KR101936882B1 - Coating method of polyurea which dose not give odor to amines in woven fabrics type - Google Patents

Abstract

The present invention relates to a polyurea coating technology which is for removing amine-based odors generated in a fabric type glove manufacturing process. More specifically, since consumers may feel uncomfortable when odors remain by amines unreacted among polyurea coating materials comprised of isocyanate and the amines which are coated on cotton or nylon fabric type gloves, provided is the technology for removing or decreasing odors generated in a fabric type glove manufacturing process by, in a polyurea coating method on a fabric type cotton or nylon glove, removing amine-based odors through processes as follows: cleaning acids for making alkaline amines, which remain in a polyurea coating material coated on a surface of cotton or nylon gloves as an unreacted state, into ammonium salt which is stable chemically and thermally, by means of supplying of acids; and cleaning and providing insoluble salt generated by reacting with amines by means of cleaning of the acid. The technology uses a principle of reacting formula 1, RCOOH+NH_2R → RCOO-N+H_3R (saltification : no odor), in which unreacted alkaline amines generate ammonium salt stabled chemically, and thermally by means of supplying of acids.

Description

TECHNICAL FIELD [0001] The present invention relates to a polyurea coating method for providing environmentally friendly fabric type gloves,

The present invention relates to a polyurea coating technique for eliminating the odor of amine-like odors generated during fabrics-type glove manufacturing process.

More particularly, polyurea coating materials composed of isocyanate and amine components coated on nylon gloves or cotton gloves of woven type are used to remove unpleasant odors from consumers due to unpleasant amine residues. Or polyurethane coating method to fabric type nylon gloves or cotton gloves to mitigate or alleviate the problem.

Gloves are defined as industrial gloves, which are used in the industrial field to prevent external cold, protect hands, or decorate with fashion.

The industrial site is designed to protect workers' safety and hands in an environment exposed to burns or various hazards such as moving objects that are colder, hotter or heavier than the general environment, handling IT products such as semiconductors, Is a very important equipment for workers. For this purpose, glove hand gloves are mostly used in cotton gloves or nylon gloves, or gloves coated with polymer to give additional functionality to gloves.

Gloves Depending on the function and application of the material, it is possible to use polymers such as nitrile-butadiene rubber, polyurethane (PU), latex (natural rubber), nitrile (synthetic rubber), vinyl chloride resin (PVC) Since the coating material is used differently depending on the application, cotton gloves made of textile or nylon gloves have been putting great effort into obtaining gloves composed of polyurea coating materials in consideration of economic efficiency, workability, environmental property and human harmfulness.

Polyurea is a state-of-the-art material developed by Texaco in the US in the early 1980s. It is divided into Pure Polyurea, Hybrid Polyurea, and Urethane Rim in reaction structure. The reaction product of polyetheramine having primary amine at the terminal with isocyanate (Spray elastomer) can be made by commercialized high-pressure, high-temperature impingement mixing spray machine, and polyetheramine can be used as a raw material. Since the catalyst is not used, the reactivity is uniform, Strength, elongation, abrasion resistance, adhesion and the like, so that many applications have been researched to find environmentally friendly applications in various industrial fields.

However, if polyurea is applied to gloves, cotton gloves or nylon gloves made of fabric may cause odor due to temperature rise or sweat discharge inside the gloves when worn for a long time, which may be an impediment to the wearing of polyurea coated gloves It is necessary to develop a coating method that is environmentally friendly and does not provide a bad influence due to odor or the like.

The coating method proposed in the related art in the field of glove manufacturing has been disclosed in Korean Patent Laid-open Publication No. 10-1843003 B1 (reference 1 technology). (A) The coating liquid is put into a dipping tank, and the palm side of the glove A dipping step of dipping the glove mounted on the mold in the coating solution by lifting the dipping tank after fixing the mold posture so as to face the mold, (b) lowering the dipping tank, and then changing the mold posture so that the fingers of the dipped gloves face the ground (C) a step of changing a mold posture in which various mold postures are sequentially changed while moving a dipped glove on a coating liquid, (d) a step of changing a mold posture in which a dipped glove is dipped in a coating liquid, A drying step of drying to form a coating layer, and (e) a stripping step of stripping the glove on which the coating layer is formed from the mold, It is doing.

Korean Patent Laid-Open Publication No. 10-2015-0046992 A (Reference 2) describes that 18-25% by weight of a polyurea obtained from a reaction mixture of a first component comprising isocyanate and a second component comprising amine is dissolved in water 75- To 85% by weight, and mixing the mixture in an agitator; a step of foaming the base of the coating liquid into a foaming machine and foaming at 500 to 1500 rpm for 30 to 60 minutes to obtain a coating liquid; placing the foamed coating liquid in a dipping tank A dipping step of dipping the coated glove to form a coating layer, and a drying step of drying the dipping glove at 75-90 DEG C for 30-50 minutes, thereby proposing a glove coating method using polyurea.

However, in order to solve the problem of skin protection and odor caused by unreacted amines during the coating process of the polyurea on the surface of cotton gloves or nylon gloves composed of fabric, the present invention is characterized in that an amine which is alkali in the washing step with acid And a new process capable of eliminating odors by the production of chemically and thermally stable ammonium salts (salt) is introduced and applied. Therefore, the present invention is different from the cited technologies 1 and 2, It is possible to provide a coating glove which is harmless to the human body since no fatal harmful substances are used and a process capable of solving the problem of odor caused by unreacted amine of polyurea coated on fabric gloves or nylon gloves can be proposed The difference from the conventional technique can be large.

The present invention relates to a method of coating a polyurea composition that does not contain environmentally harmful substances on the surface of a cotton glove or nylon glove composed of a fabric, which comprises applying alkali as a means for preventing the unreacted amine from remaining in the glove during the coating process And a step of supplying an amine at a supply stage of an acid to remove an odor source of the amine by chemically and thermally stable formation of an ammonium salt, thereby providing a polyurea coating method.

The present invention relates to a polyurea coating material composed of isocyanate and amine components coated on fabric type nylon gloves or cotton gloves, and may cause unpleasant odors if unpleasant amines remain in the polyurea coating material, Or < RTI ID = 0.0 > alleviating < / RTI >

The polyurea coating method as a means for achieving the above object is divided into a polyurea solution preparation step, A thickening step; Bubble stage; A dipping step; A primary drying step; Acid wash step; Washing step; The polyurea coating can be carried out on the surface of the fabric type glove through the construction including the secondary drying step. Hereinafter, each step will be described in detail.

Preferably, the polyurea solution preparation step is constituted such that the polyurea in which the composition of the isocyanate and the amine is stoichiometrically mixed is diluted with water in a concentration of 10 to 30% by weight, wherein the solid content of the polyurea is 10 When diluted to a concentration of not more than 1% by weight, it is possible to provide a coating glove having a low production cost, but the physical properties of the polymer coating of polyurethane coated on the surface of the cotton fabric or nylon glove made of the final fabric are weakened, And it is difficult to provide flexibility. When it is diluted with water at a concentration of 30 wt% or more, it may have an advantage that the physical properties of polyurea coated on the surface of the final glove are excellent. However, when the polyurea solid content is too high, In addition to the problems of property change during the coating process, Depending on the problem that the price is competitive is poor due to it is preferred to prepare the polyurea solution consisting of the proposed concentration.

The thickening step is intended to increase the viscosity by dissolving in water and to restrict the flowability so as to constitute a polyurea composition in the outer layer of the cotton glove made of woven fabric or nylon, (CMC, Carboxymethyl cellulose, CMC-Na, Carboxymethyl cellulose-Sodium salt, HEC, MC, Methyl cellulose, Polycarboxylic acid, Water-soluble polyurethane resin , Xanthan gum, sodium alginate, carna guanine, pectin, gelatin, guar gum, agar, and tamarind are selected and supplied to and dissolved in the prepared polyurea solution to give a viscosity of 200 to 500 cPs .

The bubble phase has the purpose of preventing the generation of bubbles in order to minimize the cause of defects due to the bubbling in the preparation step of the polyurea. There is no particular limitation on the bubble agent, and the bubble agent enters the system, And the foaming agent can be removed. The defoaming agent required for the defoaming agent is selected from a silicone emulsion, a high-alcohol emulsion, a mineral type, an ether type and a modified silicone type, based on 100 parts by weight of an aqueous solution containing polyurea By weight or less and 0.01 part by weight or less.

The term "non-bubble phase" herein refers to a micro-bubble formed on the surface of a polyurethane composition formed on the surface of a cotton glove or nylon glove through the process of adding no defoaming agent during the coating process of the polyurea, In order to facilitate the discharge of sweat when the glove is worn for a long time, it means that if the bubble generation phenomenon is insignificant after the thickening step, it means that it can proceed to the next step, the deepening step, and proceed.

The dipping step is intended to constitute a composition of polyurea on the surface of a cotton glove or nylon glove made of a fabric. The dipping step is not particularly limited, and it is possible to dip the entire part of the glove, Depending on the fingers of some gloves, or on the front or back of the glove, it can be dipped locally and dipped several times to increase the polymer thickness of the polyurea.

The primary drying step is to prevent moisture from being contained in the composition of the polyurea on the surface of the gloves by the dipping process and to deteriorate the physical properties of the polyurea due to water vapor evaporated at high speed during the hardening process of the polyurea, The object of the present invention is to slowly dry the moisture inside the polyurea through a relatively low temperature drying process. For this purpose, it is preferable to dry the polyurea in a relatively low temperature range of 65 ° C to 80 ° C.

The acid washing step may be performed in a coating material of polyurethane coated on the surface of a cotton glove or nylon glove composed of a fabric, wherein the alkaline amine remaining unreacted is chemically and thermally stabilized by the supply of an acid The present invention aims at generating an ammonium salt and removing the odor caused by the remaining amine by unreacted by the formation of the ammonium salt.

The acid necessary for the acid washing may be any one of organic acid and inorganic acid. For this purpose, sulfuric acid (H 2 SO 4), hydrochloric acid (HCl), nitric acid (HNO 3), phosphoric acid (H 3 PO 4) (Lactic acid), Lactic acid, Tartaric acid, Maleic acid, Citric acid, Succini acid, Surfamic acid, Formic acid, Oxalic acid Oxalic acid, oxalacetic acid, fumaric acid, malic acid, butyric acid, palmitic acid, tartaric acid, ascorbic acid, One of the Uric acid, Sulfinic acid, Isocitric acid, Lauric acid, Oleic acid, Linoleic acid, Myristic acid Or more, and the pH of the solution is preferably in the range of 2.5 to 6.5.

An example of the reaction in which the unreacted alkaline amine produces an ammonium salt (ammonium salt) that is chemically and thermally stable by the supply of an acid is shown in the following Reaction Scheme 1.

RCOOH + NH ₂ R? RCOO-N + H ₃ R (Salt: odorless)

The washing step is intended to wash an insoluble salt generated by reacting with an amine by an acid washing step by a washing method. Water required for the washing step is not particularly limited, It is possible to use any water that can easily wash the salt-formed material by reacting with an acid which is alkaline with the acid (Acid) without affecting the physical properties of the polyurea coated on the surface of the nylon glove have.

The secondary drying step is intended to remove the moisture provided by the washing step and to heat the polyurea coated on the cotton gloves or nylon gloves to a temperature of 100 oC or higher for complete curing, And it is preferable to heat it to a temperature of 100 ° C to 135 ° C for this purpose.

As described above, as the amines unreacted in the composition of the polyurea remain in the gloves during the coating process of the environmentally friendly polyurea on the surface of the cotton gloves or the nylon gloves, when the gloves are worn for a long time, The present invention does not favor wearing polyurea-coated gloves due to the generation of odor, while providing an aqueous washing step of the acid according to the present invention to provide chemically and thermally stable amine salts It is very effective in eliminating or minimizing the odor of the amine to largely solve the problems of the prior art.

Figure 1: Process for removing or reducing unreacted amines during the coating process on the surface of cotton gloves or nylon gloves using the polyurea resin provided herein

Before describing the embodiments of the invention for implementing the technical idea of the present application, the terms or words used in the specification or claims of the present application should not be construed as limited to ordinary or dictionary terms, The scope of protection of the present invention shall be construed in the meaning and concept consistent with the technical idea of the invention.

The embodiments of the invention disclosed herein are merely preferred embodiments of the present invention and are not intended to represent all of the technical ideas of the present invention, so that various equivalents and modifications may be made at the time of filing of the present application .

Hereinafter, the present invention will be described in detail by way of examples in which the technical idea of the present application is applied in accordance with the following embodiments.

Example 1

(Manufactured by Kukdo Chemical Co., Ltd.), diluted with water to a solid content of 18% by weight, and then carboxymethylcellulose sodium salt (CMC-Na) of KCM Co., Ltd. was supplied with stirring to obtain a viscosity of 350 cPs And a few drops of a silicone emulsion type antifoaming agent purchased from CLEAN CHEMICAL CO., LTD. Were added dropwise to prepare a polyurea solution free from bubbles.

A cotton glove was dipped in the polyurea solution, and the cotton glove was rotated to uniformly coat the composition of the polyurea on the surface of the gloves. After drying at 70 ° C until moisture was properly dried, the sulfuric acid, citric acid Was immersed in a solution of dissolved pH 4.5 for about 5 minutes, washed with water, and then completely dried by heating at a temperature of 105 DEG C for 2 hours.

Example 2

The procedure of Example 1 was repeated except that nylon gloves were used instead of cotton gloves.

Example 3

The procedure of Example 1 was repeated except that the defoaming agent was not supplied.

Example 4

The procedure of Example 2 was repeated except that the defoaming agent was not supplied.

Comparative Examples 1 to 4

Were carried out in the same manner as in Examples 1 to 4, except that they were not immersed in a solution of an acid.

In order to confirm the results of the amine according to the technique of the present invention, each of the gloves made in Comparative Examples 1 to 4 and Examples 1 to 4 was subjected to isothermal injection of 100 mm x 100 mm x 100 mm After the stopper was closed to block the inflow of the gas, the unreacted amine of the polyurea coated on the surface of the glove was kept in the isothermal chamber by heating for 1 hour at a temperature of 36 캜 similar to body temperature. The amount of amine was determined by gas chromatography (GC, Griffin G400). In order to investigate the differences and feelings between the bubble phase and the non-bubble phase in the polyurea coating process, comparative experiments were carried out by the sensory test.

The workers put into the sensory test of this comparative example and the example were based on the 38 male workers in the field, and the average feeling was obtained when wearing gloves with an average age of 47.6 for 1 hour.

The results of Comparative Examples 1 to 4 and Examples 1 to 4 are shown in Table 1.

division Types of mountains Amine (ppm) Level of discomfort Example 1 Sulfuric acid 0.12 Slightly offensive Citric acid 0.14 Slightly offensive Example 2 Sulfuric acid 0.11 Slightly offensive Citric acid 0.11 Slightly offensive Example 3 Sulfuric acid N.D. Uncomfortable Citric acid N.D. Uncomfortable Example 4 Sulfuric acid N.D. Uncomfortable Citric acid N.D. Uncomfortable Comparative Example 1 Sulfuric acid 23 Slightly offensive Citric acid 25 Slightly offensive Comparative Example 2 Sulfuric acid 21 Slightly offensive Citric acid 23 Slightly offensive Comparative Example 3 Sulfuric acid 29 Uncomfortable Citric acid 31 Uncomfortable Comparative Example 4 Sulfuric acid 30 Uncomfortable Citric acid 32 Uncomfortable N.D. means non-detectable, and the detection limit of the sample is 0.10 ppm.

As shown in Table 1, amines remaining in the polyurea by unreacted polyurea coating processes on the surface of the cotton gloves and nylon gloves of Comparative Examples 1 and 2, The results showed that the level of discomfort was higher than that of 20ppm concentration. The level of discomfort was due to the absence of pores on the surface of polyurea resin coated on cotton gloves and nylon gloves, I confirmed the opinion of the panel that people who participated in sensuality felt a little uncomfortable because of the low speed.

In addition, when the antifoaming agent was not supplied to the cotton gloves and nylon gloves of Comparative Examples 3 to 4 during the coating process of the polyurea, the amine content was lower than that of the antifoaming agent, and the level of discomfort was found to be low , Which indicates that a large amount of micropores are formed between the cotton gloves and the polyurea polymer coated on the surface of the nylon gloves, and the amount of unreacted amines is increased. In the level of discomfort, It can be easily discharged through the gloves.

On the other hand, when the results shown in Examples 3 and 4 were compared with those of Comparative Examples 3 and 4, it was confirmed that there was no discomfort at all, It was confirmed that the water was easily discharged out of the gloves through micro pores.

As shown in Examples 1 and 2, when the unreacted amine in the polyamine polymer coated on the surface of the cotton gloves or the nylon glove was immersed in the citric acid organic acid and the inorganic acid sulfuric acid solution, the amount of amine was drastically reduced, The concentration of the amine can not be confirmed when the process is applied to the non-bubble phase process. This is because the rate of permeation of the acid solution between the minute bubbles generated by the micro-bubble phase is increased, It is judged that the content is decreased.

From the above experimental results, it has been confirmed that the fabric type glove provided with the technical idea of the present invention can easily solve the problem of odor of unreacted amine while imparting tackiness, toughness and flexibility to cotton gloves or nylon gloves by using environmentally friendly raw materials Lt; / RTI >

FIG. 1 is a flow chart of a polyurea coating method for removing or reducing unreacted amines in the process of coating on the surface of cotton gloves or nylon gloves using the polyurea resin applied in the present application. No code description is required.

Claims (4)

A polyurea coating method for eliminating or reducing odor generation of unreacted amines in the production of cotton gloves or nylon gloves,
A first step of preparing a polyurea solution by diluting polyurea so that the solid content of the polyurea is 10 to 30% by weight;
A thickener is used to increase the viscosity of the polyurea solution prepared in the first step and increase the viscosity of the polyurea solution so as to form a polyurea composition on the outer layer of the cotton knitted fabric or the nylon made of fabric, A second step of adjusting the viscosity so as to form a viscosity range of 400 cPs;
A defoaming agent selected from a silicone emulsion, a higher alcohol emulsion, a mineral type, an ether type and a modified silicone type is added in an amount of 0.01 part by weight or less based on 100 parts by weight of the polyurea-containing aqueous solution prepared in the second step, A third step of obtaining a foamed polyurea composition by a defoaming process to minimize the cause of defects due to bubble generation;
A fourth step of globally or globally dipping the glove on the polyurea composition obtained through the third step;
In order to prevent the physical properties of the polyurea from being damaged by the moisture contained in the composition of the polyurea and the water vapor evaporated at high speed during the curing process of the polyurea on the surface of the gloves by the fourth step process, A fifth step of primary drying;
The alkaline amine remaining unreacted in the cotton gloves or the polyurea coating coated on the surface of the nylon glove after the fifth step drying process is chemically and thermally stabilized by the supply of acid to the ammonium salt A sixth step in which acid washing is carried out in the pH range of 2.5 to 6.5 to generate the acid;
A seventh step of washing an insoluble salt produced by reacting with an amine by washing with water by an acid washing step in the sixth step;
An eighth step of removing water formed by the washing process of the seventh step and performing a second drying process at a temperature range of 100 to 135 DEG C for curing the polyurea coated on the gloves;
Wherein the amines generated in the glove manufacturing process are pre-removed. The method according to claim 1,
The thickener used in the second step may be selected from the group consisting of CMC, Carboxymethyl cellulose, CMC-Na, HEC, Hydroxyethyl cellulose, MC, Methyl cellulose, Wherein at least one selected from the group consisting of polyacrylic acid, water-soluble polyurethane resin, xanthan gum, sodium alginate, carna guanine, pectin, gelatin, guar gum, agar and tamarind are selected and used. The method according to claim 1,
The acid used in the sixth step may be at least one selected from the group consisting of sulfuric acid (H ₂ SO ₄ ), hydrochloric acid (HCl), nitric acid (HNO ₃ ), phosphoric acid (H ₃ PO ₄ ), acetic acid, Tartaric acid, maleic acid, citric acid, succinic acid, sufamic acid, formic acid, oxalic acid, oxalacetic acid, Fumaric acid, malic acid, butyric acid, palmitic acid, tartaric acid, ascorbic acid, uric acid, sulfinic acid, characterized in that at least one selected from the group consisting of isocitric acid, lauric acid, oleic acid, linoleic acid and myristic acid is selected and used. Urea coating method. The method according to claim 1,
The application of the bubble step to be applied in the third step is omitted and the micro-bubble formed on the polyurea structure formed on the surface of the glove provides a micro-channel for the inside and the outside of the surface of the glove, Lt; / RTI >

Images