JPH0413731A - Moisture-permeable deodorant film - Google Patents

Abstract

PURPOSE:To obtain the subject film, composed of a polyamino acid urethane copolymer containing antimicrobial inorganic powder, excellent in mechanical strength and safety and useful as wigs, etc. CONSTITUTION:The objective film is obtained by supporting, e.g. a solid, liquid or gaseous antimicrobial drug (e.g. metallic ions or a compound such as silver or tin) on an inorganic carrier (e.g. zeolite having preferably 0.5-5mum particle diameter) and containing preferably 1-10 pts.wt. resultant antimicrobial inorganic powder in 100 pts.wt. polyamino acid urethane copolymer (having preferably >=4000g/m<2>/40 deg.C/24hr moisture permeability).

Description

[Detailed Description of the Invention] [Field of Industrial Application] The present invention relates to a moisture-permeable deodorizing film and a wig base material using this film, and more specifically, it has excellent moisture permeability and deodorization properties, and is suitable for use in clothing, etc. This invention relates to a film that can prevent stuffiness and odor.

[Problems to be solved by conventional techniques and inventions] Conventionally,
The base material for a wig is made by pasting a fabric such as nylon knit fabric on the outer surface of a head-shaped mold made of plaster or the like, and then fixing a soft film on top of the fabric. and,
Wigs have been manufactured by implanting hair or artificial hair into this wig base material. The film thickness of the wig base material must be thick, usually around 300 μm, in order to withstand the strength of flocking, and as a result, it has poor moisture permeability, and when the wig is worn, sweat does not evaporate, resulting in discomfort and stuffiness. It also caused the growth of microorganisms and odors.

Wig base materials that are worn on the head for long periods of time create an environment in which microorganisms can easily grow due to sweat and skin waste, which causes problems such as odor, rashes, and eczema.

SUMMARY OF THE INVENTION Therefore, an object of the present invention is to provide a wig base material that suppresses microbial proliferation, prevents the generation of bad odors, has appropriate moisture permeability, and has mechanical strength that can withstand hair transplantation.

In addition, in recent years, clothing such as socks that have deodorizing properties have been commercially available. Deodorizing properties are imparted by applying or mixing an antibacterial agent to the fibers. From the viewpoint of imparting long-lasting antibacterial activity, it is preferable to mix antibacterial inorganic powder into the fibers, but there is a problem that spinning etc. are not necessarily effective. On the other hand, if the base material is not a fiber but a film or the like, it is easy to mix in the antibacterial inorganic powder, but a film has a problem with moisture permeability and is difficult to use as clothing.

Another object of the present invention is to provide a film which has excellent antibacterial and deodorizing properties and moisture permeability, and into which antibacterial inorganic powder can be easily mixed.

[Means to solve the problem]

The present inventors have conducted intensive research on materials that have sufficient moisture permeability and appropriate mechanical strength, suppress the growth of microorganisms and the generation of bad odors, and are highly safe for the human body. As a result, by incorporating antibacterial inorganic powder into the polyamino acid urethane copolymer film, we were able to improve moisture permeability, mechanical strength, antibacterial properties,
The present invention was completed by discovering that it is possible to satisfy all of the requirements of odor resistance and safety for the human body.

That is, although the polyamino acid urethane copolymer film containing the antibacterial inorganic powder of the present invention forms a nonporous membrane with mechanical strength, it has a mechanical strength comparable to that of conventionally known porous membranes. It has moisture permeability and has antibacterial and deodorizing properties due to the antibacterial inorganic powder it contains.

The present invention will be explained below.

In the present invention, the antibacterial inorganic powder J can be exemplified by a powder in which a solid, liquid or gaseous antibacterial agent is supported on an inorganic carrier. zeolite), amorphous aluminosilicate (hereinafter referred to as AAS), hydrous oxides such as hydrous titanium oxide, silica gel, glabellar compounds such as barium titanate, activated alumina, diatomaceous earth, activated carbon, etc. It is preferable to use any one of zeolite, AAS, and hydrous titanium oxide, which have high affinity with antibacterial agents and high chemical stability.

The antibacterial agent used in producing the antibacterial inorganic powder in the present invention may be in any solid, liquid or gaseous form.For example, silver, copper, zinc, mercury, lead, soot, bismuth, cadmium, Metal ions such as thallium and their compounds, stabilized chlorine, hypochlorite, chloramine, halogen compounds such as ethylene iodide, alcohols, phenols, ethers, guanidines, thiazoles, quaternary ammonium salts , thiocarbamates, and the like. However, it is preferable to use a powder of a hydrous oxide such as zeolite containing silver, AAS, or hydrous titanium oxide because it has strong antibacterial activity, long-lasting properties, and excellent safety for the human body. The silver content contained in the antibacterial inorganic powder is preferably 1 to 30% by weight from the viewpoint of sustainability of antibacterial activity.

One embodiment of the present invention is a polyamino acid urethane copolymer film containing inorganic powder containing silver, and a wig base material in which this film is processed into a layered base fabric.

In the present invention, as the "zeolite", both natural zeolite and synthetic zeolite can be used.

Zeolites are aluminosilicates that generally have a three-dimensional skeletal structure and are represented by the formula %. Here, M represents an ion exchangeable ion and is usually a l or divalent 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 crystal water. Specific examples of zeolites include A-type zeolide, X-type zeolide, Y-type zeolide, T-type zeolide, high silica zeolite, sodalite, mordenite, analcyme, clinoptilolite, chabasite, erionite, etc. can be mentioned. However, it is not limited to these. The ion exchange capacity of these exemplary zeolites is 7 meq/g for A-type zeolide, 6 meq/g for SX-type zeolide, and 5 meq/g for Y-type zeolide.
meq/g, T-type Zeo 5 Bi 13.4 t2. 6
meq/g, Analcyme 5 seq/g % Clinoptilolite 2. 6 meq/g, chabasite 5 meq/g, erionite 3. 8 w+eq/
g, and both have sufficient capacity for ion exchange with silver ions.

The antibacterial zeolite used in the present invention includes ion exchangeable ions in the zeolite, such as sodium ions,
Part or all of calcium ions, potassium ions, magnesium ions, iron ions, etc., are replaced with silver ions, preferably ammonium ions and silver ions.

From the point of view of antibacterial properties, silver ions are contained in zeolite in an amount of 1 to 30.
It is appropriate that the content is %. Moreover, by further ion-exchanging 0.5 to 5% ammonium ions to the antibacterial zeolite, discoloration of the antibacterial zeolite can be effectively prevented. In this specification, % refers to weight % on a dry basis at 110°C.

The method for producing the antibacterial zeolite used in the present invention will be described below.0 For example, the antibacterial zeolite used in the present invention can be produced by contacting the zeolite with a mixed aqueous solution containing silver ions and ammonium ions prepared in advance, and performing ion exchange in the zeolite. Replace possible ions with the above ions. Contacting is carried out at 10-70°C, preferably 40-60°C.
It can be carried out for up to 24 hours, preferably for 10 to 24 hours, by a batch method or a continuous method (e.g. column method).

The pH of the above mixed aqueous solution is 3 to 1O1, preferably 5 to 7.
It is appropriate to adjust the 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, silver ions include silver nitrate, silver sulfate, silver perchlorate, silver acetate, diamine silver nitrate, diammine silver sulfate, etc., and ammonium ions include ammonium nitrate, ammonium sulfate, ammonium acetate, ammonium perchlorate, ammonium thiosulfate, and ammonium phosphate. etc. can be used.

The content of silver ions, etc. in the zeolite can be appropriately controlled by adjusting the concentration of each ion (salt) in the mixed solution.
1-4.8M/l, ammonium ion concentration 0.2M
/j! ~2.5M/l, the silver ion content can be adjusted to 1 to 30% and the ammonium ion content can be adjusted to 0.5M/l.
5-5% antibacterial zeolite can be obtained.

In the present invention, in addition to the mixed aqueous solution as described above, ion exchange can also be performed 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 at 70°C to 90°C under reduced pressure (1 to 30 torr).

In the present invention, an antibacterial amorphous aluminosilicate in which some or all of the ion-exchangeable ions in the amorphous aluminosilicate are replaced with silver ions can also be used as the antibacterial inorganic powder. Examples of methods for producing amorphous aluminosilicate include methods described in JP-A-53-30500 and JP-A-61-174111. The method for producing antibacterial amorphous aluminosilicate can be carried out in accordance with the method for producing antibacterial zeolite. Furthermore, hydrated oxides such as hydrated titanium oxide, hydrated zirconium oxide, hydrated tin oxide, hydrated antimony oxide, hydrated bismuth oxide, and hydrated lead oxide can also be prepared as antibacterial inorganic powders by ion-exchanging silver ions and ammonium ions. .

Furthermore, although there is no particular restriction on the particle size of the antibacterial inorganic powder, from the viewpoint of obtaining an antibacterial material with a smaller amount of powder, it is preferable that the particle size is relatively small. The particle size of the powder is
For example, it can be 0.04 to 20 μm thick, preferably 0.5 to 5 μm thick.

The "polyamino acid urethane copolymer" used in the present invention is
It is a copolymer consisting of amino acids and polyurethane, and is synthesized by adding amines and reacting the amino acids with the terminal isocyanate groups of the urethane prepolymer. Synthesis methods are described, for example, in JP-A-59-140217 and JP-A-59-14.
No. 0219, No. 59-179512, No. 61-403
No. 36 and No. 61-40315, etc.

Examples of amino acids include alanine, aspartic acid, cystine, glutamic acid, glycine, lysine, methionine, leucine, and derivatives thereof. When synthesizing polyamino acids, amino acid N-carboxylic acid anhydride obtained from amino acids and phosgene can be used. is commonly used. Polyurethane is a urethane prepolymer having an isocyanate group at the end.
) than polyol (OH). As the isocyanate, aromatic diisocyanates, aliphatic diisocyanates, and alicyclic diisocyanates may be used alone or in combination. For example, toluene 2,4-
Diisocyanate, 4.4゛diphenylmethane diisocyanate, 1.6-hexane diisocyanate, 1.4
~cyclohexane diisocyanate, etc. can be mentioned. As the polyol, polyether polyol, polyester polyol, etc. are used. Examples of polyester polyols include polyethylene glycol, polypropylene glycol, and polytetramethylene glycol. Examples of polyester polyols include reaction products of diols such as ethylene glycol and propylene glycol with dibasic acids such as adipic acid and sepatic acid, and caprolactone and the like. Mention may be made of ring-opening polymers. The amines used in the copolymerization of amino acids and polyurethane include hydrazine,
Examples include ethylenediamine, diethylamine, diethylenetriamine, diethylaminopropylamine, m-phenylenediamine, dicyanamide, triethylamine, and ethanolamine.

In the present invention, the polyamino acid urethane copolymer film has a moisture permeability of 4000 glcd/40'C/2.
It is preferable that it is 4 hours or more.

The method for producing the polyamino acid urethane copolymer film of the present invention will be described below. A urethane prepolymer having terminal isocyanate groups obtained by the reaction of an isocyanate and a polyol is melted in a solvent, and an amino acid is added thereto to completely dissolve it. Furthermore, amines are added and a polyamino acid urethane copolymer solution is obtained by a polymerization reaction. Add the above antibacterial inorganic powder and solvent to this and mix thoroughly.
The viscosity at 0° C. is adjusted to, for example, 80 to 200 voids.

When preparing the above-mentioned copolymer-containing solution, it is preferable to thoroughly mix the antibacterial inorganic powder in order to improve its dispersibility. Various mixers can be used for the mixing method, such as grinding and dispersion. Powerful Pan Bali mixer, 2
This roll mill, a kneader, a three-roll mill with weak shear dispersion power, a colloid mill, a mixer, a disper, a homomixer, a sand mill, a whole mill, etc. can also be used.

As an index for evaluating whether the mixing has been carried out appropriately, there is a measurement of the particle size of the powder in the resin liquid using a grind gauge, and it is preferable that the particle size is 20 μl or less.

Furthermore, the copolymer-containing solution may contain a crosslinking agent, oil, wax, filler, preservative, coloring agent, stabilizer, cell conditioner (surfactant), etc., as necessary.

In the present invention, the mixing ratio of the antibacterial inorganic powder to the polyamino acid urethane copolymer is such that the solid content of the copolymer is 10
From the viewpoint of exhibiting high antibacterial activity, it is appropriate that the amount of antibacterial inorganic powder be 0.1 to 30 parts by weight, preferably 1 to 10 parts by weight, relative to 0 parts by weight.

The above copolymer-containing solution is coated on release paper with a
It is coated with a thickness of μm, dried at 70-150°C, and converted into a resin to form a film. The amount of the resin solution applied was 5
~6001;z/d, preferably lO~400g/rr
f is preferable from the viewpoint of stability of antibacterial activity. There are no particular restrictions on the coating method on the release paper, and any method can be used as long as it does not cause decomposition or dissolution of the antibacterial inorganic powder, etc. be able to. Examples include spray coating, knife coating (moon-shaped coating), gravure coating, roll coating, impregnation coating, and the like. Moreover, after the above-mentioned film is made into a resin, it can be further stretched 2 to 15 times using a stretching machine while being heated to 80 to 180°C.

The film of the present invention thus obtained can be used as it is or as a coating on a suitable substrate. For example, the substrate may include various fibers, rubbers, plastics, etc. that are required to have moisture permeability, antibacterial properties, and odor resistance.

For example, footwear such as leather shoes, canvas shoes, sneakers, and boots, hats such as helmets, baseball caps, and hoods, rubber gloves for cooking, leather gloves, work gloves, gloves such as kendo trowels, sheets, pillow cases, etc. The above performance can be imparted to clothing such as bedding, sportswear, and raincoats.

In the present invention, there are no particular limitations on the type, shape, etc. of the material used as the base fabric for the wig base material, as long as it is not altered in quality by the manufacturing method steps in the method of the present invention. For example, natural fibers such as cotton, wool, silk, and linen, cellulose fibers such as rayon and cupro, polyamide fibers such as nylon 6 and nylon 66, polyester fibers such as polyethylene terephthalate fibers, polyacrylonitrile fibers, etc. Woven fabrics, knitted fabrics, nonwoven fabrics, and composites thereof, made of at least one type of fiber selected from acrylic fibers, water-insolubilized polyvinyl alcohol fibers, cellulose acetate fibers, natural leather, synthetic leather, rubber, etc. It can be used. Among these, polyamide has excellent properties as a base material for wigs due to its mechanical strength and elasticity.
Knitted fabrics made of acrylic or polyurethane fibers are preferred.
Examples of the method for applying the film layer to the base fabric include a method of laminating with heat, a method of applying an adhesive, and then pasting a resin layer.

〔Effect of the invention〕

According to the present invention, it is possible to provide a film that has moisture permeability, antibacterial properties, and deodorizing properties, and is excellent in safety for the human body.

Furthermore, according to the present invention, a wig that has mechanical strength that can withstand flocking even if the thickness of the resin layer is thinner than the conventional resin layer, has moisture permeability, antibacterial properties, and odor resistance, and is excellent in safety for the human body. 111 base materials can be provided.

〔Example〕

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

Reference example 1 (Preparation of antibacterial aluminosilicate) 110°C
Commercially available A-type zeolide powder (NazO
・AltOi' 1.95i01 ・xHlo:
average particle size 1.5 μm), mordenite powder made by Sinanen New Ceramic (Na1O・AlzOs・9.7
Sing.
．． 4 StO!・Add water to xHtO (average particle size 0.9μs) to make a slurry of 1.31, then stir and degas, and then add an appropriate amount of 0.5N nitric acid solution and water to make a slurry of 1.31.
n was adjusted to 5 to 7, and the total volume was made into a slurry of 1.8 A'.For zero-order ion exchange, a mixed aqueous solution containing antibacterial metal ions was added to make the total volume 4.81, and this slurry liquid was The temperature was maintained at ~60° C. and maintained at an equilibrium state while stirring for 24 hours. Aqueous solutions of silver nitrate, zinc nitrate, and ammonium nitrate were used as solutions for ion exchange. After the ion exchange was completed, the aluminosilicate phase was filtered and washed with warm water until excess silver, zinc, ammonium ions, etc. in the aluminosilicate phase were removed. Next, the sample was heated and dried at 110°C to obtain an antibacterial aluminosilicate powder sample. Table 1 shows the data of the obtained samples.

Reference Example 2 (Preparation of antibacterial titanium oxide) Commercially available titanium oxide (IME-400 manufactured by Toagosei Chemical Industry Co., Ltd.)
) The particle size was made into a particle size of 5 to 15 μm using a jet type ultrafine pulverizer.

Add 21 of the mixed aqueous solution containing silver, zinc, and ammonium ions used in Reference Example 1 to 1 kg of fine powder, and mix at room temperature.
After stirring for 8 hours, it was filtered and washed with warm water until no excess silver, zinc, ammonium ions, etc. Table 1 shows the data of the sample.

Examples 1 to 11 and Comparative Examples 1 to 2 (Manufacture of films and wig substrates) 1300 g of polyethylene glycol and 420 g of 1.6-hexamethylene diisocyanate were reacted at 90° C. for 4 hours to obtain a urethane prepolymer. The urethane prepolymer I Dog, 1 to 15 g of the antibacterial inorganic powder prepared in Reference Examples 1 and 2, and 90 g of methyl aspartate dissolved in 650 g of dioxane were added, and further, 50 g of a 2% triethylamine solution was added little by little, and the mixture was heated at 30°C for 7 hours. A polyamino acid urethane copolymer was obtained by a time reaction.

The above polyamino acid urethane resin liquid is applied to a film thickness of 50 mm on the release paper.
The film was coated on a micrometer using a knife coater and heat-treated at 60° C. for 2 minutes to obtain a moisture-permeable deodorizing film of the present invention.

Next, a 40-denier, 20-gauge plain weave knit fabric using 25 acrylic fiber threads was laminated onto this film and dried at 120°C for 2 minutes. This was pasted on a head-shaped mold to eliminate wrinkles, heated at 150° C. for 8 minutes, allowed to cool, and removed from the mold to obtain a wig base material of the present invention. As comparative examples, a wig base material coated with a conventional acrylic latex (Comparative Example 1) and a wig base material without antibacterial inorganic powder (Comparative Example 2) were also created. The manufacturing conditions are shown in Table 2.

Test Example 1 (Moisture Permeability Test) A portion of the wig base materials obtained in Examples 1 to 11 and Comparative Examples 1 to 2 was cut out and subjected to a moisture permeability test (JIS-Z-208 method). The results are shown in Table 2.

Test Example 2 (Antibacterial Test) A part of the wig base material obtained in Examples 1 to 11 and Comparative Examples 1 to 2 was cut into 5 x 5 cII pieces, and E. coli and Staphylococcus epidermidis (10 S pieces/ml) were added to this. 0.5 ml was sprinkled onto the cells and cultured at 37°C for 18 hours. The bacterial solution was washed away with sterilized physiological saline, and the number of Escherichia coli bacteria present in this solution was measured to evaluate antibacterial properties.

The results are shown in Table 2.

Test Example 3 (Deodorization Test) A deodorization test was conducted by having 12 testers wear the wig base materials obtained in Experimental Examples 1 to 11 and Comparative Examples 1 to 2, respectively. The device was worn for 8 hours a day for 10 days, and on the 5th and 10th days, the odor of the mouth was evaluated by a sensory method according to the following criteria, and the average value was calculated.

The results are shown in Table 2.

Claims (2)

[Claims] (1) A moisture-permeable deodorizing film made of a polyamino acid urethane copolymer containing antibacterial inorganic powder. (2) A base material for a wig, which has a layer made of the film according to claim 1 on part or all of one or both sides of the base fabric.