WO2017166282A1

WO2017166282A1 - Glove

Info

Publication number: WO2017166282A1
Application number: PCT/CN2016/078299
Authority: WO
Inventors: Tingshan ZHANG; Hiroki Tanaka; Zhiqiang Liu; Xuan Li; Ruipeng LIU
Original assignee: Dic Corporation
Priority date: 2016-04-01
Filing date: 2016-04-01
Publication date: 2017-10-05
Also published as: JP2018514654A

Abstract

Provided is a glove which has excellent abrasion resistance and has a surface having no stickness. The glove has a coagulation coating film of an aqueous resin composition an aqueous resin (A) including an aqueous urethane resin (A-1), an aqueous medium (B), and wax (C), in which the content of the wax (C) is within a range of 0.1 to 10 parts by mass with respect to 100 parts by mass of the aqueous resin (A), the melting point of the wax (C) is preferably within a range of 100℃ to 150℃, the average particle diameter of the wax (C) is preferably 10 μm or less, and the wax (C) is preferably high density polyethylene wax.

Description

GLOVE

Technical Field

The present invention relates to a glove which has excellent abrasion resistance and has a surface having no stickiness.

Background Art

As anti-slip processing of gloves, a processing method of forming a coating film on the outer surface of a glove using a solvent-based urethane resin containing an organic solvent such as N, N-dimethylformamide is widely used. However, due to the influence of the increasing societal trend toward a demand for environmentally conscious products in recent years, transition from a solvent-based urethane resin to an aqueous urethane resin is required even in glove applications.

Since gloves are used in various chemical industrial applications, gloves are required to have not only flexibility due to rubber elasticity but also high-level abrasion resistance. As a method of improving the abrasion resistance, a method of increasing the aromatic ring concentration of an aqueous urethane resin or a method of incorporating a urea bond in an aqueous urethane resin by chain extension by a diamine compound is disclosed (for example, refer to PTL 1) . However, further improvement in abrasion resistance has been strongly demanded, and the development of a method of easily improving the abrasion resistance regardless of the type of aqueous urethane resin has been demanded.

Citation List

Patent Literature

[PTL 1] WO2013/018478

Summary of Invention

Technical Problem

An object of the present invention is to provide a glove which has excellent abrasion resistance and has a surface having no stickiness.

Solution to Problem

The present invention provides a glove having a coagulation coating film of an aqueous resin composition containing an aqueous resin (A) including an aqueous urethane resin (A-1) , an aqueous medium (B) , and wax (C) , in which the content of the wax (C) is within a range of 0.1 to 10 parts by mass with respect to 100 parts by mass of the aqueous resin (A) .

Advantageous Effects of Invention

Since the glove of the present invention has excellent abrasion resistance and has a surface having no stickiness due to the coagulation coating film formed on the outer surface, the glove of the present invention can be suitably used as a glove used in various fields such as a chemical industry field, a food field, and the like.

Description of Embodiments

The aqueous resin composition used in the present invention contains an aqueous resin (A) including an aqueous urethane resin (A-1) , an aqueous medium (B) , and wax (C) as essential components, and the content of the wax (C) is within a range of 0.1 to 10 parts by mass with respect to 100 parts by mass of the aqueous resin (A) .

The aqueous urethane resin (A-1) can be dispersed in the aqueous medium (B) described below, and for example, an aqueous urethane resin having a hydrophilic group such as an anionic group, a cationic group, or a nonionic group； or an aqueous urethane resin forcibly dispersed in the aqueous medium (B) using an emulsifier can be used. These aqueous urethane resins (A-1) may be used alone or two or more types thereof may be used in combination. Among these, from the viewpoint of production stability, an aqueous urethane resin having a hydrophilic group is preferably used, and from the viewpoint of obtaining superior water dispersibility and coagulation properties by a coagulant, an aqueous urethane resin having an anionic group is more preferably used.

As a method of obtaining the aqueous urethane resin having an anionic group, a method using one or more compounds selected from the group consisting of compounds having a carboxyl group and compounds having a sulfonyl group as the raw materials is exemplified. Among these, from the viewpoint of obtaining superior water dispersibility and coagulation properties by a coagulant, a method using a compound having a carboxyl group is preferable.

As the compound having a carboxyl group, for example, a glycol compound having a carboxyl group such as 2, 2'-dimethylol propionic acid, 2, 2'-dimethylol butanoic acid, or 2, 2'-dimethylol butyric acid can be used. These compounds may be used alone or two or more types thereof may be used in combination.

As the compound having a sulfonyl group, for example, 3, 4-diaminobutane sulfonic acid, 3, 6-diamino-2-toluenesulfonic acid, 2, 6-diaminobenzene sulfonic acid, or N- (2-aminoethyl) -2-aminoethyl sulfonic acid can be used. These compounds may be used alone or two or more types thereof may be used in combination.

A part or all of the carboxyl groups and the sulfonyl groups may be neutralized with a basic compound in an aqueous resin composition. As the basic compound, for example, organic amines such as ammonia, triethylamine, pyridine, and morpholine； alkanolamines such as monoethanolamine and dimethylethanolamine； or metallic basic compounds including sodium, potassium, lithium, or calcium can be used.

As a method of obtaining the aqueous urethane resin having a cationic group, a method using one or two or more types of compounds having an amino group as the raw materials is exemplified.

As the compound having an amino group, for example, a compound having a primary or secondary amino group such as triethylenetetramine or diethylenetriamine； or a compound having a tertiary amino group such as an N-alkyldialkanolamine including N-methyldiethanolamine or N-ethyldiethanolamine or an N-alkyldiaminoalkylamine including N-methyldiaminoethylamine or N-ethyldiaminoethylamine can be used. These compounds may be used alone or two or more types thereof may be used in combination.

As a method of obtaining the aqueous urethane resin having a nonionic group, a method using one or two or more types of compounds having an oxyethylene structure as the raw materials is exemplified.

As the compound having an oxyethylene structure, for example, a polyether polyol having an oxyethylene structure such as polyoxyethylene glycol, polyoxyethylene polyoxypropylene glycol, or polyoxyethylene polyoxytetramethylene glycol can be used. These compounds may be used alone or two or more types thereof may be used in combination.

As the emulsifier which can be used when obtaining an aqueous urethane resin to be forcibly dispersed in the aqueous medium (B) , for example, a nonionic emulsifier such as polyoxyethylene nonylphenyl ether, polyoxyethylene lauryl ether, polyoxyethylene styrylphenyl ether, polyoxyethylene sorbitol tetraoleate, or a polyoxyethylene-polyoxypropylene copolymer； an anionic emulsifier such as a fatty acid salt including sodium oleate, alkyl sulfate, alkylbenzene sulfonate, alkylsulfosuccinate, naphthalene sulfonate, polyoxyethylene alkylsulfate, sodium alkanesulfonate, or sodium alkyldiphenyl ether sulfonate； or a cationic emulsifier such as an alkyl amine salt, an alkyl trimethyl ammonium salt, or an alkyl dimethyl benzyl ammonium salt can be used. These emulsifiers may be used alone or two or more types thereof may be used in combination.

As the aqueous urethane resin (A-1) , specifically, an aqueous urethane resin obtained by using a polyisocyanate (a1) , a polyol (a2) , raw materials used to produce the aqueous urethane resin having a hydrophilic group described above, and a chain extender (a3) as raw materials is preferably used. As a reaction for reacting these, a known urethanization reaction can be used.

As the polyisocyanate (a1) , for example, an aromatic polyisocyanate such as phenylene diisocyanate, toluene diisocyanate, diphenylmethane diisocyanate, naphthalene diisocyanate, polymethylene polyphenyl polyisocyanate, or carbodiimidized diphenylmethane polyisocyanates； or an aliphatic or alicyclic polyisocyanate such as hexamethylene diisocyanate, lysine diisocyanate, cyclohexane diisocyanate, isophorone diisocyanate, dicyclohexylmethane diisocyanate, xylylene diisocyanate, tetramethyl xylylene diisocyanate, dimer acid diisocyanate, or norbornene diisocyanate can be used. These polyisocyanates may be used alone or two or more types thereof may be used in combination. Among these, from the viewpoint of obtaining superior flexibility, an aromatic polyisocyanate is preferably used, and from the viewpoint of forming a hard segment having a suitable chain length and obtaining superior flexibility, diphenylmethane diisocyanate or toluene diisocyanate is more preferably used, and diphenylmethane diisocyanate is still more preferably used.

As the polyol (a2) , for example, a polyoxyalkylene polyol, a polyester polyol, a polyacrylic polyol, a polycarbonate polyol, or a polybutadiene polyol can be used. These polyols may be used alone or two or more types thereof may be used in combination. Among these, from the viewpoint of being capable of achieving both abrasion resistance and flexibility at a high level, a polyoxyalkylene polyol is preferably used. In addition, in a case where a polyoxyalkylene polyol and another polyol are used in combination, from the viewpoint of good mechanical properties, a polyester polyol and/or a polycarbonate polyol is preferably used in combination.

As the polyoxyalkylene polyol, for example, polyoxyethylene glycol, polyoxypropylene glycol, polyoxytetramethylene glycol, polyoxyethylene polyoxypropylene glycol, polyoxyethylene polyoxytetramethylene glycol, or polyoxypropylene polyoxytetramethylene glycol can be used. These polyoxyalkylene polyols may be used alone or two or more types thereof may be used in combination. Among these, from the viewpoint of being capable of obtaining superior abrasion resistance due to high strength, polyoxytetramethylene glycol is preferably used.

The number average molecular weight of the polyol (a2) is preferably within a range of 500 to 5,000 and more preferably within a range of 700 to 4,000 from the viewpoint of production stability of the aqueous urethane resin (A-1) and mechanical strength. Moreover, the number average molecular weight of the polyol (a2) indicates a value measured by gel permeation chromatography (GPC) under the following conditions.

Measuring apparatus: high speed GPC apparatus ( "HLC-8220 GPC" manufactured by Tosoh Corporation)

Column: the following columns manufactured by Tosoh Corporation are used in a state of being connected in series.

"TSKgel G5000" (7.8 mm I. D. x 30 cm) x 1

"TSKgel G4000" (7.8 mm I. D. x 30 cm) x 1

"TSKgel G3000" (7.8 mm I. D. x 30 cm) x 1

"TSKgel G2000" (7.8 mm I. D. x 30 cm) x 1

Detector: RI (differential refractometer)

Column temperature: 40℃

Eluent: tetrahydrofuran (THF)

Flow rate: 1.0 mL/min

Injection amount: 100 μL (a tetrahydrofuran solution having a sample concentration of 0.4％by mass)

Standard sample: a calibration curve is created using the following standard polystyrenes.

(Standard Polystyrene)

"TSKgel standard polystyrene A-500" manufactured by Tosoh Corporation

"TSKgel standard polystyrene A-1000" manufactured by Tosoh Corporation

"TSKgel standard polystyrene A-2500" manufactured by Tosoh Corporation

"TSKgel standard polystyrene A-5000" manufactured by Tosoh Corporation

"TSKgel standard polystyrene F-1" manufactured by Tosoh Corporation

"TSKgel standard polystyrene F-2" manufactured by Tosoh Corporation

"TSKgel standard polystyrene F-4" manufactured by Tosoh Corporation

"TSKgel standard polystyrene F-10" manufactured by Tosoh Corporation

"TSKgel standard polystyrene F-20" manufactured by Tosoh Corporation

"TSKgel standard polystyrene F-40" manufactured by Tosoh Corporation

"TSKgel standard polystyrene F-80" manufactured by Tosoh Corporation

"TSKgel standard polystyrene F-128" manufactured by Tosoh Corporation

"TSKgel standard polystyrene F-288" manufactured by Tosoh Corporation

"TSKgel standard polystyrene F-550" manufactured by Tosoh Corporation

As the chain extender (a3) , a chain extender having a number average molecular weight within a range of 50 to 450 can be used, and for example, a chain extender having an amino group such as ethylenediamine, 1, 2-propanediamine, 1, 6-hexamethylenediamine, piperazine, 2, 5-dimethylpiperazine, isophoronediamine, 1, 2-cyclohexanediamine, 1, 3-cyclohexanediamine, 1, 4-cyclohexanediamine, 4, 4'-dicyclohexyl methanediamine, 3, 3'-dimethyl-4, 4'-dicyclohexyl methanediamine, or hydrazine； or a chain extender having a hydroxyl group such as ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, dipropylene glycol, 1, 3-propanediol, 1, 3-butanediol, 1, 4-butanediol, hexamethylene glycol, saccharose, methylene glycol, glycerin, sorbitol, bisphenol A, 4, 4'-dihydroxydiphenyl, 4, 4'-dihydroxydiphenyl ether, or trimethylolpropane can be used. These chain extenders may be used alone or two or more types thereof may be used in combination. Among these, from the viewpoint of preventing a coagulation coating film from being hardened and being capable of achieving both abrasion resistance and flexibility at a high level, a chain extender having a hydroxyl group is preferably used, and from the viewpoint of forming a hard segment having a suitable chain length and obtaining superior abrasion resistance and flexibility, ethylene glycol or butane diol is more preferably used. The amount of the chain extender (a3) used is preferably within a range of 0.01％to 8％by mass and more preferably within a range of 0.05％to 5％by mass in the total mass of the raw materials configuring the urethane resin (A-1) , from the viewpoint of obtaining superior abrasion resistance and flexibility by crystallization.

In order to obtain superior flexibility and water dispersibility in addition to abrasion resistance and suppression of stickiness of a surface which are the problems to be solved by the present invention, as the aqueous urethane resin (A-1) , an aqueous urethane resin having an anionic group obtained by reacting an aromatic polyisocyanate, a polyoxyalkylene polyol, a glycol compound having a carboxyl group, and a chain extender having a hydroxyl group is preferably used.

As a production method of the aqueous urethane resin (A-1) , for example, the aqueous urethane resin (A-1) can be produced by mixing the polyisocyanate (a1) , the polyol (a2) , raw materials used to produce the aqueous urethane resin having a hydrophilic group described above, and the chain extender (a3) in the absence of a solvent or in the presence of an organic solvent and by subjecting the mixture to a urethanization reaction, for example, at a reaction temperature of 50℃ to 100℃ for 3 to 10 hours.

In addition, for example, the aqueous urethane resin (A-1) can be produced by mixing the polyisocyanate (a1) , the polyol (a2) , and raw materials used to produce the aqueous urethane resin having a hydrophilic group described above in the absence of a solvent or in the presence of an organic solvent, by reacting the mixture to produce a urethane prepolymer having an isocyanate group at a terminal of the molecule, for example, at a reaction temperature of 50℃ to 100℃ for 3 to 10 hours, and then, by reacting the urethane prepolymer with the chain extender (a3) .

The aqueous urethane resin (A-1) is preferably produced by, thereafter, neutralizing the carboxyl group in the aqueous urethane resin (A-1) if necessary, supplying the aqueous medium (B) described below thereto, and dispersing the aqueous urethane resin (A-1) in the aqueous medium (B) . In addition, in a case where an organic solvent is used when producing the aqueous urethane resin (A-1) , thereafter, the solvent is preferably further removed.

When the aqueous urethane resin (A-1) and the aqueous medium (B) are mixed, a device such as a homogenizer may be used if necessary.

In addition, when the aqueous urethane resin (A-1) is dispersed in the aqueous medium (B) , an emulsifier may be used from the viewpoint of improving the dispersion stability of the aqueous urethane resin (A-1) in the aqueous medium (B) .

As the emulsifier, for example, a nonion-based emulsifier such as polyoxyethylene nonylphenyl ether, polyoxyethylene lauryl ether, polyoxyethylene styrylphenyl ether, polyoxyethylene sorbitol tetraoleate, or a polyoxyethylene-polyoxypropylene copolymer； an anion-based emulsifier such as a fatty acid salt including sodium oleate, alkyl sulfate, alkylbenzene sulfonate, alkylsulfosuccinate, naphthalene sulfonate, polyoxyethylene alkylsulfate, sodium alkanesulfonate, or sodium alkyldiphenyl ether sulfonate； or a cation-based emulsifier such as an alkyl amine salt, an alkyl trimethyl ammonium salt, or an alkyl dimethyl benzyl ammonium salt can be used. These emulsifiers may be used alone or two or more types thereof may be used in combination.

The aqueous urethane resin (A-1) preferably has an oxyalkylene group within a range of 4 to 12 mol/kg and more preferably has an oxyalkylene group within a range of 5 to 11.5 mol/kg from the viewpoint of being capable of achieving both abrasion resistance and flexibility at a higher level. Moreover, the oxyalkylene group is supplied in a case where a polyoxyalkylene polyol is used as a raw material of the aqueous urethane resin (A-1) . Accordingly, the content of the oxyalkylene group in the aqueous urethane resin (A-1) indicates the content of the oxyalkylene group supplied from the polyoxyalkylene polyol with respect to the total mass of respective raw materials configuring the aqueous urethane resin (A-1) .

In addition, the content of the urea bond in the aqueous urethane resin (A-1) is preferably 0.2 mol/kg or less and more preferably 0.15 mol/kg or less from the viewpoint of being capable of achieving both abrasion resistance and flexibility at a higher level.

As the urea bond, a urea bond produced by a reaction with polyisocyanate in a case where a chain extender having an amino group as a raw material of the aqueous urethane resin (A-1) is used and a urea bond produced by a reaction of the amino acid, which has been produced by a reaction of isocyanate with water, with polyisocyanate are exemplified. Accordingly, by adjusting the amount of chain extender having an amino group used and by urethanizing all the isocyanate before an emulsification operation, it is possible to adjust the content of the urea bond in the aqueous urethane resin (A-1) . Moreover, the content of the urea bond indicates a value calculated by the following Equation (1) .

[Equation 1]

The average particle diameter of the aqueous urethane resin (A-1) is preferably within a range of 0.01 to 1 μm and more preferably within a range of 0.05 to 0.9 μm from the viewpoint of obtaining superior product stability due to precipitate formation prevention. Moreover, the average particle diameter of the aqueous urethane resin (A-1) indicates a value obtained by measuring the average particle diameter of the aqueous urethane resin (A-1) when the relative refractive index is 1.10 and the particle diameter is based on area, using water as a dispersing liquid, using a laser diffraction/scattering type particle size distribution measuring apparatus ("LA-910" manufactured by Horiba, Ltd. ) .

The weight average particle diameter of the aqueous urethane resin (A-1) is preferably within a range of 10,000 to 1,000,000 and more preferably within a range of 30,000 to 500,000 from the viewpoint of being capable of achieving both abrasion resistance and flexibility at a higher level. Moreover, the weight average particle diameter of the aqueous urethane resin (A-1) indicates a value obtained by measuring in the same manner as in the measurement of the number average molecular weight of the polyol (a2) .

The content of the urethane bond in the aqueous urethane resin (A-1) is preferably within a range of 500 mmol/kg to 3,500 mmol/kg and more preferably within a range of 700 mmol/kg to 3,000 mmol/kg with respect to the entirety of the aqueous urethane resin (A-1) , from the viewpoint of being capable of achieving both abrasion resistance and flexibility at a higher level. Moreover, the content of the urethane bond in the aqueous urethane resin (A-1) indicates the content of the urethane bond structure in the raw materials with respect to the total mass of respective raw materials configuring the aqueous urethane resin (A-1) .

The content of the aromatic ring in the aqueous urethane resin (A-1) is preferably within a range of 550 mmol/kg to 2,500 mmol/kg and more preferably within a range of 800 mmol/kg to 2,200 mmol/kg with respect to the entirety of the aqueous urethane resin (A-1) , from the viewpoint of being capable of achieving both abrasion resistance and flexibility at a higher level. Moreover, the content of the aromatic ring in the aqueous urethane resin (A-1) indicates the content of the aromatic ring in the raw materials with respect to the total mass of respective raw materials configuring the anionic polyurethane (A) . Moreover, the molecular weight of the aromatic ring is calculated using the molecular weight of a benzene ring or a naphthalene ring excluding the organic group. For example, in the case of toluene, the molecular weight of the aromatic ring indicates the molecular weight of the benzene ring having five hydrogen atoms excluding one methyl group, in the case of diphenylmethane diisocyanate, the molecular weight of the aromatic ring indicates the molecular weight of the benzene ring having four hydrogen atoms excluding the isocyanate group and the methylene group, and in the case of tolylene diisocyanate, the molecular weight of the aromatic ring indicates the molecular weight of the benzene ring having four hydrogen atoms excluding two methyl groups.

The aqueous resin (A) contains the aqueous urethane resin (A-1) as an essential component, and if necessary, other aqueous resins may be used in combination in terms of cost.

As other aqueous resins, for example, acrylonitrile-butadiene rubber, styrene-butadiene rubber, butadiene rubber, isoprene rubber, chloroprene rubber, or natural rubber can be used. These aqueous resins may be used alone or two or more types thereof may be used in combination. In a case where other aqueous resins are used in combination, among the above-described resins, acrylonitrile-butadiene rubber is preferably used since it is inexpensive and has good durability. In addition, the amount of other aqueous resins used in a case where other aqueous resins are used in combination is preferably within a range of 10％to 95％by mass, more preferably within a range of 30％to 95％by mass, and still more preferably within a range of 70％to 95％by mass, in terms of the solid content in the aqueous resin (A) .

The content of the aqueous resin (A) (solid content) in the aqueous resin composition is preferably within a range of 10％to 80％by mass and more preferably within a range of 20％to 60％by mass from the viewpoint of workability and production stability.

As the aqueous medium (B) , for example, water, an organic solvent miscible with water, and a mixture thereof can be used. As the organic solvent miscible with water, for example, alcohol solvents such as methanol, ethanol, n-propanol, and isopropanol； ketone solvents such as acetone and methyl ethyl ketone； polyalkylene glycol solvents such as ethylene glycol, diethylene glycol, and propylene glycol； alkyl ether solvents of polyalkylene polyol； and lactam solvents such as N-methyl-2-pyrrolidone can be used. Among these, water is preferably used from the viewpoint of environmental properties.

The content of the aqueous medium (B) in the aqueous resin composition is preferably within a range of 10％to 85％by mass and more preferably within a range of 30％to 70％by mass from the viewpoint of workability and production stability.

The wax (C) is an essential component to obtain excellent abrasion resistance. By blending the wax (C) , it is possible to easily improve the abrasion resistance regardless of the type of aqueous urethane resin.

In addition, it is essential that the content of the wax (C) is within a range of 0.1 to 10 parts by mass in terms of the solid content with respect to 100 parts by mass of the aqueous resin (A) . In a case where the content of the wax (C) is below 0.1 parts by mass, desired abrasion resistance improving effects is not obtained, and in a case where the content of the wax (C) is greater than 10 parts by mass, a problem that the external surface of a glove becomes sticky occurs. Moreover, the content of the wax (C) is preferably within a range of 0.5 to 6 parts by mass, more preferably within a range of 1 to 4 parts by mass, and still more preferably within a range of 1.5 to 3.5 parts by mass, from the viewpoint of obtaining more excellent abrasion resistance without impairing flexibility.

The melting point of the wax (C) is preferably within a range of 100℃ to 150℃, more preferably within a range of 110℃ to 140℃, and still more preferably within a range of 120℃ to 135℃, from the viewpoint of obtaining more excellent abrasion resistance due to higher crystallinity. Moreover, the melting point of the wax (C) indicates a value measured based on "5.3 Melting point test method" of JIS K 2235: 2009.

The average particle diameter of the wax (C) is preferably 10 μm or less, more preferably within a range of 0.01 to 5 μm, and still more preferably within a range of 0.5 to 3 μm, from the viewpoint of obtaining a more excellent hand feeling of the surface of a glove. Moreover, the average particle diameter of the wax (C) indicates a value measured based on a dynamic light scattering method.

As the wax (C) , specifically, wax derived from plants such as carnauba wax, rice wax, or jojoba oil； wax derived from animals such as beeswax, whale wax, or lanolin； wax derived from minerals such as montan wax, ozokerite, or ceresine； petroleum wax such as paraffin wax, microcrystalline wax, or petrolatum； or synthetic wax such as high density polyethylene wax, low density polyethylene wax, oxidized polyethylene wax, modified polyethylene wax, polypropylene wax, or silicone wax can be used. These waxes may be used alone or two or more types thereof may be used in combination. In addition, these waxes may be present alone in solid, or may be present in a state of being dispersed in water or the like.

As the wax (C) , among the above-described waxes, synthetic wax is preferably used from the viewpoint of being capable of further suppressing the stickiness of the external surface of a glove, and high density polyethylene wax is more preferably used from the viewpoint of obtaining more excellent flexibility. Moreover, the high density polyethylene wax indicates polyethylene wax having a melt flow rate within a range of 0.1 to 50 g/10 minutes, and the low density polyethylene wax indicates polyethylene wax having a melt flow rate greater than 50 g/10 minutes. Moreover, the melt flow rate indicates a value measured based on JIS K 6922-2: 2010.

As the production method of the aqueous resin composition used in the present invention, a method of adding the wax (C) into the composition of the aqueous resin (A) containing the aqueous medium (B) and mixing them is exemplified.

The aqueous resin composition used in the present invention contains the aqueous resin (A) , the aqueous medium (B), and the wax (C) , and may contain other additives, if necessary.

As the additives, for example, a thickener, an anti-foaming agent, a urethanization catalyst, a silane coupling agent, a filler, a thixo imparting agent, a tackifier, wax, a heat stabilizer, a light-resistant stabilizer, a fluorescent whitening agent, a foaming agent, a pigment, a dye, an anti-static agent, a moisture permeability improving agent, a water repellent, an oil repellent, a flame retardant, an anti-blocking agent, a hydrolysis inhibitor, a vulcanizer, or a vulcanization accelerator can be used. These additives may be used alone or two or more types thereof may be used in combination.

The thickener can be suitably used to adjust the viscosity of the aqueous resin composition and to facilitate processing to be caused by salt coagulation, and for example, a cellulose derivative such as hydroxyethyl cellulose, methyl cellulose, or carboxymethyl cellulose； or polyacrylate, polyvinylpyrrolidone, a urethane compound, or a polyether compound can be used. For example, the amount used in a case where the associative thickener is used is within a range of 0.5 to 5 parts by mass in terms of the solid content with respect to 100 parts by mass of the aqueous resin (A) .

As the anti-foaming agent, for example, an anti-foaming agent such as a silicone compound, a mineral oil compound, a polyglycol ether compound, a fatty acid ester compound, a metallic soap, or a fluorine compound can be used. These anti-foaming agents may be used alone or two or more types thereof may be used in combination.

The aqueous resin composition used in the present invention can also be used in the production of tubes such as a catheter, contraceptive devices such as a condom, or the like, in addition to gloves.

Examples of the method of preparing a coagulation coating film using the aqueous resin composition include a method of coating the surface of a release film with the aqueous resin composition, immersing the coated product in a predetermined coagulant, and drying the resultant product to thereby prepare a coagulation coating film.

As the method of coating a release film or the like with the aqueous resin composition, a method using a knife coating method, a spray method, a curtain coating method, a flow coating method, a roll coating method, or a brush coating method is exemplified. At this time, the viscosity of the aqueous resin composition is preferably within a range of 50 to 10,000 mPa·s and more preferably within a range of 1,000 to 3,000 mPa·s from the viewpoint of workability. Moreover, the viscosity of the aqueous resin composition indicates a value measured at 25℃ by using a B-type viscometer (40 P cone) .

As the coagulant in which the coated product of the aqueous resin composition is immersed, for example, a metallic salt solution of calcium nitrate, calcium chloride, zinc nitrate, zinc chloride, magnesium acetate, aluminum sulfate, or sodium chloride； or an acid solution of formic acid or acetic acid can be used. As the solvent capable of dissolving the metallic salt or acid, for example, water, methanol, ethanol, or isopropanol can be used. The metallic salt included in the coagulant is preferably contained within a range of 1％to 50％by mass with respect to the total amount of coagulant. In addition, the immersing time of the coated product in the coagulant is preferably 1 to 10 minutes. In addition, the coagulant is preferably used at a temperature of 5℃ to 60℃.

After immersing, by drying the coated product at a temperature of, for example, 50℃ to 150℃ for 1 minute to 1 hour, a coagulation coating film coagulated on the surface of a release film is formed.

In a case where a glove having the coagulation coating film is produced, first, the hand mold, a tube mold, or the like is immersed in the coagulant, subsequently, if necessary, the resultant productis dried, whereby a metallic salt in the coagulant is attached to the surface of the hand mold or the like. Next, the hand mold or the like is immersed in the aqueous resin composition, after the immersion, the surface is washed with water, and the resultant product is dried, whereby a coating film coagulated on the surface of the hand mold or the like is formed. Next, the coagulation coating film is peeled off from the hand mold or the like, thereby obtaining a glove having a coagulation coating film having a shape corresponding to the hand mold or the like on the outer surface. Even in a case where the tube is produced, it is possible to produce the tube in the same manner as described above except that the tube mold is used.

When the hand mold or the tube mold is immersed in a coagulant, the hand mold or the tube mold may be at an ordinary temperature, and may be heated to, for example, 30℃ to 70℃. In addition, the coagulant may also be at an ordinary temperature as in the hand mold or the like, but in a case where the hand mold or the like is heated, the coagulant may be heated to, for example, 30℃ to 70℃.

In addition, a glove-like product and a tube-like product formed of knitting of nylon fiber or the like may be put on the hand mold or the tube mold in advance. Specifically, first, after the hand mold on which the glove-like product or the like formed of knitting has been put is immersed in the coagulant, by drying the resultant product if necessary, the coagulant is impregnated into the glove-like product or the like. Next, after the hand mold or the like is immersed in the aqueous resin composition, by washing the surface with water and by drying the resultant product, a glove or the like formed of a coating film coagulated on the surface of the glove-like product is formed, and by peeling off the glove or the like from the hand mold, the glove-like product, or the like, it is possible to obtain a glove or the like formed of a coagulation coating film having a shape corresponding to the hand mold or the like. Even in a case where the tube mold is produced, it is possible to produce the tube mold in the same manner as described above except that the tube mold or a tube-like product formed of knitting of nylon fiber or the like is used.

The knitting is not limited to the nylon fiber, and knitting configured of polyester fiber, aramid fiber, polyethylene fiber, cotton, or the like can be used. In addition, instead of the knitting, fabric formed of the fiber described above can also be used. In addition, instead of the knitting, a glove-like product and a tube-like product formed of a resin material such as vinyl chloride, natural rubber, or synthetic rubber can also be used.

[Examples]

Hereinafter, the present invention will be described in more detail using examples.

[Preparation Example 1] Preparation of Aqueous Urethane Resin (A-1-1) Composition

895.3 parts by mass of polyoxytetramethylene glycol (number average molecular weight； 2,000, hereinafter, abbreviated to "PTMG2000" ) , 18 parts by mass of ethylene glycol (hereinafter, abbreviated to "EG" ) , 25.5 parts by mass of 2, 2'-dimethylol propionic acid (hereinafter, abbreviated to "DMPA" ) , 224 parts by mass of diphenylmethane diisocyanate (hereinafter, abbreviated to "MDI" ) , and 487 parts by mass of methyl ethyl ketone were put into a vessel which was equipped with a thermometer, a nitrogen gas introducing tube and a stirrer and whose inside was substituted with nitrogen gas, and the mixture was allowed to react at 70℃.

At the time when the viscosity of the reaction product reached a predetermined viscosity, 2.9 parts by mass of methanol was added thereto, the resultant mixture was stirred for 1 hour to finish the reaction, and 1, 257 parts by mass of methyl ethyl ketone was further added thereto as a diluent solvent, whereby an organic solvent solution of an aqueous urethane resin (A-1-1) was obtained.

Next, 19.2 parts by mass of triethylamine as a neutralizing agent was added to the organic solvent solution of the aqueous urethane resin (A-1-1) , followed by stirring, and 3,638 parts by mass of water was further added thereto, followed by stirring, whereby an aqueous dispersion of the aqueous urethane resin (A-1-1) was obtained. Next, the solvent in this aqueous dispersion was removed, whereby an aqueous urethane resin (A-1-1) composition having a nonvolatile content of 40％by mass and an acid value of 9.2 mgKOH/g was obtained. Moreover, with respect to the aqueous urethane resin (A-1-1) , the content of an oxyalkylene group was 10.7 mol/kg, the content of an aromatic ring was 1,300 mmol/kg, and the average particle diameter was 0.25 μm.

[Preparation Example 2] Preparation of Aqueous Urethane Resin (A-1-2) Composition

764.5 parts by mass of the PTMG2000, 18.9 parts by mass of butanediol (hereinafter, abbreviated to "BG" ) , 23.1 parts by mass of DMPA, 190.8 parts by mass of MDI, and 417.5 parts by mass of methyl ethyl ketone were put into a vessel which was equipped with a thermometer, a nitrogen gas introducing tube and a stirrer and whose inside was substituted with nitrogen gas, and the mixture was allowed to react at 70℃.

At the time when the viscosity of the reaction product reached a predetermined viscosity, 2.5 parts by mass of methanol was added thereto, the resultant mixture was stirred for 1 hour to finish the reaction, and 1,078.4 parts by mass of methyl ethyl ketone was further added thereto as a diluent solvent, whereby an organic solvent solution of an aqueous polyurethane resin (A-1-2) was obtained.

Next, 17.4 parts by mass of triethylamine as a neutralizing agent was added to the organic solvent solution of the aqueous urethane resin (A-1-2) , followed by stirring, and 3,200 parts by mass of water was further added thereto, followed by stirring, whereby an aqueous dispersion of the aqueous urethane resin (A-1-2) was obtained. Next, the solvent in this aqueous dispersion was removed, whereby an aqueous urethane resin (A-1-2) composition having a nonvolatile content of 40％by mass and an acid value of 9.7 mgKOH/g was obtained. Moreover, with respect to the aqueous urethane resin (A-1-2) , the content of an oxyalkylene group was 10.6 mol/kg, the content of an aromatic ring was 1,290 mmol/kg, and the average particle diameter was 0.14 μm.

[Preparation Example 3] Preparation of Aqueous Urethane Resin (A-1-3) Composition

581.4 parts by mass of the PTMG2000, 9.0 parts by mass of EG, 21.4 parts by mass of DMPA, 200 parts by mass of MDI, and 1243.7 parts by mass of methyl ethyl ketone were put into a vessel which was equipped with a thermometer, a nitrogen gas introducing tube and a stirrer and whose inside was substituted with nitrogen gas, and the mixture was allowed to react at 70℃. At the time when the reaction product reached a predetermined NCO％, the reaction was ended, whereby an organic solvent solution of an aqueous urethane resin (A-1-3) was obtained. Next, 16.2 parts by mass of triethylamine as a neutralizing agent was added to the organic solvent solution of the aqueous urethane resin (A-1-3) , followed by stirring, and 2,572.4 parts by mass of water and 17.4 parts by mass of piperazine were further added thereto, followed by stirring, whereby an aqueous dispersion of the aqueous urethane resin (A-1-3) was obtained. Next, the solvent in this aqueous dispersion was removed, whereby an aqueous urethane resin (A-1-3) composition having a nonvolatile content of 40％by mass and an acid value of 10.8 mgKOH/g was obtained. Moreover, with respect to the aqueous urethane resin (A-1-3) , the content of an oxyalkylene group was 9.7 mol/kg, the content of a urea bond was 0.24 mol/kg, and the average particle diameter was 0.83 μm.

[Preparation Example 4] Preparation of Acrylonitrile-Butadiene Rubber (X-1) Composition

145 parts of ion exchange water per 100 parts by weight of the following monomers was mixed with 0.05 part by mass of ethylenediaminetetraacetic acid, 0.25 parts by mass of a sodium salt of condensed naphthalenesulfonic acid, 1.5 parts by mass of sodium dodecyl benzenesulfonate, and 0.6 parts by mass of t-dodecyl mercaptan, and the mixture was mixed with 60％butadiene, 35％acrylonitrile, and 5％methacrylic acid in a reactor with a stirring and mixing device. The temperature of the mixture was raised to 45℃ and 0.05 parts by mass of a potassium persulfate catalyst was injected thereto to perform emulsion polymerization. When the conversion ratio from the monomers to a polymer reaches from 90％to 92％at the maximum polymerization temperature of 65℃, the polymerization was stopped with ammonia. The resultant product was cooled to an ambient temperature, and the pH thereof was adjusted to from 7.2 to 7.5 with ammonia. Thereafter, stripping was performed, and the resultant product was concentrated until the nonvolatile content became 44％. Thus, an acrylonitrile-butadiene rubber (X-1) composition of a carboxylated acrylonitrile-butadiene copolymer having a nonvolatile content of 44％by mass and a pH of 8.2 was obtained.

[Preparation Example 5] Preparation of Aqueous Resin Composition (1)

20 parts by mass of the aqueous urethane resin (A-1-1) composition, 80 parts by mass of the acrylonitrile-butadiene rubber (X-1) composition, and 1 part by mass of aqueous dispersing liquid ("ULTRALUBE MD-2000" manufactured by KEIM ADDITEC SURFACE GMBH, nonvolatile content: 50％by mass, melting point: 128℃, average particle diameter: 1.4 μm (manufacturer catalog value) , hereinafter, abbreviated to "MD-2000" ) of high density polyethylene wax (HDPE) were mixed and stirred, whereby an aqueous resin composition (1) was obtained.

[Preparation Example 6] Preparation of Aqueous Resin Composition (2)

20 parts by mass of the aqueous urethane resin (A-1-1) composition, 80 parts by mass of the acrylonitrile-butadiene rubber (X-1) composition, and 3 parts by mass of MD-2000 were blended and stirred, whereby an aqueous resin composition (2) was obtained.

[Preparation Example 7] Preparation of Aqueous Resin Composition (3)

20 parts by mass of the aqueous urethane resin (A-1-1) composition, 80 parts by mass of the acrylonitrile-butadiene rubber (X-1) composition, and 1 part by mass of oxidized polyethylene wax ("5223N4" manufactured by Shamrock Technologies, nonvolatile content: 100％by mass, melting point: 104℃, average particle diameter: 9 μm (manufacturer catalog value) , hereinafter, abbreviated to "5223N4" ) were blended and stirred, whereby an aqueous resin composition (3) was obtained.

[Preparation Example 8] Preparation of Aqueous Resin Composition (4)

20 parts by mass of the aqueous urethane resin (A-1-1) composition, 80 parts by mass of the acrylonitrile-butadiene rubber (X-1) composition, and 3 parts by mass of aqueous dispersing liquid of paraffin wax ("ULTRALUBE E-342/45FA" manufactured by KEIM ADDITEC SURFACE GMBH, nonvolatile content: 45％by mass, melting point: 57℃, average particle diameter: 0.01 to 0.5 μm (manufacturer catalog value) , hereinafter, abbreviated to "E342/45" ) were blended and stirred, whereby an aqueous resin composition (4) was obtained.

[Preparation Example 9] Preparation of Aqueous Resin Composition (5)

20 parts by mass of the aqueous urethane resin (A-1-1) composition, 80 parts by mass of the acrylonitrile-butadiene rubber (X-1) composition, and 1.5 parts by mass of aqueous dispersing liquid of high density polyethylene wax ("ULTRALUBE D-806" manufactured by KEIM ADDITEC SURFACE GMBH, nonvolatile content: 60％by mass, melting point: 128℃, average particle diameter: 7 μm (manufacturer catalog value) , hereinafter, abbreviated to "D-806" ) were blended and stirred, whereby an aqueous resin composition (5) was obtained.

[Preparation Example 10] Preparation of Aqueous Resin Composition (6)

20 parts by mass of the aqueous urethane resin (A-1-2) composition, 80 parts by mass of the acrylonitrile-butadiene rubber (X-1) composition, and 3 parts by mass of MD-2000 were mixed and stirred, whereby an aqueous resin composition (6) was obtained.

[Preparation Example 11] Preparation of Aqueous Resin Composition (7)

20 parts by mass of the aqueous urethane resin (A-1-1) composition, 80 parts by mass of the acrylonitrile-butadiene rubber (X-1) composition, and 0.06 parts by mass of MD-2000 were mixed and stirred, whereby an aqueous resin composition (7) was obtained.

[Preparation Example 12] Preparation of Aqueous Resin Composition (8)

20 parts by mass of the aqueous urethane resin (A-1-1) composition, 80 parts by mass of the acrylonitrile-butadiene rubber (X-1) composition, and 13 parts by mass of MD-2000 were mixed and stirred, whereby an aqueous resin composition (8) was obtained.

[Preparation Example 13] Preparation of Aqueous Resin Composition (9)

20 parts by mass of the aqueous urethane resin (A-1-3) composition and 80 parts by mass of the acrylonitrile-butadiene rubber (X-1) composition were mixed and stirred, whereby an aqueous resin composition (9) was obtained.

[Example 1]

A knitted glove formed of nylon fibers was put on a hand mold, then, this was immersed for 10 seconds in a calcium nitrate aqueous solution at room temperature adjusted to a concentration of 5％by mass and then pulled up, and the hand mold with the knitted glove was dried at room temperature for 4 minutes. Next, the hand mold with the knitted glove was immersed in the aqueous resin composition (1) for 2 seconds to form a coagulation coating film of the aqueous resin on the surface of the knitted glove, then, pulled up, and dried at room temperature for 10 minutes. Next, the hand mold with the knitted glove was immersed for 180 minutes in water, and then, pulled up. The hand mold with the knitted glove was dried for 20 minutes in an environment of 70℃ and further dried for 30 minutes in an environment of 120℃, and the knitted glove was taken out from the hand mold, whereby a glove coated with a coagulation coating film was obtained.

[Examples 2 to 6 and Comparative Examples 1 to 3]

A glove was obtained in the same manner as in Example 1 except that the aqueous resin composition used was replaced with the aqueous resin compositions shown in Table 1 or 2.

[Evaluation Method of Abrasion Resistance]

With respect to the palm portion of the glove obtained in each of Examples and Comparative Examples, the abrasion test was performed using a Martindale abrasion tester manufactured by INTEC CO., LTD. based on EN388: 2004, and evaluation was performed as follows.

"5" : the number of abrasions was 20,000 or more.

"4" : the number of abrasions was 13,000 or more and less than 20,000.

"3" : the number of abrasions was 8,000 or more and less than 13,000.

"2" : the number of abrasions was 2,000 or more and less than 8,000.

"1" : the number of abrasions was less than 2,000.

[Evaluation Method of Stickiness of Surface]

The surface of the glove obtained in each of Examples and Comparative Examples was touched by hand, and evaluation was performed as follows.

"A" : stickiness was not felt.

"C" : stickiness was felt.

[Evaluation Method of Flexibility]

The glove obtained in each of Examples and Comparative Examples was put on the hand, and evaluation was performed as follows according to ease of movement of the fingers.

"A" : hardness was not felt, and the fingers were very easy to move.

"C" : hardness was felt.

[Evaluation Method of Hand Feeling of Surface]

"A" : rough impression was weak, and a smooth feel was felt.

"B: a rough feel was slightly felt.

"C" : a rough feel was strongly felt.

[Table 1]

[Table 2]

It was found that the glove of the present invention had excellent abrasion resistance and had a surface having no stickiness.

On the other hand, Comparative Example 1 was an aspect in which the content of the wax (C) was below the range specified in the present invention, and the abrasion resistance was poor.

Comparative Example 2 was an aspect in which the content of the wax (C) was greater than the range specified in the present invention, and stickiness occurred on the external surface of the glove.

Comparative Example 3 was an aspect in which the wax (C) was not contained, and the abrasion resistance was poor.

Claims

A Glove, comprising:

a coagulation coating film of an aqueous resin composition containing an aqueous resin (A) including an aqueous urethane resin (A-1) , an aqueous medium (B) , and wax (C) ,

wherein the content of the wax (C) is within a range of 0.1 to 10 parts by mass with respect to 100 parts by mass of the aqueous resin (A) .
The glove according to Claim 1,

wherein the melting point of the wax (C) is within a range of 100℃ to 150℃.
The glove according to Claim 1,

wherein the average particle diameter of the wax (C) is 10 μm or less.
The glove according to Claim 1,

wherein the wax (C) is high density polyethylene wax.