JP2018514654A - gloves - Google Patents

Abstract

The problem to be solved by the present invention is to provide a glove having excellent wear resistance and having no surface stickiness. The present invention contains an aqueous resin (A) containing an aqueous urethane resin (A-1), an aqueous medium (B), and a wax (C), and the content of the wax (C) is the aqueous resin ( A) A glove characterized by having a solidified film of an aqueous resin composition in a range of 0.1 to 10 parts by mass with respect to 100 parts by mass. The melting point of the wax (C) is preferably in the range of 100 to 150 ° C. The average particle size of the wax (C) is preferably 10 μm or less. Furthermore, the wax (C) is preferably a high density polyethylene wax.

Description

  The present invention relates to a glove having excellent wear resistance and having no stickiness on the surface.

As a glove anti-slip process, a processing method is widely used in which a film is formed on the outer surface of a glove using a solvent-based urethane resin containing an organic solvent such as N, N-dimethylformamide. However, due to the influence of increasing social momentum on the recent demand for environmentally conscious products, there is a demand for a shift from solvent-based urethane resins to water-based urethane resins even in glove applications.

  Gloves are used in various chemical industry applications, and therefore require a high level of wear resistance as well as flexibility due to rubber elasticity. As a technique for improving the abrasion resistance, a technique for increasing the aromatic ring concentration of a water-based urethane resin or a method for incorporating a urea bond into a water-based urethane resin by chain extension with a diamine compound is disclosed (for example, Patent Document 1). See). However, there is a strong demand for further improvement in wear resistance, and there is a need for the development of a method for simply improving the wear resistance regardless of the type of aqueous urethane resin.

International Publication No. 2013/018478

  The problem to be solved by the present invention is to provide a glove having excellent wear resistance and having no surface stickiness.

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

  The glove of the present invention has excellent wear resistance due to the solidified film formed on the outer surface and has no stickiness on the surface, so it is used in various fields such as the chemical industry field and the food field. It can be suitably used as a glove.

  The aqueous resin composition used in the present invention contains an aqueous resin (A) containing an aqueous urethane resin (A-1), an aqueous medium (B), and a wax (C) as essential components, and The content of the wax (C) is in the 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 an aqueous medium (B) to be described later, for example, an aqueous urethane having a hydrophilic group such as an anionic group, a cationic group, or a nonionic group. Resin; an aqueous urethane resin or the like that is forcibly dispersed in the aqueous medium (B) with an emulsifier can be used. These aqueous urethane resins (A-1) may be used alone or in combination of two or more. Among these, it is preferable to use an aqueous urethane resin having a hydrophilic group from the viewpoint of production stability, and it has an anionic group from the viewpoint of obtaining further excellent water dispersibility and coagulability by a coagulant. It is more preferable to use an aqueous urethane resin.

  Examples of the method for obtaining the aqueous urethane resin having an anionic group include a method using as a raw material one or more compounds selected from the group consisting of a compound having a carboxyl group and a compound having a sulfonyl group. Among these, a method using a compound having a carboxyl group is preferable from the viewpoint of obtaining further excellent water dispersibility and coagulability by a coagulant.

  Examples of the compound having a carboxyl group include 2,2′-dimethylolpropionic acid, 2,2′-dimethylolbutanoic acid, 2,2′-dimethylolbutyric acid, and 2,2′-dimethylolpropionic acid. A glycol compound having a carboxyl group can be used. These compounds may be used alone or in combination of two or more.

  Examples of the compound having a sulfonyl group include 3,4-diaminobutanesulfonic acid, 3,6-diamino-2-toluenesulfonic acid, 2,6-diaminobenzenesulfonic acid, N- (2-aminoethyl)- 2-aminoethylsulfonic acid or the like can be used. These compounds may be used alone or in combination of two or more.

  The carboxyl group and sulfonyl group may be partially or completely neutralized with a basic compound in the aqueous resin composition. Examples of the basic compound include organic amines such as ammonia, triethylamine, pyridine, and morpholine; alkanolamines such as monoethanolamine and dimethylethanolamine; metal base compounds including sodium, potassium, lithium, calcium, and the like. Can do.

  Examples of the method for obtaining the aqueous urethane resin having a cationic group include a method using one or more of compounds having an amino group as a raw material.

  Examples of the compound having an amino group include compounds having primary and secondary amino groups such as triethylenetetramine and diethylenetriamine; N-alkyl dialkanolamines such as N-methyldiethanolamine and N-ethyldiethanolamine, and N-methyl. A compound having a tertiary amino group such as N-alkyldiaminoalkylamine such as diaminoethylamine and N-ethyldiaminoethylamine can be used. These compounds may be used alone or in combination of two or more.

  Examples of a method for obtaining the aqueous urethane resin having a nonionic group include a method using one or more compounds having an oxyethylene structure as a raw material.

  Examples of the compound having an oxyethylene structure include polyether polyols having an oxyethylene structure such as polyoxyethylene glycol, polyoxyethylene polyoxypropylene glycol, and polyoxyethylene polyoxytetramethylene glycol. These compounds may be used alone or in combination of two or more.

  Examples of the emulsifier that can be used in obtaining the aqueous urethane resin that is forcibly dispersed in the aqueous medium (B) include polyoxyethylene nonyl phenyl ether, polyoxyethylene lauryl ether, polyoxyethylene styryl phenyl ether, Nonionic emulsifiers such as polyoxyethylene sorbitol tetraoleate and polyoxyethylene / polyoxypropylene copolymers; fatty acid salts such as sodium oleate, alkyl sulfate esters, alkylbenzene sulfonates, alkyl sulfosuccinates, naphthalene sulfonates Anionic emulsifiers such as salts, polyoxyethylene alkyl sulfates, alkane sulfonate sodium salts, sodium alkyl diphenyl ether sulfonates; alkyl amine salts, alkyl trimethyl Ammonium salts, such as cationic emulsifiers such as alkyl dimethyl benzyl ammonium salts can be used. These emulsifiers may be used alone or in combination of two or more.

  Specifically as said water-based urethane resin (A-1), the polyisocyanate (a1), the polyol (a2), the raw material used in order to manufacture the water-based urethane resin which has an above described hydrophilic group, and chain extension It is preferable to use a material obtained using the agent (a3) as a raw material. These reactions can use known urethanization reactions.

  As the polyisocyanate, (a1) is, for example, an aromatic polyisocyanate such as phenylene diisocyanate, toluene diisocyanate, diphenylmethane diisocyanate, naphthalene diisocyanate, polymethylene polyphenyl polyisocyanate, carbodiimidized diphenylmethane polyisocyanate; hexamethylene diisocyanate, lysine diisocyanate, cyclohexane Aliphatic or alicyclic polyisocyanates such as diisocyanate, isophorone diisocyanate, dicyclohexylmethane diisocyanate, xylylene diisocyanate, tetramethylxylylene diisocyanate, dimer acid diisocyanate and norbornene diisocyanate can be used. These polyisocyanates may be used alone or in combination of two or more. Among these, it is preferable to use an aromatic polyisocyanate from the point that even more excellent flexibility is obtained, and from the point that even more flexibility can be obtained by forming a hard segment with an appropriate chain length, diphenylmethane diisocyanate, Or it is more preferable to use toluene diisocyanate, and it is still more preferable to use diphenylmethane diisocyanate.

  As said polyol (a2), polyoxyalkylene polyol, polyester polyol, polyacryl polyol, polycarbonate polyol, polybutadiene polyol, etc. can be used, for example. These polyols may be used alone or in combination of two or more. Among these, it is preferable to use a polyoxyalkylene polyol from the viewpoint that both wear resistance and flexibility can be achieved at a high level. Moreover, when using together a polyoxyalkylene polyol and another polyol, it is preferable to use together a polyester polyol and / or a polycarbonate polyol from the point that a mechanical physical property becomes favorable.

  Examples of the polyoxyalkylene polyol include polyoxyethylene glycol, polyoxypropylene glycol, polyoxytetramethylene glycol, polyoxyethylene polyoxypropylene glycol, polyoxyethylene polyoxytetramethylene glycol, and polyoxypropylene polyoxytetramethylene. Glycol or the like can be used. These polyoxyalkylene polyols may be used alone or in combination of two or more. Among these, it is preferable to use polyoxytetramethylene glycol because it has a high strength and can provide even more excellent wear resistance.

  The number average molecular weight of the polyol (a2) is preferably in the range of 500 to 5,000 from the viewpoint of production stability of the water-based urethane resin (A-1) and mechanical strength, and 700 to 4 More preferably, it is in the range of 1,000. In addition, the number average molecular weight of the said polyol (a2) shows the value measured on condition of the following by gel permeation chromatography (GPC) method.

Measuring device: High-speed GPC device (“HLC-8220GPC” manufactured by Tosoh Corporation)
Column: The following columns manufactured by Tosoh Corporation were connected in series.
"TSKgel G5000" (7.8 mm ID x 30 cm) x 1 "TSKgel G4000" (7.8 mm ID x 30 cm) x 1 "TSKgel G3000" (7.8 mm ID x 30 cm) x 1 “TSKgel G2000” (7.8 mm ID × 30 cm) × 1 detector: RI (differential refractometer)
Column temperature: 40 ° C
Eluent: Tetrahydrofuran (THF)
Flow rate: 1.0 mL / min Injection amount: 100 μL (tetrahydrofuran solution with a sample concentration of 0.4 mass%)
Standard sample: A calibration curve was prepared using the following standard polystyrene.

(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), those having a number average molecular weight in the range of 50 to 450 can be used. For example, ethylenediamine, 1,2-propanediamine, 1,6-hexamethylenediamine, piperazine, 2,5- Dimethylpiperazine, isophoronediamine, 1,2-cyclohexanediamine, 1,3-cyclohexanediamine, 1,4-cyclohexanediamine, 4,4'-dicyclohexylmethanediamine, 3,3'-dimethyl-4,4'-dicyclohexylmethane Chain extenders having amino groups such as diamine and hydrazine; ethylene glycol, diethylene recall, triethylene glycol, propylene glycol, dipropylene glycol, 1,3-propanediol, 1,3-butanediol, 1,4-butanediol , Hexamethylene grease Lumpur, saccharose, methylene glycol, glycerine, sorbitol, bisphenol A, 4,4'-dihydroxydiphenyl, 4,4'-dihydroxydiphenyl ether, and the like can be used a chain extender having a hydroxyl group such as trimethylol propane. These chain extenders may be used alone or in combination of two or more. Among these, it is preferable to use a chain extender having a hydroxyl group from the viewpoint of preventing hardening of the solidified film and achieving both high wear resistance and flexibility at a high level, and a hard segment having an appropriate chain length. It is more preferable to use ethylene glycol or butanediol from the standpoint of forming more excellent wear resistance and flexibility. The chain extender (a3) is used in an amount of 0 in the total mass of the raw materials constituting the urethane resin (A-1) from the standpoint of obtaining more excellent wear resistance and flexibility by crystallization. The range is preferably 0.01 to 8% by mass, and more preferably 0.05 to 5% by mass.

  As mentioned above, as said water-based urethane resin (A-1), in addition to the abrasion resistance which is a subject which this invention tends to solve, and the suppression of the stickiness of the surface, on obtaining the further outstanding softness | flexibility and water dispersibility. Then, it is preferable to use 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.

  As a manufacturing method of the said water-based urethane resin (A-1), the water-based urethane resin which has the said polyisocyanate (a1), the said polyol (a2), and the said hydrophilic group in the absence of a solvent or presence of an organic solvent, for example. It can manufacture by mixing the raw material used for manufacturing, and the said chain extender (a3), and making it urethanate at the reaction temperature of 50-100 degreeC for 3 to 10 hours, for example.

  Moreover, the water-based urethane resin (A-1) is, for example, a water-based urethane resin having the hydrophilic group and the polyisocyanate (a1), the polyol (a2), in the absence of a solvent or in the presence of an organic solvent. The raw materials used for the production are mixed and, for example, a urethane prepolymer having an isocyanate group at the molecular terminal is produced by reacting at a reaction temperature of 50 to 100 ° C. for 3 to 10 hours. It can also be produced by reacting the extender (a3).

  The aqueous urethane resin (A-1) is then neutralized with a carboxyl group or the like in the aqueous urethane resin (A-1) as necessary, and then supplied with an aqueous medium (B) to be described later. It is preferable to manufacture by dispersing the aqueous urethane resin (A-1) in the medium (B). Moreover, when using the organic solvent in the case of manufacture of the said water-based urethane resin (A-1), it is preferable to remove further after that.

  When mixing the aqueous urethane resin (A-1) and the aqueous medium (B), a machine such as a homogenizer may be used as necessary.

  Further, when the aqueous urethane resin (A-1) is dispersed in the aqueous medium (B), the dispersion stability of the aqueous urethane resin (A-1) in the aqueous medium (B) is improved. From the viewpoint, an emulsifier may be used.

  Examples of the emulsifier include nonionic emulsifiers such as polyoxyethylene nonylphenyl ether, polyoxyethylene lauryl ether, polyoxyethylene styryl phenyl ether, polyoxyethylene sorbitol tetraoleate, and polyoxyethylene / polyoxypropylene copolymer. Fatty acid salts such as sodium oleate, alkyl sulfates, alkylbenzene sulfonates, alkyl sulfosuccinates, naphthalene sulfonates, polyoxyethylene alkyl sulfates, alkane sulfonate sodium salts, sodium alkyl diphenyl ether sulfonates, etc. Anionic emulsifiers; Cationic emulsifiers such as alkylamine salts, alkyltrimethylammonium salts, and alkyldimethylbenzylammonium salts It can be used. These emulsifiers may be used alone or in combination of two or more.

  The aqueous urethane resin (A-1) preferably has an oxyalkylene group in the range of 4 to 12 mol / kg from the viewpoint that both wear resistance and flexibility can be achieved at a higher level. It is more preferable to have an oxyalkylene group in the range of ˜11.5 mol / kg. In addition, the said oxyalkylene group is supplied when a polyoxyalkylene polyol is used as a raw material of water-based urethane resin (A-1). Therefore, the content of the oxyalkylene group in the aqueous urethane resin (A-1) is supplied from the polyoxyalkylene polyol with respect to the total mass of each raw material constituting the aqueous urethane resin (A-1). The content of oxyalkylene groups is shown.

  Moreover, as said aqueous | water-based urethane resin (A-1), content of a urea bond is 0.2 mol / kg or less from the point which can make abrasion resistance and a softness | flexibility compatible at a still higher level. Is preferable, and it is more preferable that it is 0.15 mol / kg or less.

  The urea bond is formed by reacting with a polyisocyanate when a chain extender having an amino group is used as a raw material of the aqueous urethane resin (A-1), and formed by reacting an isocyanate group with water. Examples thereof include those produced by a reaction between an amino group and a polyisocyanate. Therefore, the content of urea bonds in the aqueous urethane resin (A-1) can be adjusted by adjusting the amount of the chain extender having an amino group, and by urethanizing all of the isocyanate before emulsifying operation. Can be adjusted. In addition, content of the said urea bond shows the value calculated by following General formula (1).

  The average particle size of the water-based urethane resin (A-1) is preferably in the range of 0.01 to 1 μm from the viewpoint that excellent product stability can be obtained by preventing the formation of precipitates. More preferably, it is in the range of 9 μm. In addition, the average particle diameter of the said water-based urethane resin (A-1) uses a water-based urethane resin (A-1) for the laser diffraction / scattering type particle size distribution measuring apparatus ("LA-910" by Horiba Ltd.). The average particle size when water is used as the dispersion, the relative refractive index = 1.10, and the particle size standard is area is shown.

  The weight average molecular weight of the water-based urethane resin (A-1) is in the range of 10,000 to 1,000,000 from the viewpoint that both wear resistance and flexibility can be achieved at a higher level. It is preferable that it is in the range of 30,000 to 500,000. In addition, the weight average molecular weight of the said water-based urethane resin (A-1) shows the value obtained by measuring similarly to the number average molecular weight of the said polyol (a2).

  As content of the urethane bond in the said water-based urethane resin (A-1), the said water-based urethane resin (A-1) whole from the point which can make abrasion resistance and a softness | flexibility compatible at a still higher level. Is preferably in the range of 500 mmol / kg to 3,500 mmol / kg, more preferably in the range of 700 mmol / kg to 3,000 mmol / kg. In addition, content of the urethane bond in the said water-based urethane resin (A-1) is content of the urethane bond structure which occupies in the said raw material with respect to the total mass of each raw material which comprises the said water-based urethane resin (A-1). Indicates.

  As content of the aromatic ring in the said water-based urethane resin (A-1), the said water-based urethane resin (A-1) whole from the point which can make abrasion resistance and a softness | flexibility compatible at a still higher level. Is preferably in the range of 550 mmol / kg to 2,500 mmol / kg, and more preferably in the range of 800 mmol / kg to 2,200 mmol / kg. In addition, content of the aromatic ring in the said water-based urethane resin (A-1) shows content of the aromatic ring which occupies in the said raw material with respect to the total mass of each raw material which comprises the said anionic polyurethane (A). In the calculation, the molecular weight of the benzene ring or naphthalene ring excluding the organic group is used as the molecular weight of the aromatic ring. For example, in the case of toluene, the molecular weight of a benzene ring having 5 hydrogen atoms excluding one methyl group, and in the case of diphenylmethane diisocyanate, the molecular weight of a benzene ring having 4 hydrogen atoms excluding an isocyanate group and a methylene group, In the case of tolylene diisocyanate, the molecular weight of a benzene ring having four hydrogen atoms excluding two methyl groups is shown.

  As said aqueous resin (A), although the said water-based urethane resin (A-1) is contained as an essential component, you may use other aqueous resin together from a cost point as needed.

  Examples of the other aqueous resin include acrylonitrile butadiene rubber, styrene butadiene rubber, butadiene rubber, isoprene rubber, chloroprene rubber, and natural rubber. These aqueous resins may be used alone or in combination of two or more. When the other aqueous resin is used in combination, it is preferable to use acrylonitrile butadiene rubber because it is inexpensive and has good durability. Moreover, as the usage-amount of the said other aqueous resin in the case of using the said other aqueous resin together, it is preferable that it is the range of 10-95 mass% in conversion of solid content in an aqueous resin (A), and is 30-95 mass. % Is more preferable, and 70 to 95% by mass is even more preferable.

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

  As said aqueous medium (B), water, the organic solvent mixed with water, a mixture thereof, etc. can be used, for example. Examples of the organic solvent miscible with water include 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; An alkyl ether solvent of polyol; a lactam solvent such as N-methyl-2-pyrrolidone can be used. Among these, it is preferable to use water from an environmental point of view.

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

  The wax (C) is an essential component for obtaining excellent wear resistance. By blending the wax (C), the wear resistance can be easily improved regardless of the type of the aqueous urethane resin.

  Moreover, as content of the said wax (C), it is essential that it is the range of 0.1-10 mass parts in conversion of solid content with respect to 100 mass parts of said aqueous resin (A). When the content of the wax (C) is less than 0.1 parts by mass, the desired effect of improving wear resistance cannot be obtained, and when the content exceeds 10 parts by mass, the external surface of the glove becomes sticky. Resulting in. In addition, as content of the said wax (C), it is preferable that it is the range of 0.5-6 mass parts from the point from which the further outstanding abrasion resistance is acquired, without impairing a softness | flexibility, 1-4 masses. More preferably, it is in the range of 1.5 parts to 3.5 parts by mass.

  The melting point of the wax (C) is preferably in the range of 100 to 150 ° C., and more preferably in the range of 110 to 140 ° C., from the viewpoint that even more excellent wear resistance is obtained due to high crystallinity. It is more preferable that it is in the range of 120 to 135 ° C. In addition, melting | fusing point of the said wax (C) shows the value measured based on "5.3 Melting | fusing point test method" of JISK2235: 2009.

  The average particle diameter of the wax (C) is preferably 10 μm or less, more preferably in the range of 0.01 to 5 μm, from the viewpoint that a more excellent feel on the surface of the glove is obtained. More preferably, it is in the range of 5 to 3 μm. In addition, the average particle diameter of the said wax (C) shows the value measured based on the dynamic light scattering method.

  Specific examples of the wax (C) include plant-derived waxes such as carnauba wax, rice wax, jojoba oil; waxes derived from animals such as beeswax, whale wax, lanolin; montan wax, ozokerite, ceresin, etc. Mineral-derived waxes; petroleum waxes such as paraffin wax, microcrystalline wax, petrolactam; synthetic waxes such as high-density polyethylene wax, low-density polyethylene wax, oxidized polyethylene wax, modified polyethylene wax, polypropylene wax, and silicon wax be able to. These waxes may be used alone or in combination of two or more. In addition, these waxes may be solid and present alone or dispersed in water or the like.

  As the wax (C), among those described above, it is preferable to use a synthetic wax from the viewpoint that the stickiness of the outer surface of the glove can be further suppressed, and from the point that further excellent flexibility can be obtained, a high density polyethylene wax. It is more preferable to use The high-density polyethylene wax indicates that the melt flow rate is in the range of 0.1 to 50 g / 10 minutes, and the low-density polyethylene wax indicates that the melt flow rate exceeds 50 g / 10 minutes. . In addition, the said melt flow rate shows the value measured based on JISK6922-2: 2010.

  As a method for preparing the aqueous resin composition used in the present invention, for example, a method of mixing and mixing the wax (C) with the composition of the aqueous resin (A) containing the aqueous medium (B). Can be mentioned.

  The aqueous resin composition used in the present invention contains the aqueous resin (A), the aqueous medium (B), and the wax (C), but contains other additives as necessary. You can do it.

  Examples of the additive include a thickener, an antifoaming agent, a urethanization catalyst, a silane coupling agent, a filler, a thixotropic agent, a tackifier, a wax, a heat stabilizer, a light stabilizer, and a fluorescent whitening agent. , Foaming agents, pigments, dyes, antistatic agents, moisture permeability improvers, water repellents, oil repellents, flame retardants, antiblocking agents, hydrolysis inhibitors, vulcanizing agents, vulcanization accelerators, and the like can be used. . These additives may be used alone or in combination of two or more.

  The thickener can be suitably used for adjusting the viscosity of the aqueous resin composition and facilitating processing by salt coagulation. For example, cellulose derivatives such as hydroxyethylcellulose, methylcellulose, carboxymethylcellulose; polyacrylic acid A salt, polyvinyl pyrrolidone, a urethane compound, a polyether compound, or the like can be used. As the usage-amount in the case of using the said association type | mold thickener, it is the range of 0.5-5 mass parts in conversion of solid content with respect to 100 mass parts of said aqueous resins (A), for example.

  Examples of the antifoaming agent include antifoaming agents such as silicone compounds, mineral oil compounds, polyglycol ether compounds, fatty acid ester compounds, metal soaps, and fluorine compounds. These antifoaming agents may be used alone or in combination of two or more.

  In addition to gloves, the aqueous resin composition used in the present invention can also be used in the manufacture of tubes such as catheters and contraceptives such as condoms.

  As a method for obtaining a coagulated film using the aqueous resin composition, for example, the aqueous resin composition is applied to the surface of a release film, and then the applied product is immersed in a predetermined coagulant and then dried. The method obtained by this is mentioned.

  Examples of a method for applying the aqueous resin composition to a release film include a method using a knife coater method, a spray method, a curtain coater method, a flow coater method, a roll coater method, a brush coating method, and the like. At that time, the viscosity of the aqueous resin composition is preferably in the range of 50 to 10,000 mPa · s, more preferably 1,000 to 3,000 mPa · s from the viewpoint of workability. preferable. The viscosity of the aqueous resin composition is a value measured with a B-type viscometer (40P cone) at 25 ° C.

  Examples of the coagulant for immersing the coating material of the aqueous resin composition include, for example, metal nitrate solutions such as calcium nitrate, calcium chloride, zinc nitrate, zinc chloride, magnesium acetate, aluminum sulfate, and sodium chloride; acids such as formic acid and acetic acid. A solution or the like can be used. Examples of the solvent that can dissolve the metal salt and acid include water, methanol, ethanol, and isopropanol. The metal salt contained in the coagulant is preferably contained in the range of 1 to 50% by mass with respect to the total amount of the coagulant. Moreover, it is preferable that the time for immersing the coating material in the coagulant is 1 to 10 minutes. The coagulant is preferably used at a temperature of 5 to 60 ° C.

  After the immersion, the solidified film is solidified on the surface of the release film by drying the coated material at a temperature of 50 to 150 ° C. for 1 minute to 1 hour, for example.

  When manufacturing a glove having the coagulation film, first, after immersing a hand mold, a pipe mold, etc. in the coagulant, the metal in the coagulant on the surface of the hand mold etc. is dried as necessary. Adhere salt. Next, after the hand mold or the like is immersed in the aqueous resin composition, the surface is washed with water and dried to form a solidified film on the surface of the hand mold or the like. Next, by peeling off the solidified film from the hand mold or the like, a glove having a solidified film having a shape corresponding to the hand mold or the like on the outer surface can be obtained. Also when manufacturing the said pipe | tube, it can manufacture by the method similar to the above except using the said pipe | tube type.

  The hand mold or tube mold may be at room temperature when immersed in the coagulant, and may be heated to 30 to 70 ° C., for example. Moreover, although the said coagulant may be normal temperature similarly to the said hand type | mold etc., when the said hand type | mold etc. are warmed, it may be heated at 30-70 degreeC, for example.

  The hand mold or tube mold may be preliminarily equipped with a glove-like article or tubular article made of knitted nylon fiber or the like. Specifically, first, after immersing a hand mold or the like on which the knitted glove-like article is attached in the coagulant, the coagulant is dried as necessary, so that the glove-like article is solidified. Impregnating agent. Next, after immersing the hand mold or the like in the aqueous resin composition, the surface is washed with water and dried to form a glove or the like formed of a solidified film on the surface of the glove-like material, By peeling the gloves and the like from the hand mold and the glove-like material, it is possible to obtain a glove made of a solidified film having a shape corresponding to the hand mold and the like. Also when manufacturing the said pipe | tube type, it can manufacture by the method similar to the above except using the tubular thing which consists of the said pipe | tube type and knitted materials, such as a nylon fiber.

  The knitted fabric is not limited to the nylon fiber, and a knitted fabric made of polyester fiber, aramid fiber, polyethylene fiber, cotton or the like can be used. Moreover, the textile fabric which consists of the said fiber can also be used instead of the said knitting. Moreover, instead of the knitted fabric, a glove-like article or a tubular article made of a resin material such as vinyl chloride, natural rubber, or synthetic rubber can be used.

  As described above, the glove of the present invention has excellent wear resistance due to the solidified film formed on the outer surface and has no stickiness on the surface, so that it can be used in various fields such as the chemical industry field and the food field. It can be suitably used as a used glove.

  Hereinafter, the present invention will be described in more detail with reference to examples.

[Preparation Example 1] Preparation of Aqueous Urethane Resin (A-1-1) Composition In a nitrogen-substituted container equipped with a thermometer, nitrogen gas, introduction pipe, and stirrer, the polyoxytetramethylene glycol (several Average molecular weight: 2,000, hereinafter abbreviated as “PTMG2000”) 895.3 parts by mass, ethylene glycol (hereinafter abbreviated as “EG”) 18 parts by mass, 2,2′-dimethylolpropionic acid ( (Hereinafter abbreviated as “DMPA”) was reacted at 70 ° C. in the presence of 25.5 parts by mass, 224 parts by mass of diphenylmethane diisocyanate (hereinafter abbreviated as “MDI”), and 487 parts by mass of methyl ethyl ketone.
When the reaction product reaches the specified viscosity, 2.9 parts by mass of methanol is added and stirred for 1 hour to complete the reaction. Further, 1,257 parts by mass of methyl ethyl ketone is added as a diluting solvent to add an aqueous urethane resin (A- An organic solvent solution of 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) and stirred, and further, 3,638 parts by mass of water was added and stirred to obtain an aqueous solution. An aqueous dispersion of urethane resin (A-1-1) was obtained. Subsequently, the aqueous dispersion was desolventized to obtain 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. The aqueous urethane resin (A-1-1) had an oxyalkylene group content of 10.7 mol / kg, an aromatic ring content of 1,300 mmol / kg, and an average particle size of 0.25 μm. .

[Preparation Example 2] Preparation of Aqueous Urethane Resin (A-1-2) Composition In a nitrogen-substituted container equipped with a thermometer, nitrogen gas, introduction pipe, and stirrer, 764.5 parts by mass of the PTMG2000 In the presence of 18.9 parts by weight of butanediol (hereinafter abbreviated as “BG”), 23.1 parts by weight of DMPA, 190.8 parts by weight of MDI, and 417.5 parts by weight of methyl ethyl ketone, 70 ° C. It was made to react with.
When the reaction product reaches the specified viscosity, 2.5 parts by mass of methanol is added and stirred for 1 hour to complete the reaction. Further, by adding 1,078.4 parts by mass of methyl ethyl ketone as a diluent solvent, an aqueous polyurethane resin ( An organic solvent solution of 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 water-based urethane resin (A-1-2) and stirred, and 3,200 parts by mass of water was further added and stirred. An aqueous dispersion of urethane resin (A-1-2) was obtained. Next, the aqueous dispersion was desolvated to obtain 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. The aqueous urethane resin (A-1-2) had an oxyalkylene group content of 10.6 mol / kg and an aromatic ring content of 1,290 mmol / kg and an average particle size of 0.14 μm.

[Preparation Example 3] Preparation of aqueous urethane resin (A-1-3) composition 581.4 parts by mass of PTMG2000 in a nitrogen-substituted container equipped with a thermometer, nitrogen gas, introduction pipe, and stirrer EG was reacted at 70 ° C. in the presence of 9.0 parts by mass, DMPA 21.4 parts by mass, MDI 200 parts by mass, and methylethylketone 1243.7 parts by mass. The reaction was terminated when the reaction product reached the specified NCO%, and 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 water-based urethane resin (A-1-3) and stirred, and 2,572.4 parts by mass of water and 17.37 of piperazine were added. By adding 4 parts by mass and stirring, an aqueous dispersion of an aqueous urethane resin (A-1-3) was obtained. Next, the aqueous dispersion was desolvated to obtain an aqueous urethane resin (A-1-3) composition having a nonvolatile content of 40% by mass and an acid value of 10.8 mg KOH / g. The aqueous urethane resin (A-1-3) had an oxyalkylene group content of 9.7 mol / kg, a urea bond content of 0.24 mol / kg, and an average particle size of 0.83 μm. .

[Adjustment Example 4] Preparation of acrylonitrile butadiene rubber (X-1) composition 145 parts of ion-exchanged water per 100 parts by weight of monomer, 0.05 part by weight of ethylenediaminetetraacetic acid, and sodium salt of condensed naphthalenesulfonic acid 0.25 Part by mass, 1.5 parts by mass of sodium dodecylbenzenesulfonate, 0.6 parts by mass of t-dodecyl mercaptan, and further mixed with 60% butadiene, 35% acrylonitrile, 5% methacrylic acid in a reactor equipped with a stirring mixer did. The mixture was raised to 45 ° C., 0.05 part by mass of potassium persulfate catalyst was injected, and emulsion polymerization was performed. The polymerization was terminated with ammonia when the maximum polymerization temperature was 65 ° C. and the conversion of the monomer to the polymer reached 90 to 92%. After cooling to ambient temperature, the pH is further adjusted to 7.2-7 with ammonia. 5 was prepared. Thereafter, stripping was performed, and the solution was concentrated until the nonvolatile content became 44%. 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 aqueous urethane resin (A-1-1) composition, 80 parts by mass of acrylonitrile butadiene rubber (X-1) composition, high density polyethylene Aqueous dispersion of wax (HDPE) (“ULTRALUBE MD-2000” manufactured by Keim addtec, nonvolatile content: 50 mass%, melting point: 128 ° C., average particle size: 1.4 μm (manufacturer catalog value), hereinafter “MD-2000” The aqueous resin composition (1) was obtained by mixing and stirring 1 part by mass.

[Preparation Example 6] Preparation of aqueous resin composition (2) 20 parts by mass of aqueous urethane resin (A-1-1) composition, 80 parts by mass of acrylonitrile butadiene rubber (X-1) composition, MD-2000 3 parts by mass was mixed and stirred to obtain an aqueous resin composition (2).

[Preparation Example 7] Preparation of aqueous resin composition (3) 20 parts by mass of aqueous urethane resin (A-1-1) composition, 80 parts by mass of acrylonitrile butadiene rubber (X-1) composition, polyethylene oxide wax 1 part by weight of “Shamrock“ 5223N4 ”, nonvolatile content: 100% by mass, melting point: 104 ° C., average particle size: 9 μm (manufacturer catalog value), hereinafter abbreviated as“ 5223N4 ”) is mixed and stirred. Thus, an aqueous resin composition (3) was obtained.

[Preparation Example 8] Preparation of aqueous resin composition (4) 20 parts by mass of aqueous urethane resin (A-1-1) composition, 80 parts by mass of acrylonitrile butadiene rubber (X-1) composition, paraffin wax Aqueous dispersion (“ULTRALUBE E-342 / 45FA” manufactured by Keim addtec, nonvolatile content: 45 mass%, melting point: 57 ° C., average particle size: 0.01 to 0.5 μm (manufacturer catalog value), hereinafter “E342 / 45 ”) was blended with 3 parts by mass and stirred to obtain an aqueous resin composition (4).

[Preparation Example 9] Preparation of aqueous resin composition (5) 20 parts by mass of aqueous urethane resin (A-1-1) composition, 80 parts by mass of acrylonitrile butadiene rubber (X-1) composition, high density polyethylene Aqueous dispersion of wax (“ULTRALUBE D-806” manufactured by Keim addtec, nonvolatile content: 60 mass%, melting point: 128 ° C., average particle size: 7 μm (manufacturer catalog value), hereinafter abbreviated as “D-806”. ) Was mixed with 1.5 parts by mass, and stirred to obtain an aqueous resin composition (5).

[Preparation Example 10] Preparation of aqueous resin composition (6) 20 parts by mass of aqueous urethane resin (A-1-2) composition, 80 parts by mass of acrylonitrile butadiene rubber (X-1) composition, “MD- The aqueous resin composition (6) was obtained by mixing and stirring 3 parts by weight of “2000”.

[Preparation Example 11] Preparation of aqueous resin composition (7) 20 parts by mass of aqueous urethane resin (A-1-1) composition, 80 parts by mass of acrylonitrile butadiene rubber (X-1) composition, “MD- The aqueous resin composition (7) was obtained by mixing and stirring 0.06 parts by mass of “2000”.

[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, “MD- The aqueous resin composition (8) was obtained by mixing and stirring 13 parts by mass of “2000”.

[Preparation Example 13] Preparation of aqueous resin composition (9) 20 parts by mass of aqueous urethane resin (A-1-3) composition and 80 parts by mass of acrylonitrile butadiene rubber (X-1) composition were mixed and stirred. As a result, an aqueous resin composition (9) was obtained.

[Example 1]
Nylon fiber knitted gloves were attached to the hand mold, dipped in a normal temperature calcium nitrate aqueous solution adjusted to a concentration of 5% by weight for 10 seconds, and then dried for 4 minutes at room temperature. Next, the hand mold was dipped in the aqueous resin composition (1) for 2 seconds to form a solidified film of the aqueous resin on the surface of the knitted glove, and then pulled up and dried at room temperature for 10 minutes. Next, the hand mold was dipped in water for 180 minutes and pulled up. Furthermore, the hand mold was dried in an environment of 70 ° C. for 20 minutes, and further dried in an environment of 120 ° C. for 30 minutes. Thereafter, the knitted glove was removed from the hand mold to obtain a glove coated with a solidified film.

[Examples 2-6, Comparative Examples 1-3]
Gloves were obtained in the same manner as in Example 1 except that the aqueous resin composition used was changed as shown in Tables 1 and 2.

[Abrasion resistance evaluation method]
The abrasion test of the palm part of the glove obtained in Examples and Comparative Examples was performed according to EN 388: 2004 using a Martindale abrasion tester manufactured by Intec Corporation, and evaluated as follows.
“5”: The number of wear is 20,000 or more.
“4”: The number of wears is 13,000 times or more and less than 20,000 times.
“3”: The number of wear is 8,000 times or more and less than 13,000 times.
“2”: The number of wear is 2,000 times or more and less than 8,000 times.
“1”: The number of wears is less than 2,000.

[Evaluation method of surface stickiness]
The surfaces of the gloves obtained in the examples and comparative examples were touched by hand and evaluated as follows.
“O”; no stickiness.
“×”; feels sticky.

[Flexibility evaluation method]
The gloves obtained in Examples and Comparative Examples were worn on the hand and evaluated as follows according to the ease of finger movement.
“○”: The finger is very easy to move without feeling hardness.
“×”; feels hardness.

[Surface feel evaluation method]
The surfaces of the gloves obtained in the examples and comparative examples were touched by hand and evaluated as follows.
“○”: The rough impression is weak and the feel is smooth.
“△”; feels a little rough.
“X”; a rough feel is strong.

  The glove of the present invention was found to have excellent wear resistance and no stickiness on the surface.

  On the other hand, Comparative Example 1 is an embodiment in which the content of the wax (C) is lower than the range defined in the present invention, but the wear resistance was poor.

  Comparative Example 2 is an embodiment in which the content of the wax (C) exceeds the range defined in the present invention, but stickiness occurred on the outer surface of the glove.

  Comparative Example 3 was an embodiment that did not contain wax (C), but was poor in abrasion resistance.

[Examples 2-6, Comparative Examples 1-3]
Gloves were obtained in the same manner as in Example 1 except that the aqueous resin composition used was changed as shown in Tables 1 and 2. Examples 3 and 4 are reference examples.

Claims (4)

An aqueous resin (A) containing an aqueous urethane resin (A-1), an aqueous medium (B), and a wax (C) are contained, and the content of the wax (C) is 100 masses of the aqueous resin (A). A glove having a solidified film of an aqueous resin composition in a range of 0.1 to 10 parts by mass with respect to parts. The glove according to claim 1, wherein the melting point of the wax (C) is in the range of 100 to 150 ° C. The glove according to claim 1, wherein the wax (C) has an average particle size of 10 µm or less. The glove according to claim 1, wherein the wax (C) is a high-density polyethylene wax.