfate and lead nitrate are bismuth chloride,
Cadmium ions such as bismuth iodide are cadmium perchlorate, cadmium sulfate, cadmium nitrate, and cadmium acetate; chromium ions are chromium perchlorate, chromium sulfate, ammonium chromium sulfate, chromium acetate, and thallium ion is perchloric acid. Thallium, thallium sulfate, thallium nitrate, thallium acetate and the like 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 concentration of ammonium ions in the mixed aqueous solution is 0.2 M
/〜2.5 M /, and the silver ion concentration is adjusted to 0.002 M / 〜0.15 M /, whereby the ammonium ion content is appropriately adjusted to 0.1.
An antibacterial zeolite having a content of 5 to 5% and a silver ion content of 0.1 to 5% can be obtained. Further, when the antibacterial zeolite further contains copper ions and zinc ions, the silver ion concentration in the mixed aqueous solution is 0.1M / ~ 0.85M /, and the zinc ion concentration is 0.15M / ~ 1.2M /, An antimicrobial zeolite having a copper ion content of 0.1 to 8% and a zinc ion content of 0.1 to 8% can be obtained as appropriate.

In the present invention, ion exchange can also be performed by using an aqueous solution containing each ion alone in addition to the mixed aqueous solution as described above and sequentially contacting each aqueous solution with zeolite. The concentration of each ion in each aqueous solution can be determined according to each ion concentration in the mixed aqueous solution.

The zeolite after the ion exchange is thoroughly washed with water and then dried. The drying is preferably performed at 105 ° C. to 115 ° C. at normal pressure or at 70 ° C. to 90 ° C. under reduced pressure (1 to 30 torr).

The ion-exchange of ions or organic ions without suitable water-soluble salts such as lead and bismuth can be carried out using an organic solvent solution such as alcohol or acetone so that hardly soluble basic salts do not precipitate.

In the present invention, an antibacterial amorphous aluminosilicate obtained by substituting a part or all of the ion-exchangeable ions in the amorphous aluminosilicate with an antibacterial metal ion can be used as the antibacterial powder.

In the present invention, AAS (amorphous aluminosilicate) used as a raw material is not particularly limited, and a conventionally known one can be used as it is. AAS is generally represented by the composition formula xM ₂ O.Al ₂ O ₃ .ySiO ₂ .zH ₂ O, where M is generally an alkali metal element (eg, sodium, potassium, etc.). In addition, x, y, and z indicate the molar ratios of metal oxide, silica, and water of crystallization, respectively. AAS differs from crystalline aluminosilicates, called zeolites, in that X
It is an amorphous substance that does not show a diffraction pattern even by X-ray diffraction separation, and in the synthesis process, fine zeolite crystals as small as several tens of millimeters are generated, and SiO ₂ , Al ₂ O ₃ , M ₂ O, etc. Is thought to be a structure in which an amorphous substance combined in a complex manner is attached. The production of AAS is generally carried out by preparing an aluminum salt solution, a silicon compound solution and an alkali metal salt solution at a predetermined concentration.
The reaction is carried out in a low temperature range of not higher than ℃ and washed with water before crystallization proceeds. As the production method, for example, Japanese Patent Publication No. 52-58
099 and JP-A-55-162418.

The antibacterial AAS of the present invention is ion-exchanged with ammonium ions in addition to antibacterial ions. By performing ion exchange with ammonium ions, it is possible to effectively prevent discoloration of the AAS itself and discoloration of the resin when added to the resin (including discoloration over time).

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

The amount of silver added to the antibacterial metal is 0.1 to 50%, preferably 0.5 to 5%, from the viewpoint of exhibiting excellent antibacterial activity. In addition, copper, zinc, mercury, tin,
It is preferable to contain 0.1 to 10% of any one or more metals of lead, bismuth, cadmium, chromium and thallium. Further, the antibacterial AAS of the present invention contains ammonium ion by ion exchange in addition to the above antibacterial metal. 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%, and the AAS and AAS are incorporated. It is suitable from the viewpoint of effectively preventing discoloration of the resin. In addition, in this specification,% means weight% of 110 degreeC dry basis.

The method for producing the antibacterial AAS can be carried out in accordance with the method for producing the antibacterial zeolite.

The antibacterial powder used in the present invention has a water content of 0.5
It is preferably from 30 to 30%, more preferably from 5 to 20%, from the viewpoint of obtaining a resin composition having good dispersibility. Further, the particle size of the antibacterial powder is not particularly limited, but from the viewpoint of obtaining the antibacterial fiber material with a smaller amount of powder, the particle size is preferably relatively small. The particle size of the powder can be, for example, 0.04 to 20 μm, preferably 0.5 to 2 μm.

Examples of the resin used in the present invention include, for example, natural pastes such as starch, tragacanth gum, British gum, casein, egg white, etc., synthetic pastes such as polyvinyl alcohol, polyacrylamide, carboxymethylcellulose, sodium alginate, polyacrylate and the like. Polyurethane resin, silicone resin, epoxy resin, acetal resin, ketone resin, alkyl carbite resin, urea resin, melamine resin, vinyl acetate resin, vinyl chloride resin, nylon resin, natural rubber, nitrile rubber (NB
R), various solvent types of synthetic resins such as styrene butadiene rubber (SBR), chloroprene rubber (CR), and emulsion time.

In the present invention, the mixing ratio when the antibacterial powder and the resin are mixed and applied to the base fabric is such that the antibacterial powder is contained in an amount of 0.1 to 30%, preferably 1 to 10% based on the resin solid content. It is suitable from the viewpoint that it has high antibacterial activity.

In the present invention, printing as an example of a method of applying the resin composition to the base fabric is preferably applied to the entire surface from the viewpoint of enhancing antibacterial and antifungal properties. However, in products such as towels that have high repetitive washing availability in kitchens and require high absorption and drainage, the printing interval on the base fabric is 0.2 to 0.2 from the viewpoint of having antibacterial properties and maintaining high water absorption. 4 cm, preferably 0.4-3 cm.

The above-mentioned printing is different from dip dyeing, as is well known, in that only the fiber surface portion of the base fabric can be processed and does not penetrate inside the fiber, that is, the antibacterial resin composition is printed on the base fabric. However, it does not penetrate into the interior of the fiber, and has a feature of maintaining the water absorption and drainage properties of the interior without being impaired.

In the method for producing the resin composition of the present invention, various mixers can be used. For example, a Banbury mixer having a high shear dispersing power, a two-roll mill, and a kneader, a three-roll mill having a low shear dispersing power, a colloid mill , A mixer, a disper, a homomixer, a sand mill, a ball mill and the like can also be used.

The resin composition may contain 1 to 15% by weight of a crosslinking agent, for example, a polyimine resin, a butylated melamine resin, an epoxy resin, and an isocyanate. If necessary, oils, waxes, and fillers may be used. , A preservative, a coloring agent, a stabilizer, a cell conditioner (surfactant) and the like.

In the present invention, the fiber material used as the base fabric is
There is no particular limitation on the type, shape, and the like of the manufacturing method in the method of the present invention, as long as it is not deteriorated by the manufacturing method steps. For example, natural fibers such as cotton, wool, silk, and hemp; cellulose fibers such as rayon and cupra; polyamide fibers such as nylon 6, nylon 66; polyester fibers such as polyethylene terephthalate fiber; and polyacrylonitrile fibers. Such acrylic fibers, water-insolubilized polyvinyl alcohol fibers, woven fabrics, knitted fabrics, nonwoven fabrics and composites of at least one fiber selected from cellulose acetate fibers and the like can be used. Rayon, cotton, and polyester fiber are preferred from the viewpoint of water absorption, and the weave of the woven fabric is preferably plain weave, washes weave, diaper weave, or Panas weave.

As an application method for the fiber material in the present invention,
In addition to printing, as a means for adhering only the surface of the base fabric without substantially penetrating the resin composition into the interior of the fiber, there are methods such as coating, sticking, laminating, printing or coating. A printing method using a resin is more preferable. Printing can be performed by a roll printing machine or a screen printing machine, and the pattern to be printed can be any of dots (dots), stripes (diagonal lines), and other geometric patterns.

The antibacterial fiber material obtained by the present invention can be used for various fiber products in which water absorption is important.

〔The invention's effect〕

According to the present invention, since a resin composition containing an antibacterial powder and a resin is applied to the surface of a fiber, the fiber has an effect of retaining high antibacterial power.

Moreover, since the method of applying the resin composition is such that the resin composition is applied by using a means for adhering only to the surface of the base cloth without substantially penetrating into the interior of the fiber, the water absorption inside the "cloth" or the like and the drainage The property is not impaired.In addition, since the adhesion surface is applied not at the entire surface but at intervals of 0.2 to 4 cm, it has a high antibacterial effect, and on the surface where `` towel '' etc. is used repeatedly for washing There is an effect that high water absorbability into the inside and drainage from the inside to the outside are high, and a very good cleaning cloth and the like having excellent cleaning properties can be provided.

〔Example〕

 Hereinafter, the present invention will be described in more detail with reference to Examples.

Reference Example 1 (Preparation of antibacterial zeolite) Commercially available A-type zeolite powder (N
a ₂ O ・ Al ₂ O ₃・ 1.9SiO ₂・ xH ₂ O: average particle size 1.5μm) Add water to 1kg to make a slurry of 1.3, then stir and deaerate, then add an appropriate amount of 0.5N nitric acid solution And water to adjust the pH to 5-
And adjusted to a total slurry of 1.8. Next, for ion exchange, 0.015N silver nitrate solution 3 was added and the total volume was 4.
The slurry liquid was maintained at 40 to 60 ° C., and was stirred for 24 hours to reach an equilibrium state. After the completion of the ion exchange, the zeolite phase was filtered and washed with warm water until there was no excess silver ion in the zeolite phase. Next, the sample was dried by heating at 110 ° C. to obtain an antibacterial zeolite powder sample. The resulting sample contained 2.5% silver.

Reference Example 2 (Preparation of AAS) 19.4 kg of aluminum hydroxide was added to 22.3 kg of a 49% sodium hydroxide solution, and dissolved by heating.
C. (solution I). Meanwhile, sodium silicate 42.0kg
To the mixture was added water 25.5, and the mixture was maintained at 30 ° C (Solution II). Liquids I and II were mixed with 4.1 kg of a 49% solution of sodium hydroxide in 21.3 of water.
Was poured into the reaction tank containing the solution (solution III) to which was added. After the above-described operation, the reaction was carried out for 30 minutes while maintaining the temperature at 50 ± 2 ° C. while stirring. The product was filtered, and the solid phase component was washed with warm water to remove excess alkali. Further, the sample was dried at 100 ° C. to obtain a sample. This sample has a chemical composition of Na
₂ O: Al ₂ O ₃ : SiO ₂ = 0.93: 1: 2.55, which was an amorphous aluminosilicate with no diffraction peak observed in X-ray diffraction analysis.

Reference Example 3 (Preparation of antibacterial AAS) In the composition ratio of xNa ₂ O: Al ₂ O ₃ : ySiO ₂ obtained in Reference Example 2, x is 0.9.
3. AAS with y = 2.55 was used. Take 1kg of these AAS,
Suspended in 2.3 water, 0.05N nitric acid aqueous solution in 100m
The solution was added dropwise at a rate of 1/30 minutes to adjust the pH to 3-7. Then, for the ion exchange of the slurry, a silver nitrate solution 0.01 M /,
3.5 mixed aqueous solution of antibacterial metal salt of 0.09 M / ammonium nitrate solution was added. This reaction is performed at room temperature to 60 ° C for 10 to 2
The mixture was stirred for 4 hours to reach an equilibrium state. After ion exchange A
The AS phase was filtered and washed with water at room temperature or warm water until excess silver ions in the AAS phase disappeared. Next, it was dried by heating at 110 ° C. to obtain a sample. The sample obtained was 0.54% silver,
It contained 0.36% of ammonia.

Examples 1 and 2 and Comparative Examples 1 and 2 Weaving structure of 100% cotton spun yarn fabric, warp 10th, weft 10
The following resin compositions (a) and (b) were applied to a plain woven cloth having a count of 25 times / 2.54 cm in density and 50 times / 2.54 cm in weft density, using a screen mesh 100 and an auto-screening machine (6). With a base model 1000), stripe stripes were printed with a vertical and horizontal printing interval of 10 mm and an unprinted interval of 0 to 5.0 mm. Thereafter, they were heat-treated at 130 ° C. for 3 minutes to obtain printed fabrics (Examples 1-1 to 1-9 and 2-1 to 2-9 in Table 1). Under the same conditions, printed fabrics containing no antibacterial powder (Comparative Examples 1 and 2 in Table 1) were also obtained.

Resin composition (a): 15 parts of butadiene latex (Fixer254 manufactured by Dainippon Ink and Chemicals) 5 parts of pigment and white (Ryudye-W-TA 705 manufactured by Dainippon Ink and Chemicals) 60 parts of emulsifying thickener (Dainippon Ink and Chemicals) Industrial Reducer Conc 420) Mineral turpentine 40 parts Antibacterial powder (Reference example 1) 1 part Resin composition (b): Acrylic ester emulsion 25 parts (Dexcel Clear Conc M-21 manufactured by Dainippon Ink and Chemicals, Inc.)
5) Neutralizer 0.5 parts (Dexcel Agent MO manufactured by Dainippon Ink and Chemicals) Urea 3 parts Mineral turpentine 20 parts Thickener 0.3 parts (Dexcel Agent 15V manufactured by Dainippon Ink and Chemicals) Water 54.2 parts Pigment / White 1 part Large Ryudye-W-TA705 manufactured by Nippon Ink Chemical Industry) Antibacterial powder (Reference Example 2) 2 parts Example 3 (Antibacterial Test) Antibacterial tests were performed on the cloths printed on the various stripe patterns obtained in Examples 1 and 2 and Comparative Examples 1 and 2.

For the antibacterial test, E. coli (10 ⁵ cells / ml) was
Then, 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. Table 2 shows the results.

Example 4 (Water Absorption Test) The water absorption test was evaluated by measuring the time required for 10 ml of water droplets to penetrate each cloth (50 × 50 mm). The results are shown in Table 2 above.

Example 5 (Washability test) With respect to the cloth printed on the various stripe patterns obtained in Example 1, washing (JIS-L-0217-103) was performed 10 times, and an antibacterial test was performed.

The antibacterial test was performed under the same conditions as in Example 3. The results are shown in Table 3.

 ──────────────────────────────────────────────────続 き Continuation of the front page (72) Inventor Yasuo Kurihara 3-35 Toyookadori, Mizuho-ku, Nagoya-shi, Aichi (56) References JP-A-62-238900 (JP, A) JP-A-62-47331 (JP, A) JP-A-59-129046 (JP, A)

Claims (1)

(57) [Claims] 1. Means for adhering a resin composition containing an antibacterial powder and a resin to a base cloth having water-absorbing and draining properties only on the surface of the base cloth without penetrating into the fibers of the base cloth for printing or the like. It is attached to the surface of the base fabric at intervals of 0.2 to 4 cm so that water absorption and drainage can be obtained at intervals of 0.2 to 4 cm.It has antibacterial properties and water absorbency, and is repeatedly washed. Manufacturing method of towels.