JPH0210274B2 - - Google Patents

Description

[Detailed description of the invention]

(Industrial Application Field) The present invention relates to clothing to be worn in environments with odors or unique odors, and is designed to prevent the odors from penetrating the skin and hair. More specifically, the present invention relates to clothing made of a material to which a polyurethane resin composition is applied, which provides synthetic leather, fake leather, and other various polyurethane resin products with excellent deodorizing properties that can remove unpleasant odors. Environments with odors or unique odors (hereinafter abbreviated as odors) include, for example, livestock barns, manure processing facilities, fish markets, garbage collection and processing, medical treatment for long-term patients, and sports that involve sweating profusely. There are places like this. (Prior art) Conventional odor protection methods in environments with odors include, for example, covering the entire body with clothing or wearing rubberized coats in livestock barns, manure processing facilities, etc. method was being done. (Problems with the Prior Art) However, if the entire body is simply covered with ordinary clothing, and if the clothing is even slightly breathable, the odor will pass through the clothing and form an odor layer on the skin surface. In addition, raincoats made of non-breathable rubber, vinyl, or other synthetic resin materials cannot be worn because they become stuffy with sweat and are difficult to work in, especially in the summer. In either case, once the odor has transferred to the body, the odor does not go away even after taking a bath and washing it many times, and there is a risk that it will cause discomfort to those who meet it. By the way, conventionally, organic solvent solutions, dispersions, emulsions, etc. based on polyurethane resins have been used to prepare various synthetic leathers, fake leathers, breathable sheet materials, laminated materials with various materials, composite materials, etc. made of polyurethane resins. It has been widely used in the production of polyurethane resin products. When various products obtained from this polyurethane resin composition are used in places where bad odors accumulate or are generated, deodorizing agents such as activated carbon and ferrous sulfate should be included in these products. That was considered. However, since activated carbon is black, it makes the product black, and ferrous sulfate has the problem of easily turning brown due to oxygen in the air, so it cannot be applied to clothing, which is the problem of the present invention. However, since clothing requires various colors, it was not appropriate. (Objective of the present invention) In view of the above-mentioned problems, the present invention utilizes a composition that can remove unpleasant odors from the surrounding atmosphere by absorbing unpleasant odors from the surrounding atmosphere for a long time without coloring the product. To provide deodorizing clothing that can be worn even in summer and can be easily colored in any color tone. (Means for Solving the Problems) Therefore, the deodorant clothing of the present invention is characterized in that it is made from a fabric made of a material to which a deodorizing polyurethane resin composition having the following characteristics a is applied. shall be. a In a polyurethane resin composition consisting of a polyurethane resin, a liquid medium, and an additive, at least a portion of the additive is a substantially white or colorless deodorizer consisting of a zinc compound and an organic carboxylic acid or an aluminum compound. (Preferred Embodiments) Next, the present invention will be described in more detail by citing preferred embodiments of the present invention. In the present invention, the polyurethane resin used in the deodorizing polyurethane resin composition applied to deodorant clothing (hereinafter referred to as "used in the present invention" in the description of the composition) refers to polyol, polyisocyanate, chain The resin is obtained by reacting an extender and the like, and any conventionally known polyurethane resin can be used in the present invention, and is not particularly limited. For example, as a polyol, all conventional polyurethane polyols can be used. For example, as a preferable thing, the terminal group is a hydroxyl group, the molecular weight is 300 or 4000, a polyethylemply pair, polyethylemply paddy, polyethylene bite, poly, poly. Diethylene adipate, polybutylene adipate, polyethylene succinate, polybutylene succinate, polyethylene sebacate, polybutylene sebacate, polytetramethylene ether glycol, poly-ε-caprolactone diol, polyhexamethylene adipate, carbonate polyol, polypropylene glycol, etc. and those containing an appropriate amount of polyoxyethylene chains in the above polyols. As the organic polyisocyanate, any conventionally known organic polyisocyanate can be used, but for example, preferred ones include 4,4'-diphenylmethane diisocyanate (MDI), water-added MDI, isophorone diisocyanate, 1,3-disilylene diisocyanate, 1,4-dilylene diisocyanate, 2,4-dilylene diisocyanate, 2,6-dilylene diisocyanate, 1,5-diphthalene diisocyanate, m-dienylene diisocyanate, p-dienylene diisocyanate, etc., or these Naturally, a urethane prepolymer obtained by reacting an organic polyisocyanate with a low molecular weight polyol or polyamine to form a terminal isocyanate can also be used. As the chain extender, any conventionally known ones can be used, but for example, preferred ones are:
Ethylene glycol, propylene glycol, diethylene glycol, 1,4-ditanediol, 1,6-dioxanediol, ethylenediamine, 1,2-propylenediamine, trimethylenediamine, tetramethylenediamine hexamethylenediamine, decamethylenediamine, isophoronediamine, m -Disylylenediamine Hydrazine, water, etc. The polyurethane resin composition applied to the deodorant clothing of the present invention can be prepared by dissolving or dispersing the polyurethane resin in an organic solvent, or by using water to form a W/O or O/W type emulsion. In some cases, a substantially white or colorless deodorizing agent is added as at least part of the additives. The liquid medium used in the above composition is water, an organic solvent, or a mixture thereof. For example, preferred organic solvents include methyl ethyl ketone, methyl-n-propyl ketone, methyl isobutyl ketone, diethyl ketone, methyl formate, ethyl formate,
Propyl formate, methyl acetate, ethyl acetate, butyl acetate, etc. Also, acetone, cyclohexane,
Tetrahydrofuran, dioxane, methanol,
Ethanol, isopropyl alcohol, butanol, toluene, xylene, dimethylformamide, dimethyl sulfoxide, perchloroethylene, trichloroethylene, methyl cellosolve, butyl cellosolve, cellosolve acetate, etc., and mixtures thereof in arbitrary ratios can be used. If the organic solvent used is a good solvent for the polyurethane resin, it will be a solution of the polyurethane resin, and if the liquid medium is a poor solvent, it will be a dispersion. or,
An emulsion can be obtained by emulsifying water in these organic solvent solutions or dispersions using a surfactant, or by emulsifying the above solutions or dispersions in water using a surfactant. Alternatively, the polyurethane resin may be simply emulsified in water using a surfactant. As the emulsifier, any of the conventionally known water-in-oil or oil-in-water emulsifiers can be used, but particularly preferred are polyurethane surfactants having an appropriate amount of polyoxyethylene chains in the molecule. . These emulsifiers are preferably used in an amount of about 1 to 10 parts by weight per 100 parts by weight of the solid content of the polyurethane resin solution. The polyurethane resin solution, dispersion or emulsion as described above preferably has a solid content of about 5 to 60% by weight. The deodorizing agent included in the polyurethane resin composition as described above must be white or substantially colorless, not black like activated carbon, and should not discolor. It is preferable that the composition should not deteriorate the quality of the composition, especially its colorability, and should be able to absorb unpleasant odors such as ammonia odor, amine odor, hydrogen sulfide odor, etc. that occur inside ordinary houses. Examples of the deodorizing agent having the above characteristics include a mixture of an organic carboxylic acid and a zinc compound or a mixture of a zinc compound and an aluminum compound. Preferred organic carboxylic acids are aliphatic polycarboxylic acids, aromatic polycarboxylic acids and polymeric carboxylic acids. Preferred examples of aliphatic polycarboxylic acids include:
For example, oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, fumaric acid, maleic acid, methylmaleic acid, methylfumaric acid, itaconic acid, citraconic acid, mesaconic acid, acetylenic acid, malic acid, methylmalic acid. acids, di- or tricarboxylic acids such as citric acid, isocitric acid, tartaric acid, or salts thereof, and particularly preferred are citric acid, fumaric acid, or salts thereof. Preferred examples of aromatic polycarboxylic acids include:
For example, phthalic acid, terephthalic acid, isophthalic acid, trimellitic acid, 1,2,3-benzenetricarboxylic acid, 1,3,5-benzenetricarboxylic acid, pyromellitic acid, benzenehexacarboxylic acid, naphthalenedicarboxylic acid, naphthalenetricarboxylic acid, Aromatic carboxylic acids such as naphthalenetetracarboxylic acid, diphenyltetracarboxylic acid, diphenyl ethertetracarboxylic acid, and azobenzenetetracarboxylic acid, or anhydrides thereof; particularly preferred aromatic polycarboxylic acids include benzenetricarboxylic acid, especially It is trimellitic acid. In addition, examples of polymer carboxylic acids include citric acid,
Polyurethane with terminal carboxyl groups obtained by reacting polycarboxylic acids such as tartaric acid and phthalic acid with polyhydric alcohols such as ethylene glycol, 1,4-butanediol, and diethylene glycol in excess of acid; modified with polyhydric carboxylic acids Acidic cellulose derivatives; homopolymers such as vinyl ether ester monomers of polyhydric carboxylic acids, or random copolymers, block copolymers, and graft copolymers with other common monomers; monomers such as acrylic acid or methacrylic acid homopolymers or random copolymers, block copolymers, and graft copolymers with other common monomers; homopolymers of maleic anhydride, itaconic acid, α, β-unsaturated vinyl monomers, etc. Examples include random copolymers, block copolymers, and graft copolymers with other common monomers. By adding a zinc compound to the above-mentioned organic carboxylic acid, hydrogen sulfide odor, which is another source of bad odor, can be absorbed at the same time as well as amine odor and ammonia odor. Examples of such zinc compounds include inorganic zinc compounds such as zinc oxide, zinc sulfate, zinc chloride, zinc phosphate, zinc nitrate, zinc carbonate, zinc acetate, zinc oxalate, zinc citrate, zinc fumarate, and formic acid. Organic zinc salts such as zinc can be used, but particularly preferred are zinc white (zinc oxide) and zinc carbonate. Such a zinc compound is used in an amount of 1 to 1000 parts by weight, preferably 30 to 1000 parts by weight, per 100 parts by weight of organic carboxylic acid.
Blend in a proportion of 300 parts by weight. A more preferable white or substantially colorless deodorizing agent includes one in which an aluminum compound is blended with the above-mentioned zinc compound. Such a deodorizing agent can also absorb unpleasant odors such as amine odor, ammonia odor, and hydrogen sulfide odor, which are sources of various odor, without reducing the desirable physical properties or dyeability of the polyurethane resin composition. . Preferred aluminum compounds include aluminum sulfate and potassium aluminum sulfate, and these aluminum compounds are used in an amount of 1 to 1000 parts by weight, preferably 30 to 300 parts by weight, per 100 parts by weight of the zinc compound. The deodorizing agent as described above is preferably used in an amount of about 0.5 to 50% by weight based on the total amount of the polyurethane resin composition obtained. If the amount used is less than the above range, the purpose of the composition, i.e.
The deodorizing performance for application to deodorant clothing is insufficient, and the use ratio exceeding the above range is not preferred because the physical properties are insufficient. The solution, dispersion, or emulsion of the polyurethane resin thus obtained may contain various additives, such as colorants, crosslinking agents, stabilizers, fillers, etc., as necessary. can be added arbitrarily. Examples of base materials used for producing materials such as synthetic leather, fake leather, other sheet materials, laminated materials, and composite materials from the polyurethane resin compositions described above include woven fabrics, knitted fabrics, and non-woven fabrics. etc. The method for applying the polyurethane resin composition to the substrate may be any known method such as a coating method, a dipping method, or a combination of these methods, and the amount of impregnation and/or application is approximately 5 to 5.
It can be varied within a wide range depending on the purpose, such as 2000g (compounded liquid)/m ² . Impregnated with the above polyurethane resin composition and/or
Alternatively, gelation and drying of the coated substrate may be performed in the same manner as in the prior art, for example, approximately
By drying at a temperature of about 40 to 200°C for several minutes to several hours, a polyurethane resin product with excellent properties suitable for use in deodorant clothing can be obtained. (Function) As described above, the deodorizing clothing of the present invention is a clothing to which the above polyurethane resin composition is applied,
In particular, it has excellent coloring properties and deodorizing properties, and is useful for clothes, shoes, gloves, etc. used in places where bad or strange odors occur or accumulate. Next, the present invention will be explained in more detail with reference to Examples. Note that parts and percentages in the text are based on weight. (Example) First, the form of deodorant clothing of the present invention will be described based on the example shown in the drawings. FIG. 1 shows deodorant clothing according to an example. The deodorant clothing consists of a clothing portion 1, hats 2 and 3, and trousers 4, and the hat and trousers may both be integrated with or separate from the clothing. The fabric for this clothing is obtained by applying the deodorizing polyurethane resin composition used in the present invention to a base material of a suitable material. The material may be in any stage as long as it forms a clothing product, such as a sheet, fabric, or fiber. For example, when a fibrous material is used, it is processed into a cloth at an appropriate time before being formed into a final product, such as by being woven into a fabric. The application method may be any known method such as coating, spraying, dipping, or a combination thereof. This fabric is sewn as it is, or it is further laminated or quilted and then sewn to obtain clothes, hats, and pants of appropriate shapes. Below, as examples, the deodorizing performance of deodorant clothing formed in this manner will be described using various deodorizing polyurethane resin compositions. Example 1 25 parts of Rezamin CU77LV (manufactured by Dainichiseika Chemical Industry Co., Ltd., polyurethane resin), 40 parts of aluminum sulfate, 10 parts of zinc oxide, and 40 parts of dimethylformamide were kneaded in a ball mill, and the particle size of the dispersed particles was adjusted to 5 μm or less. A polyurethane resin composition to be applied to deodorant clothing of the present invention was obtained. To 5 parts of the above composition were added 100 parts of Rezamin ME (manufactured by Dainippon Seika Kogyo, polyurethane resin), 15 parts of Seika Seven ALT (manufactured by Dainippon Seika Kogyo), 15 parts of dimethylformamide as a diluting solvent, and 20 parts of methyl ethyl ketone. After stirring until homogeneous, the mixture was degassed, coated on release paper at a rate of 120 g/m ² ·wet, and dried at 120° C. for 2 minutes to form a skin layer. Next, 100 parts of Rezamin UD660SA (manufactured by Dainichiseika Kagyo, polyurethane resin), 10 parts of Rezamin UD crosslinking agent (manufactured by Dainichiseika Kagyo), and 40 parts of methyl ethyl ketone as a diluent were added and stirred until homogeneous. 100 to 150 coated with a knife coater onto the release paper on which the above skin layer has been prepared in advance.
Apply in an amount of g/ ^m2・wet, dry at 100℃ for 30 seconds,
Immediately place and press the base fabric and dry at 120℃ for 2 minutes.
After winding, it is heat-formed at 50℃ for 24 hours. Thereafter, the release paper was peeled off to obtain a polyurethane resin synthetic leather. When the deodorizing effect of the obtained synthetic leather was measured using the method described below, results with significant differences as shown below were obtained. Deodorization test method (A) Ammonia 10μ of 28% ammonia water was collected in a 300ml Erlenmeyer flask, and after completely gasifying it,
Insert the sample (size 50 x 200 mm, 1 piece),
It was stored at 25°C, and after a predetermined period of time, the residual concentration of ammonia in the flask was measured using a Kitagawa gas detector. (B) Hydrogen sulfide Add 1 ml of 800 ppm sodium sulfide aqueous solution and 1.0 ml of 1N sulfuric acid to a 300 ml Erlenmeyer flask to generate hydrogen sulfide.
50 mm, 1 sheet), and stored at 25°C. After a predetermined period of time, the residual concentration of hydrogen sulfide in the flask was measured using a Kitagawa gas detector. Test results

【table】

[Table] Example 2 Deodorizer of the present invention prepared in the same manner as in Example 1 except that 30 parts of potassium aluminum sulfate and 20 parts of zinc carbonate were used as deodorizers in the resin composition obtained in Example 1. Add 5 parts of a resin composition to be applied to clothing to 100 parts of Rezaroid LU1500 (manufactured by Dainippon Seika Kogyo, polyurethane surface treatment agent) and stir evenly to obtain a surface treatment solution. After adding 100 parts of Rezamin ME (polyurethane resin manufactured by Dainichiseika Chemical Industry Co., Ltd.), 15 parts of Seika Seven ALT (manufactured by Dainichiseika Chemical Industry Co., Ltd.), 15 parts of dimethylformamide as a diluting solvent, and 20 parts of methyl ethyl ketone, the mixture was stirred until uniform. Degassed and placed on release paper
It was applied at a rate of 120 g/m ² ·wet and dried at 120°C for 7 minutes to form a skin layer. Next, 100 parts of Rezamin UD660SA (manufactured by Dainichiseika Kagyo, polyurethane resin), 10 parts of Rezamin UD crosslinking agent (manufactured by Dainichiseika Kagyo), 10 parts of Rezamin UD102 accelerator (manufactured by Dainichiseika Kagyo), Add 40 parts of methyl ethyl ketone and stir until homogeneous. Apply 100 to 150 parts of the mixture using a knife coater onto the release paper on which the above skin layer has been prepared.
Apply in an amount of g/ ^m2・wet, dry at 100℃ for 30 seconds,
Immediately place and press the base fabric and dry at 120℃ for 2 minutes.
After winding, heat it at 50℃ for 24 hours. Thereafter, the release paper was peeled off, and the above surface treatment agent was applied once using a 120-mesh plate using a gravure printing machine, and dried to obtain a polyurethane resin synthetic leather. When the deodorizing effect of the obtained synthetic leather was measured using the method described above, the following significant differences were obtained. Test results

[Table] Rippin

[Table] Product Example 3 Deodorizer of the present invention prepared in the same manner as in Example 1 except that 20 parts of zinc oxide and 5 parts of citric acid were used as the deodorizer in the resin composition obtained in Example 1. 5 parts of a resin composition for use in clothing, 100 parts of Rezamin CU (polyurethane resin, manufactured by Dainichiseika Chemical Industries), 5 to 20 parts of Seika Seven BS (manufactured by Dainichiseika Chemical Industries), 3 parts of surfactant, diluting agent Add 50 parts of dimethylformamide and stir until homogeneous. After defoaming, pour 1
Apply at a thickness of 50 mm, solidify in water for about 10 minutes,
Dimethylformamide was extracted and removed in warm water at 20°C for 30 minutes, further washed in water at 20°C, and dried at 100°C to obtain a porous sheet material. When the deodorizing effect of the obtained porous sheet material was measured using the method described above, results with significant differences as shown below were obtained. Test results

[Table] Rippin

[Table] Product Example 4 Deodorizer of the present invention prepared in the same manner as in Example 1 except that 20 parts of zinc oxide and 10 parts of trimellitic acid were used as the deodorizer in the resin composition obtained in Example 1. 5 parts of a resin composition for use in clothing, 100 parts of Rezamin CU (manufactured by Dainichiseika Kagyo, polyurethane resin), 0 to 5 parts of Seika Seven BS (manufactured by Dainichiseika Kagyo), 3 parts of surfactant, diluting agent Add 200 parts of dimethylformamide and stir until homogeneous. After defoaming, impregnate onto a raised cloth and squeeze with a pick-up rate of 300%. Coagulate in water for about 10 minutes, and dimethylformamide in warm water at 50°C for 30 minutes. The formamide was extracted and removed, further washed in water at 20°C, and dried at 100°C to obtain an impregnated napkin. A synthetic leather made of a polyurethane resin was obtained using this raised cloth and using the method described in Example 2. When the deodorizing effect of the obtained synthetic leather was measured using the method described above, the following significant differences were obtained. Test results

[Table] Rippin

[Table] Product Example 5 1000 parts of 1,4-butane ethylene adipate (average molecular weight approximately 1000, hydroxyl value 112), 31 parts of 1,4-butanediol, and 333 parts of diphenylmethane diisocyanate were added to 3183 parts of methyl ethyl ketone.
The reaction was carried out at 70°C for 8 hours to obtain a polyurethane resin solution (A) with an average molecular weight of 65,000 and a solid content of 30%. The above (A), emulsifier, organic solvent, and water were stirred in a homomixer to prepare a polyurethane emulsion to be applied to deodorant clothing of the present invention as described below. (1) Polyurethane emulsion (A) Polyurethane solution (A) 100 parts Urethane emulsifier 2 parts Zinc oxide 5 parts Potassium aluminum sulfate 3 parts Methyl ethyl ketone 20 parts Toluene 20 parts Water 80 parts The above emulsion A was mixed with release paper. Coating amount: 200g/m ²
After drying at 130° C. for 2 hours, the coating was peeled off to obtain a porous sheet. When the deodorizing effect of the obtained porous sheet was measured using the method described above, results with significant differences as shown below were obtained. Test results

[Table] Rippin

[Table] Product Example 6 Polytetramethylene glycol (average molecular weight approx.
1000, hydroxyl value 112) 1000 parts, ethylene glycol 24 parts and diphenylmethane diisocyanate
Add 340 parts to 3183 parts of methyl ethyl ketone and add 70
The reaction was carried out at ℃ for 9 hours to obtain a polyurethane resin solution (B) having an average molecular weight of 52,000 and a solid content of 30%. The above (B), emulsifier, organic solvent, and water were stirred in a homomixer to prepare a polyurethane emulsion to be applied to deodorant clothing of the present invention as described below. (2) Polyurethane emulsion (B) Polyurethane solution (B) 100 parts Zinc oxide 5 parts Polyacrylic acid 5 Urethane emulsifier 2 parts Methyl ethyl ketone 20 parts Toluene 20 parts Water 80 parts The above emulsion B was placed on release paper. Coating amount: 200g/m ²
After drying at 130° C. for 2 minutes, the coating was peeled off to obtain a porous sheet. When the deodorizing effect of the obtained porous sheet was measured using the method described above, results with significant differences as shown below were obtained. Test results

[Table] Rippin

[Table] Product Example 7 The deodorizing polyurethane resin composition obtained in Example 1 was applied to nylon fabric in the same manner as in Example 1 instead of the polyurethane resin in Example 1 to obtain a nylon processed fabric. Ta. When the deodorizing effect of the obtained processed cloth was measured using the method described below, results with significant differences as shown below were obtained. Deodorization test method (A) Ammonia Collect 10μ of 28% ammonia water into a 300ml Erlenmeyer flask, completely gasify it, then add the sample (size 50 x 200mm, 1 piece), 25
The flask was stored at ℃, and after a predetermined period of time, the residual concentration of ammonia in the flask was measured using a Kitagawa gas detector. (B) Hydrogen sulfide Put 1 ml of 800 ppm sodium sulfide aqueous solution and 1.0 ml of 1N sulfuric acid into a 300 ml Erlenmeyer flask.
Generate hydrogen sulfide and sample (size 50×
200 mm, 1 piece) was placed in the flask, stored at 25°C, and after a predetermined period of time, the residual concentration of hydrogen sulfide in the flask was measured using a Kitagawa gas detector. Test results

[Table] Rippin

[Table] Product (Effects of the Invention) According to the deodorizing clothing of the present invention described above, it is possible to completely prevent odors, it is possible to work comfortably even in summer without getting stuffy, and it does not cause discomfort to others after work. There is no risk of giving. The deodorizing clothing of the present invention can protect both the clothing itself and human skin, hair, etc. from odors, and
Any color tone can be easily obtained. Also, as mentioned above, not only odors that come from the outside of clothing, but also odors that come from the inside of clothing, such as odors from sweat, physical constitution, or intake of large amounts of alcohol, certain spices such as garlic, etc. can also be prevented if necessary.

[Brief explanation of drawings]

Figure 1: Outline diagram of deodorant clothing according to the present invention 1...Clothes, 2, 3...Hat, 4...Pants.

Claims (1)

[Scope of Claims] 1. Deodorizing clothing made from a fabric made from a material to which a deodorizing polyurethane resin composition having the following characteristics a. A polyurethane-based garment made of a polyurethane resin, a liquid medium, and an additive. In the resin composition, at least a part of the additive is a substantially white or colorless deodorizing agent consisting of a zinc compound and an organic carboxylic acid or an aluminum compound. 2. The deodorant clothing according to claim 1, wherein the organic carboxylic acid is an aliphatic polycarboxylic acid. 3. The deodorant clothing according to claim 1, wherein the organic carboxylic acid comprises an aromatic polycarboxylic acid. 4. The deodorant clothing according to claim 1, wherein the organic carboxylic acid comprises a polymer carboxylic acid.