US20100138978A1 - Chemical resistant glove - Google Patents

Chemical resistant glove Download PDF

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Publication number
US20100138978A1
US20100138978A1 US12/629,280 US62928009A US2010138978A1 US 20100138978 A1 US20100138978 A1 US 20100138978A1 US 62928009 A US62928009 A US 62928009A US 2010138978 A1 US2010138978 A1 US 2010138978A1
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United States
Prior art keywords
layer
chloroprene
glove
nbr
rubber
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Abandoned
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US12/629,280
Inventor
Yuji Ikeda
Katsuki Shudo
Yukari Aoyagi
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Showa Glove Co
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Showa Glove Co
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Filing date
Publication date
Priority claimed from JP2008312025A external-priority patent/JP2010133068A/en
Priority claimed from JP2008322118A external-priority patent/JP2010144278A/en
Application filed by Showa Glove Co filed Critical Showa Glove Co
Assigned to SHOWA GLOVE CO. reassignment SHOWA GLOVE CO. ASSIGNMENT OF ASSIGNORS INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: Aoyagi, Yukari, IKEDA, YUJI, Shudo, Katsuki
Publication of US20100138978A1 publication Critical patent/US20100138978A1/en
Abandoned legal-status Critical Current

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Classifications

    • AHUMAN NECESSITIES
    • A41WEARING APPAREL
    • A41DOUTERWEAR; PROTECTIVE GARMENTS; ACCESSORIES
    • A41D19/00Gloves
    • A41D19/0055Plastic or rubber gloves
    • A41D19/0058Three-dimensional gloves
    • A41D19/0065Three-dimensional gloves with a textile layer underneath
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B29WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29CSHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C41/00Shaping by coating a mould, core or other substrate, i.e. by depositing material and stripping-off the shaped article; Apparatus therefor
    • B29C41/02Shaping by coating a mould, core or other substrate, i.e. by depositing material and stripping-off the shaped article; Apparatus therefor for making articles of definite length, i.e. discrete articles
    • B29C41/14Dipping a core
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B29WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29CSHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C41/00Shaping by coating a mould, core or other substrate, i.e. by depositing material and stripping-off the shaped article; Apparatus therefor
    • B29C41/02Shaping by coating a mould, core or other substrate, i.e. by depositing material and stripping-off the shaped article; Apparatus therefor for making articles of definite length, i.e. discrete articles
    • B29C41/22Making multilayered or multicoloured articles
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L11/00Compositions of homopolymers or copolymers of chloroprene
    • C08L11/02Latex
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L9/00Compositions of homopolymers or copolymers of conjugated diene hydrocarbons
    • C08L9/02Copolymers with acrylonitrile
    • C08L9/04Latex
    • DTEXTILES; PAPER
    • D06TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06NWALL, FLOOR, OR LIKE COVERING MATERIALS, e.g. LINOLEUM, OILCLOTH, ARTIFICIAL LEATHER, ROOFING FELT, CONSISTING OF A FIBROUS WEB COATED WITH A LAYER OF MACROMOLECULAR MATERIAL; FLEXIBLE SHEET MATERIAL NOT OTHERWISE PROVIDED FOR
    • D06N3/00Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof
    • D06N3/04Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof with macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • D06N3/10Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof with macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds with styrene-butadiene copolymerisation products or other synthetic rubbers or elastomers except polyurethanes
    • DTEXTILES; PAPER
    • D06TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06NWALL, FLOOR, OR LIKE COVERING MATERIALS, e.g. LINOLEUM, OILCLOTH, ARTIFICIAL LEATHER, ROOFING FELT, CONSISTING OF A FIBROUS WEB COATED WITH A LAYER OF MACROMOLECULAR MATERIAL; FLEXIBLE SHEET MATERIAL NOT OTHERWISE PROVIDED FOR
    • D06N3/00Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof
    • D06N3/18Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof with two layers of different macromolecular materials
    • D06N3/183Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof with two layers of different macromolecular materials the layers are one next to the other
    • AHUMAN NECESSITIES
    • A62LIFE-SAVING; FIRE-FIGHTING
    • A62BDEVICES, APPARATUS OR METHODS FOR LIFE-SAVING
    • A62B17/00Protective clothing affording protection against heat or harmful chemical agents or for use at high altitudes
    • A62B17/006Protective clothing affording protection against heat or harmful chemical agents or for use at high altitudes against contamination from chemicals, toxic or hostile environments; ABC suits
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B29WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29LINDEXING SCHEME ASSOCIATED WITH SUBCLASS B29C, RELATING TO PARTICULAR ARTICLES
    • B29L2031/00Other particular articles
    • B29L2031/48Wearing apparel
    • B29L2031/4842Outerwear
    • B29L2031/4864Gloves
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08KUse of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00Use of inorganic substances as compounding ingredients
    • C08K3/18Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20Oxides; Hydroxides
    • C08K3/22Oxides; Hydroxides of metals
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L11/00Compositions of homopolymers or copolymers of chloroprene
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L9/00Compositions of homopolymers or copolymers of conjugated diene hydrocarbons
    • C08L9/02Copolymers with acrylonitrile

Definitions

  • the present invention relates to a chemical resistant glove coated with a rubber, and particularly to a chemical resistant glove that is obtained by coating a fabric glove with a chloroprene-based rubber, which has not only greatly improved chemical resistance, safety and reliability, but also tactile feeling and abrasion resistance.
  • Liquid proof gloves in which the surface of a fabric glove has been coated with a rubber or a resin are widely used as working gloves.
  • the rubber or the resin to be applied include a natural rubber (NR), a styrene-butadiene rubber (SBR), a nitrile-butadiene rubber (NBR), a chloroprene rubber (CR), a polyurethane (PU), and a vinyl chloride resin (PVC).
  • NR natural rubber
  • SBR styrene-butadiene rubber
  • NBR nitrile-butadiene rubber
  • CR chloroprene rubber
  • PU polyurethane
  • PVC vinyl chloride resin
  • a chloroprene rubber is known to be excellent in weather resistance, thermal resistance, oil resistance, and chemical resistance, especially in acid resistance and alkali resistance. Therefore, gloves in which the surface of gloves made of a fiber is covered with a chloroprene rubber have been widely used as chemical resistant gloves.
  • chloroprene rubber for gloves for example, in Japanese Laid-open Patent Publication 2007-106994, a chloroprene-based polymer latex for gloves that is well balanced with regard to flexibility lasting, tensile strength and tensile elongation has been proposed.
  • rubber-coated gloves are problematic in that when a person grips an object with a gloved hand, the object is prone to slip. This problem is more serious particularly when the surface of the glove is wet with a chemical liquid.
  • a first aspect of the present invention relates to a chemical resistant glove which comprises a chloroprene-based rubber layer as a first layer and a mixed rubber layer containing a nitrile-butadiene-based rubber and a chloroprene-based rubber as a second layer sequentially formed on a fabric glove, wherein a mixing ratio of the nitrile-butadiene-based rubber and the chloroprene-based rubber in the mixed rubber layer as the second layer is 60:40 to 10:90 in a solid weight ratio.
  • a second aspect of the present invention relates to a chemical resistant glove, wherein the mixing ratio of the nitrile-butadiene-based rubber and the chloroprene-based rubber in the mixed rubber layer as the second layer is 40:60 to 20:80 in a solid weight ratio.
  • a third aspect of the present invention relates to a chemical resistant glove, wherein a chloroprene-based rubber layer as an intermediate layer is further formed between the chloroprene-based rubber layer as the first layer and the mixed rubber layer containing the nitrile-butadiene-based rubber and the chloroprene-based rubber as the second layer.
  • a fourth aspect of the present invention relates to a chemical resistant glove, wherein nitrile-butadiene-based rubber particles are contained in the mixed rubber layer as the second layer in an amount of 20 to 60 parts by weight, on a solid content basis, based on 100 parts by weight of a latex of the mixed rubber layer as the second layer.
  • a fifth aspect of the present invention relates to a chemical resistant glove, wherein a content of the nitrile-butadiene-based rubber particles is 30 to 50 parts by weight, on a solid basis, based on 100 parts by weight of the mixed rubber layer as the second layer.
  • a sixth aspect of the present invention relates to a chemical resistant glove, wherein a thickness of the first layer is in a range of from 0.18 to 0.23 mm.
  • a seventh aspect of the present invention relates to a chemical resistant glove, wherein a thickness of the second layer is in a range of from 0.14 to 0.18 mm.
  • a eighth aspect of the present invention relates to a chemical resistant glove, wherein a thickness of the intermediate layer is in a range of from 0.18 to 0.23 mm.
  • a glove that is excellent in chemical resistance, good in protection and reliability, and good in tactile feeling and abrasion resistance is provided by forming a chloroprene-based rubber layer as the first layer and a mixed rubber layer containing a nitril butadiene-based rubber and a chloroprene-based rubber as the second layer sequentially on a fabric glove.
  • a glove that has more improved chemical resistance is provided by further forming a chloroprene-based rubber layer as an intermediate layer between the first layer and the second layer.
  • a glove that is excellent in slip resistance addition to the above mentioned effects is provided by causing the mixed rubber layer to contain nitrile-butadiene-based rubber particles.
  • the chemical resistant glove of the present invention is characterized in that a chloroprene-based rubber layer as a first layer and a mixed rubber layer containing a nitrile-butadiene-based rubber and a chloroprene-based rubber as a second layer sequentially formed on a fabric glove, wherein a mixing ratio of the nitrile-butadiene-based rubber and the chloroprene-based rubber in the mixed rubber layer as the second layer is 60:40 to 10:90 in a solid weight ratio.
  • the chemical resistant glove of the present invention is characterized in that a chloroprene-based rubber layer is further formed between the chloroprene-based rubber layer as the first layer and the mixed rubber layer of the nitrile-butadiene-based rubber and the chloroprene-based rubber as the second layer in the foregoing chemical resistant glove.
  • the chemical resistant glove of the present invention is characterized in that nitrile-butadiene-based rubber particles are contained in the mixed rubber layer as the second layer.
  • Various types of fibers can be used as the fabric glove for use in the present invention.
  • gloves produced by knitting cotton, polyester, polyurethane, high-strength drawn polyethylene, e.g., DYNEEMA (registered trademark), aramide, e.g., KEVLAR (registered trademark) or their mixed spun yarns, or by sewing woven fabrics or nonwoven fabrics can be used.
  • aqueous dispersion latex of chloroprene polymers and chloroprene-based copolymers of chloroprene and other copolymerizable components are common as the chloroprene-based rubber layer, which is the first layer.
  • solvent-based solutions and solvent-based dispersion liquids can also be used.
  • Exemplary commercially-available products include SHOPRENE (registered trademark) 671A (produced by Showa Denko K.K.), SHOPRENE (registered trademark) 571 (produced by Showa Denko K.K.), SHOPRENE (registered trademark) 750 (produced by Showa Denko K.K.), SKYPRENE (registered trademark) latex LA-502 (produced by TOSOH CORPORATION), DENKA CHLOROPRENE (registered trademark) LM-61 (produced by DENKI KAGAKU KOGYO KABUSHIKI KAISHA), DENKA CHLOROPRENE (registered trademark) LM-50 (produced by DENKI KAGAKU KOGYO KABUSHIKI KAISHA), DENKA CHLOROPRENE (registered trademark) LV-60N (produced by DENKI KAGAKU KOGYO KABUSHIKI KAISHA), and Lipren-T (produced by PolymerLatex). These are used singly or in combination of two or
  • the thickness of the first layer after curing is preferably in a range of from about 0.18 mm to about 0.23 mm.
  • An attempt to form a chloroprene-based rubber layer having a thickness of less than 0.18 mm tends to cause penetration of a raw material to the inside of a fabric glove and, as a result, a resulting glove gives very bad tactile feeling when being worn.
  • an attempt to form a chloroprene-based rubber layer having a thickness of more than 0.23 mm tends to impair uniform adhesion of a raw material to gloves made of a fiber and, as a result, uniform chemical resistance and so on cannot be obtained with a resulting glove.
  • examples of the nitrile-butadiene-based rubber (hereinafter, a nitrile-butadiene-based rubber is sometimes referred to as an NBR) to be used together with the chloroprene-based rubber as the mixed rubber layer, which is the second layer, include Nipol (registered trademark) Lx-550 (produced by ZEON CORPORATION), Nipol (registered trademark) Lx-551 (produced by ZEON CORPORATION), Nipol (registered trademark) Lx-556 (produced by ZEON CORPORATION), PERBUNAN (registered trademark) N LATEX VT-LA (produced by PolymerLatex), PERBUNAN (registered trademark) N LATEX X 1130 (produced by PolymerLatex), PERBUNAN (registered trademark) N LATEX X 1138 (produced by PolymerLatex), PERBUNAN (registered trademark) N LATEX X 1150 (produced by PolymerLatex), PERBUNAN (
  • the thickness of the second layer after curing is preferably in a range of from about 0.14 mm to about 0.18 mm.
  • An attempt to form a mixed rubber layer having a thickness of less than 0.14 mm tends to be difficult to form a film and thus it tends to be difficult to form the second layer.
  • an attempt to form a mixed rubber layer having a thickness of more than 0.18 mm tends to cause a resulting glove to become stiffer.
  • the mixing ratio of the NBR-based rubber and the chloroprene-based rubber, in a solid weight ratio is 60:40 to 10:90, and preferably 40:60 to 20:80. If the proportion of the NBR-based rubber is more than the foregoing ratio, a glove having a stiff tactile feeling is produced. If the proportion of the NBR-based rubber is less than the foregoing ratio, problems that a latex coagulates at the time of mixing and that the abrasion resistance decreases are caused and, as a result, it may become difficult to produce a glove.
  • a latex of the NBR-based rubber As to the mixing of a latex of the NBR-based rubber and a latex of the chloroprene-based rubber, it is desirable to use an aqueous dispersion latex or solution in the same solvent system or dispersions in the same solvent system.
  • the chloroprene-based rubber latex to be used for the chloroprene-based rubber layer of the first layer or the intermediate layer and the chloroprene-based rubber latex to be used by being mixed with the NBR-based latex in the mixed rubber layer of the second layer the same latex or different latices selected from the above-mentioned chloroprene-based polymer latex and latex of chloroprene-based copolymers may be used.
  • the thickness of the intermediate layer after curing is preferably in a range of from about 0.18 mm to about 0.23 mm. If the thickness is less than 0.18 mm, there is a tendency that a film is difficult to be formed and thus it is difficult to form an intermediate layer. If the thickness exceeds 0.23 mm, uniform film forming tends to be impaired.
  • the viscosity of the chloroprene-based rubber latex as the first and the intermediate layers or the latex of the mixed rubber composed of an NBR-based rubber and a chloroprene-based rubber as the second layer is important for adjustment of the coating film thickness or workability of application, and it is preferably in V6 viscosity, 2800 to 3200 mPa ⁇ sec for the first layer, 1500 to 2000 mPa ⁇ sec for the second layer, and 1800 to 2200 mPa ⁇ sec for the intermediate layer.
  • the slip resistance of the chemical resistant glove in the present invention can be further improved by adding NBR-based rubber particles to the mixed rubber layer as the second layer.
  • the NBR-based rubber particles are less prone to leave from a glove after the production of the glove and thus exhibit higher slip resistance in comparison to particles of other resins or rubbers.
  • the shape of the NBR-based rubber particles is not particularly limited, and examples thereof include a spherical shape, a polyhedral shape, a hemispherical shape, and a bowl-like shape.
  • a product prepared by pulverizing a sheet-shaped NBR-based rubber can also be used suitably.
  • the sheet-shaped NBR-based rubber is produced by, for example, incorporating commonly-used rubber additives such as clay, titanium, plasticizers, vulcanizing agents, vulcanization accelerators, antiaging agents, and sulfur in NBR-based rubbers.
  • the pulverizing method is not particularly limited, freeze pulverization is preferred because pulverization heat is often generated, which may cause change in quality or degradation of the rubber.
  • NBR-based particles examples include BAYMOD (registered trademark) N34.52 (produced by Bayer), BAYMOD (registered trademark) N34.82 (produced by Bayer), BAYMOD (registered trademark) NXL34.23VP (produced by Bayer), and BAYMOD (registered trademark) NXL34.12 (produced by Bayer). These are used singly or in combination of two or more, if necessary.
  • the size of the NBR-based particles is preferably 1000 ⁇ m or less, more preferably 50 to 850 ⁇ m, and even more preferably 100 to 710 ⁇ l. If it is greater than 1000 ⁇ m, the uniform adhesion of the particles tends to be impaired. If it is excessively small, a sufficient slip resisting effect tends not to be obtained.
  • the NBR-based rubber particles are contained in an amount of 20 to 60 parts by weight, in a solid content basis, based on 100 parts by weight of the latex of the mixed rubber layer as the second layer. If the amount of the NBR-based rubber particles is less than 20 parts by weight, a sufficient slip resisting effect can be obtained neither under dry conditions nor under wet conditions. On the other hand, if it exceeds 60 parts by weight, resulting gloves come to have harder tactile feeling or it is impossible to obtain gloves to which particles adhere uniformly.
  • the method for forming the first layer, the second layer and the intermediate layer on a fabric glove dipping in a latex liquid, spray coating, coating with a brush or the like can be used. At the time of coating, it is common and convenient to set a fabric glove on a hand mold.
  • a hand mold metal molds, ceramic molds, wooden molds, plastic molds, and so on can be used.
  • a metal oxide In view of, for example, the easiness of processing, and the flexibility or the stability of strength of a rubber coating film after vulcanization, it is desirable to blend to the latex a metal oxide, a vulcanization accelerator, sulfur, a surfactant, an antiaging agent, a pH adjuster, a plasticizer, a filler, and so on.
  • the metal oxide examples include zinc oxide, lead oxide, and trilead tetraoxide. These are used singly or in combination of two or more, if necessary.
  • the amount of the metal oxide is preferably 1 to 10 parts by weight to 100 parts by weight of the solid content of a rubber latex. If the amount is less than 1 part by weight, it is difficult to obtain tensile strength and basic characteristics of modulus due to insufficient crosslinking. If the amount is more than 10 parts by weight, the modulus becomes excessively high and a resulting glove becomes stiff.
  • thiuram-based, dithiocarbamate-based, thiourea-based and guanidine-based vulcanization accelerators are commonly used for chloroprene-based rubber latex.
  • the thiuram-based vulcanization accelerators and the dithiocarbamate-based vulcanization accelerators are particularly preferred.
  • the thiuram-based valcanization accelerator include tetraethylthiuram disulfide, and tetrabutylthiuram disulfide.
  • Examples of the dithiocarbamate-based vulcanization accelerator include sodium dibutylthiodicarbamate, zinc dibutylthiodicarbamate, and zinc diethylthiodicarbamate.
  • Examples of the thiourea-based vulcanization accelerator include ethylenethiourea, diethylthiourea, trimethylthiourea, and N,N′-diphenylthiourea. Among these, N,N′-diphenylthiourea is particularly preferable.
  • Examples of the guanidine-based vulcanization accelerator include diphenylguanidine and diorthotoluidineguanidine. These are used singly or in combination of two or more, if necessary.
  • the amount of the vulcanization accelerator is preferably 0.5 to 5.0 parts by weight to 100 parts by weight of the solid content of a rubber latex. If the amount is less than 0.5 parts by weight, the vulcanization acceleration effect is insufficient. If the amount is more than 5.0 parts by weight, problems may arise. For example, even if a glove is produced, the resulting glove may feel hard or cause scorching by initial vulcanization.
  • sulfur is usually used together.
  • the amount of sulfur is preferably 0.1 to 3.0 parts by weight to 100 parts by weight of the solid content of a rubber latex. If the amount is less than 0.1 parts by weight, it is difficult to obtain tensile strength and basic characteristics of modulus due to insufficient crosslinking. If the amount is more than 3.0 parts by weight, there is a tendency that the modulus becomes excessively high and a resulting glove tends to become stiff.
  • surfactant examples include sodium alkylsulfate, sodium alkylbenzenesulfonate, sodium salt of naphthalenesulfonic acid-formaldehyde condensate, rosin acid soap, and fatty acid soap. These are used singly or in combination of two or more, if necessary.
  • the amount of the surfactant is preferably 0.1 to 10.0 parts by weight to 100 parts by weight of the solid content of a rubber latex. If the amount is less than 0.1 parts by weight, the latex tends to become unstable. If the amount exceeds 10.0 parts by weight, the latex tends to become excessively stable and it becomes difficult to form a film.
  • antiaging agent examples include naphthylamine-based compounds, diphenylamine-based compounds, p-phenylenediamine-based compounds, quinoline-based compounds, hydroquinone derivative-based compounds, monophenol-based compounds, bisphenol-based compounds, polyphenol-based compounds, imidazole-based compounds, nickel dithiocarbamate-based compounds, phosphite ester-based compounds, organic thioacid-based compounds, and thiourea-based compounds.
  • Examples of the naphthylamine-based compounds include phenyl-1-naphthylamine and phenyl- ⁇ -naphthylamine.
  • Examples of the diphenylamine-based compounds include 4,4-bis( ⁇ , ⁇ -dimethylbenzyl)diphenylamine, p-(p-toluenesulfonylamide)diphenylamine, alkylated diphenylamine and octylated diphenylamine.
  • Examples of the p-phenylenediamine-based compounds include N,N′-diphenyl-p-phenylenediamine, N-phenyl-N′-isopropyl-p-phenylenediamine, N,N′-di-2-naphthyl-p-phenylenediamine, N-phenyl-M-(1,3-dimethylbutyl)-p-phenylenediamine and N-phenyl-M-(3-methacryloyloxy-2-hydroxypropyl)-p-phenylenediamine.
  • Examples of the quinoline-based compounds include a 2,2,4-trimethyl-1,2-dihydroquinoline polymer and 6-ethoxy-1,2-dihydro-2,2,4-trimethylquinoline.
  • Examples of the hydroquinone derivative-based compounds include hydroquinone, methoquinone and 2,5-diphenyl-p-benzoquinone.
  • Examples of the monophenol-based compounds include 2,6-di-tert-butyl-4-methyl phenol, mono( ⁇ -methylbenzylphenol, di( ⁇ -methylbenzyl)phenol and tri( ⁇ -methylbenzyl)phenol.
  • Examples of the bisphenol-based compounds include 2,2′-methylenebis(4-methyl-6-tert-butyl phenol), 4,4′-butylidenebis(3-methyl-6-tert-butyl phenol) and 4,4′-thiobis(3-methyl-6-tert-butylphenol).
  • Examples of the polyphenol-based compounds include 2,5-di-tert-butylhydroquinone and 2,5-di-tert-amyl hydroquinone.
  • Examples of the imidazole-based compounds include 2-mercaptobenzimidazole, 2-mercaptomethylbenzimidazole and zinc salts of 2-mercaptobenzimidazole.
  • nickel dithiocarbamate-based compounds examples include nickel diethyldithiocarbamate and nickel dibutyldithiocarbamate.
  • phosphite-based compounds examples include tris(nonylphenyl)phosphite.
  • organic thioacid-based compounds examples include dilauryl thiodipropionate.
  • thiourea-based compounds examples include 1,3-bis(dimethylaminopropyl)-2-thiourea and tributylthiourea. These are used singly or in combination of two or more, if necessary. Among these, monophenol-based compounds or bisphenol-based compounds are preferable.
  • the amount of the antiaging agent is preferably 0.5 to 5.0 parts by weight to 100 parts by weight of the solid content of a rubber latex. If the amount is less than 0.5 parts by weight, it is difficult to obtain a sufficient retarding effect of degradation. If the amount is more than 5.0 parts by weight, the retarding effect of degradation is not enhanced and the strength may decrease occasionally.
  • an alkali or a weak acid such as amino acid or acetic acid may be used for the purpose of stabilizing a latex or adjusting the thickness of a coating film.
  • the alkali include potassium hydroxide and ammonia and examples of the weak acid include glycine. These are used singly or in combination of two or more, if necessary. It is desirable that the pH adjuster be added in the form of an aqueous solution before use so that the stability of a latex is not impaired.
  • the amount of the pH adjuster in a compound using a chloroprene-based rubber latex it is desirable to add the pH adjuster so that the pH becomes 10.0 to 11.5 when all additives including the pH adjuster are incorporated. Specifically, it is more desirable to add the pH adjuster so that the pH becomes 10.0 to 10.5. If the pH is lower than 10.0, the latex becomes unstable and becomes solidified. If the pH exceeds 11.5, the latex becomes excessively stable and the latex becomes difficult to coagulate and, as a result, it tends to become difficult to form a rubber film.
  • a pH adjuster so that the pH becomes 9.0 to 10.5 when all additives including the pH adjuster are compounded. Specifically, it is more desirable to add a pH adjuster so that the pH becomes 10.0 to 10.5. If the pH is lower than 9.0, the latex becomes unstable and becomes solidified. If the pH exceeds 10.5, the latex comes to contain an excess alkali, so that the latex may solidify occasionally.
  • plasticizer examples include phthalate esters such as dimethyl phthalate, diethyl phthalate, dibutyl phthalate, diisobutyl phthalate, dioctyl phthalate, butyloctyl phthalate, di(2-ethylhexyl)phthalate, diisooctyl phthalate, and diisodecyl phthalate; fatty acid esters such as dimethyl adipate, diisobutyl adipate, di(2-ethylhexyl)adipate, diisooctyl adipate, diisodecyl adipate, octyldecyl adipate, di(2-ethylhexyl)azelate, diisooctyl azelate, diisobutyl azelate, dibutyl sebacate, di(2-ethylhexyl)sebacate and diisooc
  • the amount of the plasticizer is preferably 0.001 to 10.0 parts by weight to 100 parts by weight of the solid content of a rubber latex. If the amount is less than 0.001 parts by weight, plasticization tends to be insufficiently. If the amount exceeds 10.0 parts by weight, bleeding of the plasticizer tends to occur.
  • Examples of the inorganic filler include oxide fillers, carbonate fillers, silicate filler, and nitride fillers.
  • Examples of the oxide fillers include silica, titanium oxide, magnesium oxide, diatomaceous earth, alumina, iron oxide and tin oxide. Among those, silica, titanium oxide and iron oxide are preferable.
  • Examples of the carbonate fillers include calcium carbonate, magnesium carbonate and zinc carbonate. Among those, calcium carbonate is preferable.
  • Examples of the silicate fillers include aluminum silicates such as clay, kaolinite and pyrophyllite; magnesium silicates such as talc; calcium silicates such as wollastonite and xonotlite; bentonite, glass beads and glass fiber. Among those, aluminum silicates, magnesium silicates and bentonite are preferable. These are used singly or in combination of two or more, if necessary.
  • the amount of the filler is preferably 5 to 15 parts by weight to 100 parts by weight of the solid content of a rubber latex. If the amount is less than 5 parts by weight, blisters tend to be formed during a cure step in the glove production. If the amount exceeds 15 parts by weight, the stability of a rubber latex may be impaired occasionally.
  • additives other than those mentioned above for example, pigments, colorants, wetting agents, and defoaming agents, may be appropriately added, if necessary, to a chloroprene-based rubber latex or a mixture of a chloroprene-based rubber latex and an NBR-based rubber latex.
  • the thickness of both a first layer and an intermediate layer was 0.2 mm and the thickness of a second layer was 0.15 mm.
  • Nipol registered trademark
  • SBR styrene-butadiene rubber ZEON CORPORATION
  • NOCCELER registered vulcanization accelerator OUCHI SHINKO CHEMICAL trademark
  • a cotton-polyester (50:50) mixed-spun seamless glove knitted with a 18-gauge knitter was set on a ceramic hand mold, followed by dipping into a coagulant bath.
  • a coagulant liquid composed of methanol and calcium nitrate (100:2.0) was used.
  • the glove was dwelled for about 3 seconds in a bath containing a rubber compound liquid of the first layer given in Table 2 and then was picked up from the bath, immediately followed by dipping into a 15% aqueous calcium nitrate solution.
  • the hand mold with the rubber-coated was dried for 3 minutes in a dryer of 75° C., so that a chloroprene-based rubber layer as the first layer was formed.
  • the aforementioned hand mold was dipped for 3 seconds in a bath containing a mixed rubber compound liquid of the second layer given in Table 3 and then was picked up from the bath, followed by cure.
  • the cure was performed by heating at 75° C. for 60 minutes and then heating at 140° C. for 30 minutes.
  • a mixed rubber layer as the second layer was formed.
  • the coated glove was removed from the hand mold, washed with water and dried, so that a chemical resistant glove in which the chloroprene-based rubber layer as the first layer and the mixed rubber layer as the second layer formed on a fabric glove was obtained.
  • a chemical resistant glove in which a chloroprene-based rubber layer as the first layer and a mixed rubber layer as the second layer had been formed on a fabric glove was obtained in the same way as in Example 1 except for changing the mixed rubber compound liquid of the second layer to the mixed rubber compound liquid shown in Table 4.
  • a chemical resistant glove in which a chloroprene-based rubber layer as the first layer and a mixed rubber layer as the second layer had been formed on a fabric glove was obtained in the same way as in Example 1 except for changing the mixed rubber compound liquid of the second layer to the mixed rubber compound liquid shown in Table 5.
  • a chemical resistant glove in which a chloroprene-based rubber layer as the first layer and a mixed rubber layer as the second layer had been formed on a fabric glove was obtained in the same way as in Example 1 except for changing the mixed rubber compound liquid of the second layer to the mixed rubber compound liquid shown in Table 6.
  • a chemical resistant glove in which a chloroprene-based rubber layer as the first layer and a mixed rubber layer as the second layer had been formed on a fabric glove was obtained in the same way as in Example 1 except for changing the mixed rubber compound liquid of the second layer to the mixed rubber compound liquid shown in Table 7.
  • a chemical resistant glove in which a chloroprene-based rubber layer as the first layer and a mixed rubber layer as the second layer had been formed on a fabric glove was obtained in the same way as in Example 1 except for changing the mixed rubber compound liquid of the second layer to the mixed rubber compound liquid shown in Table 8.
  • a chemical resistant glove in which a chloroprene-based rubber layer as the first layer had been formed on a fabric glove was obtained in the same way as in Example 1 except for not being dipped in a bath containing a mixed rubber compound liquid of the second layer, the cure, and heating after forming a chloroprene-based rubber layer as the first layer.
  • a chemical resistant glove in which a chloroprene-based rubber layer as the first layer and a chloroprene-based rubber layer as the second layer had been formed on a fabric glove was obtained in the same way as in Example 1 except for changing the mixed rubber compound liquid of the second layer to the chloroprene-based rubber compound liquid shown in Table 9.
  • a chemical resistant glove in which a chloroprene-based rubber layer as the first layer and a mixed rubber layer as the second layer had been formed on a fabric glove was obtained in the same way as in Example 1 except for changing the mixed rubber compound liquid of the second layer to the mixed rubber compound liquid shown in Table 10.
  • a chemical resistant glove in which a chloroprene-based rubber layer as the first layer and a mixed rubber layer as the second layer had been formed on a fabric glove was obtained in the same way as in Example 1 except for changing the mixed rubber compound liquid of the second layer to the mixed rubber compound liquid shown in Table 11.
  • a chemical resistant glove in which a chloroprene-based rubber layer as the first layer and a mixed rubber layer as the second layer had been formed on a fabric glove was obtained in the same way as in Example 3 except for replacing the NBR latex “PERBUNAN (registered trademark) N LATEX X 1150” in the mixed rubber compound liquid of the second layer given in Table 5 with an SBR latex “Nipol (registered trademark) Lx470A
  • a chloroprene-based rubber layer as the first layer was formed in the same way as in Example 1 by mounting a fabric glove on a ceramic hand mold, performing a coagulant treatment, dipping the hand mold with the glove into a bath containing a rubber compound liquid of the first layer given in Table 2, picking up the hand mold with the glove, and performing a drying treatment. Subsequently, a chloroprene-based rubber layer as the intermediate layer was formed by dipping the hand mold with the glove into a bath containing a rubber compound liquid of the intermediate layer given in Table 12, followed by picking-up and a drying treatment in the same way as those for the first layer.
  • a chemical resistant glove in which a chloroprene-based rubber layer as the first layer, a chloroprene-based rubber layer as the intermediate layer and a mixed rubber layer as the second layer had been formed on a fabric glove was obtained in the same way as in Example 7 except for changing the mixed rubber compound liquid of the second layer to the mixed rubber compound liquid of the second layer shown in Table 4.
  • a chemical resistant glove in which a chloroprene-based rubber layer as the first layer, a chloroprene-based rubber layer as the intermediate layer and a mixed rubber layer as the second layer had been formed on a fabric glove was obtained in the same way r as in Example 7 except for changing the mixed rubber compound liquid of the second layer to the mixed rubber compound liquid of the second layer shown in Table 5.
  • a chemical resistant glove in which a chloroprene-based rubber layer as the first layer, a chloroprene-based rubber layer as the intermediate layer and a mixed rubber layer as the second layer had been formed on a fabric glove was obtained in the same way as in Example 7 except for changing the mixed rubber compound liquid of the second layer to the mixed rubber compound liquid of the second layer shown in Table 6.
  • a chemical resistant glove in which a chloroprene-based rubber layer as the first layer, a chloroprene-based rubber layer as the intermediate layer and a mixed rubber layer as the second layer had been formed on a fabric glove was obtained in the same way as in Example 7 except for changing the mixed rubber compound liquid of the second layer to the mixed rubber compound liquid of the second layer shown in Table 7.
  • a chloroprene-based rubber layer as the first layer was formed in the same way as in Example 1 by setting a fabric glove on a ceramic hand mold, performing a coagulant treatment, dipping the hand mold with the glove into a bath containing a rubber compound liquid of the first layer given in Table 2, picking up the hand mold with the glove, and performing a drying treatment. Subsequently, the hand mold with the glove was dipped into a bath containing a rubber compound liquid of the intermediate layer given in Table 12, followed by picking-up and drying treatment. Thus, a chemical resistant glove in which chloroprene-based rubber layers as the first layer and the intermediate layer had been formed on a fabric glove was obtained.
  • a chemical resistant glove in which a chloroprene-based rubber layer as the first layer, a chloroprene-based rubber layer as the intermediate layer and a chloroprene-based rubber layer as the second layer had been formed on a fabric glove was obtained in the same way as in Example 7 except for changing the mixed rubber compound liquid of the second layer to the rubber compound liquid shown in Table 9.
  • a chemical resistant glove in which a chloroprene-based rubber layer as the first layer, a chloroprene-based rubber layer as the intermediate layer and a mixed rubber layer as the second layer had been formed on a fabric glove was obtained in the same way as in Example 7 except for changing the mixed rubber compound liquid of the second layer to the mixed rubber compound liquid shown in Table 10.
  • a chemical resistant glove in which a chloroprene-based rubber layer as the first layer, a chloroprene-based rubber layer as the intermediate layer and a mixed rubber layer as the second layer had been formed on a fabric glove was obtained in the same way as in Example 7 except for changing the mixed rubber compound liquid of the second layer to the mixed rubber compound liquid shown in Table 11.
  • a chemical resistant glove in which a chloroprene-based rubber layer as the first layer, a chloroprene-based rubber layer as the intermediate layer and a mixed rubber layer as the second layer had been formed on a fabric glove was obtained in the same way as in Example 9 except for replacing the NBR latex “PERBUNAN (registered trademark) N LATEX X 1150” in the mixed rubber compound liquid of the second layer given in Table 5 with an SBR latex “Nipol (registered trademark) Lx470A.”
  • a cotton-polyester (50:50) mixed-spun seamless glove knitted with a 18-gauge knitter was set on a ceramic hand mold, followed by dipping into a coagulant bath.
  • a coagulant liquid composed of methanol and calcium nitrate (100:2.0) was used.
  • the glove was dipped for about 3 seconds in a bath of a rubber compound liquid of the first layer given in Table 2 and then was picked up from the bath, immediately followed by dipping into a 15% aqueous calcium nitrate solution.
  • the hand mold with the rubber-coated glove set thereon was dried for 3 minutes in a dryer of 75° C., so that a chloroprene-based rubber layer as the first layer was formed.
  • the hand mold with the aforementioned first layer-coated glove mounted thereon was dipped for 3 seconds in a bath of a mixed rubber compound liquid containing NBR particles of the second layer given in Table 13 and then was picked up from the bath, followed by cure.
  • the cure was performed by heating at 75° C. for 60 minutes and then heating at 140° C. for 30 minutes.
  • a mixed rubber layer as the second layer was formed.
  • the coated glove was removed from the hand mold, washed with water and dried, so that a chemical resistant glove in which the chloroprene-based rubber layer as the first layer and the mixed rubber layer containing NBR particles as the second layer formed on a fabric glove was obtained.
  • a chemical resistant glove in which a chloroprene-based rubber layer as the first layer and a mixed rubber layer containing NBR particles as the second layer had been formed on a fabric glove was obtained in the same way as in Example 12 except for changing the mixed rubber compound liquid of the second layer to the mixed rubber compound liquid shown in Table 14.
  • a chemical resistant glove in which a chloroprene-based rubber layer as the first layer and a mixed rubber layer containing NBR particles as the second layer had been formed on a fabric glove was obtained in the same way as in Example 12 except for changing the mixed rubber compound liquid of the second layer to the mixed rubber compound liquid shown in Table 15.
  • a chemical resistant glove in which a chloroprene-based rubber layer as the first layer and a mixed rubber layer containing NBR particles as the second layer had been formed on a fabric glove was obtained in the same way as in Example 12 except for changing the mixed rubber compound liquid of the second layer to the mixed rubber compound liquid shown in Table 16.
  • a chemical resistant glove in which a chloroprene-based rubber layer as the first layer and a mixed rubber layer containing NBR particles as the second layer had been formed on a fabric glove was obtained in the same way as in Example 12 except for changing the mixed rubber compound liquid of the second layer to the mixed rubber compound liquid shown in Table 17.
  • a chemical resistant glove in which a chloroprene-based rubber layer as the first layer and a mixed rubber layer containing NBR particles as the second layer had been formed on a fabric glove was obtained in the same way as in Example 12 except for changing the mixed rubber compound liquid of the second layer to the mixed rubber compound liquid shown in Table 18.
  • a chemical resistant glove in which a chloroprene-based rubber layer as the first layer and a mixed rubber layer containing NBR particles as the second layer had been formed on a fabric glove was obtained in the same way as in Example 12 except for changing the mixed rubber compound liquid of the second layer to the mixed rubber compound liquid shown in Table 19.
  • a chemical resistant glove in which a chloroprene-based rubber layer as the first layer and a mixed rubber layer containing NBR particles as the second layer had been formed on a fabric glove was obtained in the same way as in Example 12 except for changing the mixed rubber compound liquid of the second layer to the mixed rubber compound liquid shown in Table 20.
  • a chemical resistant glove in which a chloroprene-based rubber layer as the first layer and a chloroprene-based rubber layer containing NBR particles as the second layer had been formed on a fabric glove was obtained in the same way as in Example 12 except for changing the mixed rubber compound liquid of the second layer to the chloroprene-based rubber compound liquid shown in Table 21.
  • a chemical resistant glove in which a chloroprene-based rubber layer as the first layer and a mixed rubber layer containing NBR particles as the second layer had been formed on a fabric glove was obtained in the same way as in Example 12 except for changing the mixed rubber compound liquid of the second layer to the mixed rubber compound liquid shown in Table 22.
  • a chemical resistant glove in which a chloroprene-based rubber layer as the first layer and a mixed rubber layer containing NBR particles as the second layer had been formed on a fabric glove was obtained in the same way as in Example 12 except for changing the mixed rubber compound liquid of the second layer to the mixed rubber compound liquid shown in Table 23.
  • a chemical resistant glove in which a chloroprene-based rubber layer as the first layer and a mixed rubber layer containing NBR particles as the second layer had been formed on a fabric glove was obtained in the same way as in Example 12 except for replacing the NBR latex “PERBUNAN N LATEX X 1150” in the mixed rubber compound liquid of the second layer given in Table 15 with an SBR latex “Nipol Lx470A.”
  • a chemical resistant glove in which a chloroprene-based rubber layer as the first layer and a mixed rubber layer containing CR particles as the second layer had been formed on a fabric glove was obtained in the same way as in Example 14 except for replacing the NBR particles “BAYMOD NXL32.12” in the mixed rubber compound liquid of the second layer given in Table 15 with CR particles.
  • the CR particles were obtained by kneading the raw materials given in Table 24, press-vulcanizing the resulting sheet at 150° C. for 30 minutes, followed by pulverization with a freeze pulverizer.
  • the particle diameter of the CR particles was adjusted with a sieve to be not larger than 700 and not smaller than 50 ⁇ m.
  • Chloroprene rubber SKYPRENE 640 100 Metal oxide zinc oxide 5 Vulcanization accelerator SANCELER 22-C 1 Vulcanization supplement accelerator magnesium oxide 4 Vlcanization accelerating auxiliary stearic acid 1 Filler clay 30 Mineral oil type softener naphthene 10 type process oil
  • a chemical resistant glove in which a chloroprene-based rubber layer as the first layer and a mixed rubber layer containing SBR particles as the second layer had been formed on a fabric glove was obtained in the same way as in Example 14 except for replacing the NBR particles “BAYMOD NXL32.12” in the mixed rubber compound liquid of the second layer given in Table 15 with SBR particles.
  • the SBR particles were obtained by kneading the raw materials given in Table 25, press-vulcanizing the resulting sheet at 150° C. for 30 minutes, followed by pulverization with a freeze pulverizer.
  • the particle diameter of the SBR particles was adjusted with a sieve to be not larger than 700 ⁇ m and not smaller than 50 ⁇ m.
  • a chloroprene-based rubber layer as the first layer was formed in the same way as in Example 12 by mounting a fabric glove on a ceramic hand mold, performing a coagulant treatment, dipping the hand mold with the glove into a bath of a rubber compound liquid of the first layer given in Table 2, picking up the hand mold with the glove, and performing a drying treatment. Subsequently, a chloroprene-based rubber layer as the intermediate layer was formed by dipping the hand mold with the glove into a bath of a rubber compound liquid of the intermediate layer given in Table 12, followed by picking-up and a drying treatment in the same way as those for the first layer.
  • a chemical resistant glove in which a chloroprene-based rubber layer as the first layer, a chloroprene-based rubber layer as the intermediate layer and a mixed rubber layer containing NBR particles as the second layer had been formed on a fabric glove was obtained in the same way as in Example 20 except for changing the mixed rubber compound liquid of the second layer to the mixed rubber compound liquid of the second layer shown in Table 14.
  • a chemical resistant glove in which a chloroprene-based rubber layer as the first layer, a chloroprene-based rubber layer as the intermediate layer and a mixed rubber layer containing NBR particles as the second layer had been formed on a fabric glove was obtained in the same way as in Example 20 except for changing the mixed rubber compound liquid of the second layer to the mixed rubber compound liquid of the second layer shown in Table 15.
  • a chemical resistant glove in which a chloroprene-based rubber layer as the first layer, a chloroprene-based rubber layer as the intermediate layer and a mixed rubber layer containing NBR particles as the second layer had been formed on a fabric glove was obtained in the same way as in Example 20 except for changing the mixed rubber compound liquid of the second layer to the mixed rubber compound liquid of the second layer shown in Table 16.
  • a chemical resistant glove in which a chloroprene-based rubber layer as the first layer, a chloroprene-based rubber layer as the intermediate layer and a mixed rubber layer containing NBR particles as the second layer had been formed on a fabric glove was obtained in the same way as in Example 20 except for changing the mixed rubber compound liquid of the second layer to the mixed rubber compound liquid of the second layer shown in Table 17.
  • a chemical resistant glove in which a chloroprene-based rubber layer as the first layer, a chloroprene-based rubber layer as the intermediate layer and a mixed rubber layer containing NBR particles as the second layer had been formed on a fabric glove was obtained in the same way as in Example 20 except for changing the mixed rubber compound liquid of the second layer to the mixed rubber compound liquid of the second layer shown in Table 18.
  • a chemical resistant glove in which a chloroprene-based rubber layer as the first layer, a chloroprene-based rubber layer as the intermediate layer and a mixed rubber layer containing NBR particles as the second layer had been formed on a fabric glove was obtained in the same way as in Example 20 except for changing the mixed rubber compound liquid of the second layer to the mixed rubber compound liquid of the second layer shown in Table 19.
  • a chemical resistant glove in which a chloroprene-based rubber layer as the first layer, a chloroprene-based rubber layer as the intermediate layer and a mixed rubber layer containing NBR particles as the second layer had been formed on a fabric glove was obtained in the same way as in Example 20 except for changing the mixed rubber compound liquid of the second layer to the mixed rubber compound liquid of the second layer shown in Table 20.
  • a chloroprene-based rubber layer as the first layer was formed in the same way as in Example 20 by mounting a fabric glove on a ceramic hand mold, performing a coagulant treatment, dipping the hand mold with the glove into a bath of a rubber compound liquid of the first layer given in Table 2, picking up the hand mold with the glove, and performing a drying treatment. Subsequently, the hand mold with the glove was dipped into a bath of a rubber compound liquid of the intermediate layer given in Table 12, followed by picking-up and drying treatment. Furthermore, the hand mold with the glove was dipped in a bath of a rubber compound liquid containing NBR particles of the second layer given in Table 21 and then was picked up, followed by operations the same as those performed in Example 20.
  • a chemical resistant glove in which a chloroprene-based rubber layer as the first layer, a chloroprene-based rubber layer as the intermediate layer and a mixed rubber layer containing NBR particles as the second layer had been formed on a fabric glove was obtained in the same way as in Example 22 except for changing the mixed rubber compound liquid of the second layer to the mixed rubber compound liquid shown in Table 22.
  • a chemical resistant glove in which a chloroprene-based rubber layer as the first layer, a chloroprene-based rubber layer as the intermediate layer and a mixed rubber layer containing NBR particles as the second layer had been formed on a fabric glove was obtained in the same way as in Example 22 except for changing the mixed rubber compound liquid of the second layer to the mixed rubber compound liquid shown in Table 23.
  • a chemical resistant glove in which a chloroprene-based rubber layer as the first layer, a chloroprene-based rubber layer as the intermediate layer and a mixed rubber layer containing NBR particles as the second layer had been formed on a fabric glove was obtained in the same way as in Example 22 except for replacing the NBR latex “PERBUNAN N LATEX X 1150” in the mixed rubber compound liquid of the second layer given in Table 15 with an SBR latex “Nipol Lx470A.”
  • a chemical resistant glove in which a chloroprene-based rubber layer as the first layer, a chloroprene-based rubber layer as the intermediate layer and a mixed rubber layer containing CR particles as the second layer had been formed on a fabric glove was obtained in the same way as in Example 22 except for replacing the NBR particles “BAYMOD NXL32.12” in the mixed rubber compound liquid of the second layer given in Table 15 with CR particles.
  • the CR particles were obtained by kneading the raw materials given in Table 24, press-vulcanizing the resulting sheet at 150° C. for 30 minutes, followed by pulverization with a freeze pulverizer.
  • the particle diameter of the CR particles was adjusted with a screen to be not larger than 700 ⁇ m and not smaller than 50 ⁇ m.
  • a chemical resistant glove in which a chloroprene-based rubber layer as the first layer, a chloroprene-based rubber layer as the intermediate layer and a mixed rubber layer containing SBR particles as the second layer had been formed on a fabric glove was obtained in the same way as in Example 22 except for replacing the NBR particles “BAYMOD NXL32.12” in the mixed rubber compound liquid of the second layer given in Table 15 with SBR particles.
  • the SBR particles were obtained by kneading the raw materials given in Table 25, press-vulcanizing the resulting sheet at 150° C. for 30 minutes, followed by pulverization with a freeze pulverizer.
  • the particle diameter of the SBR particles was adjusted with a screen to be not larger than 700 ⁇ m and not smaller than 50 ⁇ m.
  • CR represents a chloroprene-based rubber
  • NBR represents a nitrile-butadiene-based rubber
  • SBR represents a styrene-butadiene-based rubber
  • the gloves of Examples 1 to 27 and the gloves of Comparative Examples 1 to 22 were subjected to an abrasion resistance test according to EN388 and the abrasion strength was evaluated according to the following criteria. Generally, a glove with a time of withstanding abrasions of less than 500 is judged to be unsuitable for a protective glove such as a chemical resistant glove.
  • A A sufficient slip-resisting effect is observed under both dry conditions and wet conditions.
  • the gloves of Examples 12 to 27 and the gloves of Comparative Examples 11 to 22 were subjected to a abrasion resistance test according to EN388 and were evaluated according to the following criteria.
  • CR CR CR NBR 40 10.6 14.8 7.4 14.9 480 A C A A 0.55
  • Example 17 Comp. CR CR NBR 25 NBR 15 7.9 9.5 6.1 8.0 480 A A C A 0.55
  • Example 18 CR 75 Comp. CR CR NBR 25 NBR 65 11.0 12.0 7.6 12.6 480 C A A A 0.55
  • Example 19 CR 75 Comp. CR CR SBR 25 NBR 40 9.8 10.8 4.7 9.8 480 C C A A 0.55
  • Example 20 CR 75 Comp. CR CR NBR 25 CR 40 10.4 11.1 6.8 8.8 480 A A A C 0.55
  • Example 21 CR 75 Comp. CR CR NBR 25 SBR 40 9.6 13.1 6.4 11.7 480 A A A A C 0.55
  • Example 22 CR 75
  • a glove excellent in chemical resistance and safety and good in tactile feeling and abrasion resistance the glove being suitable as a protective glove, can be provided by forming a chloroprene-based rubber layer as a first layer and a mixed rubber layer of an NBR-based rubber and a chloroprene-based rubber as a second layer sequentially on a fabric glove.
  • a glove that has more improved chemical resistance can be provided by further forming a chloroprene-based rubber layer as an intermediate layer between the first layer and the second layer.
  • a glove excellent in chemical resistance and safety and good in tactile feeling and abrasion resistance as well as in slip resistance can be provided by causing the mixed rubber layer to contain NBR-based rubber particles.

Abstract

A chemical resistant glove is provided which comprises a chloroprene-based rubber as a first layer and a mixed rubber layer containing a nitrile-butadiene-based rubber and a chloroprene-based rubber as a second layer sequentially formed on a fabric glove, wherein a mixing ratio of the nitrile-butadiene-based rubber and the chloroprene-based rubber in the mixed rubber layer as the second layer is 60:40 to 10:90 in a solid weight ratio. The chemical resistant glove of the present invention is excellent in chemical resistance, tactile feeling and the abrasion resistance.

Description

    BACKGROUND OF THE INVENTION
  • 1. Field of the Invention
  • The present invention relates to a chemical resistant glove coated with a rubber, and particularly to a chemical resistant glove that is obtained by coating a fabric glove with a chloroprene-based rubber, which has not only greatly improved chemical resistance, safety and reliability, but also tactile feeling and abrasion resistance.
  • 2. Description of the Prior Art
  • Liquid proof gloves in which the surface of a fabric glove has been coated with a rubber or a resin are widely used as working gloves. Examples of the rubber or the resin to be applied include a natural rubber (NR), a styrene-butadiene rubber (SBR), a nitrile-butadiene rubber (NBR), a chloroprene rubber (CR), a polyurethane (PU), and a vinyl chloride resin (PVC). Among these, a chloroprene rubber is known to be excellent in weather resistance, thermal resistance, oil resistance, and chemical resistance, especially in acid resistance and alkali resistance. Therefore, gloves in which the surface of gloves made of a fiber is covered with a chloroprene rubber have been widely used as chemical resistant gloves.
  • As a chloroprene rubber for gloves, for example, in Japanese Laid-open Patent Publication 2007-106994, a chloroprene-based polymer latex for gloves that is well balanced with regard to flexibility lasting, tensile strength and tensile elongation has been proposed.
  • SUMMARY OF THE INVENTION
  • However, even if a chloroprene-based polymer such as mentioned above is applied, when a coat layer is formed of only a single layer of a chloroprene rubber, overlooked defects of the coating may result in an accident caused by a hazardous liquid during use. On the other hand, if a multilayer structure is formed in order to solve these problems, a resulting glove becomes hard and stiff in tactile feeling, resulting in a problem that the glove is difficult to use.
  • In addition, rubber-coated gloves are problematic in that when a person grips an object with a gloved hand, the object is prone to slip. This problem is more serious particularly when the surface of the glove is wet with a chemical liquid.
  • In the light of the aforementioned situations, it is hence an object of the present invention to solve the above-mentioned problems in the prior art and to provide gloves for works handling chemicals such as acidic chemicals and alkaline chemicals which are not only improved in safety and reliability against chemicals, without impairing tactile feeling and workability, but also are excellent in abrasion resistance.
  • A first aspect of the present invention relates to a chemical resistant glove which comprises a chloroprene-based rubber layer as a first layer and a mixed rubber layer containing a nitrile-butadiene-based rubber and a chloroprene-based rubber as a second layer sequentially formed on a fabric glove, wherein a mixing ratio of the nitrile-butadiene-based rubber and the chloroprene-based rubber in the mixed rubber layer as the second layer is 60:40 to 10:90 in a solid weight ratio.
  • A second aspect of the present invention relates to a chemical resistant glove, wherein the mixing ratio of the nitrile-butadiene-based rubber and the chloroprene-based rubber in the mixed rubber layer as the second layer is 40:60 to 20:80 in a solid weight ratio.
  • A third aspect of the present invention relates to a chemical resistant glove, wherein a chloroprene-based rubber layer as an intermediate layer is further formed between the chloroprene-based rubber layer as the first layer and the mixed rubber layer containing the nitrile-butadiene-based rubber and the chloroprene-based rubber as the second layer.
  • A fourth aspect of the present invention relates to a chemical resistant glove, wherein nitrile-butadiene-based rubber particles are contained in the mixed rubber layer as the second layer in an amount of 20 to 60 parts by weight, on a solid content basis, based on 100 parts by weight of a latex of the mixed rubber layer as the second layer.
  • A fifth aspect of the present invention relates to a chemical resistant glove, wherein a content of the nitrile-butadiene-based rubber particles is 30 to 50 parts by weight, on a solid basis, based on 100 parts by weight of the mixed rubber layer as the second layer.
  • A sixth aspect of the present invention relates to a chemical resistant glove, wherein a thickness of the first layer is in a range of from 0.18 to 0.23 mm.
  • A seventh aspect of the present invention relates to a chemical resistant glove, wherein a thickness of the second layer is in a range of from 0.14 to 0.18 mm.
  • A eighth aspect of the present invention relates to a chemical resistant glove, wherein a thickness of the intermediate layer is in a range of from 0.18 to 0.23 mm.
  • According to the present invention, a glove that is excellent in chemical resistance, good in protection and reliability, and good in tactile feeling and abrasion resistance is provided by forming a chloroprene-based rubber layer as the first layer and a mixed rubber layer containing a nitril butadiene-based rubber and a chloroprene-based rubber as the second layer sequentially on a fabric glove.
  • Moreover, a glove that has more improved chemical resistance is provided by further forming a chloroprene-based rubber layer as an intermediate layer between the first layer and the second layer.
  • Furthermore, a glove that is excellent in slip resistance addition to the above mentioned effects is provided by causing the mixed rubber layer to contain nitrile-butadiene-based rubber particles.
  • DETAILED DESCRIPTION OF THE INVENTION
  • In a first embodiment, the chemical resistant glove of the present invention is characterized in that a chloroprene-based rubber layer as a first layer and a mixed rubber layer containing a nitrile-butadiene-based rubber and a chloroprene-based rubber as a second layer sequentially formed on a fabric glove, wherein a mixing ratio of the nitrile-butadiene-based rubber and the chloroprene-based rubber in the mixed rubber layer as the second layer is 60:40 to 10:90 in a solid weight ratio.
  • In a second embodiment, the chemical resistant glove of the present invention is characterized in that a chloroprene-based rubber layer is further formed between the chloroprene-based rubber layer as the first layer and the mixed rubber layer of the nitrile-butadiene-based rubber and the chloroprene-based rubber as the second layer in the foregoing chemical resistant glove.
  • In a third embodiment, the chemical resistant glove of the present invention is characterized in that nitrile-butadiene-based rubber particles are contained in the mixed rubber layer as the second layer.
  • Various types of fibers can be used as the fabric glove for use in the present invention. For example, gloves produced by knitting cotton, polyester, polyurethane, high-strength drawn polyethylene, e.g., DYNEEMA (registered trademark), aramide, e.g., KEVLAR (registered trademark) or their mixed spun yarns, or by sewing woven fabrics or nonwoven fabrics can be used.
  • In the present invention, aqueous dispersion latex of chloroprene polymers and chloroprene-based copolymers of chloroprene and other copolymerizable components are common as the chloroprene-based rubber layer, which is the first layer. But, solvent-based solutions and solvent-based dispersion liquids can also be used. Exemplary commercially-available products include SHOPRENE (registered trademark) 671A (produced by Showa Denko K.K.), SHOPRENE (registered trademark) 571 (produced by Showa Denko K.K.), SHOPRENE (registered trademark) 750 (produced by Showa Denko K.K.), SKYPRENE (registered trademark) latex LA-502 (produced by TOSOH CORPORATION), DENKA CHLOROPRENE (registered trademark) LM-61 (produced by DENKI KAGAKU KOGYO KABUSHIKI KAISHA), DENKA CHLOROPRENE (registered trademark) LM-50 (produced by DENKI KAGAKU KOGYO KABUSHIKI KAISHA), DENKA CHLOROPRENE (registered trademark) LV-60N (produced by DENKI KAGAKU KOGYO KABUSHIKI KAISHA), and Lipren-T (produced by PolymerLatex). These are used singly or in combination of two or more, if necessary.
  • The thickness of the first layer after curing is preferably in a range of from about 0.18 mm to about 0.23 mm. An attempt to form a chloroprene-based rubber layer having a thickness of less than 0.18 mm tends to cause penetration of a raw material to the inside of a fabric glove and, as a result, a resulting glove gives very bad tactile feeling when being worn. On the other hand, an attempt to form a chloroprene-based rubber layer having a thickness of more than 0.23 mm tends to impair uniform adhesion of a raw material to gloves made of a fiber and, as a result, uniform chemical resistance and so on cannot be obtained with a resulting glove.
  • In the present invention, examples of the nitrile-butadiene-based rubber (hereinafter, a nitrile-butadiene-based rubber is sometimes referred to as an NBR) to be used together with the chloroprene-based rubber as the mixed rubber layer, which is the second layer, include Nipol (registered trademark) Lx-550 (produced by ZEON CORPORATION), Nipol (registered trademark) Lx-551 (produced by ZEON CORPORATION), Nipol (registered trademark) Lx-556 (produced by ZEON CORPORATION), PERBUNAN (registered trademark) N LATEX VT-LA (produced by PolymerLatex), PERBUNAN (registered trademark) N LATEX X 1130 (produced by PolymerLatex), PERBUNAN (registered trademark) N LATEX X 1138 (produced by PolymerLatex), PERBUNAN (registered trademark) N LATEX X 1150 (produced by PolymerLatex), PERBUNAN (registered trademark) N LATEX X 1172 (produced by PolymerLatex), PERBUNAN (registered trademark) N LATEX 2890 (produced by PolymerLatex), PERBUNAN (registered trademark) N LATEX 3415 M (produced by PolymerLatex), PERBUNAN (registered trademark) N LATEX X 1200 (produced by PolymerLatex), Synthomer (registered trademark) EL2675 (produced by Synthomer), Synthomer (registered trademark) 6311 (produced by Synthomer), Synthomer (registered trademark) 6501 (produced by Synthomer), Synthomer (registered trademark) 6617 (produced by Synthomer), and Synthomer (registered trademark) 6710 (produced by Synthomer). These are used singly or in combination of two or more, if necessary.
  • The thickness of the second layer after curing is preferably in a range of from about 0.14 mm to about 0.18 mm. An attempt to form a mixed rubber layer having a thickness of less than 0.14 mm tends to be difficult to form a film and thus it tends to be difficult to form the second layer. On the other hand, an attempt to form a mixed rubber layer having a thickness of more than 0.18 mm tends to cause a resulting glove to become stiffer.
  • In the mixed rubber layer as the second layer, the mixing ratio of the NBR-based rubber and the chloroprene-based rubber, in a solid weight ratio, is 60:40 to 10:90, and preferably 40:60 to 20:80. If the proportion of the NBR-based rubber is more than the foregoing ratio, a glove having a stiff tactile feeling is produced. If the proportion of the NBR-based rubber is less than the foregoing ratio, problems that a latex coagulates at the time of mixing and that the abrasion resistance decreases are caused and, as a result, it may become difficult to produce a glove.
  • As to the mixing of a latex of the NBR-based rubber and a latex of the chloroprene-based rubber, it is desirable to use an aqueous dispersion latex or solution in the same solvent system or dispersions in the same solvent system.
  • In the present invention, as to the chloroprene-based rubber latex to be used for the chloroprene-based rubber layer of the first layer or the intermediate layer and the chloroprene-based rubber latex to be used by being mixed with the NBR-based latex in the mixed rubber layer of the second layer, the same latex or different latices selected from the above-mentioned chloroprene-based polymer latex and latex of chloroprene-based copolymers may be used.
  • The thickness of the intermediate layer after curing is preferably in a range of from about 0.18 mm to about 0.23 mm. If the thickness is less than 0.18 mm, there is a tendency that a film is difficult to be formed and thus it is difficult to form an intermediate layer. If the thickness exceeds 0.23 mm, uniform film forming tends to be impaired.
  • The viscosity of the chloroprene-based rubber latex as the first and the intermediate layers or the latex of the mixed rubber composed of an NBR-based rubber and a chloroprene-based rubber as the second layer is important for adjustment of the coating film thickness or workability of application, and it is preferably in V6 viscosity, 2800 to 3200 mPa·sec for the first layer, 1500 to 2000 mPa·sec for the second layer, and 1800 to 2200 mPa·sec for the intermediate layer.
  • The slip resistance of the chemical resistant glove in the present invention can be further improved by adding NBR-based rubber particles to the mixed rubber layer as the second layer. The NBR-based rubber particles are less prone to leave from a glove after the production of the glove and thus exhibit higher slip resistance in comparison to particles of other resins or rubbers.
  • The shape of the NBR-based rubber particles is not particularly limited, and examples thereof include a spherical shape, a polyhedral shape, a hemispherical shape, and a bowl-like shape. Moreover, a product prepared by pulverizing a sheet-shaped NBR-based rubber can also be used suitably. The sheet-shaped NBR-based rubber is produced by, for example, incorporating commonly-used rubber additives such as clay, titanium, plasticizers, vulcanizing agents, vulcanization accelerators, antiaging agents, and sulfur in NBR-based rubbers. Although the pulverizing method is not particularly limited, freeze pulverization is preferred because pulverization heat is often generated, which may cause change in quality or degradation of the rubber. Examples of commercial names of NBR-based particles include BAYMOD (registered trademark) N34.52 (produced by Bayer), BAYMOD (registered trademark) N34.82 (produced by Bayer), BAYMOD (registered trademark) NXL34.23VP (produced by Bayer), and BAYMOD (registered trademark) NXL34.12 (produced by Bayer). These are used singly or in combination of two or more, if necessary.
  • The size of the NBR-based particles is preferably 1000 μm or less, more preferably 50 to 850 μm, and even more preferably 100 to 710 μl. If it is greater than 1000 μm, the uniform adhesion of the particles tends to be impaired. If it is excessively small, a sufficient slip resisting effect tends not to be obtained.
  • The NBR-based rubber particles are contained in an amount of 20 to 60 parts by weight, in a solid content basis, based on 100 parts by weight of the latex of the mixed rubber layer as the second layer. If the amount of the NBR-based rubber particles is less than 20 parts by weight, a sufficient slip resisting effect can be obtained neither under dry conditions nor under wet conditions. On the other hand, if it exceeds 60 parts by weight, resulting gloves come to have harder tactile feeling or it is impossible to obtain gloves to which particles adhere uniformly.
  • As the method for forming the first layer, the second layer and the intermediate layer on a fabric glove, dipping in a latex liquid, spray coating, coating with a brush or the like can be used. At the time of coating, it is common and convenient to set a fabric glove on a hand mold. As the hand mold, metal molds, ceramic molds, wooden molds, plastic molds, and so on can be used.
  • In view of, for example, the easiness of processing, and the flexibility or the stability of strength of a rubber coating film after vulcanization, it is desirable to blend to the latex a metal oxide, a vulcanization accelerator, sulfur, a surfactant, an antiaging agent, a pH adjuster, a plasticizer, a filler, and so on.
  • Examples of the metal oxide include zinc oxide, lead oxide, and trilead tetraoxide. These are used singly or in combination of two or more, if necessary. The amount of the metal oxide is preferably 1 to 10 parts by weight to 100 parts by weight of the solid content of a rubber latex. If the amount is less than 1 part by weight, it is difficult to obtain tensile strength and basic characteristics of modulus due to insufficient crosslinking. If the amount is more than 10 parts by weight, the modulus becomes excessively high and a resulting glove becomes stiff.
  • As the vulcanization accelerator, thiuram-based, dithiocarbamate-based, thiourea-based and guanidine-based vulcanization accelerators are commonly used for chloroprene-based rubber latex. Among those, the thiuram-based vulcanization accelerators and the dithiocarbamate-based vulcanization accelerators are particularly preferred. Examples of the thiuram-based valcanization accelerator include tetraethylthiuram disulfide, and tetrabutylthiuram disulfide. Examples of the dithiocarbamate-based vulcanization accelerator include sodium dibutylthiodicarbamate, zinc dibutylthiodicarbamate, and zinc diethylthiodicarbamate. Examples of the thiourea-based vulcanization accelerator include ethylenethiourea, diethylthiourea, trimethylthiourea, and N,N′-diphenylthiourea. Among these, N,N′-diphenylthiourea is particularly preferable. Examples of the guanidine-based vulcanization accelerator include diphenylguanidine and diorthotoluidineguanidine. These are used singly or in combination of two or more, if necessary.
  • The amount of the vulcanization accelerator is preferably 0.5 to 5.0 parts by weight to 100 parts by weight of the solid content of a rubber latex. If the amount is less than 0.5 parts by weight, the vulcanization acceleration effect is insufficient. If the amount is more than 5.0 parts by weight, problems may arise. For example, even if a glove is produced, the resulting glove may feel hard or cause scorching by initial vulcanization.
  • When vulcanization proceeds poorly with only a vulcanization accelerator, sulfur is usually used together. The amount of sulfur is preferably 0.1 to 3.0 parts by weight to 100 parts by weight of the solid content of a rubber latex. If the amount is less than 0.1 parts by weight, it is difficult to obtain tensile strength and basic characteristics of modulus due to insufficient crosslinking. If the amount is more than 3.0 parts by weight, there is a tendency that the modulus becomes excessively high and a resulting glove tends to become stiff.
  • Examples of the surfactant include sodium alkylsulfate, sodium alkylbenzenesulfonate, sodium salt of naphthalenesulfonic acid-formaldehyde condensate, rosin acid soap, and fatty acid soap. These are used singly or in combination of two or more, if necessary.
  • The amount of the surfactant is preferably 0.1 to 10.0 parts by weight to 100 parts by weight of the solid content of a rubber latex. If the amount is less than 0.1 parts by weight, the latex tends to become unstable. If the amount exceeds 10.0 parts by weight, the latex tends to become excessively stable and it becomes difficult to form a film.
  • Examples of the antiaging agent include naphthylamine-based compounds, diphenylamine-based compounds, p-phenylenediamine-based compounds, quinoline-based compounds, hydroquinone derivative-based compounds, monophenol-based compounds, bisphenol-based compounds, polyphenol-based compounds, imidazole-based compounds, nickel dithiocarbamate-based compounds, phosphite ester-based compounds, organic thioacid-based compounds, and thiourea-based compounds.
  • Examples of the naphthylamine-based compounds include phenyl-1-naphthylamine and phenyl-β-naphthylamine. Examples of the diphenylamine-based compounds include 4,4-bis(α,α-dimethylbenzyl)diphenylamine, p-(p-toluenesulfonylamide)diphenylamine, alkylated diphenylamine and octylated diphenylamine. Examples of the p-phenylenediamine-based compounds include N,N′-diphenyl-p-phenylenediamine, N-phenyl-N′-isopropyl-p-phenylenediamine, N,N′-di-2-naphthyl-p-phenylenediamine, N-phenyl-M-(1,3-dimethylbutyl)-p-phenylenediamine and N-phenyl-M-(3-methacryloyloxy-2-hydroxypropyl)-p-phenylenediamine. Examples of the quinoline-based compounds include a 2,2,4-trimethyl-1,2-dihydroquinoline polymer and 6-ethoxy-1,2-dihydro-2,2,4-trimethylquinoline. Examples of the hydroquinone derivative-based compounds include hydroquinone, methoquinone and 2,5-diphenyl-p-benzoquinone. Examples of the monophenol-based compounds include 2,6-di-tert-butyl-4-methyl phenol, mono(α-methylbenzylphenol, di(α-methylbenzyl)phenol and tri(α-methylbenzyl)phenol. Examples of the bisphenol-based compounds include 2,2′-methylenebis(4-methyl-6-tert-butyl phenol), 4,4′-butylidenebis(3-methyl-6-tert-butyl phenol) and 4,4′-thiobis(3-methyl-6-tert-butylphenol). Examples of the polyphenol-based compounds include 2,5-di-tert-butylhydroquinone and 2,5-di-tert-amyl hydroquinone. Examples of the imidazole-based compounds include 2-mercaptobenzimidazole, 2-mercaptomethylbenzimidazole and zinc salts of 2-mercaptobenzimidazole. Examples of the nickel dithiocarbamate-based compounds include nickel diethyldithiocarbamate and nickel dibutyldithiocarbamate. Examples of the phosphite-based compounds include tris(nonylphenyl)phosphite. Examples of the organic thioacid-based compounds include dilauryl thiodipropionate. Examples of the thiourea-based compounds include 1,3-bis(dimethylaminopropyl)-2-thiourea and tributylthiourea. These are used singly or in combination of two or more, if necessary. Among these, monophenol-based compounds or bisphenol-based compounds are preferable.
  • The amount of the antiaging agent is preferably 0.5 to 5.0 parts by weight to 100 parts by weight of the solid content of a rubber latex. If the amount is less than 0.5 parts by weight, it is difficult to obtain a sufficient retarding effect of degradation. If the amount is more than 5.0 parts by weight, the retarding effect of degradation is not enhanced and the strength may decrease occasionally.
  • As a pH adjuster, an alkali or a weak acid such as amino acid or acetic acid may be used for the purpose of stabilizing a latex or adjusting the thickness of a coating film. Examples of the alkali include potassium hydroxide and ammonia and examples of the weak acid include glycine. These are used singly or in combination of two or more, if necessary. It is desirable that the pH adjuster be added in the form of an aqueous solution before use so that the stability of a latex is not impaired.
  • As to the amount of the pH adjuster in a compound using a chloroprene-based rubber latex, it is desirable to add the pH adjuster so that the pH becomes 10.0 to 11.5 when all additives including the pH adjuster are incorporated. Specifically, it is more desirable to add the pH adjuster so that the pH becomes 10.0 to 10.5. If the pH is lower than 10.0, the latex becomes unstable and becomes solidified. If the pH exceeds 11.5, the latex becomes excessively stable and the latex becomes difficult to coagulate and, as a result, it tends to become difficult to form a rubber film.
  • In a compound in which a chloroprene-based rubber latex and an NBR-based rubber latex are mixed, it is desirable to add a pH adjuster so that the pH becomes 9.0 to 10.5 when all additives including the pH adjuster are compounded. Specifically, it is more desirable to add a pH adjuster so that the pH becomes 10.0 to 10.5. If the pH is lower than 9.0, the latex becomes unstable and becomes solidified. If the pH exceeds 10.5, the latex comes to contain an excess alkali, so that the latex may solidify occasionally.
  • Examples of the plasticizer include phthalate esters such as dimethyl phthalate, diethyl phthalate, dibutyl phthalate, diisobutyl phthalate, dioctyl phthalate, butyloctyl phthalate, di(2-ethylhexyl)phthalate, diisooctyl phthalate, and diisodecyl phthalate; fatty acid esters such as dimethyl adipate, diisobutyl adipate, di(2-ethylhexyl)adipate, diisooctyl adipate, diisodecyl adipate, octyldecyl adipate, di(2-ethylhexyl)azelate, diisooctyl azelate, diisobutyl azelate, dibutyl sebacate, di(2-ethylhexyl)sebacate and diisooctyl sebacate; trimellitate esters such as isodecyl trimellitate, octyl trimellitate, n-octyl trimellitate, and isononyl trimellitate; di(2-ethylhexyl) fumarate, diethylene glycol monooleate, glyceryl monoricinolate, trilauryl phosphate, tristearyl phosphate, tri-(2-ethylhexyl) phosphate, tricresyl phosphate, epoxidized soybean oil, and polyether ester. These are used singly or in combination of two or more, if necessary.
  • The amount of the plasticizer is preferably 0.001 to 10.0 parts by weight to 100 parts by weight of the solid content of a rubber latex. If the amount is less than 0.001 parts by weight, plasticization tends to be insufficiently. If the amount exceeds 10.0 parts by weight, bleeding of the plasticizer tends to occur.
  • Examples of the inorganic filler include oxide fillers, carbonate fillers, silicate filler, and nitride fillers. Examples of the oxide fillers include silica, titanium oxide, magnesium oxide, diatomaceous earth, alumina, iron oxide and tin oxide. Among those, silica, titanium oxide and iron oxide are preferable. Examples of the carbonate fillers include calcium carbonate, magnesium carbonate and zinc carbonate. Among those, calcium carbonate is preferable. Examples of the silicate fillers include aluminum silicates such as clay, kaolinite and pyrophyllite; magnesium silicates such as talc; calcium silicates such as wollastonite and xonotlite; bentonite, glass beads and glass fiber. Among those, aluminum silicates, magnesium silicates and bentonite are preferable. These are used singly or in combination of two or more, if necessary.
  • The amount of the filler is preferably 5 to 15 parts by weight to 100 parts by weight of the solid content of a rubber latex. If the amount is less than 5 parts by weight, blisters tend to be formed during a cure step in the glove production. If the amount exceeds 15 parts by weight, the stability of a rubber latex may be impaired occasionally.
  • In the present invention, additives other than those mentioned above, for example, pigments, colorants, wetting agents, and defoaming agents, may be appropriately added, if necessary, to a chloroprene-based rubber latex or a mixture of a chloroprene-based rubber latex and an NBR-based rubber latex.
  • The present invention is described in more detail with reference to examples below, but the present invention is not limited to the examples.
  • In the following examples and comparative examples, the thickness of both a first layer and an intermediate layer was 0.2 mm and the thickness of a second layer was 0.15 mm.
  • The raw materials used in the following examples and comparative examples are shown in Table 1.
  • TABLE 1
    Trade names Raw materials Manufacturers
    SHOPRENE (registered chloroprene rubber latex Showa Denko K.K.
    trademark) 671A
    PERBUNAN (registered NBR latex Polymer Latex GmbH
    trademark) N LATEX X 1150
    Nipol (registered trademark) SBR latex ZEON CORPORATION
    Lx470A
    DARVAN WAQ surfactant R.T. Vanderbilt Company,
    Inc.
    DARVAN SMO surfactant R.T. Vanderbilt Company,
    Inc.
    NOCCELER (registered vulcanization accelerator OUCHI SHINKO CHEMICAL
    trademark) BZ INDUSTRIAL CO., LTD.
    Vulkanox BKF antiaging agent LANXESS K.K.
    Nopco (registered trademark) defoaming agent SAN NOPCO LIMITED
    DF-122-NS
    A-7075 thickener TOAGOSEI CO., LTD.
    CHROMOFINE BLUE HS-4 pigment Dainichiseika Color &
    Chemicals Mfg. Co., Ltd.
    BAYMOD (registered trademark) NBR particles* LANXESS K.K.
    NXL32.12
    SKYPRENE (registered chloroprene rubber (CR) TOSOH CORPORATION
    trademark) 640
    SANCELER (registered vulcanization accelerator SANSHIN CHEMICAL
    trademark) 22-C INDUSTRY CO., LTD.
    Nipol (registered trademark) 1502 styrene-butadiene rubber ZEON CORPORATION
    (SBR)
    NOCCELER (registered vulcanization accelerator OUCHI SHINKO CHEMICAL
    trademark) DM INDUSTRIAL CO., LTD.
    *The particles of 50 μm or smaller were removed with a sieve and then used. (The particle diameter was not larger than 700 μm and not smaller than 50 μm.)
  • Example 1
  • A cotton-polyester (50:50) mixed-spun seamless glove knitted with a 18-gauge knitter was set on a ceramic hand mold, followed by dipping into a coagulant bath. A coagulant liquid composed of methanol and calcium nitrate (100:2.0) was used. Subsequently, the glove was dwelled for about 3 seconds in a bath containing a rubber compound liquid of the first layer given in Table 2 and then was picked up from the bath, immediately followed by dipping into a 15% aqueous calcium nitrate solution. Furthermore, the hand mold with the rubber-coated was dried for 3 minutes in a dryer of 75° C., so that a chloroprene-based rubber layer as the first layer was formed.
  • TABLE 2
    Parts by weight
    (solid
    Rubber compound liquid of the first layer content basis)
    Chloroprene rubber latex SHOPRENE 671A 100
    Surfactant DARVAN WAQ 1
    Surfactant DARVAN SMO 1
    pH adjuster potassium hydroxide 0.18
    Filler clay 10
    Vulcanizing agent sulfur 1
    Metal oxide zinc oxide 10
    Vulcanization accelerator NOCCELER BZ 2
    Antiaging agent Vulkanox BKF 2
    Inorganic filler titanium oxide 0.4
    Pigment CHROMOFINE BLUE HS-4 1
    Defoaming agent Nopco DF-122-NS 0.05
    Thickener A-7075 0.42
    water 5.4
    Concentration of the solid content 50% by weight
    V6 viscosity 3000 mPa · sec
  • Subsequently, the aforementioned hand mold was dipped for 3 seconds in a bath containing a mixed rubber compound liquid of the second layer given in Table 3 and then was picked up from the bath, followed by cure. The cure was performed by heating at 75° C. for 60 minutes and then heating at 140° C. for 30 minutes. Thus, a mixed rubber layer as the second layer was formed. Then, the coated glove was removed from the hand mold, washed with water and dried, so that a chemical resistant glove in which the chloroprene-based rubber layer as the first layer and the mixed rubber layer as the second layer formed on a fabric glove was obtained.
  • TABLE 3
    Parts by weight
    (solid
    Mixed rubber compound liquid of the second layer content basis)
    NBR latex PERBUNAN N LATEX 10
    X 1150
    Chloroprene rubber latex SHOPRENE 671A 90
    Surfactant DARVAN WAQ 1
    Surfactant DARVAN SMO 1
    pH adjuster potassium hydroxide 1
    Vulcanizing agent sulfur 1
    Metal oxide zinc oxide 5
    Vulcanization accelerator NOCCELER BZ 1
    Antiaging agent Vulkanox BKF 2
    Inorganic filler titanium oxide 0.4
    Pigment CHROMOFINE BLUE HS-4 0.5
    Defoaming agent Nopco DF-122-NS 0.05
    Thickener A-7075 1
    water 53.6
    Concentration of the solid content 35% by weight
    V6 viscosity 2000 mPa · sec
  • Example 2
  • A chemical resistant glove in which a chloroprene-based rubber layer as the first layer and a mixed rubber layer as the second layer had been formed on a fabric glove was obtained in the same way as in Example 1 except for changing the mixed rubber compound liquid of the second layer to the mixed rubber compound liquid shown in Table 4.
  • TABLE 4
    Parts by weight
    (solid
    Mixed rubber compound liquid of the second layer content basis)
    NBR latex PERBUNAN N LATEX 20
    X 1150
    Chloroprene rubber latex SHOPRENE 671A 80
    Surfactant DARVAN WAQ 1
    Surfactant DARVAN SMO 1
    pH adjuster potassium hydroxide 1
    Vulcanizing agent sulfur 1
    Metal oxide zinc oxide 5
    Vulcanization accelerator NOCCELER BZ 1
    Antiaging agent Vulkanox BKF 2
    Inorganic filler titanium oxide 0.4
    Pigment CHROMOFINE BLUE HS-4 0.5
    Defoaming agent Nopco DF-122-NS 0.05
    Thickener A-7075 1
    water 48.1
    Concentration of the solid content 35% by weight
    V6 viscosity 2000 mPa · sec
  • Example 3
  • A chemical resistant glove in which a chloroprene-based rubber layer as the first layer and a mixed rubber layer as the second layer had been formed on a fabric glove was obtained in the same way as in Example 1 except for changing the mixed rubber compound liquid of the second layer to the mixed rubber compound liquid shown in Table 5.
  • TABLE 5
    Parts by weight
    (solid
    Mixed rubber compound liquid of the second layer content basis)
    NBR latex PERBUNAN N LATEX 25
    X 1150
    Chloroprene rubber latex SHOPRENE 671A 75
    Surfactant DARVAN WAQ 1
    Surfactant DARVAN SMO 1
    pH adjuster potassium hydroxide 1
    Vulcanizing agent sulfur 1
    Metal oxide zinc oxide 5
    Vulcanization accelerator NOCCELER BZ 1
    Antiaging agent Vulkanox BKF 2
    Inorganic filler titanium oxide 0.4
    Pigment CHROMOFINE BLUE HS-4 0.5
    Defoaming agent Nopco DF-122-NS 0.05
    Thickener A-7075 1
    water 45.3
    Concentration of the solid content 35% by weight
    V6 viscosity 2000 mPa · sec
  • Example 4
  • A chemical resistant glove in which a chloroprene-based rubber layer as the first layer and a mixed rubber layer as the second layer had been formed on a fabric glove was obtained in the same way as in Example 1 except for changing the mixed rubber compound liquid of the second layer to the mixed rubber compound liquid shown in Table 6.
  • TABLE 6
    Parts by weight
    (solid
    Mixed rubber compound liquid of the second layer content basis)
    NBR latex PERBUNAN N LATEX 40
    X 1150
    Chloroprene rubber latex SHOPRENE 671A 60
    Surfactant DARVAN WAQ 1
    Surfactant DARVAN SMO 1
    pH adjuster potassium hydroxide 1
    Vulcanizing agent sulfur 1
    Metal oxide zinc oxide 5
    Vulcanization accelerator NOCCELER BZ 1
    Antiaging agent Vulkanox BKF 2
    Inorganic filler titanium oxide 0.4
    Pigment CHROMOFINE BLUE HS-4 0.5
    Defoaming agent Nopco DF-122-NS 0.05
    Thickener A-7075 1
    water 36.9
    Concentration of the solid content 35% by weight
    V6 viscosity 2000 mPa · sec
  • Example 5
  • A chemical resistant glove in which a chloroprene-based rubber layer as the first layer and a mixed rubber layer as the second layer had been formed on a fabric glove was obtained in the same way as in Example 1 except for changing the mixed rubber compound liquid of the second layer to the mixed rubber compound liquid shown in Table 7.
  • TABLE 7
    Parts by weight
    (solid
    Mixed rubber compound liquid of the second layer content basis)
    NBR latex PERBUNAN N LATEX 50
    X 1150
    Chloroprene rubber latex SHOPRENE 671A 50
    Surfactant DARVAN WAQ 1
    Surfactant DARVAN SMO 1
    pH adjuster potassium hydroxide 1
    Vulcanizing agent sulfur 1
    Metal oxide zinc oxide 5
    Vulcanization accelerator NOCCELER BZ 1
    Antiaging agent Vulkanox BKF 2
    Inorganic filler titanium oxide 0.4
    Pigment CHROMOFINE BLUE HS-4 0.5
    Defoaming agent Nopco DF-122-NS 0.05
    Thickener A-7075 1
    water 31.4
    Concentration of the solid content 35% by weight
    V6 viscosity 2000 mPa · sec
  • Example 6
  • A chemical resistant glove in which a chloroprene-based rubber layer as the first layer and a mixed rubber layer as the second layer had been formed on a fabric glove was obtained in the same way as in Example 1 except for changing the mixed rubber compound liquid of the second layer to the mixed rubber compound liquid shown in Table 8.
  • TABLE 8
    Parts by weight
    (solid
    Mixed rubber compound liquid of the second layer content basis)
    NBR latex PERBUNAN N LATEX 60
    X 1150
    Chloroprene rubber latex SHOPRENE 671A 40
    Surfactant DARVAN WAQ 1
    Surfactant DARVAN SMO 1
    pH adjuster potassium hydroxide 1.3
    Vulcanizing agent sulfur 1
    Metal oxide zinc oxide 5
    Vulcanization accelerator NOCCELER BZ 1
    Antiaging agent Vulkanox BKF 2
    Inorganic filler titanium oxide 0.4
    Pigment CHROMOFINE BLUE HS-4 0.5
    Defoaming agent Nopco DF-122-NS 0.05
    Thickener A-7075 0.7
    water 36.4
    Concentration of the solid content 35% by weight
    V6 viscosity 2000 mPa · sec
  • Comparative Example 1
  • A chemical resistant glove in which a chloroprene-based rubber layer as the first layer had been formed on a fabric glove was obtained in the same way as in Example 1 except for not being dipped in a bath containing a mixed rubber compound liquid of the second layer, the cure, and heating after forming a chloroprene-based rubber layer as the first layer.
  • Comparative Example 2
  • A chemical resistant glove in which a chloroprene-based rubber layer as the first layer and a chloroprene-based rubber layer as the second layer had been formed on a fabric glove was obtained in the same way as in Example 1 except for changing the mixed rubber compound liquid of the second layer to the chloroprene-based rubber compound liquid shown in Table 9.
  • TABLE 9
    Parts by weight
    (solid
    Rubber compound liquid of the second layer content basis)
    Chloroprene rubber latex SHOPRENE 671A 100
    Surfactant DARVAN WAQ 1
    Surfactant DARVAN SMO 1
    pH adjuster potassium hydroxide 0.6
    Vulcanizing agent sulfur 1
    Metal oxide zinc oxide 5
    Vulcanization accelerator NOCCELER BZ 1
    Antiaging agent Vulkanox BKF 2
    Inorganic filler titanium oxide 0.4
    Pigment CHROMOFINE BLUE HS-4 0.5
    Defoaming agent Nopco DF-122-NS 0.05
    Thickener A-7075 1
    water 66
    Concentration of the solid content 35% by weight
    V6 viscosity 2000 mPa · sec
  • Comparative Example 3
  • A chemical resistant glove in which a chloroprene-based rubber layer as the first layer and a mixed rubber layer as the second layer had been formed on a fabric glove was obtained in the same way as in Example 1 except for changing the mixed rubber compound liquid of the second layer to the mixed rubber compound liquid shown in Table 10.
  • TABLE 10
    Parts by weight
    (solid
    Mixed rubber compound liquid of the second layer content basis)
    NBR latex PERBUNAN N LATEX 5
    X 1150
    Chloroprene rubber latex SHOPRENE 671A 95
    Surfactant DARVAN WAQ 1
    Surfactant DARVAN SMO 1
    pH adjuster potassium hydroxide 0.6
    Vulcanizing agent sulfur 1
    Metal oxide zinc oxide 5
    Vulcanization accelerator NOCCELER BZ 1
    Antiaging agent Vulkanox BKF 2
    Inorganic filler titanium oxide 0.4
    Pigment CHROMOFINE BLUE HS-4 0.5
    Defoaming agent Nopco DF-122-NS 0.05
    Thickener A-7075 1
    water 63.2
    Concentration of the solid content 35% by weight
    V6 viscosity 2000 mPa · sec
  • Comparative Example 4
  • A chemical resistant glove in which a chloroprene-based rubber layer as the first layer and a mixed rubber layer as the second layer had been formed on a fabric glove was obtained in the same way as in Example 1 except for changing the mixed rubber compound liquid of the second layer to the mixed rubber compound liquid shown in Table 11.
  • TABLE 11
    Parts by weight
    Mixed rubber compound liquid of the second layer (solid content basis)
    NBR latex PERBUNAN 70
    N LATEX X 1150
    Chloroprene rubber SHOPRENE 671A 30
    latex
    Surfactant DARVAN WAQ 1
    Surfactant DARVAN SMO 1
    pH adjuster potassium hydroxide 0.97
    Vulcanizing agent sulfur 1
    Metal oxide zinc oxide 5
    Vulcanization NOCCELER BZ 1
    accelerator
    Antiaging agent Vulkanox BKF 2
    Inorganic filler titanium oxide 0.4
    Pigment CHROMOFINE BLUE HS-4 0.5
    Defoaming agent Nopco DF-122-NS 0.05
    Thickener A-7075 0.63
    water 39.8
    Concentration of the solid content 35% by weight
    V6 viscosity 2000 mPa · sec
  • Comparative Example 5
  • A chemical resistant glove in which a chloroprene-based rubber layer as the first layer and a mixed rubber layer as the second layer had been formed on a fabric glove was obtained in the same way as in Example 3 except for replacing the NBR latex “PERBUNAN (registered trademark) N LATEX X 1150” in the mixed rubber compound liquid of the second layer given in Table 5 with an SBR latex “Nipol (registered trademark) Lx470A
  • Example 7
  • A chloroprene-based rubber layer as the first layer was formed in the same way as in Example 1 by mounting a fabric glove on a ceramic hand mold, performing a coagulant treatment, dipping the hand mold with the glove into a bath containing a rubber compound liquid of the first layer given in Table 2, picking up the hand mold with the glove, and performing a drying treatment. Subsequently, a chloroprene-based rubber layer as the intermediate layer was formed by dipping the hand mold with the glove into a bath containing a rubber compound liquid of the intermediate layer given in Table 12, followed by picking-up and a drying treatment in the same way as those for the first layer. Subsequently, the hand mold with the glove was dipped in a bath containing a mixed rubber compound liquid of the second layer given in Table 3, followed by picking-up and cure in the same way as in Example 1. Thus, a chemical resistant glove in which the chloroprene-based rubber layer as the first layer, the chloroprene-based rubber layer as the intermediate layer, and the mixed rubber layer as the second layer had been formed on a fabric glove was obtained.
  • TABLE 12
    Parts by weight
    Rubber compound liquid of the intermediate layer (solid content basis)
    Chloroprene rubber SHOPRENE 671A 100
    latex
    Surfactant DARVAN WAQ 1
    Surfactant DARVAN SMO 1
    pH adjuster potassium hydroxide 0.12
    Filler clay 10
    Vulcanizing agent sulfur 1
    Metal oxide zinc oxide 10
    Vulcanization NOCCELER BZ 2
    accelerator
    Antiaging agent Vulkanox BKF 2
    Inorganic filler titanium oxide 0.4
    Pigment CHROMOFINE BLUE HS-4 1
    Defoaming agent Nopco DF-122-NS 0.05
    Thickener A-7075 0.28
    water 12.1
    Concentration of the solid content 50% by weight
    V6 viscosity 2000 mPa · sec
  • Example 8
  • A chemical resistant glove in which a chloroprene-based rubber layer as the first layer, a chloroprene-based rubber layer as the intermediate layer and a mixed rubber layer as the second layer had been formed on a fabric glove was obtained in the same way as in Example 7 except for changing the mixed rubber compound liquid of the second layer to the mixed rubber compound liquid of the second layer shown in Table 4.
  • Example 9
  • A chemical resistant glove in which a chloroprene-based rubber layer as the first layer, a chloroprene-based rubber layer as the intermediate layer and a mixed rubber layer as the second layer had been formed on a fabric glove was obtained in the same way r as in Example 7 except for changing the mixed rubber compound liquid of the second layer to the mixed rubber compound liquid of the second layer shown in Table 5.
  • Example 10
  • A chemical resistant glove in which a chloroprene-based rubber layer as the first layer, a chloroprene-based rubber layer as the intermediate layer and a mixed rubber layer as the second layer had been formed on a fabric glove was obtained in the same way as in Example 7 except for changing the mixed rubber compound liquid of the second layer to the mixed rubber compound liquid of the second layer shown in Table 6.
  • Example 11
  • A chemical resistant glove in which a chloroprene-based rubber layer as the first layer, a chloroprene-based rubber layer as the intermediate layer and a mixed rubber layer as the second layer had been formed on a fabric glove was obtained in the same way as in Example 7 except for changing the mixed rubber compound liquid of the second layer to the mixed rubber compound liquid of the second layer shown in Table 7.
  • Comparative Example 6
  • A chloroprene-based rubber layer as the first layer was formed in the same way as in Example 1 by setting a fabric glove on a ceramic hand mold, performing a coagulant treatment, dipping the hand mold with the glove into a bath containing a rubber compound liquid of the first layer given in Table 2, picking up the hand mold with the glove, and performing a drying treatment. Subsequently, the hand mold with the glove was dipped into a bath containing a rubber compound liquid of the intermediate layer given in Table 12, followed by picking-up and drying treatment. Thus, a chemical resistant glove in which chloroprene-based rubber layers as the first layer and the intermediate layer had been formed on a fabric glove was obtained.
  • Comparative Example 7
  • A chemical resistant glove in which a chloroprene-based rubber layer as the first layer, a chloroprene-based rubber layer as the intermediate layer and a chloroprene-based rubber layer as the second layer had been formed on a fabric glove was obtained in the same way as in Example 7 except for changing the mixed rubber compound liquid of the second layer to the rubber compound liquid shown in Table 9.
  • Comparative Example 8
  • A chemical resistant glove in which a chloroprene-based rubber layer as the first layer, a chloroprene-based rubber layer as the intermediate layer and a mixed rubber layer as the second layer had been formed on a fabric glove was obtained in the same way as in Example 7 except for changing the mixed rubber compound liquid of the second layer to the mixed rubber compound liquid shown in Table 10.
  • Comparative Example 9
  • A chemical resistant glove in which a chloroprene-based rubber layer as the first layer, a chloroprene-based rubber layer as the intermediate layer and a mixed rubber layer as the second layer had been formed on a fabric glove was obtained in the same way as in Example 7 except for changing the mixed rubber compound liquid of the second layer to the mixed rubber compound liquid shown in Table 11.
  • Comparative Example 10
  • A chemical resistant glove in which a chloroprene-based rubber layer as the first layer, a chloroprene-based rubber layer as the intermediate layer and a mixed rubber layer as the second layer had been formed on a fabric glove was obtained in the same way as in Example 9 except for replacing the NBR latex “PERBUNAN (registered trademark) N LATEX X 1150” in the mixed rubber compound liquid of the second layer given in Table 5 with an SBR latex “Nipol (registered trademark) Lx470A.”
  • Example 12
  • A cotton-polyester (50:50) mixed-spun seamless glove knitted with a 18-gauge knitter was set on a ceramic hand mold, followed by dipping into a coagulant bath. A coagulant liquid composed of methanol and calcium nitrate (100:2.0) was used. Subsequently, the glove was dipped for about 3 seconds in a bath of a rubber compound liquid of the first layer given in Table 2 and then was picked up from the bath, immediately followed by dipping into a 15% aqueous calcium nitrate solution. Furthermore, the hand mold with the rubber-coated glove set thereon was dried for 3 minutes in a dryer of 75° C., so that a chloroprene-based rubber layer as the first layer was formed.
  • Subsequently, the hand mold with the aforementioned first layer-coated glove mounted thereon was dipped for 3 seconds in a bath of a mixed rubber compound liquid containing NBR particles of the second layer given in Table 13 and then was picked up from the bath, followed by cure. The cure was performed by heating at 75° C. for 60 minutes and then heating at 140° C. for 30 minutes. Thus, a mixed rubber layer as the second layer was formed. Then, the coated glove was removed from the hand mold, washed with water and dried, so that a chemical resistant glove in which the chloroprene-based rubber layer as the first layer and the mixed rubber layer containing NBR particles as the second layer formed on a fabric glove was obtained.
  • TABLE 13
    Parts by weight
    Mixed rubber compound liquid of the second layer (solid content basis)
    NBR latex PERBUNAN N 10
    LATEX X 1150
    Chloroprene rubber SHOPRENE 671A 90
    latex
    Surfactant DARVAN WAQ 1
    Surfactant DARVAN SMO 1
    pH adjuster potassium hydroxide 1
    Vulcanizing agent sulfur 1
    Metal oxide zinc oxide 5
    Vulcanization NOCCELER BZ 1
    accelerator
    Antiaging agent Vulkanox BKF 2
    Inorganic filler titanium oxide 0.4
    NBR particles BAYMOD N XL 32.12 40
    Pigment CHROMOFINE BLUE HS-4 0.5
    Defoaming agent Nopco DF-122-NS 0.05
    Thickener A-7075 1
    water 127.9
    Concentration of the solid content 35% by weight
    V6 viscosity 2000 mPa · sec
  • Example 13
  • A chemical resistant glove in which a chloroprene-based rubber layer as the first layer and a mixed rubber layer containing NBR particles as the second layer had been formed on a fabric glove was obtained in the same way as in Example 12 except for changing the mixed rubber compound liquid of the second layer to the mixed rubber compound liquid shown in Table 14.
  • TABLE 14
    Parts by weight
    Mixed rubber compound liquid of the second layer (solid content basis)
    NBR latex PERBUNAN N LATEX 20
    X 1150
    Chloroprene rubber latex SHOPRENE 671A 80
    Surfactant DARVAN WAQ 1
    Surfactant DARVAN SMO 1
    pH adjuster potassium hydroxide 1
    Vulcanizing agent sulfur 1
    Metal oxide zinc oxide 5
    Vulcanization accelerator NOCCELER BZ 1
    Antiaging agent Vulkanox BKF 2
    Inorganic filler titanium oxide 0.4
    NBR particles BAYMOD N XL 32.12 40
    Pigment CHROMOFINE BLUE 0.5
    HS-4
    Defoaming agent Nopco DF-122-NS 0.05
    Thickener A-7075 1
    water 122.3
    Concentration of the solid content 35% by weight
    V6 viscosity 2000 mPa · sec
  • Example 14
  • A chemical resistant glove in which a chloroprene-based rubber layer as the first layer and a mixed rubber layer containing NBR particles as the second layer had been formed on a fabric glove was obtained in the same way as in Example 12 except for changing the mixed rubber compound liquid of the second layer to the mixed rubber compound liquid shown in Table 15.
  • TABLE 15
    Parts by weight
    Mixed rubber compound liquid of the second layer (solid content basis)
    NBR latex PERBUNAN N LATEX 25
    X 1150
    Chloroprene rubber latex SHOPRENE 671A 75
    Surfactant DARVAN WAQ 1
    Surfactant DARVAN SMO 1
    pH adjuster potassium hydroxide 1
    Vulcanizing agent sulfur 1
    Metal oxide zinc oxide 5
    Vulcanization accelerator NOCCELER BZ 1
    Antiaging agent Vulkanox BKF 2
    Inorganic filler titanium oxide 0.4
    NBR particles BAYMOD N XL 32.12 40
    Pigment CHROMOFINE BLUE 0.5
    HS-4
    Defoaming agent Nopco DF-122-NS 0.05
    Thickener A-7075 1
    water 119.5
    Concentration of the solid content 35% by weight
    V6 viscosity 2000 mPa · sec
  • Example 15
  • A chemical resistant glove in which a chloroprene-based rubber layer as the first layer and a mixed rubber layer containing NBR particles as the second layer had been formed on a fabric glove was obtained in the same way as in Example 12 except for changing the mixed rubber compound liquid of the second layer to the mixed rubber compound liquid shown in Table 16.
  • TABLE 16
    Parts by weight
    (solid content
    Mixed rubber compound liquid of the second layer basis)
    NBR latex PERBUNAN N LATEX 40
    X 1150
    Chloroprene rubber latex SHOPRENE 671A 60
    Surfactant DARVAN WAQ 1
    Surfactant DARVAN SMO 1
    pH adjuster potassium hydroxide 1
    Vulcanizing agent sulfur 1
    Metal oxide zinc oxide 5
    Vulcanization accelerator NOCCELER BZ 1
    Antiaging agent Vulkanox BKF 2
    Inorganic filler titanium oxide 0.4
    NBR particles BAYMOD N XL 32.12 40
    Pigment CHROMOFINE BLUE HS-4 0.5
    Defoaming agent Nopco DF-122-NS 0.05
    Thickener A-7075 1
    water 111.2
    Concentration of the solid content 35% by weight
    V6 viscosity 2000 mPa · sec
  • Example 16
  • A chemical resistant glove in which a chloroprene-based rubber layer as the first layer and a mixed rubber layer containing NBR particles as the second layer had been formed on a fabric glove was obtained in the same way as in Example 12 except for changing the mixed rubber compound liquid of the second layer to the mixed rubber compound liquid shown in Table 17.
  • TABLE 17
    Parts by weight
    Mixed rubber compound liquid of the second layer (solid content basis)
    NBR latex PERBUNAN N LATEX 50
    X 1150
    Chloroprene rubber latex SHOPRENE 671A 50
    Surfactant DARVAN WAQ 1
    Surfactant DARVAN SMO 1
    pH adjuster potassium hydroxide 1
    Vulcanizing agent sulfur 1
    Metal oxide zinc oxide 5
    Vulcanization accelerator NOCCELER BZ 1
    Antiaging agent Vulkanox BKF 2
    Inorganic filler titanium oxide 0.4
    NBR particles BAYMOD N XL 32.12 40
    Pigment CHROMOFINE BLUE 0.5
    HS-4
    Defoaming agent Nopco DF-122-NS 0.05
    Thickener A-7075 1
    water 105.7
    Concentration of the solid content 35% by weight
    V6 viscosity 2000 mPa · sec
  • Example 17
  • A chemical resistant glove in which a chloroprene-based rubber layer as the first layer and a mixed rubber layer containing NBR particles as the second layer had been formed on a fabric glove was obtained in the same way as in Example 12 except for changing the mixed rubber compound liquid of the second layer to the mixed rubber compound liquid shown in Table 18.
  • TABLE 18
    Parts by weight
    (solid content
    Mixed rubber compound liquid of the second layer basis)
    NBR latex PERBUNAN N LATEX 60
    X 1150
    Chloroprene rubber latex SHOPRENE 671A 40
    Surfactant DARVAN WAQ 1
    Surfactant DARVAN SMO 1
    pH adjuster potassium hydroxide 1
    Vulcanizing agent sulfur 1
    Metal oxide zinc oxide 5
    Vulcanization accelerator NOCCELER BZ 1
    Antiaging agent Vulkanox BKF 2
    Inorganic filler titanium oxide 0.4
    NBR particles BAYMOD N XL 32.12 40
    Pigment CHROMOFINE BLUE HS-4 0.5
    Defoaming agent Nopco DF-122-NS 0.05
    Thickener A-7075 1
    water 100.1
    Concentration of the solid content 35% by weight
    V6 viscosity 2000 mPa · sec
  • Example 18
  • A chemical resistant glove in which a chloroprene-based rubber layer as the first layer and a mixed rubber layer containing NBR particles as the second layer had been formed on a fabric glove was obtained in the same way as in Example 12 except for changing the mixed rubber compound liquid of the second layer to the mixed rubber compound liquid shown in Table 19.
  • TABLE 19
    Parts by weight
    (solid content
    Mixed rubber compound liquid of the second layer basis)
    NBR latex PERBUNAN N LATEX 25
    X 1150
    Chloroprene rubber latex SHOPRENE 671A 75
    Surfactant DARVAN WAQ 1
    Surfactant DARVAN SMO 1
    pH adjuster potassium hydroxide 1
    Vulcanizing agent sulfur 1
    Metal oxide zinc oxide 5
    Vulcanization accelerator NOCCELER BZ 1
    Antiaging agent Vulkanox BKF 2
    Inorganic filler titanium oxide 0.4
    NBR particles BAYMOD N XL 32.12 20
    Pigment CHROMOFINE BLUE HS-4 0.5
    Defoaming agent Nopco DF-122-NS 0.05
    Thickener A-7075 1
    water 82.4
    Concentration of the solid content 35% by weight
    V6 viscosity 2000 mPa · sec
  • Example 19
  • A chemical resistant glove in which a chloroprene-based rubber layer as the first layer and a mixed rubber layer containing NBR particles as the second layer had been formed on a fabric glove was obtained in the same way as in Example 12 except for changing the mixed rubber compound liquid of the second layer to the mixed rubber compound liquid shown in Table 20.
  • TABLE 20
    Parts by weight
    Mixed rubber compound liquid of the second layer (solid content basis)
    NBR latex PERBUNAN N LATEX 25
    X 1150
    Chloroprene rubber latex SHOPRENE 671A 75
    Surfactant DARVAN WAQ 1
    Surfactant DARVAN SMO 1
    pH adjuster potassium hydroxide 1
    Vulcanizing agent sulfur 1
    Metal oxide zinc oxide 5
    Vulcanization accelerator NOCCELER BZ 1
    Antiaging agent Vulkanox BKF 2
    Inorganic filler titanium oxide 0.4
    NBR particles BAYMOD N XL 32.12 60
    Pigment CHROMOFINE BLUE 0.5
    HS-4
    Defoaming agent Nopco DF-122-NS 0.05
    Thickener A-7075 1
    water 156.7
    Concentration of the solid content 35% by weight
    V6 viscosity 2000 mPa · sec
  • Comparative Example 11
  • A chemical resistant glove in which a chloroprene-based rubber layer as the first layer and a chloroprene-based rubber layer containing NBR particles as the second layer had been formed on a fabric glove was obtained in the same way as in Example 12 except for changing the mixed rubber compound liquid of the second layer to the chloroprene-based rubber compound liquid shown in Table 21.
  • TABLE 21
    Parts by weight
    Rubber compound liquid of the second layer (solid content basis)
    Chloroprene rubber latex SHOPRENE 671A 100
    Surfactant DARVAN WAQ 1
    Surfactant DARVAN SMO 1
    pH adjuster potassium hydroxide 1
    Vulcanizing agent sulfur 1
    Metal oxide zinc oxide 5
    Vulcanization accelerator NOCCELER BZ 1
    Antiaging agent Vulkanox BKF 2
    Inorganic filler titanium oxide 0.4
    NBR particles BAYMOD N XL 32.12 40
    Pigment CHROMOFINE BLUE 0.5
    HS-4
    Defoaming agent Nopco DF-122-NS 0.05
    Thickener A-7075 1
    water 133.4
    Concentration of the solid content 35% by weight
    V6 viscosity 2000 mPa · sec
  • Comparative Example 12
  • A chemical resistant glove in which a chloroprene-based rubber layer as the first layer and a mixed rubber layer containing NBR particles as the second layer had been formed on a fabric glove was obtained in the same way as in Example 12 except for changing the mixed rubber compound liquid of the second layer to the mixed rubber compound liquid shown in Table 22.
  • TABLE 22
    Parts by weight
    Mixed rubber compound liquid of the second layer (solid content basis)
    NBR latex PERBUNAN N LATEX 25
    X 1150
    Chloroprene rubber latex SHOPRENE 671A 75
    Surfactant DARVAN WAQ 1
    Surfactant DARVAN SMO 1
    pH adjuster potassium hydroxide 1
    Vulcanizing agent sulfur 1
    Metal oxide zinc oxide 5
    Vulcanization accelerator NOCCELER BZ 1
    Antiaging agent Vulkanox BKF 2
    Inorganic filler titanium oxide 0.4
    NBR particles BAYMOD N XL 32.12 15
    Pigment CHROMOFINE BLUE 0.5
    HS-4
    Defoaming agent Nopco DF-122-NS 0.05
    Thickener A-7075 1
    water 87
    Concentration of the solid content 35% by weight
    V6 viscosity 2000 mPa · sec
  • Comparative Example 13
  • A chemical resistant glove in which a chloroprene-based rubber layer as the first layer and a mixed rubber layer containing NBR particles as the second layer had been formed on a fabric glove was obtained in the same way as in Example 12 except for changing the mixed rubber compound liquid of the second layer to the mixed rubber compound liquid shown in Table 23.
  • TABLE 23
    Parts by weight
    Mixed rubber compound liquid of the second layer (solid content basis)
    NBR latex PERBUNAN N LATEX 25
    X 1150
    Chloroprene rubber latex SHOPRENE 671A 75
    Surfactant DARVAN WAQ 1
    Surfactant DARVAN SMO 1
    pH adjuster potassium hydroxide 1
    Vulcanizing agent sulfur 1
    Metal oxide zinc oxide 5
    Vulcanization accelerator NOCCELER BZ 1
    Antiaging agent Vulkanox BKF 2
    Inorganic filler titanium oxide 0.4
    NBR particles BAYMOD N XL 32.12 65
    Pigment CHROMOFINE BLUE 0.5
    HS-4
    Defoaming agent Nopco DF-122-NS 0.05
    Thickener A-7075 1
    water 179.9
    Concentration of the solid content 35% by weight
    V6 viscosity 2000 mPa · sec
  • Comparative Example 14
  • A chemical resistant glove in which a chloroprene-based rubber layer as the first layer and a mixed rubber layer containing NBR particles as the second layer had been formed on a fabric glove was obtained in the same way as in Example 12 except for replacing the NBR latex “PERBUNAN N LATEX X 1150” in the mixed rubber compound liquid of the second layer given in Table 15 with an SBR latex “Nipol Lx470A.”
  • Comparative Example 15
  • A chemical resistant glove in which a chloroprene-based rubber layer as the first layer and a mixed rubber layer containing CR particles as the second layer had been formed on a fabric glove was obtained in the same way as in Example 14 except for replacing the NBR particles “BAYMOD NXL32.12” in the mixed rubber compound liquid of the second layer given in Table 15 with CR particles.
  • The CR particles were obtained by kneading the raw materials given in Table 24, press-vulcanizing the resulting sheet at 150° C. for 30 minutes, followed by pulverization with a freeze pulverizer. The particle diameter of the CR particles was adjusted with a sieve to be not larger than 700 and not smaller than 50 μm.
  • TABLE 24
    Amount
    (parts
    CR particles by weight)
    Chloroprene rubber SKYPRENE 640 100
    Metal oxide zinc oxide 5
    Vulcanization accelerator SANCELER 22-C 1
    Vulcanization supplement accelerator magnesium oxide 4
    Vlcanization accelerating auxiliary stearic acid 1
    Filler clay 30
    Mineral oil type softener naphthene 10
    type process oil
  • Comparative Example 16
  • A chemical resistant glove in which a chloroprene-based rubber layer as the first layer and a mixed rubber layer containing SBR particles as the second layer had been formed on a fabric glove was obtained in the same way as in Example 14 except for replacing the NBR particles “BAYMOD NXL32.12” in the mixed rubber compound liquid of the second layer given in Table 15 with SBR particles.
  • The SBR particles were obtained by kneading the raw materials given in Table 25, press-vulcanizing the resulting sheet at 150° C. for 30 minutes, followed by pulverization with a freeze pulverizer. The particle diameter of the SBR particles was adjusted with a sieve to be not larger than 700 μm and not smaller than 50 μm.
  • TABLE 25
    Amount
    (parts
    SBR particles by weight)
    Styrene-butadiene rubber Nipol 1502 100
    Vulcanizing agent sulfur 2
    Metal oxide zinc oxide 5
    Vulcanization accelerator NOCCELER BZ 2
    Vulcanization accelerating auxiliary stearic acid 1.5
    Filler titanium oxide 10
  • Example 20
  • A chloroprene-based rubber layer as the first layer was formed in the same way as in Example 12 by mounting a fabric glove on a ceramic hand mold, performing a coagulant treatment, dipping the hand mold with the glove into a bath of a rubber compound liquid of the first layer given in Table 2, picking up the hand mold with the glove, and performing a drying treatment. Subsequently, a chloroprene-based rubber layer as the intermediate layer was formed by dipping the hand mold with the glove into a bath of a rubber compound liquid of the intermediate layer given in Table 12, followed by picking-up and a drying treatment in the same way as those for the first layer. Subsequently, the hand mold with the glove was dipped in a bath of a mixed rubber compound liquid containing NBR particles of the second layer given in Table 13, followed by picking-up and cure in the same way as in Example 12. Thus, a chemical resistant glove in which the chloroprene-based rubber layer as the first layer, the chloroprene-based rubber layer as the intermediate layer, and the mixed rubber layer containing NBR particles as the second layer had been formed on a fabric glove was obtained.
  • Example 21
  • A chemical resistant glove in which a chloroprene-based rubber layer as the first layer, a chloroprene-based rubber layer as the intermediate layer and a mixed rubber layer containing NBR particles as the second layer had been formed on a fabric glove was obtained in the same way as in Example 20 except for changing the mixed rubber compound liquid of the second layer to the mixed rubber compound liquid of the second layer shown in Table 14.
  • Example 22
  • A chemical resistant glove in which a chloroprene-based rubber layer as the first layer, a chloroprene-based rubber layer as the intermediate layer and a mixed rubber layer containing NBR particles as the second layer had been formed on a fabric glove was obtained in the same way as in Example 20 except for changing the mixed rubber compound liquid of the second layer to the mixed rubber compound liquid of the second layer shown in Table 15.
  • Example 23
  • A chemical resistant glove in which a chloroprene-based rubber layer as the first layer, a chloroprene-based rubber layer as the intermediate layer and a mixed rubber layer containing NBR particles as the second layer had been formed on a fabric glove was obtained in the same way as in Example 20 except for changing the mixed rubber compound liquid of the second layer to the mixed rubber compound liquid of the second layer shown in Table 16.
  • Example 24
  • A chemical resistant glove in which a chloroprene-based rubber layer as the first layer, a chloroprene-based rubber layer as the intermediate layer and a mixed rubber layer containing NBR particles as the second layer had been formed on a fabric glove was obtained in the same way as in Example 20 except for changing the mixed rubber compound liquid of the second layer to the mixed rubber compound liquid of the second layer shown in Table 17.
  • Example 25
  • A chemical resistant glove in which a chloroprene-based rubber layer as the first layer, a chloroprene-based rubber layer as the intermediate layer and a mixed rubber layer containing NBR particles as the second layer had been formed on a fabric glove was obtained in the same way as in Example 20 except for changing the mixed rubber compound liquid of the second layer to the mixed rubber compound liquid of the second layer shown in Table 18.
  • Example 26
  • A chemical resistant glove in which a chloroprene-based rubber layer as the first layer, a chloroprene-based rubber layer as the intermediate layer and a mixed rubber layer containing NBR particles as the second layer had been formed on a fabric glove was obtained in the same way as in Example 20 except for changing the mixed rubber compound liquid of the second layer to the mixed rubber compound liquid of the second layer shown in Table 19.
  • Example 27
  • A chemical resistant glove in which a chloroprene-based rubber layer as the first layer, a chloroprene-based rubber layer as the intermediate layer and a mixed rubber layer containing NBR particles as the second layer had been formed on a fabric glove was obtained in the same way as in Example 20 except for changing the mixed rubber compound liquid of the second layer to the mixed rubber compound liquid of the second layer shown in Table 20.
  • Comparative Example 17
  • A chloroprene-based rubber layer as the first layer was formed in the same way as in Example 20 by mounting a fabric glove on a ceramic hand mold, performing a coagulant treatment, dipping the hand mold with the glove into a bath of a rubber compound liquid of the first layer given in Table 2, picking up the hand mold with the glove, and performing a drying treatment. Subsequently, the hand mold with the glove was dipped into a bath of a rubber compound liquid of the intermediate layer given in Table 12, followed by picking-up and drying treatment. Furthermore, the hand mold with the glove was dipped in a bath of a rubber compound liquid containing NBR particles of the second layer given in Table 21 and then was picked up, followed by operations the same as those performed in Example 20. Thus, a chemical resistant glove in which a chloroprene-based rubber layer as the first layer, a chloroprene-based layer as the intermediate layer and a chloroprene-based rubber layer containing NBR particles as the second layer had been formed on a fabric glove was obtained.
  • Comparative Example 18
  • A chemical resistant glove in which a chloroprene-based rubber layer as the first layer, a chloroprene-based rubber layer as the intermediate layer and a mixed rubber layer containing NBR particles as the second layer had been formed on a fabric glove was obtained in the same way as in Example 22 except for changing the mixed rubber compound liquid of the second layer to the mixed rubber compound liquid shown in Table 22.
  • Comparative Example 19
  • A chemical resistant glove in which a chloroprene-based rubber layer as the first layer, a chloroprene-based rubber layer as the intermediate layer and a mixed rubber layer containing NBR particles as the second layer had been formed on a fabric glove was obtained in the same way as in Example 22 except for changing the mixed rubber compound liquid of the second layer to the mixed rubber compound liquid shown in Table 23.
  • Comparative Example 20
  • A chemical resistant glove in which a chloroprene-based rubber layer as the first layer, a chloroprene-based rubber layer as the intermediate layer and a mixed rubber layer containing NBR particles as the second layer had been formed on a fabric glove was obtained in the same way as in Example 22 except for replacing the NBR latex “PERBUNAN N LATEX X 1150” in the mixed rubber compound liquid of the second layer given in Table 15 with an SBR latex “Nipol Lx470A.”
  • Comparative Example 21
  • A chemical resistant glove in which a chloroprene-based rubber layer as the first layer, a chloroprene-based rubber layer as the intermediate layer and a mixed rubber layer containing CR particles as the second layer had been formed on a fabric glove was obtained in the same way as in Example 22 except for replacing the NBR particles “BAYMOD NXL32.12” in the mixed rubber compound liquid of the second layer given in Table 15 with CR particles.
  • The CR particles were obtained by kneading the raw materials given in Table 24, press-vulcanizing the resulting sheet at 150° C. for 30 minutes, followed by pulverization with a freeze pulverizer. The particle diameter of the CR particles was adjusted with a screen to be not larger than 700 μm and not smaller than 50 μm.
  • Comparative Example 22
  • A chemical resistant glove in which a chloroprene-based rubber layer as the first layer, a chloroprene-based rubber layer as the intermediate layer and a mixed rubber layer containing SBR particles as the second layer had been formed on a fabric glove was obtained in the same way as in Example 22 except for replacing the NBR particles “BAYMOD NXL32.12” in the mixed rubber compound liquid of the second layer given in Table 15 with SBR particles.
  • The SBR particles were obtained by kneading the raw materials given in Table 25, press-vulcanizing the resulting sheet at 150° C. for 30 minutes, followed by pulverization with a freeze pulverizer. The particle diameter of the SBR particles was adjusted with a screen to be not larger than 700 μm and not smaller than 50 μm.
  • For the chemical resistant gloves obtained in Examples 1 to 11 and Comparative Examples 1 to 10, a chemical resistance test according to ISO 6529 was performed and the breakthrough time (min) was measured. Moreover, tactile feeling, abrasion resistance were evaluated by the methods described below. The results are shown in Tables 26 and 27.
  • For the chemical resistant gloves obtained in Examples 12 to 27 and Comparative Examples 11 to 22, a chemical resistance test according to ISO 6529 was performed and the breakthrough time (min) was measured. Moreover, tactile feeling, abrasion resistance, slip resistance and drop-off of particles were evaluated by the methods described below. The results are shown in Tables 28 and 29.
  • In Tables 26 to 29, CR represents a chloroprene-based rubber, NBR represents a nitrile-butadiene-based rubber, and SBR represents a styrene-butadiene-based rubber.
  • “Tactile Feeling”
  • Ten subjects wore the gloves of Examples 1 to 27 and the gloves of Comparative Examples 1 to 22 and evaluated the tactile feeling according to the following criteria.
  • A: The gloves feel soft.
  • B: The gloves feel a little stiff but soft.
  • C: The gloves feel stiff and are hard.
  • “Abrasion Resistance”
  • The gloves of Examples 1 to 27 and the gloves of Comparative Examples 1 to 22 were subjected to an abrasion resistance test according to EN388 and the abrasion strength was evaluated according to the following criteria. Generally, a glove with a time of withstanding abrasions of less than 500 is judged to be unsuitable for a protective glove such as a chemical resistant glove.
  • A: 1001 times or more.
  • B: Not less than 501 times and less than 1000 times.
  • C: Less than 500 times.
  • “Slip Resistance”
  • Ten subjects wore the gloves of Examples 12 to 27 and the gloves of Comparative Examples 11 to 22 and sensorily evaluated, according to the criteria given below, the slip resisting effect exhibited against glass as a working object under dry conditions and under wet conditions produced with water.
  • A: A sufficient slip-resisting effect is observed under both dry conditions and wet conditions.
  • B: A sufficient slip-resisting effect is observed under dry conditions and a slip-resisting effect that is slightly weak but has no practical problem is observed under wet conditions.
  • C: The slip-resisting effect is low under both dry conditions and wet conditions.
  • “Drop-off of Particles”
  • The gloves of Examples 12 to 27 and the gloves of Comparative Examples 11 to 22 were subjected to a abrasion resistance test according to EN388 and were evaluated according to the following criteria.
  • A: Drop-off of particles from the glove was not observed even at 51 or more abrasions.
  • C: Drop-off of particles from the glove was observed at 50 or less abrasions.
  • TABLE 26
    Coating layers
    of the chemical Chemical resistance (min) Total
    resistant glove Ethyl Tactile Abrasion thickness of
    1st Intermediate 2nd MEK acetate Chloroform Toluene Methanol feeling resistance layers (mm)
    Example 1 CR NBR 10 2.23 3.38 1.59 1.98 480 A B 0.35
    CR 90
    Example 2 CR NBR 20 1.82 2.23 1.32 2.01 480 A A 0.35
    CR 80
    Example 3 CR NBR 25 1.64 2.01 1.28 2.54 480 A A 0.35
    CR 75
    Example 4 CR NBR 40 1.64 1.95 1.19 2.58 480 A A 0.35
    CR 60
    Example 5 CR NBR 50 1.62 1.89 1.15 2.76 480 B A 0.35
    CR 50
    Example 6 CR NBR 60 1.6 1.86 1.12 2.98 480 B A 0.35
    CR 40
    Comp. CR 0.46 1.37 0.46 0.82 480 A C 0.2
    Example 1
    Comp. CR CR 2.34 3.44 1.77 1.81 480 A C 0.35
    Example 2
    Comp. CR NBR 5 2.3 3.39 1.6 1.84 480 A C 0.35
    Example 3 CR 95
    Comp. CR NBR 70 1.58 1.77 1.06 3.23 480 C A 0.35
    Example 4 CR 30
    Comp. CR SBR 25 1.82 1.85 0.99 2 480 C C 0.35
    Example 5 CR 75
  • TABLE 27
    Coating layers
    of the chemical Chemical resistance (min) Total
    resistant glove Ethyl Tactile Abrasion thickness of
    1st Intermediate 2nd MEK acetate Chloroform Toluene Methanol feeling resistance layers (mm)
    Example 7 CR CR NBR 10 6.79 9.39 5.64 6.01 480 A B 0.55
    CR 90
    Example 8 CR CR NBR 20 6.62 8.88 5.62 6.27 480 A A 0.55
    CR 80
    Example 9 CR CR NBR 25 6.57 8.67 5.54 6.47 480 A A 0.55
    CR 75
    Example 10 CR CR NBR 40 6.43 8.73 5.32 6.78 480 A A 0.55
    CR 60
    Example 11 CR CR NBR 50 6.22 8.12 5.16 6.99 480 B A 0.55
    CR 50
    Comp. CR CR 4.84 5.66 4.48 5.47 480 A C 0.4
    Example 6
    Comp. CR CR CR 6.83 9.46 5.68 5.83 480 A C 0.55
    Example 7
    Comp. CR CR NBR 5 6.82 9.43 5.66 5.99 480 A C 0.55
    Example 8 CR 95
    Comp. CR CR NBR 70 5.89 7.66 4.83 7.12 480 C A 0.55
    Example 9 CR 30
    Comp. CR CR SBR 25 7 8.34 3.67 5.16 480 C B 0.55
    Example 10 CR 75
  • TABLE 28
    Coating layers of the
    chemical resistant glove
    Added Chemical Drop- Total
    Inter- particles resistance (min) Slip off thickness
    me- Mate- Ethyl Chlo- Tol- Meth- Tactile Abrasion re- of of layers
    1st diate 2nd rial Amount MEK acetate roform uene anol feeling resistance sistance particles (mm)
    Example 12 CR NBR 10 NBR 40 3.4 3.2 1.6 4.2 480 A B A A 0.35
    CR 90
    Example 13 CR NBR 20 NBR 40 3.0 3.1 1.6 4.2 480 A A A A 0.35
    CR 80
    Example 14 CR NBR 25 NBR 40 2.7 2.8 1.6 4.4 480 A A A A 0.35
    CR 75
    Example 15 CR NBR 40 NBR 40 2.6 2.6 1.6 4.8 480 A A A A 0.35
    CR 60
    Example 16 CR NBR 50 NBR 40 2.4 2.6 1.5 4.9 480 B A A A 0.35
    CR 50
    Example 17 CR NBR 60 NBR 40 2.3 2.5 1.5 5.0 480 B A A A 0.35
    CR 40
    Example 18 CR NBR 25 NBR 20 2.0 2.2 1.3 3.8 480 A A B A 0.35
    CR 75
    Example 19 CR NBR 25 NBR 60 2.9 3.2 1.8 4.7 480 B A A A 0.35
    CR 75
    Comp. CR CR NBR 40 3.6 3.4 1.6 4.0 480 A C A A 0.35
    Example 11
    Comp. CR NBR 25 NBR 15 2.0 2.2 1.4 3.1 480 A A C A 0.35
    Example 12 CR 75
    Comp. CR NBR 25 NBR 65 3.1 3.4 2.2 5.0 480 C A A A 0.35
    Example 13 CR 75
    Comp. CR SBR 25 NBR 40 2.6 2.5 1.4 3.7 480 C C A A 0.35
    Example 14 CR 75
    Comp. CR NBR 25 CR 40 2.7 2.7 1.6 3.6 480 A A A C 0.35
    Example 15 CR 75
    Comp. CR NBR 25 SBR 40 2.3 2.5 1.5 4.2 480 A A A C 0.35
    Example 16 CR 75
  • TABLE 29
    Coating layers of the
    chemical resistant glove
    Added Chemical Drop- Total
    Inter- particles resistance (min) Slip off thickness
    me- Mate- Ethyl Chlo- Tol- Meth- Tactile Abrasion re- of of layers
    1st diate 2nd rial Amount MEK acetate roform uene anol feeling resistance sistance particles (mm)
    Example 20 CR CR NBR 10 NBR 40 10.1 13.7 7.2 13.8 480 A B A A 0.55
    CR 90
    Example 21 CR CR NBR 20 NBR 40 9.9 13.5 7.1 12.7 480 A A A A 0.55
    CR 80
    Example 22 CR CR NBR 25 NBR 40 9.9 13.3 6.9 12.1 480 A A A A 0.55
    CR 75
    Example 23 CR CR NBR 40 NBR 40 9.6 13.2 6.8 11.9 480 A A A A 0.55
    CR 60
    Example 24 CR CR NBR 50 NBR 40 9.4 12.6 6.7 11.7 480 B A A A 0.55
    CR 50
    Example 25 CR CR NBR 60 NBR 40 9.3 12.3 6.5 11.2 480 B A A A 0.55
    CR 40
    Example 26 CR CR NBR 25 NBR 20 9.0 11.6 6.6 9.4 480 A A B A 0.55
    CR 75
    Example 27 CR CR NBR 25 NBR 60 10.1 13.6 7.7 11.3 480 B A A A 0.55
    CR 75
    Comp. CR CR CR NBR 40 10.6 14.8 7.4 14.9 480 A C A A 0.55
    Example 17
    Comp. CR CR NBR 25 NBR 15 7.9 9.5 6.1 8.0 480 A A C A 0.55
    Example 18 CR 75
    Comp. CR CR NBR 25 NBR 65 11.0 12.0 7.6 12.6 480 C A A A 0.55
    Example 19 CR 75
    Comp. CR CR SBR 25 NBR 40 9.8 10.8 4.7 9.8 480 C C A A 0.55
    Example 20 CR 75
    Comp. CR CR NBR 25 CR 40 10.4 11.1 6.8 8.8 480 A A A C 0.55
    Example 21 CR 75
    Comp. CR CR NBR 25 SBR 40 9.6 13.1 6.4 11.7 480 A A A C 0.55
    Example 22 CR 75
  • As described above, according to the present invention, a glove excellent in chemical resistance and safety and good in tactile feeling and abrasion resistance, the glove being suitable as a protective glove, can be provided by forming a chloroprene-based rubber layer as a first layer and a mixed rubber layer of an NBR-based rubber and a chloroprene-based rubber as a second layer sequentially on a fabric glove.
  • Moreover, a glove that has more improved chemical resistance can be provided by further forming a chloroprene-based rubber layer as an intermediate layer between the first layer and the second layer.
  • Furthermore, a glove excellent in chemical resistance and safety and good in tactile feeling and abrasion resistance as well as in slip resistance, the glove being suitable as a protective glove, can be provided by causing the mixed rubber layer to contain NBR-based rubber particles.

Claims (8)

1. A chemical resistant glove which comprises a chloroprene-based rubber layer as a first layer and a mixed rubber layer containing a nitrile-butadiene-based rubber and a chloroprene-based rubber as a second layer sequentially formed on a fabric glove, wherein a mixing ratio of the nitrile-butadiene-based rubber and the chloroprene-based rubber in the mixed rubber layer as the second layer is 60:40 to 10:90 in a solid weight ratio.
2. The chemical resistant glove of claim 1, wherein the mixing ratio of the nitrile-butadiene-based rubber and the chloroprene-based rubber in the mixed rubber layer as the second layer is 40:60 to 20:80 in a solid weight ratio.
3. The chemical resistant glove of claim 1, wherein a chloroprene-based rubber layer as an intermediate layer is further formed between the chloroprene-based rubber layer as the first layer and the mixed rubber layer containing the nitrile-butadiene-based rubber and the chloroprene-based rubber as the second layer.
4. The chemical resistant glove of claim 1, wherein nitrile-butadiene-based rubber particles are contained in the mixed rubber layer as the second layer in an amount of 20 to 60 parts by weight, on a solid content basis, based on 100 parts by weight of a latex of the mixed rubber layer as the second layer.
5. The chemical resistant glove of claim 4, wherein a content of the nitrile-butadiene-based rubber particles is 30 to 50 parts by weight, on a solid basis, based on 100 parts by weight of the mixed rubber layer as the second layer.
6. The chemical resistant glove of claim 1, wherein a thickness of the first layer is in a range of from 0.18 to 0.23 mm.
7. The chemical resistant glove of claim 1, wherein a thickness of the second layer is in a range of from 0.14 to 0.18 mm.
8. The chemical resistant glove of claim 3, wherein a thickness of the intermediate layer is in a range of from 0.18 to 0.23 mm.
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US10154699B2 (en) * 2015-09-10 2018-12-18 Ansell Limited Highly chemical resistant glove
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US10927240B2 (en) 2016-09-01 2021-02-23 Lg Chem, Ltd. Latex composition for dip-molding, and molded article prepared from same
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