JP2002249909A - Glove with recessed surface structure and method for producing the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a pair of gloves uniformly and densely having on the skin surface thereof a recessed structure like a foaming spongy sectional layer, and also to provide a method for producing the pair of gloves. SOLUTION: This pair of gloves is formed on a glove base material with a skin having on the surface a finely recessed part made through coating the surface of the glove base material with a polyvinylchloride resin material or a rubber material, spraying wax on the coated material in a half-gelatinized condition followed by subjecting the resultant product to a heat treatment to create skin and washing and removing wax from the skin surface.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a glove having a concave surface structure having a non-slip effect and a method for manufacturing the same.

[0002]

2. Description of the Related Art Conventionally, in order to prevent slippage of work or horticultural gloves, an organic or inorganic filler such as PVC powder, rubber powder, EVA powder, etc. is added to a compound and mixed to form a base cloth or a base material. A convex structure is formed by applying a coating method or a dipping method to the surface of the film and performing a heat treatment.
However, the hardness, shape, and adhesion density of the formed convex structure are limited, and in water work, objects will be gripped with a water film interposed between the glove surface, so they are still slippery. It is the current situation.

[0003] A flexible organic substance is externally applied to the surface of the glove film,
For example, some fibers are sprayed with fibers such as cotton and cellulose. However, although the anti-slip effect is improved, the flexible organic matter is easily removed.

[0004] Further, when the film layer on the surface of the glove is semi-gelled, the glove is immersed in an organic solvent to form an uneven pattern. Even with this uneven pattern, a water film also intervenes between the object and the glove surface. As a result, a sufficient slip prevention effect cannot be obtained.

Therefore, it has been studied to form a concave structure such as a cross-sectional layer of a foamed sponge on the surface of the film so as to break the water film and allow the water to escape. For example, JP
In JP-A-11267, an open-cell body is manufactured by adding and mixing vaseline to a plastisol containing a polyvinyl chloride resin and / or a copolymer thereof and a foaming agent, followed by heat treatment. JP-A-52-112659 discloses that a hydrocarbon-based wax or an ester-based wax is added to a mixture containing a polyvinyl chloride emulsion homopolymer or a vinyl chloride emulsion copolymer and a foaming agent, and molded into a sheet. By heating, an open cell is produced. Furthermore, soluble components such as sodium chloride, polyvinyl alcohol, sodium bicarbonate, calcium carbonate, etc. are internally added, or sprayed, static electricity, sprayed from the outside by a shower processing method, etc.
A concave structure is formed by extracting with alkaline water or a solvent.

[0006]

However, according to the above-mentioned method of adding an organic or inorganic foaming agent, microcapsules, etc., a dense sponge cell structure can be formed inside, but the surface of the coating film is formed. Often results in a smooth skin layer.

Further, in the method of internally adding a soluble component, it is not possible to sufficiently extract the soluble component even if the extraction takes a long time. In the method in which the soluble component is sprayed from the outside, the soluble component and the film are fused during heating, and the soluble component cannot be sufficiently extracted.

An object of the present invention is to provide a glove having a concave structure such as a foamed sponge cross-section layer uniformly and densely on the surface of a film and a method for producing the glove.

[0009]

SUMMARY OF THE INVENTION In order to solve the above-mentioned problems, the present invention is to cover the surface of a glove base material with a polyvinyl chloride resin material or a rubber material and spray wax when the coated material is semi-gelled. Gloves having a concave surface structure, wherein a film having fine concave portions on the surface is formed on the glove base by heating to form a film and then removing wax on the film surface by washing and removing the film. And a method for producing the same.

[0010] Also, a concave surface characterized by having a coating made of a polyvinyl chloride resin material or a rubber material on a glove base material and having fine concave portions formed on the surface by wax sprayed during semi-gelling. Provide structural gloves.

Here, the glove base material refers to a base fabric made of cotton, polyester, polyamide, or the like, or a base material film made of polyvinyl chloride resin or the like, which is formed into a predetermined glove shape. The polyvinyl chloride resin material is mainly composed of one of a polyvinyl chloride resin homopolymer and a polyvinyl chloride-vinyl acetate copolymer, or a mixture of both, and is composed of well-known phthalic acid, polyester, and adipic acid. A plasticizer, a stabilizer, a thickener, a solvent, etc. are added, and organic or inorganic particles or a foaming agent that gives a concavo-convex structure to the film are added and mixed as necessary to obtain a paste sol or an organosol. Used. This paste sol or organosol is adhered to a glove base material surface in a predetermined area intended to prevent slippage by a dipping process or a coating method using a heat-sensitive agent or a coagulant.

The rubber material may be a synthetic rubber such as natural rubber, isoprene, chloroprene, acrylate, styrene-butadiene copolymer, acrylonitrile-butadiene copolymer, urethane, etc. as a homopolymer latex or a copolymer latex. Or by blending them and further blending other materials, such as butyl rubber, polybutadiene rubber, ethylene-vinyl acetate copolymer, ethylene-propylene rubber, silicone rubber, chlorosulfonated polyethylene, etc. ,
Add a vulcanization accelerator, an antioxidant, a thickener, etc., an organic or inorganic filler, a plasticizer, etc., and add and mix microcapsules etc. that give the film an uneven structure as necessary, Use a mixture. The rubber latex mixture is applied to the surface of the glove substrate in a predetermined area intended to prevent slippage by a dipping method or a coating method using a heat-sensitive agent or a coagulant.

The term natural rubber includes not only natural rubber alone, but also natural rubber-methyl methacrylate copolymer and epoxidized modified natural rubber copolymer (latex). When natural rubber is used, the wax is sprayed and then immersed in a solution of calcium chloride or calcium nitrate to solidify the surface, thereby preventing fusion between the wax and the rubber during the heat treatment, and having a sharp concave upper end. Structure can be formed.

Acrylonitrile-butadiene rubber has two
It means a copolymer (latex) containing 0 to 40% by weight of acrylonitrile and having 10% by weight or less of a carboxyl modifying group.

Urethane rubber is an elastomer having a urethane bond in the main chain, and is a homopolymer of urethane (ie, a polymer of an isocyanate and an active hydrogen-containing compound), urethane, acrylate, ethylene, acrylic acid, It means a copolymer (latex) with at least one of methacrylic acid and the like.

The styrene-butadiene rubber is 20-50
It means a copolymer (latex) containing 5% by weight or less of styrene and having 5% by weight or less of a carboxyl modifying group.
The chloroprene rubber means a chloroprene homopolymer or a copolymer (latex) with methacrylic acid, acrylic acid, acrylate, acrylonitrile, or the like.

The isoprene rubber means a copolymer (latex) of polyisoprene, isoprene and at least one of ethylene, styrene, butadiene, methyl methacrylate, acrylic acid, methacrylic acid and the like.

Acrylate rubbers include n-butyl acrylate, n-butyl methacrylate, iso-butyl acrylate, iso-butyl methacrylate, ethyl acrylate, 2-ethylhexyl acrylate,
A homopolymer or a copolymer such as -ethylhexyl methacrylate, iso-propyl acrylate, or iso-propyl methacrylate, which contains acrylonitrile, methyl methacrylate, allyl methacrylate, N-methylol acrylamide, acrylic acid, methacrylic acid, or the like. Polymers. This rubber is primarily used to blend with other rubber latexes, such as urethane rubber, styrene-butadiene rubber, acrylonitrile-butadiene rubber, to provide cold resistance or flexibility.

The wax is a solid or semi-solid at room temperature, melts at about 100 ° C., has a low viscosity at the time of melting, and does not dissolve mutually with the coating material. Spray evenly using a sprayer and static electricity. Due to this, at the same time as the coating material gels due to the heat treatment for several tens of minutes, the wax melts to a low-viscosity liquid, and gradually diffuses into the coating, while a part stays on the coating surface, It is considered that a fine wax pool exposed to the air is formed, and the wax in the wax pool can be easily washed and removed, so that a concave structure such as a foamed sponge sectional layer can be formed.

At this time, a dense and uniform desired concave structure can be obtained by appropriately selecting the kind, the melting point range, the particle size, and the amount of spraying of the wax. For example, paraffin wax (particle diameter: about 200 μm) is applied to the surface of the base material by about 25 particles / mm.
^{When the} dispersion is uniformly applied in step ² , after the heat treatment and the wax washing, the concave portions having an inner diameter of about 220 μm are formed with the same distribution.

As the wax, either a natural wax or a synthetic wax can be used. Examples of natural waxes include candelilla wax, carnauba wax, rice wax, wood wax, jojoba oil, beeswax, lanolin, whale wax, montan wax, ozokerite, ceresin, paraffin wax, microcrystalline wax, petrolatum, and the like. Synthetic waxes include Fischer-Tropsch wax, polyethylene wax, montan wax derivative, paraffin wax derivative, microcrystalline wax derivative, hydrogenated castor oil, hydrogenated castor oil derivative, 1.2-hydroxystearic acid, stearamide, phthalic anhydride Examples include imides and chlorinated hydrocarbons.

The removal of the wax can be performed by immersing the wax in hot water or a hot solvent on a production line. Solvents that can be used include xylene, toluene, benzene, limonene, turpentine, carbon tetrachloride, trichloroethylene, and the like. However, use of warm water is preferred because the film may swell.

[0023]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The present invention will be specifically described below with reference to examples. However, these examples do not limit the present invention. The weight described in the examples can be read as mass.

(Example 1) A metal hand mold was covered with an oil-repellent cotton thread, and the following (Composition 1) was applied to the surface of the metal hand mold, and heated at 200 ° C for 1 minute in a heating furnace. Then, it was immersed in the following (Composition 2), and the paraffin wax was evenly sprayed on the semi-gelled film, and heated in a heating furnace at 190 ° C. *
9min. Cure. After that, remove the hand mold from the heating furnace and remove the paraffin wax on the surface of the formed film at 50 ° C.
-Washed with limonene and dried at 60 ° C * 60min. (Composition 1) Vinyl chloride paste resin (1650 polymerization degree) 100 parts by weight Plasticizer (phthalate ester) 117 parts by weight Epoxidized soybean oil 3 parts by weight Stabilizer (Ca-Ba-Zn) Suitable amount Thickener (organic bentonite type) Note) Paraffin wax is a powder manufactured by Nippon Seiro Co., Ltd., particle diameter 200 μm, average molecular weight about 1000, melting point 105 ° C; limonene is a product of Yashara Chemical Co., Ltd., boiling point 176-178 ° C.
Hereinafter, detailed description will be omitted when the same product is used. (Composition 2) Vinyl chloride paste resin (1650 degree of polymerization) 100 parts by weight Plasticizer (phthalic ester) 117 parts by weight Epoxidized soybean oil 3 parts by weight Stabilizer (Ca-Ba-Zn) Suitable amount Thickener (anhydrous silica) 0.4 parts by weight Pigment appropriate amount (Example 2) Cover an original metal treated with oil repellency on a metal hand mold, apply (composition 1) described in Example 1 on its surface, and heat in a heating furnace at 200 ° C * 1 min. The coating was immersed in the following (Composition 3), paraffin wax was uniformly sprayed on the semi-gelled film, and cured at 200 ° C. for 9 minutes in a heating furnace. Thereafter, the hand mold was taken out of the heating furnace, and the paraffin wax on the surface of the formed film was washed with limonene at 50 ° C and dried at 60 ° C for 60 minutes. (Composition 3) 100 parts by weight of vinyl chloride-vinyl acetate paste resin (vinyl acetate; 8% by weight) Plasticizer (phthalic ester) 107 parts by weight Epoxidized soybean oil 3 parts by weight Stabilizer (Ca-Ba-Zn) Viscous agent (anhydrous silica) 0.4 parts by weight Pigment appropriate amount (Example 3) Cover the ceramic hand mold with the drained oil, raise the mold surface temperature to 60 ° C in a heating furnace, and coagulate 1.2% -calcium nitrate in methanol. After immersion in the solution and drying at room temperature for 30 seconds, the palm alone was immersed in the following (Composition 4), and paraffin wax was evenly spread on the semi-gelled film,
Curing was performed at 100 ° C for 10 minutes in a heating furnace. After that, remove the hand mold from the heating furnace, wash the paraffin wax on the surface of the formed film with 50 ° C warm water, release the gloves, and remove the glove to 45 ° C * 6.
After leaching for 0 min, it was dried at 100 ° C. for 60 min. (Composition 4) Natural rubber 90 parts by weight Natural rubber-methyl methacrylate 10 parts by weight (methyl methacrylate; 15% by weight) Sulfur 1 part by weight Zinc oxide 1 part by weight Vulcanization accelerator (dithiocarbamate) 0.6 part by weight Aging Inhibitor (bisphenol-based) 0.5 parts by weight Pigment appropriate amount (Example 4) Gloves were produced in the same manner as in Example 3 using the following (Composition 5). (Composition 5) Acrylonitrile-butadiene copolymer 100 parts by weight (acrylonitrile; 27%) Sulfur 0.5 parts by weight Zinc oxide 2 parts by weight Vulcanization accelerator 0.3 parts by weight Antioxidant 0.5 parts by weight Thickener proper amount pigment proper amount (Example) 5) In the same manner as in Example 4, using (Composition 5) described in Example 4, instead of paraffin wax, polyethylene wax (manufactured by Mitsui Chemicals, Inc., low-density polyethylene, particle diameter of about 300 to 500 μm, (Melting point: 109 ° C.) to produce gloves.

(Example 6) Carnauba wax (manufactured by Toa Kasei Co., Ltd., particle size of about 200 μm) was prepared in the same manner as in Example 4 except that (Composition 5) described in Example 4 was used instead of paraffin wax. , Melting point 82 ° C) to produce gloves.

Example 7 A glove was produced in the same manner as in Example 4 using the following (Composition 6). (Composition 6) Styrene-butadiene copolymer 100 parts by weight (styrene; 23% by weight) Sulfur 1 part by weight Zinc oxide 2 parts by weight Vulcanization accelerator 0.3 part by weight Antioxidant 0.5 part by weight Thickener proper amount pigment proper amount Example 8) In the same manner as in Example 4, gloves were produced using the following (Composition 7). (Composition 7) Urethane latex 100 parts by weight (acid value 15, molecular weight about 200,000) Pigment appropriate amount (Example 9) In the same manner as in Example 4, gloves were produced using the following (Composition 8). (Composition 8) n-BA-AN-AA copolymer 60 parts by weight (n-butyl acrylate / acrylonitrile / acrylic acid = 88/10/2, molecular weight about 200,000) acrylonitrile-butadiene copolymer 40 parts by weight (acrylonitrile) ; 27% by weight) Sulfur 0.5 parts by weight Zinc oxide 2 parts by weight Vulcanization accelerator 0.3 parts by weight Antioxidant 0.5 parts by weight Pigment suitable amount (Example 10) In the same manner as in Example 4, the following (Composition 9) Gloves were used to make them. (Composition 9) Chloroprene latex 100 parts by weight Sulfur 1 part by weight Zinc oxide 2 parts by weight Vulcanization accelerator 0.6 parts by weight Antioxidant 0.5 parts by weight Pigment suitable amount (Example 11) In the same manner as in Example 4, the following ( A glove was produced using composition 10). (Composition 10) 100 parts by weight of isoprene latex 1 part by weight of sulfur 2 parts by weight of zinc oxide 0.6 parts by weight of a vulcanization accelerator 0.5 parts by weight of an antioxidant Suitable amount of pigment (Comparative Example 1) An original oil-treated metal hand mold The surface was coated with (composition 1) described in Example 1 and heated at 200 ° C. * 1 min. In a heating furnace, immersed in (composition 2) described in Example 1, and heated in a heating furnace at 190 ° C. ℃ * 9min. Cure was performed.

(Comparative Example 2) A metal hand mold was covered with an oil-repellent raw metal, and the surface was coated with (composition 1) described in Example 1, and heated in a heating furnace at 200 ° C for 1 min. Then, it was immersed in the following (Composition 11) and cured in a heating furnace at 190 ° C. for 9 minutes. (Composition 11) Vinyl chloride paste resin (1650 degree of polymerization) 100 parts by weight Vinyl chloride granulated resin (about 150 μm) 200 parts by weight Plasticizer (phthalate ester) 150 parts by weight Epoxidized soybean oil 3 parts by weight Stabilizer (Ca- Ba-Zn) Suitable amount Thickener (anhydrous silica) 4 parts by weight Pigment suitable amount Diluent (alkylbenzene) 120 parts by weight (Composition 1) described above was applied, heated in a heating furnace at 200 ° C. * 1 min., Immersed in the following (Composition 12), and cured in a heating furnace at 190 ° C. * 9 min. (Composition 12) Vinyl chloride paste resin (1650 degree of polymerization) 100 parts by weight Paraffin wax 10 parts by weight Plasticizer (phthalate ester) 117 parts by weight Epoxidized soybean oil 3 parts by weight Stabilizer (Ca-Ba-Zn) Suitable amount Thickening (Anhydrous silica) 0.4 parts by weight Pigment appropriate amount (Comparative Example 4) Cover the hand with the oil removed on a ceramic hand mold, raise the mold surface temperature to 60 ° C in a heating furnace, and add a methanol coagulation liquid of 1.2% -calcium nitrate. After drying at room temperature for 30 seconds, only palm was dipped in (composition 5) described in Example 4 and cured at 100 ° C. for 10 minutes in a heating furnace. Thereafter, the hand mold was taken out of the heating furnace, the gloves were released, and leaching was performed at 45 ° C. for 60 minutes, followed by drying at 100 ° C. for 60 minutes.

(Comparative Example 5) A ceramic hand mold was covered with a drained original, and the mold surface temperature was raised to 60 ° C in a heating furnace.
It was immersed in a methanol coagulation solution of 2% -calcium nitrate, dried at room temperature for 30 seconds, immersed in only the palm (composition 13) below, and cured in a heating furnace at 100 ° C. for 10 minutes. Thereafter, the hand mold was taken out of the heating furnace, the gloves were released, and leaching was performed at 45 ° C. for 60 minutes, followed by drying at 100 ° C. for 60 minutes. (Composition 13) Acrylonitrile-butadiene copolymer 100 parts by weight (acrylonitrile; 27% by weight) Acrylonitrile-butadiene particles 10 parts by weight (particle diameter: about 200 μm, acrylonitrile; 34% by weight) Sulfur 0.5 part by weight Zinc oxide 2 parts by weight Vulcanization Accelerator 0.3 parts by weight Anti-aging agent 0.5 parts by weight Thickener proper amount pigment proper amount (Comparative Example 6) Cover the ceramic hand mold with the drained oil, raise the mold surface temperature to 60 ° C in a heating furnace, and add 1.2% -Immerse in a methanol coagulation solution of calcium nitrate, dry at room temperature for 30 seconds, and soak only palm in the following (Composition 14), and heat in a heating furnace for 10 seconds.
Cured at 0 ° C * 10min. Thereafter, the hand mold was taken out of the heating furnace, the gloves were released, and leaching was performed at 45 ° C. for 60 minutes, followed by drying at 100 ° C. for 60 minutes. (Composition 14) Acrylonitrile-butadiene copolymer 100 parts by weight (acrylonitrile; 27% by weight) Paraffin wax 10 parts by weight Sulfur 0.5 parts by weight Zinc oxide 2 parts by weight Vulcanization accelerator 0.3 parts by weight Antioxidant 0.5 parts by weight Thickener Appropriate amount Pigment Appropriate amount (Comparative Example 7) In the same manner as in Example 3, gloves were produced without spraying wax.

Comparative Example 8 In the same manner as in Example 7, gloves were produced without spraying wax. (Comparative Example 9) In the same manner as in Example 8, gloves were produced without spraying wax.

(Comparative Example 10) In the same manner as in Example 9,
Gloves were produced without sprinkling wax. (Comparative Example 11) A glove was produced in the same manner as in Example 10 without spraying wax.

Comparative Example 12 In the same manner as in Example 11, gloves were produced without spraying wax. As described above, Examples 1 to 11 and Comparative Examples 1 to
A test piece was cut out from the palm of the glove manufactured in Comparative Example 12,
The coefficient of kinetic friction was measured to evaluate the anti-slip effect. The measuring method and the evaluation method are as follows. The results are shown in Table 1. (Measurement method of dynamic friction coefficient) AS
According to TM D 1894, a test piece was attached to a moving weight, and the surface was wet on a stainless plate with a certain amount of water.
After running 130 mm at 0 mm / min., The running resistance (dynamic friction coefficient) generated by the friction between the test piece and the stainless steel plate is measured.

Contact area of moving weight 63.5 mm × 63.5 mm Weight of moving weight 200 g Calculation formula μK (dynamic friction coefficient) = C / D, where C = average load value (g) after uniform running D) Weight of moving weight (200 g) (Evaluation of anti-slip effect) It was evaluated that the greater the value of the dynamic friction coefficient, the greater the anti-slip effect.

[0033]

[Table 1] As shown in Table 1, in the gloves of Examples 1 to 11 in which a concave structure was formed in the film using wax, the coefficient of kinetic friction, which is an index of the anti-slip effect during water work, was 1.2 to 1. .
9

On the other hand, Comparative Example 1, Comparative Example 4, Comparative Example 7, Comparative Example 8, Comparative Example 9, Comparative Example 10, Comparative Example 11,
The glove of Comparative Example 12 shows the slip prevention effect of the coating surface itself, and the dynamic friction coefficient is 0.4-0.7. The dynamic friction coefficients of the gloves of Comparative Examples 2 and 5 in which a convex structure was formed on the film surface by the particles were 0.5 and 0.4, respectively. There is not much difference with the film of. Furthermore, in the gloves of Comparative Examples 3 and 6 in which wax was internally added to the film surface layer, Comparative Examples 1 and 2 differed only by the fact that pores were slightly opened in the film surface or no wax was added. Compared with the glove of Comparative Example 5, the dynamic friction coefficient is increased by 0.1-0.2.

As described above, the gloves of the present invention of Examples 1 to 11 have a slip preventing effect of 217-425% during water work as compared with the conventional gloves of Comparative Examples 1 to 12. I have.

[0036]

As described above, according to the present invention, wax is sprayed on a coating material in a semi-gelled state,
A concave structure can be formed densely and uniformly on the surface of the glove film, and a sufficient anti-slip effect can be obtained in water work with gloves attached, thereby improving work safety.

Claims (4)

[Claims] 1. The surface of a glove substrate is coated with a polyvinyl chloride resin material or a rubber material, wax is sprayed when the coated material is semi-gelled, and then heat-treated to form a film. A glove having a concave surface structure, wherein a film having fine concave portions on the surface is formed on the glove base material by washing and removing. 2. The concave surface structure according to claim 1, wherein the polyvinyl chloride resin material is one of a polyvinyl chloride resin and a polyvinyl chloride-vinyl acetate copolymer, or a mixture of both. Glove manufacturing method. 3. The rubber material is a natural rubber, isoprene, chloroprene, acrylate, styrene-butadiene copolymer, acrylonitrile-butadiene copolymer,
The method for producing gloves having a concave surface structure according to claim 1, wherein the urethane is one kind or a mixture of several kinds of urethane. 4. A concave surface characterized by having a film made of a polyvinyl chloride resin material or a rubber material on a glove base material and having fine concave portions formed on the surface by wax sprayed during semi-gelation. Construction gloves.