KR100687899B1 - Foam polyurethane water dispersion coated gloves and preparation method thereof - Google Patents

Abstract

Water-dispersive polyurethane coated foam gloves and a method of manufacturing the same are provided to improve user's fatigue and wearing sensation by forming fine pores. The water-dispersive polyurethane coated foam glove includes gloves, a coagulant layer primarily coated acid or basic solutions on a surface of the gloves, and a formed layer mechanically foamed a mixture of mixing non-silicon based additives with resin ingredients in which anionic or cationic water-dispersive polyurethane resins are mixed nonionic water-dispersive polyurethane resins on the primary coated surface of the gloves by a homo mixer. The resin ingredients are mixture of the anionic or cationic water-dispersive polyurethane resins of 70 to 99 wt.% with the nonionic water-dispersive polyurethane resins of 1 to 30 wt.%.

Description

Foamed Polyurethane Water Dispersion coated gloves and preparation method

The present invention relates to a foamed glove coated with a water-dispersed polyurethane foam and a method for manufacturing the same, the process of forming a coagulant layer by putting a glove on the glove mold and applying a coagulant, the specific cation or anion to the coagulant layer formed Foam gloves produced by a process in which a foam layer is formed by mechanically foaming a solution in which a water-dispersed polyurethane resin, a non-ionic water-dispersed polyurethane resin, and a non-silicone-based additive or the like are mixed. Excellent wearing comfort and anti-slip effect, excellent foaming, breathability, waterproofness, and foamed glove coated with environment-friendly foamed water-dispersed polyurethane that does not use organic solvents during manufacture It is about a method.

In the case of gloves used in the conventional industrial field, gloves having pores similar to the present invention are largely manufactured in the following two types, such as wet polyurethane gloves and latex gloves. The first method is a method of forming a microporous coating by applying a wet polyurethane resin, and the second method is a method of manufacturing by vulcanization by foaming latex.

In the case of gloves manufactured by applying the wet polyurethane resin, which is the first method, it has excellent wearability and durability due to the microporous coating property, but water and organic solvent DMF (N, N'-Dimethyl formamide) is mixed during manufacturing. As the solidification operation proceeds in the aqueous solution, environmental pollution due to wastewater generation in the manufacturing process is inevitable, and dimethylformamide (DMF) may remain in the glove even after manufacture. In addition, there is a problem that the sliding phenomenon of the gloves and the peeling of the finger coating part easily occurs during continuous use, and yellowing phenomenon occurs in the product during long-term storage.

Secondly, synthetic rubber gloves manufactured by vulcanizing latex foam can be improved in the form of foam, which improves moisture permeability, breathability, and fit.However, internal inflow of external contaminants due to large pores In order to remove the calcium chloride or calcium nitrate used as a coagulant during processing and manufacturing by wet method is inevitable, waste water is generated, and the manufacturing process is lengthened because it must be vulcanized. In addition, the disadvantage that the additive is transferred to the surface when using gloves and the problem that causes environmental pollution due to the use of vulcanizing agents and vulcanization accelerator when the final disposal.

In order to improve the disadvantages of such conventional gloves, recently, the development of dry foamed gloves containing a large amount of solvent in the water-dispersed polyurethane resin has been made, but this is still in the research stage.

Accordingly, the present inventors have tried to improve the environmental problems due to the physical properties such as breathability, and fit of the glove and the contaminants inevitably generated in the manufacturing process. As a result, by using a mixture of a cation or anionic water-dispersed polyurethane resin and a nonionic water-dispersed polyurethane resin, it is possible to exert moisture permeability, air permeability, and water resistance with a pore-type coating, and to improve adhesion. The present invention was completed by knowing that durability, anti-slip function is excellent, eco-friendly with the use of organic solvents and dry processing, and there is no internal material transfer to the glove surface by using a component that excludes silicone.

Therefore, the present invention does not feel discomfort and fatigue when the operator wears gloves with breathable, breathable, waterproof, durable, excellent anti-slip function effect and eco-friendly polyurethane foam coated gloves and a method of manufacturing the same. The purpose is to provide.

The invention glove,

On the surface of the glove, a coagulant layer to which an acidic or basic solution is first applied,

A foam layer in which the mixed solution containing a cationic or anionic water-dispersed polyurethane resin, a nonionic water-dispersed polyurethane resin, and a non-silicone additive on the primary coating surface is mechanically foamed by a homomixer. It is characterized by the foamed gloves coated with the water-dispersed polyurethane formed.

Hereinafter, the present invention will be described in detail.

The present invention uses an anionic or cationic water-dispersed polyurethane resin and a nonionic resin together with a pore-type coating to improve durability by supplementing adhesiveness with excellent touch and to some extent the gloves themselves when raining. Its water-absorbing ability gives a non-slip effect that does not slip into water. The resin is prepared using a pretreatment coagulation method that does not require a washing process because it does not use coagulants such as calcium chloride and calcium nitrate, which are alkali materials used in organic solvents such as dimethylformamide (DMF), which is a conventional wet polyurethane gloves, and latex gloves. Preventing penetration into the glove minimizes the discomfort or fatigue the operator feels when wearing the glove.

In addition, all components used in the present invention are made of materials that exclude silicon, so that there is no internal material transfer to the glove surface, and therefore it can be applied to high-tech industries such as electronic, semiconductor and automotive industries where fingerprint resistance is required. Functional foam gloves and their manufacture.

The foamed gloves coated with the water-dispersible polyurethane according to the present invention will be described in more detail as follows.

The components used in the foamed gloves coated with the foamed water-dispersed polyurethane according to the present invention is a resin component and an additive component containing no silicone, and the resin component is an anionic or cationic water-dispersed polyurethane resin. Resin mixed with a nonionic water-dispersed polyurethane resin is used.

The anionic, cationic and nonionic water-dispersed polyurethane resin is generally used in the art, but is not particularly limited, but excellent in water absorption ability to effectively absorb sweat in the present invention cationic or anionic water The dispersed polyurethane resin has a particle size in the range of 100 to 200 nm, and the nonionic water-dispersible polyurethane resin has a particle size in the range of 50 to 150 nm and has different particle sizes. The warm water-dispersed polyurethane resin is intended to maximize the level of penetration (half impregnation) into the glove and the adhesive effect with the glove.

If the particle size of the cationic or anionic water-dispersed polyurethane resin is less than 100 nm, the penetration into the glove becomes easy and the gloss is slightly degraded before coagulation, and if it exceeds 200 nm, the leveling property of the dry film is somewhat poor. A problem arises. In addition, when the particle size is less than 50 nm, the nonionic water-dispersed polyurethane resin has a severe penetration into the glove, resulting in heterogeneity with the skin when worn, and a problem that the adhesion effect is relatively poor when the particle size exceeds 150 nm. do.

When the nonionic water-dispersed polyurethane resin is used in a mixture of 1 to 30% by weight, if the mixing ratio is less than 1% by weight, the amount thereof is too small, so that the desired effect is difficult to be expressed, and when it exceeds 30% by weight, the solidification characteristics It is preferable to maintain the above range because the non-ionic nature of the resin does not penetrate the resin into the glove, and the glove is hardened due to the characteristics of the dry processing method.

The resin uses a coagulant to control the penetration inside the glove and the thickness and flowability. The coagulant uses an acidic or basic solution, and its pH is preferably 1.0 to 5.0 or 10.0 to 14.0. Acid solutions are prepared using formic acid, acetic acid, hydrochloric acid, sulfuric acid, lactic acid and phosphoric acid, and basic solutions are prepared using calum hydroxide, sodium hydroxide, sodium chloride and the like. In order to control the coagulation rate, volatile solvents such as isopropyl alcohol, ethyl alcohol and acetone having a volatilization temperature of 85 ° C. or lower and water may be appropriately added to the coagulant to adjust the acid / base content. The coagulant may be used in an amount of 30 to 80 parts by weight of isopropyl alcohol or ethyl alcohol, 5 to 30 parts by weight of acetone, and 10 to 50 parts by weight of water, based on 100 parts by weight of the total coagulant. Such a coagulant can prevent the resin from penetrating into the gloves when the gloves are impregnated with the water-dispersed polyurethane resin.

The said resin component consists of 50 to 95 weight% and 5 to 50 weight% of non-silicone additives. If silicone is contained in the component of the additive, most of the incompatibility is shifted to the surface of the glove to cause fingerprints, so there is a problem to use in the precision industry such as electronics and semiconductors, so it is preferable to exclude the use. When the amount of the resin component is less than 50% by weight, it is difficult to form a proper coating thickness and a smooth film due to low solids to weight, and when it exceeds 95% by weight, an appropriate amount of additives is added to the wet and leveling properties of the film. The problem that surface characteristics, such as, arises is bad.

As a non-silicone additive, a thickener, a colorant, etc. are used, the thickener plays a role of adjusting and maintaining the viscosity according to the thickness of the resin to be applied, the degree of impregnation, and the degree of coloring. Allow adjustment to the 2.0 mm range. At this time, an acrylic thickener, an amide thickener, a urethane thickener, a cellulose thickener, or the like may be used as the thickener. In addition, the colorant is used to obtain a desired color, and an aqueous pigment or the like is used for mixing stability.

In addition, functional additives such as foam stabilizers, antistatic agents and surface conditioners may be further contained as additive components, and it is preferable to use those in which silicone components are excluded.

In addition, the glove may be used by mixing one or two or more selected from polyamide-based, acrylic, polyethylene, and polyester-based, such as cotton, nylon and kebra.

On the other hand, the present invention is a process for forming a coagulant layer by putting a glove on the mold, and then applying an acidic or basic solution to the glove as a coagulant, the cation or anionic water dispersion polyurethane resin, and a nonionic water dispersion polyurethane resin Another characteristic of the method for producing a water-dispersed polyurethane-coated foamed glove comprising a process of forming, drying and demolding a foamed layer obtained by mechanically foaming a solution containing a mixed resin component and a non-silicone additive in a homomixer have.

Application of the coagulant is generally used in the art, but is not particularly limited, but the present invention uses spraying and impregnation.

The drying is dried for 5 to 10 minutes at room temperature and then treated for 20 to 40 minutes in a drying furnace with a hot air having a temperature of about 100 to 130 ° C. Thus, the separation in the two-step drying process involves dipping the resin and then room temperature. In case of sudden drying at high temperature, problems such as cracking phenomenon and large pinhole occur in the foamed film, so two steps of room temperature drying and high temperature drying process are required to minimize the problems. .

Unlike wet polyurethane gloves or latex gloves, such a process requires only a water drying step without a washing process, thereby simplifying the manufacturing process, thereby maximizing production efficiency by reducing the manufacturing time.

The foaming is usually chemical, physical and mechanical foaming, but when performing the chemical foaming using the blowing agent in the present invention due to the nature of the resin in the form of pores (pore) is not smooth foaming is not performed properly, physical foaming If performed, there is a problem that the surface becomes uneven and implemented.

Thus, in the present invention, by performing a mechanical foam using a homomixer to adjust the desired pore size (cell size) and density, it is possible to use a predetermined amount of foam stabilizer components for more effective foaming. The foamed layer formed by mechanical foaming as in the present invention has a pore size (cell size) of 1 to 50 ㎛ range 50 to 70% range, 50 to 200 ㎛ range will coexist in a ratio of 30 to 50% range.

Hereinafter, the present invention will be described in more detail by the following examples, but the present invention is not limited by the examples.

Example 1

Nylon (seam thickness: 15 males) was mounted in a mold to prepare foam gloves, which was then impregnated with 2% aqueous formic acid solution (pH 2.0) for 2 seconds. Anionic water-dispersed polyurethane resin (T & L, Akuarane DTP 1322) with an average particle size of 150 nm prepared in advance and a nonionic water-dispersed polyurethane resin (T & L, Akuarane N 101) with an average particle size of 100 nm are 90:10. To 100 g of mixed resin by weight, 0.3 g of acrylic thickener (Rom & Haas, RM825), 2 g of aqueous white toner (UNK, 705K), and antistatic agent (altochem, A-2000H) as a functional additive were 3 g was added to impregnate the glove with foamed mixed resin using a homomixer for 2 seconds. After drying for 5 minutes at room temperature, and then dried for 25 minutes in a drying furnace with a hot air in the range 110 ℃ and then the gloves were demolded in a mold to prepare a foam gloves. At this time, all the additive components used in the resin preparation used a component that does not contain silicone.

Example 2

In the same manner as in Example 1, the ratio of the anionic water-dispersed polyurethane resin (T & L, Akuarane DTP 1322) and the nonionic water-dispersed polyurethane resin (T & L, Akuarane N 101) is 100: 0 weight ratio, 70: Foamed gloves were prepared using different mixing in 30 weight ratio, 50:50 weight ratio, 20:80 weight ratio and 0: 100 weight ratio.

Example 3

In the same manner as in Example 1, but instead of the anionic water-dispersed polyurethane resin, a cationic water-dispersed polyurethane resin (T & L, Akuarane CDA 1000) having an average particle size of 150 nm and a nonionic water having an average particle size of 100 nm Foamed gloves were prepared using a mixture of a dispersed polyurethane resin (T & L, Akuarane N 101) in a 90:10 weight ratio.

Example 4

In the same manner as in Example 1, using a homomixer while foaming using a foam stabilizer (Altochem, S9000) 1g to prepare a foam glove.

Comparative Example 1

In the same manner as in Example 1, except using a homomixer, foaming was prepared by foaming using a physical blowing agent (Matsumoto, MICROPEARL) and foam stabilizer (Altochem, S9000).

Comparative Example 2: Dry Dispersed Polyurethane Gloves

Nylon (seam thickness: 15 males) was mounted in a mold to prepare foam gloves, which was then impregnated with 2% aqueous formic acid solution (pH 2.0) for 2 seconds. Add 100 g of anionic water-dispersed polyurethane resin (T & L, Akuarane DTP 1322) to a separate container, add 0.3 g of acrylic thickener (Rom & Haas, RM825), and 2 g of water-dispersed white toner (UNI, 705K) After the defoaming process, the gloves were impregnated for 2 seconds. After impregnation was dried for 25 minutes in a drying furnace having a hot air temperature of about 110 ℃ and then the gloves were demolded from the mold to prepare a foam gloves.

Comparative Example 3: Wet Polyurethane Resin Gloves

Nylon (seam thickness: 15) was mounted on the mold, and then 140 parts by weight of dimethylformamide (DMF) and 3 parts by wet processing aid (Altochem, S-8A) based on 100 parts by weight of polyurethane resin in a separate container. 1 part by weight of a wet white pigment (Altochem, W100) was uniformly stirred, followed by defoaming to remove bubbles contained in the polyurethane resin formulation, and the gloves were impregnated for 2 seconds. The gloves were placed in a 5% aqueous dimethylformamide (DMF) solution and allowed to solidify for 5 minutes, washed with water at 50 ° C. for 20 minutes, dried in a drying furnace with a hot air at a temperature of about 100 ° C. for 45 minutes, and then the gloves were removed from the mold. Demoulding to prepare foamed gloves.

Comparative Example 4 PVC-coated Gloves

Nylon (thickness: 15 males) was mounted on the mold, and then 100 parts by weight of polyvinyl chloride (PVC) and 100 parts by weight of plasticizer dioctyl phthalate (DOP) were impregnated into the mixture mixed uniformly for 2 seconds. After impregnation, the drying was performed for 35 minutes in a drying furnace having a hot air temperature of about 160 ℃ and then the gloves were demolded from the mold to prepare a foam gloves.

Comparative Example 5: Latex Gloves

Nylon (seam thickness: 15 males) was mounted in a mold, which was impregnated with a 5% calcium chloride solution for 2 seconds, and in a separate container 100 g of nitrile butadiene rubber (NBR) latex resin, an acrylic thickener (Rom & Haas). , RM825), 0.3 g of water-dispersed white toner (UNI, 705K), and 5 g of vulcanizing agent (Sapphire Gold, Sulfur) were added, followed by defoaming. Impregnated. After impregnation, washing with water for about 10 minutes at room temperature, 20 minutes in water of about 40 ℃, and then dried for 35 minutes in a drying furnace with a hot air temperature of about 120 ℃, the gloves were demolded in a mold to prepare foamed gloves. .

The physical properties of the foamed gloves prepared in Examples 1 to 4 and Comparative Examples 1 to 5 were performed by the following measuring method.

[Measurement of physical properties]

1. fit; Worker sense

2. Coating / adhesive strength (wear resistance); Abrasion Resistance Meter (50-02; SODEMAT)

3. fingerprint resistance; Visual inspection

4. Moisture permeability (water absorption); Sweating Guarded Hotplate (Technox)

5. surface resistance; Resistance meter (475; ACL Staticide)

6. Surface condition; Visual inspection

7. coagulation force; Visual inspection (time measurement)

Experimental Example 1 Comparison of Foaming Forms and Physical Properties According to Processing Methods

Wearing the foamed form, surface condition and processed gloves of the gloves prepared in Examples 1, 4 and Comparative Examples 1 and 2 to the worker to measure the wearing feeling, moisture absorption rate and film strength of the gloves during the day work, and the results It is shown in Table 1 below.

division Foam form Surface condition Water absorption (g / min) Fit Wear resistance Example 1 Uniform micropores Good 2.7 and below Soft and easy to sweat  Good (level 3 or above) Example 4 Uniform micropores Good 1 or less Soft and easy to sweat  Good (level 3 or above) Comparative Example 1 Uneven micropores Performance of Blowing Agent Almost none Discomfort from sweat Good (level 4) Comparative Example 2 none Good No absorption Discomfort from sweat Good (level 3)  * The wear resistance is based on EN-388 test.

As shown in Table 1, Examples 1 and 4 according to the present invention forms a fine pore (pore) of a certain size to facilitate the discharge of sweat from the inside of the glove with a soft fit to the operator, the particle size is different In addition to the form, it was confirmed that by using a non-ionic water-dispersed polyurethane resin mixed, the film strength and peeling phenomenon can be improved, and can form a good surface state.

In Comparative Example 1, a strong film strength can be obtained, while it is difficult to control the transition phenomenon and the pore size due to the addition of a large amount of physical blowing agent for foaming, and most of the sweat is in the form of a closed cell. It is not easy to discharge and may cause discomfort to the worker with Comparative Example 2, and showed a problem of poor surface smoothness due to the transition of the physical blowing agent.

That is, according to the present invention, when the mechanical foaming method using a homomixer or mechanical foaming with an appropriate amount of foam stabilizer, the density and size of the cells can be properly adjusted, thereby obtaining an optimum foaming form.

Experimental Example 2

The coagulation force, adhesive strength, and fit of the foamed gloves according to the ratio of the anionic water-dispersed polyurethane resin and the nonionic water-dispersed polyurethane resin were measured, and the results are shown in Table 2 below.

division Type and amount of resin (weight ratio) Coagulation power Adhesive strength Fit One Anion: 100 Good Somewhat weak Good Non-ion: 0 2 Anion: 70 Good Good Good Non-ion: 30 3 Anion: 50 weakness Good Somewhat hard Non-ion: 50 4 Anion: 20 weakness Strong crustiness Non-ion: 80 5 Anion: 0 Not solidified Strong crustiness Nonion: 100

As shown in Table 2, it can be seen that the more the ratio of the non-ionic water-dispersed polyurethane resin that is not solidified, the easier the penetration into the glove can increase the adhesive strength. However, when the ratio of the nonionic water-dispersed polyurethane resin is out of the weight ratio of 30, the physical properties are rather decreased. This is because the internal penetration of nonionic resin without coagulation force and the dried film of the resin penetrated during the drying process are formed and become a hard form, resulting in worker fatigue and heterogeneity when worn.

Experimental Example 3

The physical properties of the foam gloves prepared in Example 4 and Comparative Examples 2 to 5 were measured, and the results are shown in Table 3 below.

division Fit Wear resistance Anti-fingerprint Water absorption (g / min) Surface resistance (Ω) Example 4 Softness Good (level 3 or above) Good 1 or less 10 ⁹ Comparative Example 2 Somewhat soft Good (level 3) Good none 10 ¹² Comparative Example 3 Softness Good (level 3 or above) Fingerprint Generation 1 or less 10 ¹² Comparative Example 4 Somewhat hard Good (level 2 or above) Fingerprint Generation none 10 ¹² Comparative Example 5 Somewhat soft Good (level 3 or above) Fingerprint Generation none 10 ¹¹  * The wear resistance is based on EN-388 test.

As shown in Table 3, Example 4 according to the present invention was found to be softer than the comparative examples 2, 4, 5 and sweat does not occupy the inside of the glove, and excellent film strength than Comparative Examples 2, 4, In particular, it was confirmed that the fingerprint resistance was good and the surface resistance was about 10 ⁹ lower than that of other comparative examples. This is because the surface migration can be prevented by the use of an additive that does not contain a silicone component, and charging characteristics can be obtained using a functional antistatic agent.

As described above, the foamed glove manufactured according to the present invention forms fine pores by using mechanical foaming through a homomixer, thereby improving fit and worker fatigue with moisture permeability and a certain level of waterproof characteristics, By using nonionic resin, it can improve the film strength by supplementing the adhesive strength to protect the worker even in the harsh environment, and use the additives and the antistatic agent that do not contain silicon to advanced industries such as semiconductor and electric / electronic It can be applied for the purpose of using, and since the organic solvent is not used from the use of raw materials to manufacturing, the effect of the environmental pollution is relatively small and the effect is expected.

Claims (10)

Gloves, On the surface of the glove, a coagulant layer to which an acidic or basic solution is first applied, A foam layer in which a mixed solution containing a cationic or anionic water-dispersed polyurethane resin, a nonionic water-dispersed polyurethane resin, and a non-silicone additive on the primary coating surface is mechanically foamed by a homomixer. Foamed glove coated with a water-dispersed polyurethane, characterized in that formed. The water-dispersed polyurethane according to claim 1, wherein the resin component is a mixture of 99 to 70% by weight of a cationic or anionic water-dispersed polyurethane resin and 1 to 30% by weight of a nonionic water-dispersed polyurethane resin. This coated gloves. The foamed gloves according to claim 1 or 2, wherein the resin component is 50 to 95% by weight, and the non-silicone additive is contained in an amount of 5 to 50% by weight. The particle size of the cationic or anionic water-dispersed polyurethane resin is in the range of 100 to 200 nm, and the particle size of the non-ionic water-dispersed polyurethane resin is in the range of 50 to 150 nm. Foamed gloves coated with a water-soluble polyurethane. The foamed glove coated with water-dispersed polyurethane according to claim 1 or 2, wherein the cationic or anionic water-dispersed polyurethane resin and the non-ionic water-dispersed polyurethane resin have different particle sizes. The method of claim 1, wherein the gloves are one or two or more selected from cotton, nylon, acrylic, kebra, polyethylene and polyester foam gloves coated with water-dispersed polyurethane. The foamed glove of claim 1, wherein the additive component is selected from a thickener, a colorant, a foam stabilizer, an antistatic agent and a surface conditioner. According to claim 1, wherein the foam layer has a pore size (cell size) of 50 to 70% in the range of 1 to 50 ㎛, 50 to 200 ㎛ range of water dispersion polyurethane, characterized in that formed in a ratio of 30 to 50% Applied foam gloves. Putting gloves on the mold, and then applying an acidic or basic solution to the gloves as a coagulant to form a coagulant layer, On the coagulant layer, a foam layer formed by mechanically foaming a solution containing a cationic or anionic water-dispersed polyurethane resin, a non-ionic water-dispersed polyurethane resin, and a non-silicone additive in a homomixer is formed and dried, Demolding process Method for producing a foamed gloves coated with a water-dispersed polyurethane, characterized in that it comprises a. 10. The method of claim 9, wherein the drying is carried out at room temperature, followed by hot air drying at a temperature in the range of 100 to 130 ° C.