KR101002714B1 - Water-based polyurethane coating composition and manufacturing method of water-based polyurethane coated gloves with excellent moisture permeability and wear resistance - Google Patents

Abstract

The present invention relates to a method for preparing a water-dispersible polyurethane with an anionic group such as a carboxyl group or a sulfonate group or a cationic group such as a tertiary amine in the main chain, and wet-coagulating it to prepare an aqueous polyurethane moisture-permeable coated glove. After impregnating and coating the endothelial glove woven with various yarns (nylon, polyester, polyethylene, kevlar and cotton, etc.), a mixture of water repellent, dispersant, antifoaming agent, colorant, viscosity control agent and other additives , Coagulate with a coagulation solution (coagulation solution consisting of an aqueous solution of an acid, an aqueous solution of a salt, a base solution or a mixture of two or more thereof) to form micropores to impart air permeability, and the aqueous polyurethane is coated through a washing process, drying, and a crosslinking process. Method of manufacturing environmentally friendly breathable gloves.

The glove manufactured by the manufacturing method of the present invention has a better wear resistance due to the stronger film strength of the surface than conventional oil-based polyurethane wet products, and has a low slip when the gloves are worn by penetrating the resin to the back of the endothelial, which is excellent in workability and uniformity. It has the characteristics of breathability, soft fit and eco-friendly coating gloves due to micropores.

The manufacturing method of the present invention can use the existing oil-based wet process as it is, do not use any organic solvents such as DMF (Dimethyl formamide) is environmentally friendly, excellent coating molding manufacturing to improve glove productivity by excellent de-molding It is a way.

Water-based polyurethane, coated gloves, moisture permeability, wear resistance

Description

Coating composition of aqueous polyurethane dispersion and method for producing a breathable coated glove of using same

The present invention relates to a coating composition using an anionic or cationic aqueous polyurethane dispersion and a method for producing a coating glove having excellent moisture permeability, and a wet type poly for forming micropores with a chemical coagulant using an aqueous polyurethane dispersion. It relates to a urethane coated glove manufacturing method.

Conventional gloves manufacturing method using polyurethane, there is a wet method using an oil-based polyurethane resin.

The oil-based wet manufacturing method is a coagulant that is coated with oil-based wet resin on the glove endothelium and is compatible with DMF (Dimethyl formamide), an organic solvent used for dissolving polyurethane, and is not compatible with polyurethane. The organic solvent present in the polyurethane coating layer is passed through the coagulation bath to be diffused into the coagulation solution in the coagulation bath to form fine pores inside the resin through the coagulation process. , Excellent fit.

However, this manufacturing process uses DMF (Dimethyl formamide), which is a highly toxic organic solvent, which is harmful to the human body, causes environmental pollution, weak durability due to micropores, and yellowing during long-term storage. .

In order to solve this problem, there has been a great interest in a method of preparing coated gloves using an aqueous polyurethane.

In the manufacture of gloves using an aqueous polyurethane, there is a dry method of pretreatment of a coagulant or a water repellent to the endothelial glove, and coating and drying the resin so that the resin does not enter the endothelium when the coating solution is impregnated.

This dry manufacturing method has the advantage of using environmentally friendly water-based resins, but the coating layer of the glove is a film or a high density, the moisture permeability and breathability is not expressed or weak, and at the laboratory level, but in mass production, depending on the pretreatment environment However, it is difficult to secure penetration and reproducibility of uniform coating layer formation.

On the other hand, in order to ensure moisture permeability in a dry manufacturing method using an aqueous polyurethane, a dry method using a mechanical foam and a chemical blowing agent has been attempted.

Since it is a dry manufacturing method, first, a pretreatment of a coagulant or a water repellent is applied to the endothelial glove, and in order to secure moisture permeability, an attempt has been made using a mechanical foam or a chemical foaming agent.

The dry method by mechanical foaming forms bubbles by simple high speed agitation or by using a mechanical foaming machine, so that the uniformity and fineness of the pores are significantly inferior to the wet chemical porous forming method. As a result, the moisture permeability and wear resistance are poor, and this also prevents penetration by pretreatment and reproducibility of uniform coating surface formation.

Another method of forming a pore using a chemical blowing agent is to form pores using a boiling point when drying by adding a large amount of low boiling point solvent to an aqueous resin, or forming a pore using a blowing agent that decomposes at a high temperature to generate gas. There is a way. Since these methods use organic solvents or blowing agents harmful to the human body, there is room for environmental pollution, and it is difficult to secure formation and uniformity of micropores. Therefore, in order to replace the existing oil-based wet gloves, the dry manufacturing method using water-based polyurethane had many problems in quality such as breathability, moisture permeability, abrasion resistance, and soft fit. For this reason, coated gloves using water-based polyurethane are still The reality was that only manufacturing at the laboratory level was possible.

Therefore, the development of a new polyurethane coated gloves manufacturing method that is environmentally friendly, excellent properties and productivity is required.

An object of the present invention to overcome the problems of the conventional coated gloves produced by the DMF wet method using an oil-based resin, to provide a method of producing a coating glove excellent in moisture-permeable coating prepared by an aqueous wet coagulation method with an aqueous polyurethane mixture. There is.

An object of the present invention is to provide a method for producing an eco-friendly polyurethane coated gloves while minimizing the equipment investment by using the conventional oil-grown gloves manufacturing equipment as it is.

Still another object of the present invention is to provide a method for producing a glove with excellent de-moulding ability while forming a uniform and fine pores through chemical coagulation method, expressing excellent moisture permeability, and having excellent abrasion resistance than oil-based wet gloves. have.

Coating glove manufacturing method of the present invention, after impregnating coating the coating solution of a water-based polyurethane dispersion with additives such as water repellents, dispersants, antifoaming agents, colorants and viscosity modifiers in the glove endothelium, and chemical coagulation method, that is, acid aqueous solution, aqueous salt solution, Coagulate with a coagulant solution consisting of an aqueous base solution or a mixture of two or more of these solutions, and wash and dry to complete the coating glove. In other words, impregnated with the aqueous polyurethane coating solution without pretreatment in the glove endothelium, the coating step to penetrate the inner surface of the glove, the coagulation step to coagulate with the coagulation solution, washing, drying step.

The coated glove manufacturing method of the present invention is similar to the oil-based wet process, but because it uses an aqueous wet method that does not use any organic solvents such as DMF (dimethyl formamide), it is environmentally friendly, has excellent de-molding properties, and a chemical coagulation method. By using the microporous to form, including the uniform micropore, the film surface strength of the glove surface is improved, it is characterized by excellent wear resistance, moisture permeability, breathability of the glove.

More specifically, the method for producing a breathable coating gloves using the water-based polyurethane according to the present invention, in the diol (diol) or diamine containing an anionic group of the carboxyl group or sulfonate group or a cationic group of the tertiary amine in the main chain Preparing an aqueous polyurethane dispersion prepared by dispersing a covalently bonded polyurethane prepolymer in water and chain-extensioning it with diamines,

A coating solution manufacturing step of preparing a coating solution by adding 0.1 to 5 parts by weight of a water repellent, 0.1 to 6 parts by weight of a dispersant, 0.1 to 3 parts by weight of an antifoaming agent and 0.1 to 3 parts by weight of a viscosity modifier,

Impregnating and coating the coating solution so that the coating solution completely penetrates into the inner surface of the gloves by impregnating the mold with the glove endothelium in the coating solution;

A solidification step of immersing the coated glove mold in a coagulation solution (coagulation solution consisting of an aqueous acid solution, an aqueous salt solution, an aqueous base solution or a mixture of two or more thereof) to form a micropore,

Water washing step of washing and neutralizing the obtained product after the coagulation process if necessary according to the type of coagulant, and

It is a method of manufacturing a coated glove through a drying step by drying to 60 ~ 120 ℃ in a drying furnace.

A colorant may be added to the additive, and when the colorant is added, less than 5 parts by weight may be added. In order to improve the physical properties of the aqueous polyurethane coating solution, 100 parts by weight of the aqueous polyurethane dispersion may include latex resin, acrylic resin, poly 1 to 100 parts by weight of an ester resin or a resin mixture containing two or more thereof, and 1 to 15 parts by weight of an isocyanate, oxazoline, melamine, aziridine-based or a crosslinking agent containing two or more thereof may be added. Here, the solid content of the resin mixture and the crosslinking agent is used at 12 to 30% by weight.

According to the present invention, the polyurethane coated gloves are manufactured by a wet solidification method of an aqueous polyurethane mixed solution, so that the resin penetrates to the inner surface of the glove endothelium, thereby reducing the slip of the endothelium and hands during operation, and thus excellent workability, such as oil-based wet gloves. It exhibits moisture permeability and soft fit, and wear resistance is improved due to chemical coagulation, so that the surface of the glove is improved, which is superior to oil-based gloves, so that an environmentally-friendly coating gloves can be manufactured. That is, the coating film strength of the surface is improved while including uniform micropores, thereby providing excellent wear resistance, moisture permeability, and breathability.

In addition, the manufacturing method of the water-based polyurethane coated gloves of the present invention is similar to the oil-based wet process, but does not use organic solvents such as DMF (dimethyl formamide), the effect of preventing a pleasant working environment and environmental pollution, and existing oil-based It also provides the economic effect of using the equipment as it is.

Hereinafter, a method of manufacturing an aqueous polyurethane coated glove will be described in more detail.

-Manufacturing step of aqueous polyurethane dispersion-

The anionic and cationic water-dispersed polyurethane emulsion is obtained by dispersing in a water a polyurethane in which a cationic group is covalently bonded by an anionic group such as a carboxyl group or a sulfonate group or a diol containing a tertiary amine in the main chain.

That is, the aqueous polyurethane dispersion contains a hydrophilic chain extender to allow self-emulsification in the reaction of an isocyanate and a polyol to prepare a polyisocyanate-type prepolymer that is water dispersible, and disperse the prepolymer in water, followed by chain extension. Zero polymerized is used.

As the isocyanate used in the preparation of the prepolymer, aromatic, aliphatic and alicyclic diisocyanates or mixtures thereof may be used. For example, tolylene-2,4-diisocyanate, tolylene-2,6-diisocyanate, meta-phenylene diisocyanate, biphenylene-4,4'- diisocyanate, methylenebis ((4-phenyl Isocyanate), 4-chloro-1,3-phenylene diisocyanate, naphthalene-1,5-diisocyanate, tetramethylene-1,4-diisocyanate, hexamethylene-1,6-diisocyanate, decamethylene-1, 10-diisocyanate, cyclohexylene-1,4-diisocyanate, methylenebis (4-cyclohexyl isocyanate), tetrahydronaphthylene diisocyanate, isophorone diisocyanate, 4,4'-methylenebis (cyclohexyl isocyanate) Or a mixture selected from the group consisting of two or more of them, preferably isophorone diisocyanate, hexamethylene-1,6-diisocyanate, cyclohexylene-1,4-diisocyanate, 4,4 '-Methylenebis (cyclohexyl isocyanate) and the like can be used.

Examples of the polyol used to prepare the prepolymer include polyester polyols and polyether polyols. Suitable polyester polyols are preferably obtained by condensation of a dicarboxylic acid compound with a diol compound, wherein the dicarboxylic acid compound is succinic acid, glutaric acid, adipic acid, subberic acid, azelanic acid. , Sebacic acid, dodecanedicarboxylic acid, hexahydrophthalic acid, isophthalic acid, terephthalic acid, ortho-phthalic acid, tetrachlorophthalic acid, 1,5-naphthalenedicarboxylic acid, fumaric acid, maleic acid, itaconic acid, citraconic acid, mesaconic acid And tetrahydrophthalic acid. Examples of the diol compound include ethylene glycol, propylene glycol, 1,3-propanediol, 1,3-butanediol, 1,4-butanediol, 1.5-pentanediol, and 1,6-hexane. Diol, neopentyl glycol, diethylene glycol, dipropylene glycol, triethylene glycol, tetraethylene glycol, dibutylene glycol, 2-methyl-1,3-pentanediol, 2,2,4-trimethyl-1,3- Pentanediol, 1,4-cyclohexanedimethane All may be mentioned, for example. Suitable polyether polyols include polyethylene glycol, polypropylene glycol, polytetramethylene glycol, and the like. The molecular weight of the polyols varies from 400 to 10,000, but the suitable molecular weight is about 400 to 3,000.

Anionic chain extenders and cationic chain extenders may be used as ionic chain extenders for self-emulsification of prepolymers.

As the anionic chain extender, a compound containing a carboxyl group or a sulfonate group may be used. For example, 2,2-dimethylolpropionic acid, 2,2-dimethylolbutanoic acid, polypropylene glycol with sodium sulfonate group, 2 , 4-diamino-5-methylbenzenesulfonic acid and the like can be used.

As the cationic chain extender, tertiary amine diols and diamine compounds, for example, methyl diethanolamine may be used.

The ionic chain extender may include 0.5 to 25% by weight, preferably 2 to 7% by weight based on the total polyurethane.

Neutralizing agents are used to convert the ionic groups into salts in order to enable the dispersion of the anionic or cationic groups covalently bonded in the main chain of the polyurethane for self-emulsification.

Such neutralizing agents include, when anionic, sodium hydroxide, potassium hydroxide, lithium hydroxide, ammonia, trimethylamine, triethylamine, triisopropylamine, tributylamine, ene, ene-dimethylcyclohexylamine, ene, ene-dimethylaniline , En-methylmorpholine, en-methylpiperazine, en-methylpyrrolidine, en-methylpiperidine, and the like.

In the case of cationic, an acid type such as phosphoric acid, hydrochloric acid, acetic acid, formic acid and malic acid may be used. It can be used more than 80% stoichiometrically with respect to the ionic group. The isocyanate and polyol are reacted at a ratio of 1.1: 1 to 4.0: 1 to form polyisocyanate.

The prepolymer may be further polymerized by reaction with a chain extender after it is dispersed in water. Polyamine may be used as the chain extender. Examples of the polyamine include hydrazine, ethylenediamine, piperazine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, pentaethylenehexamine, N, N, N-tris (2-aminoethyl) amine, N- (2-piperazinoethyl) ethylenediamine, ene, ene'-bis (2-aminoethyl) piperazine, ene, ene, ene'-tris (2-aminoethyl) ethylenediamine, ene- [ene- (2 -Aminoethyl) -2-aminoethyl] -ene '-(2-aminoethyl) piperazine, en- (2-aminoethyl) -ene'-(2-piperazinoethyl) ethylenediamine, en, ene- Bis (2-aminoethyl) -ene- (2-piperazinoethyl) amine, n, ene-bis (2-piperazinoethyl) amine, guanidine, melamine, en- (2-aminoethyl) -1, 3-propanediamine, 3,3'-diaminobenzidine, 2,4,6-triaminopyrimidine, dipropylenetriamine, tetrapropylenepentamine, tripropylenetetramine, n, ene-bis (6-aminohexyl ) Amine, n, ene'-bis (3-aminopropyl) ethylenedia , 2,4-bis (4'-aminobenzyl) aniline, 1,4-butanediamine, 1,6-hexanediamine, 1,8-octanediamine, 1,10-decanediamine, 2-methylpentamethylenediamine, 1,12-dodecanediamine, isophoronediamine (or 1-amino-3-aminomethyl-3,5,5-trimethyl-cyclohexane), bis (4-aminocyclohexyl) methane (or bis (aminocyclohexane -4-yl) -methane) and the like.

The water-dispersed polyurethane thus obtained is preferably prepared as an aqueous polyurethane dispersion by adjusting the resin content to 15 to 50%, more preferably 30 to 45% as a solid content, and the particle size to 50 to 200 nm. In addition, such aqueous polyurethane dispersions can be purchased commercially and used.

-Manufacturing step of aqueous polyurethane coating solution-

 -0.1 to 5 parts by weight of water repellent-

The aqueous polyurethane coating solution consists of a mixture of the following additives.

It should be noted that the water repellent was not added as an additive to the polyurethane coating composition, typically in the manufacture of coated gloves. However, in the present invention, after manufacturing gloves, a water repellent is used to improve water repellency, fouling resistance and water resistance.

 As the water repellent, a fluorine compound or a silicon compound may be used. It can be purchased and used commercially by those skilled in the art. Particularly, it is preferable to use a non-silicon fluorine compound for gloves for semiconductor clean room.

When the water repellent is used in less than 0.1 parts by weight, there may be a problem that the water resistance and water repellent effect of the obtained glove products is significantly lowered, on the contrary, when used in excess of 5 parts by weight, mechanical properties, tactile feel of the obtained synthetic leather And appearance that results in undesirable results in bleeding.

0.1 to 6 parts by weight of dispersant-

Anionic emulsifier or nonionic emulsifier may be used as the dispersant, preferably sodium bis (2-ethylhexyl) sulfosuccinate, sodium lauryl sulfate, sodium isopropyl naphthalenesulfonate, sodium bis (tridecyl Sulfosuccinate, disodium lauryl ether sulfosuccinate, N-octadecyl disodium sulfosuccinate, ammonium stearate, octylphenoxypoly (ethyleneoxy) ethanol, trimethylnonyloxy poly (ethyleneoxy) ethanol , Nonylphenoxy poly (ethyleneoxy) ethanol, glyceryl trioleate, ethylene glycol ethylene monostearate, sorbitan trioleate, sorbitan tristearate or a mixture of two or more thereof may be used. . The dispersant has a function of increasing the dispersion stability of the coating liquid and helping to form a coating film of the coating layer.

-0.1 to 3 parts by weight of antifoaming agent-

In the above, the antifoaming agent may be used silicon and non-silicone, in particular, the semiconductor clean room gloves using a non-silicone antifoaming agent. Such antifoaming agents can be understood to be well known to those skilled in the art to be readily available and commercially available. The antifoaming agent deflates and defoams bubbles, in particular bubbles in a polyurethane dispersion coated on the surface of the substrate, to remove bubbles and pinholes of several tens of microns or more in the coating surface of the final obtained glove.

When the antifoaming agent is used in less than 0.1 parts by weight, deterioration of the antifoaming causes bubbles and pinholes, which are problematic in quality, to the inside and the surface of the coating layer. Also, stains may occur on the glove surface.

-0 to 5 parts by weight of colorant-

As the colorant, a commercially available colorant made of a non-silicone dispersant may be used. The colorant may be used without white, and may be used up to 5 parts by weight when hiding power is required due to the color of the inner skin. have.

-0.1 to 3 parts by weight of a viscosity regulator-

The viscosity modifier may be used up to 0.1 to 3 parts by weight, depending on the solids content of the mixed solution, preferably may be adjusted to 200 to 1,500cps, more preferably 300 to 900cps before use. Acrylic, cellulose, or urethane may be used as a commercially available viscosity modifier.

-Other resins-

The coating solution mixture obtained by mixing the additives as described above may be used alone, but if necessary, a mixed solution such as natural and synthetic rubber latex, acrylic resin, polyester resin, etc. may be added in an amount of 0 to 100 parts by weight for economical or mechanical properties. It is possible to use a crosslinking agent, such as isocyanate, oxazoline, melamine, aziridine-based, etc., for the purpose of strengthening the physical properties, at 0 to 15 parts by weight.

Solid content of the mixed solution and the crosslinking agent to be mixed may be preferably used in 12 to 30% by weight. In the conventional coating liquid viscosity described above, if the solid content is less than 12%, the coating layer may be insufficient due to the lack of formation of the coating layer, and the mechanical properties such as tensile strength and wear resistance may be lowered, and the solid content is more than 30%. In this case, the moisture permeability and soft fit of the glove can be reduced.

Degassing work to remove the air bubbles of the coating liquid may be used in a low pressure stirrer of normal pressure, or commercialized as a pressure vessel capable of reducing the pressure. Through such a defoaming process can be prepared a coating liquid.

-Coating step-

As a general dipping coating method of gloves, it can be achieved by a method of impregnating the coating liquid with a mold equipped with a glove endothelium woven from nylon, polyester, polyethylene, kevlar and cotton for 1 to 15 seconds.

Here, it is noted that the coating step of the present invention is impregnated coating to the extent that the coating liquid can completely penetrate the inner surface of the glove.

This improves the adhesion between the hand and the glove endothelium, thereby preventing the glove from slipping off the hand from the glove. In the prior art, there was a high risk of slipping in the hand with gloves in general, and especially when the hand is dry, the glove slips from the hand in many cases, resulting in poor fit of the glove. However, in the present invention, since the coating liquid penetrates deeply into the inner surface of the glove endothelium, adhesion between the hand and the glove may be improved when the glove is worn, thereby eliminating the inconvenience of slipping the glove from the hand.

In addition, the coating step includes a process of processing the balance after coating, such a balance is to achieve a uniform coating, it can be made through the movement and rotation of the fingertips as the mold moves. Such a coating technique can be easily understood by those skilled in the art.

-Solidification stage-

The coagulation step may be achieved by immersing the impregnated coated gloves in a coagulation bath containing a coagulation solution.

The coagulating solution is composed of various acid aqueous solutions, aqueous salt solutions, aqueous base solutions or a mixture of two or more of them. In the aqueous solution of the acid, acids such as hydrochloric acid, sulfuric acid, phosphoric acid, nitric acid, hydrogen bromide, hydrogen iodide, nitrous acid, hypochlorous acid, hydrofluoric acid, hydrogen sulfide, carbonate, sodium carbonate, gluconic acid, citric acid, malic acid, acetic acid, formic acid, propionic acid, etc. Salt solutions include sodium chloride, potassium chloride, calcium chloride, silver chloride, copper chloride, mercury chloride, ammonium chloride, silver bromide, ammonium bromide, silver iodide, barium carbonate, calcium carbonate, magnesium carbonate, sodium carbonate, silver nitrate, copper sulfate, sodium sulfate , Calcium sulfate, ammonium sulfate, and the like, and the aqueous base solution may include sodium hydroxide, potassium hydroxide, calcium hydroxide, magnesium hydroxide, ammonia, triethylamine, aminomethylpropanol, and the like, and a mixture of two or more of them. Can be. An appropriate coagulation liquid may be used depending on the type of hydrophilic group of the aqueous polyurethane coating liquid, and the temperature of the coagulation liquid in the coagulation bath may be 5 to 50 ° C.

In the method of using the coagulation solution in the coagulation step, the concentration of the coagulation solution may be preferably 1 to 35% by weight, more preferably 5 to 25% by weight, and when the concentration of the coagulation solution is less than 5% by weight, When the coated glove mold is obtained into the coagulating solution, the coating solution may be loosened and the drying of the micropores may occur due to the lack of coagulation. In contrast, when the coated glove mold exceeds 25% by weight, a problem with washing may occur.

-Washing and drying steps-

The obtained product after the coagulation bath is subjected to post-treatment such as water washing in a washing tank of 30 ° C. to 80 ° C. according to the type of coagulant, and completely dried at 60 to 120 ° C. in a next drying furnace to obtain gloves as a final product. Can be.

Hereinafter, with reference to the accompanying embodiments of the present invention will be described in detail. However, the attached embodiments are for illustrating the present invention, and the present invention is not limited to the embodiments.

Example  One

To prepare a coating solution in the composition ratio shown in Table 1.

ingredient content
(Parts by weight) Aqueous Polyurethane Dispersion ^* 100  Water Repellent (Fluorine Repellent) 2.0  Dispersant (disodium lauryl ether sulfosuccinate) 3.0  Defoamer (Non-silicone Defoamer, MD-20) 1.0  Colorant (Toner, Solids 80%) 3.0  Viscosity Modifier (Urethane Viscosity Modifier) 2.0  Water (purified water) 76.0  * The water-based polyurethane is Nanopol NPC-5000 (Nanox Co., Ltd.), an anionic water-based polyurethane having a solid content of 30% by weight and an ion content of 3.5% by weight.

After degassing the coating liquid mixed with the solid content of 20% by weight in the composition ratio of Table 1, impregnating the coating solution with a nylon woven glove endothelial for 2 to 5 seconds to make a penetration coating, 10% by weight A coagulation bath containing an aqueous solution of gluconic acid was impregnated and coagulated for 5 minutes, washed with a water bath at 50 ° C. for 10 minutes, dried in a drying furnace at 80 to 100 ° C., and recovered by a glove from a mold. The entirety of the glove obtained was photographed with a digital camera, shown in FIG. 1, the inside of FIG. 2, and the cross section taken with a microscope. As shown in FIG. 2, it can be seen that the resin penetrates into the endothelium, and fine pores are uniformly formed in FIG. 3, so that moisture permeability and abrasion resistance are excellent as shown in Table 4, and the coating is recovered from the glove mold. It can be seen that adult de-molding property is also excellent.

Example  2

Gloves were obtained in the same manner as in Example 1, except that 10% by weight aqueous sodium chloride solution was used as the coagulation solution. The cross section of the obtained glove is photographed in a microscope and shown in FIG. 4. As shown in Figure 6, it can be seen that the micropores of the coating layer is formed uniformly.

Example  3

A coating solution was prepared at the composition ratio shown in Table 2 below.

ingredient content
(Parts by weight) Aqueous Polyurethane Dispersion ^* 100  Water Repellent (Fluorine Repellent) 2.0  Dispersant (disodium lauryl ether sulfosuccinate) 3.0  Defoamer (Non-silicone Defoamer, MD-20) 1.0  Colorant (Toner, Solids 80%) 3.0  Viscosity Modifier (Urethane Viscosity Modifier) 2.0  NBR Latex (Nipol LX550 from Xeon) 50.0  Water (purified water) 138.0  * The water-based polyurethane is Nanopol NPC-5000 (Nanox Co., Ltd.), an anionic water-based polyurethane having a solid content of 30% by weight and an ion content of 3.5% by weight.

Gloves were obtained in the same manner as in Example 1, except that NBR Latex was introduced at the composition ratio of Table 2 to prepare a coating solution containing 20 wt% of solids. Although the coagulation rate was slightly slowed during coagulation by using latex, it can be seen that micropores are formed relatively uniformly as shown in FIG.

Example  4

To prepare a coating solution in the ratio of the composition shown in Table 3.

ingredient content
(Parts by weight) Aqueous Polyurethane Dispersion ^* 100  Water Repellent (Fluorine Repellent) 2.0  Dispersant (Octylphenoxypoly (ethyleneoxy) ethanol) 3.0  Defoamer (Non-silicone Defoamer, MD-20) 1.0  Colorant (Toner, Solids 80%) 3.0  Viscosity Modifier (Urethane Viscosity Modifier) 2.0  Water (purified water) 76.0  * The aqueous polyurethane is a lab product of NANUX Co., Ltd., cationic aqueous polyurethane of 30% by weight of solid content, 4.0% by weight of ionic content is used.

Cationic aqueous polyurethane dispersion was used in the composition ratio of Table 3, and the gloves were obtained in the same manner as in Example 1 except that 10% by weight of triethylamine aqueous solution was used as the coagulation solution. The cross section of the obtained glove was photographed under a microscope and this is shown in FIG. 6. As shown in Figure 6 it was confirmed that the micropores are uniformly formed. According to this, it can be seen that the cationic aqueous polyurethane dispersion can also be solidified with an aqueous base solution to prepare gloves.

Comparative example  One

Drying method, that is, pretreatment of the glove endothelium mounted on the mold with the coagulating solution of Example 1, that is, first impregnated and dried for 30 to 60 seconds, and then impregnated and coated with the coating liquid as shown in Table 1 for 2 to 5 seconds to the inside. After allowing it to be coated outside without penetrating, it was immediately dried in a drying furnace without passing a coagulation bath to obtain a glove. The cross section of the obtained glove was photographed in a microscope and shown in FIG. 7. Resin was hardly penetrated into the glove, and thus it was found that the workability decreased due to slip between the hand and the nylon endothelium, and in FIG. It can be seen.

Comparative example  2

In the composition ratio of Table 1, using the water in 263 parts by weight was performed in the same manner as in Example 1 except that the solid content is used in 10% by weight to obtain a glove. The cross section of the obtained glove was photographed in a microscope and shown in FIG. 8. As shown in FIG. 8, the formation of the coating layer is insufficient, so that the endothelium is lifted, and thus the purpose of coating as a coating glove is lost.

Comparative example  3

6 parts by weight of water in the composition ratio of Table 1 was carried out in the same manner as in Example 1 except that the solid content is used in 32% by weight to obtain a glove. The cross section of the obtained glove is shown in FIG. 9 by magnifying under a microscope. As shown in Figure 9, it can be seen that the density of the coating layer is increased, the area of the pores is significantly reduced. This confirmed that the moisture permeability and wearing comfort of the coated gloves.

Comparative example  4

The conventional commercialized oil-based wet polyurethane gloves were purchased, and the cross section was taken under a microscope and shown in FIG.

division Example 1 Example
2 Example
3 Example
4 Comparative example
One Comparative example
2 Comparative example
3 Comparative example
4 Breathability ^{1 )}
(g / m ² / 24h)
8930
8650
7290
7750
2260
15830
3950
9320 Abrasion Resistance I ^{2 )}
(Count)
6130
5970
4980
6260
5610
1340
6530
2680 Wear resistance II ^{3 )}
(Count)
9260
8640
8090
8510
5750
3650
9910
5940 Comfort ^{4 )} 5 4 4 4 4 3 One 5

[How to measure]

1) Water vapor permeability: measured by calcium chloride method of KS K 0594 standard.

2) Abrasion degree I: Measured according to ISO 5470-1, Wear ring: CS-10, Load: 500g, Rotation speed: 60 times / minute, End point evaluation: When the coating layer is worn out and the endothelial fabric enters.

3) Wear degree II: Measured according to ISO 5470-1, Wear ring: H-18, Load: 500g, Rotation speed: 60 times / minute, End point evaluation: The point of time where the endothelial fabric is damaged.

4) Wearing comfort: Gloves prepared according to the present invention were randomly worn by 20 people for 1 hour, and the average of the feelings was shown as upper: 5, middle: 4, middle: 3, middle: 2, and lower: 1.

As shown in the above embodiments, according to the present invention, as shown in Figures 3, 4, 5 and 6 it was confirmed that the size and distribution of the micropores is formed very uniformly, thereby excellent in moisture permeability and fit It can be seen that a variety of coating gloves having excellent de-molding properties can be manufactured.

In Example 3, it was found that not only an acid aqueous solution but also an aqueous salt solution could be used as a coagulation solution.

In addition, in Example 4 it can be seen that by adding a synthetic rubber-based latex to the aqueous polyurethane coating solution can be prepared by the same wet method. Instead of the synthetic rubber latex, natural rubber latex, acrylic resin, polyester resin and the like can be prepared by adding.

In addition, it can be seen from Example 5 that the cationic polyurethane dispersion can also be prepared by a wet coagulation method using the same aqueous base solution as the anionic dispersion.

The dry method in Comparative Example 1 is difficult to secure reproducibility because the coating surface state and penetration degree vary depending on the amount of coagulant present in the endothelium during coating, and the manufactured gloves have poor moisture permeability and slip between hand and endothelium. It can be seen that the workability is also bad.

In Comparative Examples 2 and 3, it was found that when the solid content of the coating liquid was less than 12% by weight, it was difficult to form the coating layer, and when it exceeded 30% by weight, the moisture permeability and wearability of the gloves were deteriorated. In addition, in Comparative Example 4, as shown in Table 4, as a conventional general growth pack has a low limit of the strength of the sword, it is not free from toxic DMF solvent regulation.

Overall, according to the present invention, it can be seen that the coating composition of the aqueous polyurethane dispersion can be prepared through the wet coagulation method of the moisture-permeable coating gloves.

1 is a photograph taken with a digital camera of the glove obtained in accordance with Example 1 of the present invention.

2 is a 50 times magnified image of the inside of the glove obtained according to Example 1 of the present invention with an optical microscope.

3 to 10 is a magnified photograph of the cross section of the glove obtained according to Examples 1 to 4 and Comparative Examples 1 to 4 of the present invention by an optical microscope.

Claims (10)

Preparing a coating solution by combining an additive with an aqueous polyurethane dispersion, Impregnating and coating the coating solution so that the coating solution completely penetrates into the inner surface of the gloves by impregnating the mold with the glove endothelium in the coating solution; A solidification step of immersing the coated glove mold in a coagulation solution consisting of an aqueous acid solution, an aqueous salt solution, a base aqueous solution, or a mixed solution of two or more thereof to form micropores, and Method for producing an aqueous polyurethane coated gloves excellent in moisture permeability and wear resistance, characterized in that it comprises washing and drying steps. The method of claim 1, The aqueous polyurethane dispersion disperses the polyurethane prepolymer covalently bound in water by diol or diamine containing an anionic group of a carboxyl group or a sulfonate group or a cationic group of a tertiary amine in the main chain, and diamine ( Method for producing an aqueous polyurethane coated gloves, characterized in that the chain lengthened by diamine). The method of claim 1, The coating solution is 100 parts by weight of an aqueous polyurethane dispersion, an aqueous polyurethane containing 0.1 to 5 parts by weight of an additive, 0.1 to 6 parts by weight of a dispersant, 0.1 to 3 parts by weight of an antifoaming agent, and 0.1 to 3 parts by weight of a viscosity modifier. Method of manufacturing coated gloves. The method according to any one of claims 1 to 3, In order to improve the physical properties of the aqueous polyurethane coating composition, 100 parts by weight of an aqueous polyurethane dispersion, 1 to 100 parts by weight of a latex resin, an acrylic resin, a polyester resin, or a resin mixture containing two or more thereof, 1 to 15 parts by weight of a isocyanate, oxazoline, melamine, aziridine-based or a crosslinking agent comprising two or more thereof is added. The method of claim 4, wherein Solid content of the resin mixture and the crosslinking agent is a method for producing an aqueous polyurethane coating gloves, characterized in that used in 12 to 30% by weight. The method of claim 1, In the coagulant, The acid aqueous solution may be hydrochloric acid, sulfuric acid, phosphoric acid, nitric acid, hydrogen bromide, hydrogen iodide, nitrous acid, hydrochloric acid, hydrofluoric acid, hydrogen sulfide, carbonate, sodium carbonate, gluconic acid, citric acid, malic acid, acetic acid, formic acid, propionic acid or two or more of these. It is an aqueous solution containing acid, The salt solution is sodium chloride, potassium chloride, calcium chloride, silver chloride, copper chloride, mercury chloride, ammonium chloride, silver bromide, ammonium bromide, silver iodide, barium carbonate, calcium carbonate, magnesium carbonate, sodium carbonate, silver nitrate, copper sulfate, sodium sulfate, calcium sulfate , Ammonium sulfate or an aqueous solution containing two or more salts thereof, The base aqueous solution is a method of producing an aqueous polyurethane coating gloves, characterized in that the sodium hydroxide, potassium hydroxide, calcium hydroxide, magnesium hydroxide, ammonia, triethylamine, aminomethylpropanol or an aqueous solution containing two or more of these bases.        Excellent moisture permeability and abrasion resistance to form micropores through a wet type chemical coagulation process in which the aqueous polyurethane coating solution is immersed in a coagulant solution consisting of an aqueous acid solution, an aqueous salt solution, an aqueous base solution, or a mixture of two or more of them. Method for producing aqueous polyurethane coated gloves. In an aqueous polyurethane coating composition used for the production of polyurethane gloves, Polyurethane prepolymers covalently bound by diol or diamine containing anionic groups of carboxyl or sulfonate groups or cationic groups of tertiary amines in the main chain are dispersed in water and chain-extended with diamines. Preparing an aqueous polyurethane dispersion, To 100 parts by weight of the aqueous polyurethane dispersion, 0.1 to 5 parts by weight of a water repellent, 0.1 to 6 parts by weight of a dispersant, 0.1 to 3 parts by weight of an antifoaming agent, and 0.1 to 3 parts by weight of a viscosity modifier are added, In order to improve the physical properties of the aqueous polyurethane coating composition, 100 parts by weight of the aqueous polyurethane dispersion, 1 to 100 parts by weight of a latex resin, an acrylic resin, a polyester resin, or a resin mixture containing two or more thereof, 1 to 15 parts by weight of an isocyanate, oxazoline, melamine, aziridine-based or a crosslinking agent comprising two or more thereof. delete The method of claim 8, Solid content of the resin mixture and the crosslinking agent is used in an aqueous polyurethane coating composition, characterized in that used in 12 to 30% by weight.

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