JPH078952B2 - Deodorant polyurethane resin composition - Google Patents

Description

TECHNICAL FIELD The present invention relates to a deodorant polyurethane-based resin composition, and more specifically, to synthetic leather, artificial leather, and various other types that are excellent in deodorizing property capable of removing unpleasant odors. The present invention relates to a polyurethane resin composition that gives a polyurethane resin composition.

(Prior Art) Conventionally, for organic solvent solutions, dispersions or emulsions based on polyurethane resins, manufacture of polyurethane resin products such as synthetic leather, artificial leather, breathable sheet materials made of polyurethane resins Widely used in.

(Problems to be Solved by the Invention) When various products obtained from the above polyurethane-based resin composition are used in a place where a bad odor is accumulated or generated, activated carbon is added to these products. It is conceivable to include a deodorant such as iron or ferrous sulfate.

However, since activated carbon is black, it makes the product black, and ferrous sulfate has a problem that it is easily discolored to brown by oxygen in the air. Therefore, various polyurethane resins that require various beautiful coloring are required. It could not be used for products.

Therefore, a deodorant polyurethane resin product that can absorb an unpleasant odor in the ambient atmosphere for a long time to remove the unpleasant odor from the surroundings without coloring the polyurethane resin product and that can be easily colored in any color tone is provided. Is requested.

(Means for Solving the Problems) As a result of earnest research to meet the demands of the above-described conventional techniques, the present inventor has found that as at least a part of the additive for the polyurethane resin composition, a substantially white or colorless deodorant is obtained. It was found that the object of the present invention can be achieved by using the agent.

That is, the present invention relates to a deodorant polyurethane resin composition comprising a polyurethane resin, a liquid medium and a deodorant, wherein the deodorant is a mixture of a zinc compound and an aluminum compound. It is a thing.

(Preferred Embodiment) Next, the present invention will be described in more detail with reference to preferred embodiments.

The polyurethane resin used in the present invention is a resin obtained by reacting a polyol, a polyisocyanate, a chain extender and the like, and any conventionally known polyurethane resin can be used in the present invention and is particularly limited. Not done. For example, as the polyol, any conventionally known polyol for polyurethane resin can be used, for example,
Preferred is that the terminal group is a hydroxyl group, and the molecular weight is
300 to 4,000 polyethylene adipate, polyethylene propylene adipate, polyethylene butylene adipate, polydiethylene adipate, polybutylene adipate, polyethylene succinate, polybutylene succinate, polyethylene sebacate, polybutylene sebacate, polytetramethylene ether glycol, poly-ε -Caprolactone diol, polyhexamethylene adipate carbonate polyol, polypropylene glycol and the like, and those containing an appropriate amount of polyoxyethylene chain in the above polyol.

As the organic polyisocyanate, any conventionally known one can be used, but preferred examples include 4,4′-diphenylmethane diisocyanate (MDI), hydrogenated MDI, isophorone diisocyanate, 1,3-xylylene diisocyanate, There are 1,4-xylylene diisocyanate, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, 1,5-naphthalene diisocyanate, m-phenylene diisocyanate, p-phenylene diisocyanate, etc. Urethane prepolymers obtained by reacting an isocyanate with a low molecular weight polyol or polyamine so as to form a terminal isocyanate, and the like can of course be used.

As the chain extender, any conventionally known one can be used, but preferred examples thereof include ethylene glycol, propylene glycol, diethylene glycol, 1,4-butanediol, 1,6-hexanediol, ethylenediamine, and 1,2. -Propylenediamine, trimethylenediamine, tetramethylenediamine, hexamethylenediamine, decamethylenediamine, isophoronediamine, m-xylylenediamine, hydrazine, water and the like.

The polyurethane resin composition of the present invention, the polyurethane resin is dissolved or dispersed in an organic solvent,
Alternatively, in the case of forming a W / O or O / W type emulsion using water, a deodorant consisting of a mixture of a substantially white or colorless zinc compound and an aluminum compound is used as at least a part of the additive. It is characterized by being added.

The liquid medium used in the present invention is water or an organic solvent or a mixture thereof. For example, preferred organic solvents are 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., and also acetone, cyclohexane, tetrahydrofuran, dioxane, methanol,
Examples include ethanol, isopropyl alcohol, butanol, toluene, xylene, dimethylformamide, dimethylsulfoxide, perchlorethylene, trichloroethylene, methylcellosolve, butylcellosolve, cellosolve acetate, and mixtures thereof in any ratio.

If the organic solvent used is a good solvent for the polyurethane resin, it becomes a solution of the polyurethane resin, and if the liquid medium is a poor solvent, it becomes a dispersion liquid. Further, an emulsion can be obtained by emulsifying water by using a surfactant in the solution or dispersion of these organic solvents, or by emulsifying the above solution or dispersion with the surfactant in water. . Alternatively, the polyurethane resin may be simply emulsified in water using a surfactant.

As the emulsifier, any conventionally known water-in-oil type or oil-in-water type emulsifier can be used, but a particularly preferable one is a polyurethane surfactant having an appropriate amount of polyoxyethylene chain in the molecule. is there. These emulsifiers are used in an amount of about 1 to 10 per 100 parts by weight of the solid content of the polyurethane resin solution.
It is preferably used in a proportion of parts by weight.

The polyurethane resin solution, dispersion or emulsifier as described above preferably has a solid content of about 5 to 60% by weight.

The deodorant included in the polyurethane resin composition as described above is required to be white or substantially colorless and not discolorable, not black like activated carbon.
Further, it should not deteriorate the quality of the polyurethane resin composition, especially the coloring property, and should absorb well the unpleasant odors such as ammonia odor, amine odor, hydrogen sulfide odor, etc. that are generated in the general house and the like. It is preferable.

A mixture of a zinc compound and an aluminum compound can be used as the deodorant having the above characteristics.

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.

Preferred aluminum compounds to be mixed with the above zinc compounds are aluminum sulfate and potassium aluminum sulfate, and these aluminum compounds are 1 to 1,000 parts by weight, preferably 30 to 300 parts by weight, based on 100 parts by weight of the zinc compound. Used in part ratio.

By adding and mixing an aluminum compound to the zinc compound as described above, it is possible to use various malodorous sources together with amine odor and ammonia odor, which are various malodorous sources, without deteriorating preferable physical properties and dyeability of the polyurethane resin composition. It can also absorb a certain hydrogen sulfide odor at the same time.

The deodorant as described above is preferably used in a proportion of about 0.5 to 50% by weight in the total amount of the polyurethane resin composition obtained. When the amount used is at the end of the above range, the main purpose of the present invention, that is, the deodorizing performance is insufficient,
Further, if the use ratio exceeds the above range, the physical properties of the obtained product will be insufficient, which is not preferable.

The solution, dispersion or emulsion of the polyurethane resin thus obtained may contain various additives, if necessary, known additives such as colorants, crosslinking agents, stabilizers and fillers. It can be added arbitrarily.

Examples of the base material used for producing a product such as synthetic leather, pseudo leather, or other sheet material from the polyurethane resin composition as described above include various release papers, woven fabrics, knitted fabrics, non-woven fabrics, Any substrate such as release paper, plastic film, metal plate, glass plate, etc. may be used.

The polyurethane resin composition may be applied to the substrate by any known method such as coating method, dipping method, and combination method thereof, and the impregnation and / or coating amount thereof is about 5 to 2,000. It can be varied within a wide range depending on the purpose, such as g (blended liquid) / m ² .

Gelling and drying of the substrate impregnated and / or coated with the above-mentioned polyurethane resin composition may be the same as in the prior art, for example, at a temperature of about 40 to 200 ° C for several minutes to several minutes. A polyurethane resin product having excellent properties can be obtained by drying for a long time.

(Functions / Effects) The synthetic leather, artificial leather, and other products obtained by a conventional method using the polyurethane resin composition of the present invention as described above are particularly excellent in their coloring property and deodorizing property. For example, it is useful as medical care, shoes, gloves, bags, etc. used in places where bad odors or offensive odors are generated or accumulated.

(Example) Next, an Example is given and this invention is demonstrated still more concretely.
In the text, parts and% are based on weight unless otherwise specified.

Example 1 25 parts of Resamine CU77LV (manufactured by Dainichiseika Kogyo 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 to make the particle diameter of dispersed particles 5 μm or less. A polyurethane resin composition of the present invention was obtained.

To 5 parts of the above composition, 100 parts of Resamine ME (Dainichi Seika Kogyo, polyurethane resin), 15 parts of Seika Seven ALT (Dainichi Seika Kogyo), 15 parts of dimethylformamide as a diluting solvent and 20 parts of methyl ethyl ketone are added and homogenized The mixture was stirred until it became degassed, defoamed, coated on a 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, Resamine UD660SA (Dainichi Seika Kogyo, polyurethane resin) 100 parts, Resamine UD cross-linking agent (Dainichi Seika Kogyo) 1
0 parts, 40 parts of methyl ethyl ketone as a diluent was added,
As it becomes uniform, stir it with a knife coater on the release paper on which the above-mentioned skin layer has been formed.
Apply in an amount of 0 to 150 g // m ² · Wet, dry at 100 ℃ for 30 seconds, immediately place the base cloth and press it and dry at 120 ℃ for 2 minutes,
After winding, age at 50 ° C 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 by the following method, the following significant results were obtained.

Deodorization test method (A) In an Erlenmeyer flask containing 300 ml of ammonia, 10 μl of 28% ammonia water is added.
After collection and complete gasification, sample (size 50
(× 200 mm, one sheet) was charged and stored at 25 ° C. After a predetermined time, the residual ammonia concentration in the flask was measured using a Kitagawa gas detector.

(B) A 300 ml Erlenmeyer flask of hydrogen sulfide was charged with 1 ml of 800 ppm sodium sulfide aqueous solution and 1.0 ml of 1N sulfuric acid to generate hydrogen sulfide, and a sample of the same size as above (size 50 × 50 mm, 1
The amount of hydrogen sulfide remaining in the flask was measured using a Kitagawa gas detector after a lapse of a predetermined time.

Test results Example 2 30 parts of potassium aluminum sulfate and 20 parts of zinc carbonate were used as the deodorant in the resin composition of the present invention obtained in Example 1,
Otherwise, 5 parts of the resin composition of the present invention prepared in the same manner as in Example 1 is added to 100 parts of Rezaroid LU1500 (manufactured by Dainichiseika Kagaku Kogyo Co., Ltd., a polyurethane-based surface treatment agent) and uniformly stirred to obtain a surface treatment liquid.

Resamine ME (Dainichi Seika Kogyo, polyurethane resin 100
Part, Seika Seven ALT (manufactured by Dainichi Seika Kogyo Co., Ltd.), 15 parts of dimethylformamide as a diluting solvent and 20 parts of methyl ethyl ketone, and stirred until uniform, followed by defoaming treatment, and 120 g / m ² on release paper -Applied at a ratio of Wet and dried at 120 ° C for 7 minutes to form a skin layer.

Next, Resamine UD660SA (Dainichi Seika Kogyo, polyurethane resin) 100 parts, Resamine UD cross-linking agent (Dainichi Seika Kogyo) 1
0 part, Resamine UD102 accelerator (manufactured by Dainichiseika Kogyo Co., Ltd.), and 40 parts of methyl ethyl ketone as a diluent were added and stirred until uniform. 100 to 150 g / m ² with a knife coater
・ Apply in a wet amount, dry at 100 ° C for 30 seconds, immediately place the base cloth on it and press it to dry at 120 ° C for 2 minutes, and then wind it at 50 ° C for 24 seconds.
Mature for hours. Thereafter, the release paper was peeled off, the surface treatment agent was applied once with a 120 mesh plate by a gravure printing machine, and dried to obtain a polyurethane resin synthetic leather.

When the deodorizing effect of the obtained synthetic leather was measured by the above method, the following significant difference was obtained.

Test results Example 3 1,4-butane ethylene adipate (average molecular weight about 1,000,
Hydroxyl value 112) 1,000 parts, 1,4-butanediol 31 parts, and diphenylmethane diisocyanate 333 parts were added to methyl ethyl ketone 3,183 parts and reacted at 70 ° C for 8 hours to give a solid content of 30% with an average molecular weight of 65,000. A polyurethane resin solution (A) was obtained.

The above resin solution (A), the emulsifier, the organic solvent and water were stirred with a homomixer to prepare the following polyurethane emulsion of the present invention.

(1). Polyurethane-based emulsion Polyurethane-based solution (A) 100 parts Urethane-based emulsifier 2 parts Zinc oxide 5 parts Aluminum potassium sulfate 3 parts Methyl ethyl ketone 20 parts Toluene 20 parts Water 80 parts Coating amount of the above emulsion A on release paper 200g / It was applied at a ratio of m ² and dried at 130 ° C. for 2 minutes, and then the coating film was peeled off to obtain a porous sheet.

When the deodorizing effect of the obtained porous sheet was measured by the above method, the following significant difference was obtained.

Test results

Claims (1)

[Claims] 1. A deodorant polyurethane resin composition comprising a polyurethane resin, a liquid medium and a deodorant, wherein the deodorant comprises a mixture of a zinc compound and an aluminum compound. .