JP2709942B2 - Manufacturing method of work gloves - Google Patents

Description

Description: FIELD OF THE INVENTION The present invention relates to a method for producing gloves having antibacterial properties and not impairing stretchability and air permeability, and more specifically, a resin composition containing an antibacterial powder. The present invention relates to a method for manufacturing gloves, comprising applying an object to a glove surface.

[Prior Art] Conventionally, working gloves for handling fresh fish, dust, and the like include rubberized and leather gloves. However, these have problems such as poor air permeability and poor diffusion of perspiration, so that microorganisms proliferate and emit a bad smell. As a countermeasure, a glove in which a resin layer containing a quaternary ammonium salt is applied to the entire inner surface (Japanese Patent Application Laid-Open No. 62-15308) is disclosed. However, since the antibacterial agent used is an organic compound, volatilization and decomposition are apt to occur, causing skin irritation and failing to exhibit a stable antibacterial effect.

[Problems to be Solved by the Invention] The antibacterial processing method of gloves for work that seems to be harmful to microorganisms handling fresh fish, dust, etc. is necessary. (A) High safety to human body (2) The elasticity and texture are soft and the workability is good. (C) The antibacterial effect is large. (D) The antibacterial effect is long lasting. (E) The air permeability is good. No (f) It is required that processing methods are simple and processing costs are low. However, those satisfying the above points are not disclosed.

Therefore, an object of the present invention is to process an antibacterial powder such as an antibacterial zeolite, which is extremely safe for the human body, easily into a glove, without impairing stretchability, texture, air permeability, etc. It is an object of the present invention to provide a method of manufacturing a glove having antibacterial properties capable of having an effective antibacterial effect.

[Means for Solving the Problems] The present invention applies a resin composition containing an antibacterial powder, a resin and a solvent through a coarse screen mesh on a work glove, thereby providing an antibacterial property and appropriate elasticity, a feeling of texture, This is a method of manufacturing a work glove having air permeability or the like.

 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, antibacterial zeolite or antibacterial amorphous aluminosilicate (hereinafter referred to as AAS) is used as the antibacterial powder.
) Can be used.

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

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 skeletal structure, and has a general formula of XM _{2 / n} O.Al ₂ O ₃ .Y
Displayed as SiO 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
-Zeolite, high silica zeolite, 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 exemplary zeolites is A-type zeolite 7meq / g,
X-type zeolite 6.4 meq / g, Y-type zeolite 5 meq / g, T
-Type zeolite 3.4meq / g, sodalite 11.5meq / g, mordenite 2.6meq /, analcyme 5meq / m, clinoptilolite 2.6meq / g, chabazite 5meq / g, erionite
3.8 meq / g, all of which have sufficient capacity for ion exchange with antibacterial metal ions.

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 18%. 0.1-18% of silver ion and 0.1-18 of copper ion or zinc ion
% Is more preferable. 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 method or a continuous method (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, and silver ions include silver nitrate, silver sulfate, silver perchlorate, silver acetate, diammine silver nitrate, and diammine silver sulfate. Copper ions are silver nitrate (II), copper perchlorate, copper acetate, kalim tetracyanocuprate, copper sulfate, etc. Zinc ions are zinc nitrate (II), zinc zinc perchlorate, zinc thiocyanate,
Zinc acetate or 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
/ l to 2.5 M / l, and by setting the silver ion concentration to 0.002 M / l to 0.15 M / l, an ammonium ion content of 0.5 to
An antimicrobial zeolite having 5% and a silver ion content of 0.1 to 5% can be obtained. When the antibacterial zeolite further contains copper ions and zinc ions, the copper ion concentration in the mixed aqueous solution is 0.1 M / l to 2.30 M / l, and the zinc ion concentration is 0.1 M / l.
By setting the content to 5 M / l to 2.8 M / l, the copper ion content may be appropriately adjusted.
An antimicrobial zeolite with 0.1 to 18% and a zinc ion content of 0.1 to 18% can be obtained.

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. Drying is preferably performed at 105 ° C. to 115 ° C. under normal pressure, or at 70 ° C. to 90 ° C. under reduced pressure (1 to 30 torr).

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.). X, y, and z are metal oxides, respectively.
It shows the molar ratio of silica and water of crystallization. AAS differs from crystalline aluminosilicates, which are called zeolites,
It is an amorphous substance that does not show a diffraction pattern even in X-ray diffraction analysis. In the synthesis process, fine zeolite crystals as small as several tens of millimeters are formed, 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 generally involves the preparation of an aluminum salt solution, a silicon compound solution and an alkali metal 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 a production method, for example, Japanese Patent Publication No. 52-580
No. 99 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, discoloration of the AAS itself and discoloration of the resin when added to the resin (including discoloration over time) can be effectively prevented.

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. Further, it is preferable to contain 0.1 to 18% of one or two metals of copper and zinc.

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%, the AAS
And from the viewpoint of effectively preventing discoloration of the resin into which AAS is kneaded. In addition, in this specification,% is
Refers to the weight% on a dry basis at 110 ° C.

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. Furthermore, the particle size of the antibacterial powder is not particularly limited, but from the viewpoint of obtaining an antibacterial fiber product 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.

As the resin used in the present invention, for example, starch, tragacanth rubber, British rubber, casein,
Natural paste such as egg white, polyvinyl alcohol, polyacrylamide, carboxymethylcellulose, sodium alginate, synthetic paste such as polyacrylate, and other polyurethane resins, silicone resins, epoxy resins,
Acetal resin, ketone resin, alkyl carbamate resin, urea resin, melamine resin, vinyl acetate resin, vinyl chloride resin, nylon resin, natural rubber, nitrile rubber (NB
R), various solvent types and emulsion types of synthetic resins such as styrene butadiene rubber (SBR) and chloroprene rubber (CR).

In the present invention, as a solvent to be used, a system containing water is preferable from the viewpoint of workability and simplicity of a drying step. Further organic solvents, for example, trichloroethylene, perchlorethylene, 1,1,1-trichloroethane, toluene, xylene,
A single or mixed solvent such as mineral spirit or a mixed solvent of water can also be used.

In the present invention, the mixing ratio when the antibacterial powder, the resin and the solvent are mixed and applied to gloves is such that the antibacterial powder is contained in an amount of 0.1 to 30%, preferably 1 to 10% with respect to the resin solid content. It is suitable from the viewpoint that it is prepared to have high antibacterial activity.

In the present invention, the method of application to gloves is textile printing, and it is preferable to apply a large amount to the entire surface from the viewpoint of enhancing antibacterial and antifungal properties. However, gloves need to have the appropriate elasticity and texture of the gloves. When printing on the base cloth, the screen mesh should be 60 to 20 mesh (0.25 mm to 0.83 mm in pore size), preferably 50 to 30 mesh. It is a mesh. Work gloves have a fiber diameter of 1 mm to 0.2 mm as is well known
It is composed of fibers. Therefore, when a fine screen mesh of 80 mesh or more is used for a rough woven fabric having large irregularities such as a glove surface composed of a relatively large fiber diameter, only a small amount of the resin composition to be applied is printed. It is not printed and it is difficult to apply uniformly.

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 homomic key, a sand mill, a ball mill and the like can also be used.

The resin composition may contain a crosslinking agent, oils, waxes, fillers, preservatives, coloring agents, stabilizers, cell conditioners (surfactants), and the like, if necessary.

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. 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. Is preferred from the viewpoint of stretchability and air permeability, and the knitting method of the knitted fabric is preferably rubber knitting or knitting which is excellent in stretchability.

The method for applying to the fiber material in the present invention is printing, of which a roll printing machine or a screen printing machine can be used. The pattern to be printed can be any of dots (dots), stripes (diagonal lines), and full-surface printing of a ground pattern.

The antibacterial fiber product obtained by the present invention can be used for various fiber products in which stretchability and air permeability are important.

〔The invention's effect〕

According to the present invention, since a resin composition comprising an antibacterial powder, a resin and a solvent is applied through a screen mesh of 60 to 20 mesh to a glove surface composed of fibers having a fiber diameter of 1 mm to 0.2 mm, There is an effect that a high antibacterial effect can be provided on the surface of the gloves without impairing the elasticity, feel, and air permeability inherent to the gloves.

〔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 1.3l slurry, then stir to degas, and further add appropriate amount of 0.5N nitric acid PH was adjusted to 5 by adding the solution and water.
The total volume was adjusted to 1.8 liters of slurry. Next, for ion exchange, 0.03N silver nitrate solution 1 and 2.5N zinc nitrate solution 1
, A mixed solution of 0.2N ammonium nitrate solution 1 was added to make a total volume of 4.8 liters, and the slurry was kept at 40 to 60 ° C and stirred for 24 hours to reach an equilibrium state. After the completion of ion exchange, the zeolite phase was filtered and washed with warm water until excess silver, zinc and ammonium ions in the zeolite phase were eliminated. Next, the sample was dried by heating at 110 ° C. to obtain an antibacterial zeolite powder sample. The resulting sample contained 2.5% silver, 16.5% zinc, and 1% ammonium.

Example 1, Comparative Examples 1 and 2 and Test Examples 1 After the following resin composition was kneaded with a commercially available 100% cotton glove (thick knitted fabric) for 3 hours using a sand grinder, a stripe stripe (mark) was passed through a predetermined screen mesh. Printing interval 10mm,
An unprinted space of 10 mm) was printed with an auto-screening machine (6 units, model 1000). Thereafter, they were heat treated at 130 ° C. for 3 minutes to obtain gloves for antibacterial work. Working gloves containing no antibacterial powder under the same conditions (Table 1, Comparative Example 2)
Also got.

(Resin composition): A. Acrylic emulsion 20 parts (Ryudye-W Fixer 730 manufactured by Dainippon Ink and Chemicals) B. Mineral turpentine (solvent) 52 parts C. Emulsifying thickener 25 parts (Dainippon Ink and Chemicals Reducer Conc 400) D / Pigment / White 1 part (Ryudye-W TA 705 manufactured by Dainippon Ink and Chemicals, Inc.) E. Antibacterial powder (Reference Example 1) 2 parts A test piece (50 × 50 mm) was prepared for each sample obtained. Cut out, elongation modulus at 3% elongation as shown in JIS-L-1096 for evaluation of the amount of resin composition adhered, elasticity, and air permeability of the Frazier type tester for evaluation of air permeability. As a test, the number of bacteria after 18 hours was measured by the AATCC-100 method using Escherichia coli (initial bacterial count: 2 × 10 ⁵ ). The results are shown in Table 1.

Example 2, Comparative Example 3 and Test Example 2 The same kind of resin composition as in Example 1 but having the following compounding ratio (A, B of the resin composition of Example 1: the others are the same) is as follows. Printing was performed using a screen mesh 50 to obtain antibacterial gloves. Wash with each glove obtained (JIS-L-0217-103 method)
20 times the antibacterial powder shedding rate was measured,
A touch feeling (20-person sensitivity test, 5 levels) and an antibacterial test were conducted.

The antibacterial test was performed under the same conditions as in Example 1. Table 2 shows the results.

Test Example 3 The gloves of Example 1-2 and Comparative Example 2 were used by workers handling fresh fish for 4 to 10 days, and then the amounts of methyl mercaptan and isobutyric acid, which are offensive odor components, were determined by a gas detection tube method. The results are shown in Table-3.

 ──────────────────────────────────────────────────続 き Continuation of the front page (56) References JP-A-60-181002 (JP, A) JP-A-55-6221 (JP, A) JP-A-56-3056 (JP, A) 732 (JP, U) Actually open 58-143804 (JP, U)

Claims (4)

(57) [Claims] 1. A method comprising applying a resin composition containing an antibacterial powder, a resin and a solvent to a surface of a glove made of fibers having a fiber diameter of 1 mm to 0.2 mm through a screen of 60 to 20 mesh. Glove manufacturing method. 2. An antibacterial powder wherein zeolite or amorphous aluminosilicate is obtained by substituting part or all of ion-exchangeable ions with silver, copper or zinc ions.
The glove manufacturing method described. 3. The amount of the resin composition to be applied is 0.3 to 1 m ^{2 of the} base fabric.
2. The method of claim 1, wherein the weight is 1 g. 4. The method of claim 1, wherein the resin composition has a resin solid content of 5 to 20%.