WO2017183271A1 - 手袋 - Google Patents
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- WO2017183271A1 WO2017183271A1 PCT/JP2017/005658 JP2017005658W WO2017183271A1 WO 2017183271 A1 WO2017183271 A1 WO 2017183271A1 JP 2017005658 W JP2017005658 W JP 2017005658W WO 2017183271 A1 WO2017183271 A1 WO 2017183271A1
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- WIPO (PCT)
- Prior art keywords
- urethane resin
- mass
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- fluorine compound
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Classifications
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- A—HUMAN NECESSITIES
- A41—WEARING APPAREL
- A41D—OUTERWEAR; PROTECTIVE GARMENTS; ACCESSORIES
- A41D19/00—Gloves
- A41D19/015—Protective gloves
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- A—HUMAN NECESSITIES
- A41—WEARING APPAREL
- A41D—OUTERWEAR; PROTECTIVE GARMENTS; ACCESSORIES
- A41D19/00—Gloves
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- A—HUMAN NECESSITIES
- A41—WEARING APPAREL
- A41D—OUTERWEAR; PROTECTIVE GARMENTS; ACCESSORIES
- A41D19/00—Gloves
- A41D19/0055—Plastic or rubber gloves
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/22—Esters containing halogen
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/08—Processes
- C08G18/0804—Manufacture of polymers containing ionic or ionogenic groups
- C08G18/0819—Manufacture of polymers containing ionic or ionogenic groups containing anionic or anionogenic groups
- C08G18/0823—Manufacture of polymers containing ionic or ionogenic groups containing anionic or anionogenic groups containing carboxylate salt groups or groups forming them
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/30—Low-molecular-weight compounds
- C08G18/34—Carboxylic acids; Esters thereof with monohydroxyl compounds
- C08G18/348—Hydroxycarboxylic acids
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
- C08G18/44—Polycarbonates
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
- C08G18/75—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic
- C08G18/751—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring
- C08G18/752—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group
- C08G18/753—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group containing one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group having a primary carbon atom next to the isocyanate or isothiocyanate group
- C08G18/755—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group containing one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group having a primary carbon atom next to the isocyanate or isothiocyanate group and at least one isocyanate or isothiocyanate group linked to a secondary carbon atom of the cycloaliphatic ring, e.g. isophorone diisocyanate
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
- C08G18/75—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic
- C08G18/758—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing two or more cycloaliphatic rings
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
- C08L33/04—Homopolymers or copolymers of esters
- C08L33/14—Homopolymers or copolymers of esters of esters containing halogen, nitrogen, sulfur, or oxygen atoms in addition to the carboxy oxygen
- C08L33/16—Homopolymers or copolymers of esters containing halogen atoms
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L75/00—Compositions of polyureas or polyurethanes; Compositions of derivatives of such polymers
- C08L75/04—Polyurethanes
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
- C09D175/04—Polyurethanes
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
- C09D175/04—Polyurethanes
- C09D175/08—Polyurethanes from polyethers
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- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
- D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
- D06M15/37—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
- D06M15/564—Polyureas, polyurethanes or other polymers having ureide or urethane links; Precondensation products forming them
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- A—HUMAN NECESSITIES
- A41—WEARING APPAREL
- A41D—OUTERWEAR; PROTECTIVE GARMENTS; ACCESSORIES
- A41D2400/00—Functions or special features of garments
- A41D2400/80—Friction or grip reinforcement
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- A—HUMAN NECESSITIES
- A41—WEARING APPAREL
- A41D—OUTERWEAR; PROTECTIVE GARMENTS; ACCESSORIES
- A41D2500/00—Materials for garments
- A41D2500/50—Synthetic resins or rubbers
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- A—HUMAN NECESSITIES
- A41—WEARING APPAREL
- A41D—OUTERWEAR; PROTECTIVE GARMENTS; ACCESSORIES
- A41D2500/00—Materials for garments
- A41D2500/50—Synthetic resins or rubbers
- A41D2500/54—Synthetic resins or rubbers in coated form
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/01—Use of inorganic substances as compounding ingredients characterized by their specific function
- C08K3/013—Fillers, pigments or reinforcing additives
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/0008—Organic ingredients according to more than one of the "one dot" groups of C08K5/01 - C08K5/59
- C08K5/0075—Antistatics
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/54—Silicon-containing compounds
- C08K5/541—Silicon-containing compounds containing oxygen
- C08K5/5415—Silicon-containing compounds containing oxygen containing at least one Si—O bond
- C08K5/5419—Silicon-containing compounds containing oxygen containing at least one Si—O bond containing at least one Si—C bond
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/54—Aqueous solutions or dispersions
Definitions
- the present invention relates to a glove having a film made of an aqueous urethane resin composition.
- Synthetic rubbers such as natural rubber and nitrile rubber, which are generally used as elastic materials, can cause allergies due to contact with them, so they may be avoided in glove applications.
- rubber elasticity A relatively flexible solvent-type urethane resin having a high molecular weight is widely used.
- a glove using the water-based urethane resin for example, a glove using a water-dispersed resin liquid containing water-based urethane and an organic filler is known (see, for example, Patent Document 1).
- a glove using a water-dispersed resin liquid containing water-based urethane and an organic filler is known (see, for example, Patent Document 1).
- the film made of the water-based urethane resin is formed on the outside of the glove, there is a problem that the grip (non-slip) property is poor.
- the problem to be solved by the present invention is to provide a glove having improved oil grip properties using a water-based urethane resin.
- the present invention is a glove having a film formed of an aqueous urethane resin composition containing an aqueous urethane resin (A), an aqueous medium (B), and a fluorine compound (C), the fluorine compound (C) Is a polymerizable monomer having a fluorinated alkyl group having 4 to 6 carbon atoms (c1-1) and a polymerizable monomer having a polyoxyethylene structure represented by the following general formula (2) (c1- 2) a polymerizable compound (C2-1), which is a polymerized product, or a polymerizable monomer (c2-1) having a polymerizable unsaturated group at both ends of a poly (perfluoroalkylene ether) chain, and the following general formula
- the present invention provides a glove characterized by being a fluorine compound (C-2) which is a polymer of a polymerizable monomer (c2-2) having a polyoxyalkylene structure represented by (4).
- R represents a hydrogen atom or a methyl group
- n represents an integer in the range of 1 to 30.
- R represents a hydrogen atom or a methyl group
- X and Y each represents an independent alkylene group
- n and m each independently represents 0 or an integer in the range of 1 to 30, and The sum of n and m is 1 or more.
- the glove of the present invention has excellent oil grip properties. Moreover, since the water-based urethane resin composition is used, the environmental load at the time of glove manufacture is also small. Therefore, the glove of the present invention can be suitably used as an industrial glove used in various fields such as the chemical industry field, food field, and medical field.
- the glove of the present invention has a film formed of an aqueous urethane resin composition containing an aqueous urethane resin (A), an aqueous medium (B), and a specific fluorine compound (C).
- the aqueous urethane resin (A) can be dispersed in an aqueous medium (B) to be described later.
- the aqueous urethane resin (A) has a hydrophilic group such as an anionic group, a cationic group, or a nonionic group; Those that are forcibly dispersed in the aqueous medium (B) can be used.
- These aqueous urethane resins (A) may be used alone or in combination of two or more.
- an aqueous urethane resin having a hydrophilic group it is preferable to use an aqueous urethane resin having an anionic group having the best water dispersion stability.
- 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, it is preferable to use a compound having a carboxyl group and / or a compound having a sulfonyl group from the viewpoint of obtaining further excellent water dispersion stability and oil grip properties.
- the compound having a carboxyl group for example, 2,2-dimethylolpropionic acid, 2,2-dimethylolbutanoic acid, 2,2-dimethylolbutyric acid, 2,2-valeric acid and the like 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 urethane resin composition.
- a 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 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-alkyldialkanolamines 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 the 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, alkyl diphenyl ether sodium sulfonates; alkyl amine salts, alkyl trimethyl
- aqueous urethane resin (A) a polyol (a1), a polyisocyanate (a2), a chain extender (a3), and an aqueous urethane resin having a hydrophilic group as described above are produced as necessary.
- a polyol (a1), a polyisocyanate (a2), a chain extender (a3), and an aqueous urethane resin having a hydrophilic group as described above are produced as necessary.
- those obtained by reacting the raw materials used for the purpose can be used.
- polyol (a1) examples include polyether polyol, polyester polyol, polyacryl polyol, polycarbonate polyol, polybutadiene polyol, compound having a carboxyl group, compound having a sulfonyl group, compound having an amino group, and oxy A compound having an ethylene structure or the like can be used. These polyols may be used alone or in combination of two or more. Among these, the polyol (a1) includes at least one selected from the group consisting of polyester polyols, polyether polyols, and polycarbonate polyols from the viewpoint that oil grip properties, flexibility, and chemical resistance can be further improved. It is preferable to contain.
- polyester polyol for example, a reaction product of a compound having a hydroxyl group and a polybasic acid can be used.
- Examples of the compound having a hydroxyl group include ethylene glycol, propylene glycol, butanediol, pentanediol, hexanediol, heptanediol, octanediol, nonanediol, decanediol, diethylene glycol, dipropylene glycol, neopentyl glycol, and 3-methyl.
- Pentanediol, cyclohexanedimethanol, trimethylolpropane, trimethylolethane, glycerin and the like can be used. These compounds may be used alone or in combination of two or more.
- polybasic acid examples include oxalic acid, malonic acid, succinic acid, adipic acid, sebacic acid, azelaic acid, 1,12-dodecanedicarboxylic acid, maleic acid, glutaric acid, pimelic acid, itaconic acid, chlorendic acid, 1,2,4-butane-tricarboxylic acid, chlorendic acid, terephthalic acid, isophthalic acid, phthalic acid, 1,4-naphthalenedicarboxylic acid, 2,5-naphthalenedicarboxylic acid, 2,6-naphthalenedicarboxylic acid, naphthalic acid, Biphenyldicarboxylic acid, 1,2-bis (phenoxy) ethane-p, p'-dicarboxylic acid and anhydrides or ester-forming derivatives of these dicarboxylic acids; p-hydroxybenzoic acid, p- (2-hydroxyethoxy) benzoic acid and These hydroxycarboxylic acids
- the hydroxyl value of the polyester polyol is preferably in the range of 20 to 230 mgKOH / g, more preferably in the range of 28 to 110 mgKOH / g, from the viewpoint of further improving oil grip properties and flexibility.
- the hydroxyl value of the polyester polyol is a value measured according to JISK0070-1992.
- polyether polyol examples include polyoxyethylene polyol, polyoxypropylene polyol, polyoxytetramethylene polyol, polyoxyethylene polyoxypropylene polyol, polyoxyethylene polyoxytetramethylene polyol, polyoxypropylene polyoxytetramethylene polyol. Etc. can be used. These polyether polyols may be used alone or in combination of two or more.
- polycarbonate polyol for example, those obtained by reacting a carbonate ester and / or phosgene with a compound having two or more hydroxyl groups can be used.
- carbonate ester for example, methyl carbonate, dimethyl carbonate, ethyl carbonate, diethyl carbonate, cyclocarbonate, diphenyl carbonate and the like can be used. These carbonates may be used alone or in combination of two or more.
- the same compounds as the chain extender having the hydroxyl group can be used. These compounds may be used alone or in combination of two or more. Among these, it is preferable to use an aliphatic polyol and / or an alicyclic polyol from the viewpoint that the cutting property can be further improved. 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol More preferably, at least one compound selected from the group consisting of 1,4-cyclohexanedimethanol is used.
- the total amount of the polyester polyol, the polyether polyol and the polycarbonate polyol is preferably 70% by mass or more in the polyol (a1) from the viewpoint of further improving oil grip properties and flexibility. More preferably.
- polyisocyanate (a2) examples include aromatic polyisocyanates such as phenylene diisocyanate, tolylene diisocyanate, diphenylmethane diisocyanate, naphthalene diisocyanate, polymethylene polyphenyl polyisocyanate, carbodiimidized diphenylmethane polyisocyanate; hexamethylene diisocyanate, lysine diisocyanate, Aliphatic or alicyclic polyisocyanates such as cyclohexane 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, aromatic polyisocyanate is preferably used, and dipheny
- chain extender (a3) examples include ethylenediamine, 1,2-propanediamine, 1,6-hexamethylenediamine, piperazine, 2,5-dimethylpiperazine, isophoronediamine, 1,2-cyclohexanediamine, 1, Chain extenders having amino groups such as 3-cyclohexanediamine, 1,4-cyclohexanediamine, 4,4′-dicyclohexylmethanediamine, 3,3′-dimethyl-4,4′-dicyclohexylmethanediamine, hydrazine; ethylene glycol , Diethylene recall, triethylene glycol, propylene glycol, dipropylene glycol, 1,3-propanediol, 1,3-butanediol, 1,4-butanediol, hexamethylene glycol, saccharose, methylene glycol, glyce Emissions, sorbitol, bisphenol A, 4,4'-dihydroxydiphenyl, 4,4'-dio
- the polyol (a1), the polyisocyanate (a2), and the chain extender (a3) are mixed in the absence of a solvent or in the presence of an organic solvent
- a process for producing by reacting in the range of 50 to 100 ° C. for 3 to 15 hours; mixing the polyol (a1) and the polyisocyanate (a2) in the absence of a solvent or in the presence of an organic solvent;
- a urethane prepolymer having an isocyanate group is obtained by reacting in the range of 100 ° C. for 3 to 15 hours, and then the urethane prepolymer is reacted with the chain extender (a3). It is done.
- An organic solvent was used in the reaction
- the reaction of the polyol (a1), the polyisocyanate (a2), and the chain extender (a3) is carried out by adding the total of hydroxyl groups and amino groups of the polyol (a1) and the chain extender (a3),
- the equivalent ratio [isocyanate group / hydroxyl group and amino group] of the isocyanate group of the isocyanate (a2) is preferably in the range of 0.9 to 1.1, and preferably in the range of 0.95 to 1.05. More preferred.
- Examples of the organic solvent that can be used in producing the aqueous urethane resin (A) include ketone solvents such as acetone and methyl ethyl ketone; ether solvents such as tetrahydrofuran and dioxane; acetate solvents such as ethyl acetate and butyl acetate. Nitrile solvents such as acetonitrile; amide solvents such as dimethylformamide and N-methylpyrrolidone can be used.
- the said organic solvent may be used independently or may use 2 or more types together.
- the weight average molecular weight of the water-based urethane resin (A) obtained by the above method is in the range of 30,000 to 1,000,000 from the viewpoint of further improving oil grip properties, flexibility and mechanical strength. It is preferable that it is in the range of 50,000 to 500,000.
- the weight average molecular weight of the said water-based urethane resin (A) shows the value measured on condition of the following by the 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 ⁇ L (tetrahydrofuran solution with a sample concentration of 0.4 mass%) Standard sample: A calibration curve was prepared using the following standard polystyrene.
- the content of the water-based urethane resin (A) is preferably in the range of 10 to 60% by mass in the water-based urethane resin composition from the viewpoint that storage stability and workability can be improved. A range is more preferable.
- aqueous medium (B) for example, water, an organic solvent miscible with water, a mixture thereof, or the like can be used.
- 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.
- the content of the aqueous medium (B) is preferably in the range of 30 to 85% by mass, and in the range of 45 to 75% by mass in the aqueous urethane resin composition, from the viewpoint of improving storage stability and workability. It is more preferable that
- the fluorine compound (C) is an essential component for obtaining an excellent oil grip property.
- the fluorine compound (C-1) or the fluorine compound (C-2) a very excellent oil Grip properties can be obtained.
- the fluorine compound (C-1) includes the polymerizable monomer (c1-1) having a fluorinated alkyl group having 4 to 6 carbon atoms and a polyoxyethylene structure represented by the general formula (2). And a polymerizable product of the polymerizable monomer (c1-2).
- the reason why a very excellent oil grip property can be obtained by using the fluorine compound (C-1) is that the hydrophilic component has only a polyoxyethylene structure, and therefore, the fluorine atom is contained in the aqueous urethane resin (A). It can be considered that it is easy to be oriented on the particle surface or the surface of the film, and that it is difficult to remove in the washing step.
- the fluorine compound (C-2) is represented by a polymerizable monomer (c2-1) having a polymerizable unsaturated group at both ends of a poly (perfluoroalkylene ether) chain and the general formula (4). This is a polymer of a polymerizable monomer (c2-2) having a polyoxyalkylene structure.
- the reason why a very excellent oil grip property can be obtained by using the fluorine compound (C-2) is that it has a poly (perfluoroalkylene ether) chain having a continuous structure of fluorine atoms. It is considered that the effectiveness of fluorine atoms is easily exhibited. In the above (C-1) and (C-2), it is preferable to use (C-2) in terms of oil grip.
- the fluorine compound (C-1) or the fluorine compound (C-2) has a relatively low water solubility, so that it does not easily flow out or drop off when manufacturing gloves. A very good oil grip can be obtained with a small amount of use.
- Examples of the polymerizable monomer (c1-1) having a fluorinated alkyl group having 4 to 6 carbon atoms, which is a raw material of the fluorine compound (C-1), are represented by the following general formula (1). Can be used.
- R represents a hydrogen atom, a fluorine atom, a methyl group, a cyano group, a phenyl group, a benzyl group, or —C n H 2n —Rf ′ (n represents an integer of 1 to 8, Rf ′ Represents any one group of the following formulas (Rf-1) to (Rf-7)), and L represents any one group of the following formulas (L-1) to (L-10): Rf represents any one of the following formulas (Rf-1) to (Rf-7).
- n represents an integer of 1 to 8.
- m represents an integer of 1 to 8
- n represents an integer of 0 to 8.
- Rf ′′ represents any one of the following formulas (Rf-1) to (Rf-7).
- n represents an integer of 4 to 6.
- m is an integer of 1 to 5, and n is 0 to 4
- p is 0.
- It is an integer of ⁇ 4, and the sum of m, n, and p is 4 to 5.
- R is a hydrogen atom or a fluorine atom
- L is 1 when n is 1 from the viewpoint that a further excellent oil grip property can be obtained. It is preferable to use those having an integer of from 4 to (L-1) and Rf being (Rf-1).
- the polymer monomer (c1-2) has a polyoxyethylene structure represented by the following general formula (2).
- R represents a hydrogen atom or a methyl group
- n represents an integer in the range of 1 to 30.
- n represents an integer in the range of 5 to 15 from the viewpoint that a further excellent oil grip property can be obtained. Is preferred.
- the mass ratio [(c1-1) is obtained because much better oil grip properties can be obtained.
- ) / (C1-2)] is preferably in the range of 30/70 to 70/30, and more preferably in the range of 40/60 to 60/40.
- the content of fluorine atoms in the fluorine compound (C-1) is preferably in the range of 1 to 40% by mass from the viewpoint that even better oil grip properties can be obtained. A range is more preferable.
- the fluorine atom content in the fluorine compound (C-1) is a value calculated from the mass ratio of fluorine atoms to the total amount of the polymerizable monomers (c1-1) and (c1-2). Show.
- the weight average molecular weight of the fluorine compound (C-1) is preferably in the range of 2,000 to 100,000, and more preferably in the range of 2,500 to 50,000, from the viewpoint that even better oil grip properties can be obtained. The range of is more preferable.
- the weight average molecular weight of the fluorine compound (C-1) is a value in terms of polystyrene based on GPC measurement.
- the measurement conditions for GPC are as follows.
- the poly (perfluoroalkylene ether) chain for example, one having a structure in which divalent fluorocarbon groups having 1 to 3 carbon atoms and oxygen atoms are alternately connected can be used.
- the divalent fluorocarbon group having 1 to 3 carbon atoms may be one kind or a mixture of plural kinds. Specifically, it is represented by the following general formula (3). Can be used.
- X represents the following formulas (S1) to (S5), and all X in the general formula (3) may have the same structure, or a plurality of structures May be present randomly or in blocks, and n represents an integer of 1 or more representing the number of repeating units.
- the perfluoromethylene structure represented by the above formula (S1) and the perfluoroethylene structure represented by the above formula (S2) coexist because a further excellent oil grip property can be obtained.
- the abundance ratio between the perfluoromethylene structure represented by the formula (S1) and the perfluoroethylene structure represented by the formula (S2) is a molar ratio [structure (S1) / structure (S2)].
- the total number of fluorine atoms contained in one poly (perfluoroalkylene ether) chain is 18 to 200 from the viewpoint that a further excellent oil grip property can be obtained.
- the range is preferable, and the range of 25 to 150 is more preferable.
- Examples of the compound before introducing the radically polymerizable unsaturated group at both ends as the raw material of the prepolymerizable monomer (c2-1) include the following formulas (V-1) to (V-6): .
- “—PFPE—” represents the poly (perfluoroalkylene ether) chain.
- radical polymerizable unsaturated group having both ends of the poly (perfluoroalkylene ether) chain of the polymerizable monomer (c2-1) include those represented by the following formulas (U-1) to (U-4): What has the radically polymerizable unsaturated group represented is mentioned.
- (meth) acrylic acid chloride is removed from a compound having one hydroxyl group at both ends of a poly (perfluoroalkylene ether) chain.
- a method obtained by reacting with hydrochloric acid a method obtained by dehydrating (meth) acrylic acid, a method obtained by urethanizing 2- (meth) acryloyloxyethyl isocyanate, a method obtained by esterifying itaconic anhydride;
- 2-hydroxyethyl (meth) method of introducing by reacting an acrylate a method of reacting 2-hydroxyethyl (meth) acrylamide.
- a method obtained by dehydrochlorinating (meth) acrylic acid chloride with respect to a compound having one hydroxyl group at both ends of a poly (perfluoroalkylene ether) chain and 2- (meth) acryloyloxy
- the method obtained by urethanization of ethyl isocyanate is preferred in that it is easily obtained synthetically.
- (meth) acryloyl group refers to a methacryloyl group and / or acryloyl group
- (meth) acrylate refers to methacrylate and / or acrylate
- (meth) acrylic acid And methacrylic acid and / or acrylic acid.
- polymerizable monomer (c2-1) examples include those represented by the following formulas (c2-1-1) to (c2-1-10).
- —PFPE— represents a poly (perfluoroalkylene ether) chain.
- the above formulas (c2-1-1), (c2-1-2), (c2-1-5), or (The poly (perfluoroalkylene ether) chain represented by the above formula (c2-1-1) is preferably used since the oil represented by c2-1-6) is preferably used. Those having an acryloyl group at both ends are more preferred.
- the polymer monomer (c2-2) has a polyoxyalkylene structure represented by the following general formula (4).
- R represents a hydrogen atom or a methyl group
- X and Y each represents an independent alkylene group
- n and m each independently represents 0 or an integer in the range of 1 to 30, and The sum of n and m is 1 or more.
- X and Y in the said General formula (4) are alkylene groups, this alkylene group may have a substituent.
- Specific examples of the —O— (XO) n— (YO) m— moiety include, for example, ethylene glycol in which the number of repeating units n is 1 and m is 0, and X is ethylene, and the number of repeating units n is 1.
- n is 1 and m is 0, and X is butylene glycol in which X is butylene, the repeating unit number n is an integer of 2 or more and m is Polyethylene glycol in which X is 0 and X is ethylene, polypropylene glycol in which the number of repeating units n is an integer of 2 or more and m is 0, and both X is 1-methylethylene (propylene), the number of repeating units n and Copolymerization of ethylene oxide and propylene oxide, where m is an integer of 1 or more, and X or Y is ethylene and the other is 1-methylethylene (propylene) Polyalkylene glycol and the like.
- the degree of polymerization of these polyalkylene glycols is preferably in the range of 1 to 50, more preferably in the range of 2 to 10.
- the repeating unit containing X and the repeating unit containing Y may be arranged randomly or in blocks.
- the polymerizable monomer having an oxyalkylene structure (c2-2) is an alkylene glycol such as ethylene glycol, propylene glycol, butylene glycol, etc. when the number of repeating units n is 1 and m is 0.
- Mono (meth) acrylic acid ester of this alkylene glycol mono (meth) acrylic acid ester whose end is not a (meth) acrylic acid ester is sealed with an alkyl group having 1 to 6 carbon atoms, the number of repeating units
- n and m is an integer of 2 or more
- a poly (alkylene glycol) mono (meth) acrylate ester, a terminal of the polyalkylene glycol mono (meth) acrylate ester that is not a (meth) acrylate ester is And those sealed with an alkyl group having 1 to 6 carbon atoms.
- polymerizable monomer (c2-2) examples include polypropylene glycol mono (meth) acrylate, polyethylene glycol mono (meth) acrylate, polytetramethylene glycol (meth) acrylate, poly (ethylene glycol ⁇ Propylene glycol) mono (meth) acrylate, polyethylene glycol / polypropylene glycol mono (meth) acrylate, poly (ethylene glycol / tetramethylene glycol) mono (meth) acrylate, polyethylene glycol / polytetramethylene glycol mono (meth) acrylate, poly ( Propylene glycol / tetramethylene glycol) mono (meth) acrylate, polypropylene glycol / polytetramethylene glycol mono (meth) acrylate, Polypropylene glycol / polytetramethylene glycol mono (meth) acrylate Poly (propylene glycol / butylene glycol) mono (meth) acrylate, polypropylene glycol
- Poly (ethylene glycol / propylene glycol) means a random copolymer of ethylene glycol and propylene glycol
- polyethylene glycol / polypropylene glycol means a block copolymer of ethylene glycol and propylene glycol.
- polymerizable monomers (c2-2) polypropylene glycol mono (meth) acrylate and / or polyethylene from the viewpoint of polymerizability with the polymerizable monomer (c2-1) and oil grip properties. It is preferable to use glycol mono (meth) acrylate.
- Examples of the polymerizable monomer (c2-2) include “NK ester M-20G”, “NK ester M-40G”, “NK ester M-90G” manufactured by Shin-Nakamura Chemical Co., Ltd. “NK Ester M-230G”, “NK Ester AM-90G”, “NK Ester AMP-10G”, “NK Ester AMP-20G”, “NK Ester AMP-60G”, “Blemmer PE-” manufactured by NOF Corporation 90, “Blemmer PE-200”, “Blemmer PE-350”, “Blemmer PME-100”, “Blemmer PME-200”, “Blemmer PME-400”, “Blemmer PME-4000”, “Blemmer PP-1000” ”,“ Blemmer PP-500 ”,“ Blemmer PP-800 ”,“ Blemmer 70PEP-350B ”,“ Blemmer PP-500 ” Nimmer 55PET-800 ",” Blemmer 50POEP-800B “,” Blemmer 10PPB-500B
- a mass ratio [(c2-1) can be obtained from the viewpoint that a further excellent oil grip property can be obtained.
- ) / (C2-2)] preferably in the range of 5/95 to 50/50, more preferably in the range of 10/90 to 40/60.
- the fluorine atom content in the fluorine compound (C-2) is preferably in the range of 1 to 40% by mass from the standpoint of obtaining even better oil grip properties. A range is more preferable.
- the fluorine atom content in the fluorine compound (C-2) is a value calculated from the mass ratio of fluorine atoms to the total amount of the polymerizable monomers (c2-1) and (c2-2). Show.
- the weight average molecular weight of the fluorine compound (C-2) is preferably in the range of 2,000 to 100,000, and more preferably in the range of 2,500 to 50,000, from the viewpoint that even better oil grip properties can be obtained. The range of is more preferable.
- the weight average molecular weight of the fluorine compound (C-2) is a value measured in the same manner as the weight average molecular weight of the fluorine compound (C-1).
- the water-based urethane resin composition used in the present invention contains the water-based urethane resin (A), the water-based medium (B), and the fluorine compound (C) as essential components, and other additives as necessary. You may contain.
- additives examples include associative thickeners, antifoaming agents, urethanization catalysts, silane coupling agents, fillers, thixotropic agents, tackifiers, waxes, heat stabilizers, and light resistance stabilizers.
- Fluorescent brightener foaming agent, foam stabilizer, thermoplastic resin, thermosetting resin, pigment, dye, conductivity imparting agent, antistatic agent, moisture permeability imparting agent, water repellent, oil repellent, hollow foam
- a crystal water-containing compound, a flame retardant, a water absorbent, a moisture absorbent, a deodorant, a fungicide, an antiseptic, an algae, a pigment dispersant, an antiblocking agent, a hydrolysis inhibitor, and the like can be used. These additives may be used alone or in combination of two or more.
- water-based urethane resin composition used in the present invention requires different durability and flexibility depending on the intended use, for example, styrene-butadiene copolymer (SBR), butadiene copolymer (BR), Isoprene copolymer (IR), ethylene-propylene-diene copolymer (EPDM), chloroprene polymer (CR), acrylonitrile-butadiene copolymer (NBR), butyl polymer (IIR), natural rubber (NR), etc. It may contain.
- SBR styrene-butadiene copolymer
- BR butadiene copolymer
- IR Isoprene copolymer
- EPDM ethylene-propylene-diene copolymer
- CR chloroprene polymer
- NBR acrylonitrile-butadiene copolymer
- IIR acrylonitrile-butadiene copolymer
- NR natural rubber
- the carboxyl group in the said water-based urethane resin (A) is neutralized as needed, Then, The aqueous medium (B) is supplied and mixed, and the aqueous urethane resin (A) is dispersed in the aqueous medium (B). Next, when an organic solvent is used during the production of the aqueous urethane resin (A), the solvent is removed. Then, the method of manufacturing by adding and stirring the said fluorine compound (C) and the said other additive as needed is mentioned.
- a machine such as a homogenizer may be used as necessary.
- the viscosity of the aqueous urethane resin composition is preferably in the range of 50 to 10,000 mPa ⁇ s, more preferably in the range of 1,000 to 3,000 mPa ⁇ s, from the viewpoint that workability can be further improved. .
- the viscosity of the aqueous urethane resin composition is a value measured with a B-type viscometer at 25 ° C.
- aqueous urethane resin composition used in the present invention can be used not only for gloves but also for medical tubes such as catheter tubes.
- a method for producing a glove having a film obtained by using the aqueous urethane resin composition for example, after first dipping a hand mold, a tube mold, etc. in a coagulant described later, it is dried as necessary. Then, after the metal salt or the like in the coagulant is attached to the surface of the hand mold or the like, and then the hand mold or the like is immersed in the aqueous urethane resin composition, the surface is washed with water and dried.
- a method for producing a glove having a solidified film on the surface of the hand mold or the like can be mentioned.
- the coagulant examples include metal salt solutions such as calcium nitrate, calcium chloride, zinc nitrate, zinc chloride, magnesium acetate, aluminum sulfate, and sodium chloride; acid solutions such as formic acid and acetic acid.
- 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 an amount of about 1 to 50% by mass with respect to the total amount of the coagulant.
- the time for immersing the coated material in the coagulant is preferably about 1 to 10 minutes.
- the coagulant is preferably used at a temperature of about 5 to 60 ° C.
- the hand mold or tube mold When the hand mold or tube mold is immersed in the coagulant, it may be at room temperature or may be heated to approximately 30 to 70 ° C. Further, the coagulant may be at normal temperature as in the hand mold or the like, but may be heated to approximately 30 to 70 ° C. when the hand mold or the like is heated.
- the hand shape or tube shape may be preliminarily equipped with a glove-like material or a tubular material made of knitted material such as nylon fiber. 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 urethane resin composition, the surface is washed with water and dried to form a glove made of a solidified film on the surface of the glove-like material.
- a glove made of a solidified film having a shape corresponding to the hand mold or the like can be obtained. Also when manufacturing the said pipe
- the knitted fabric is not limited to the nylon fiber, but may be made of polyester fiber, aramid fiber, polyethylene fiber, cotton or the like. 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.
- the content of fluorine atoms in the film obtained by the above method is in the range of 0.01 to 9% by mass from the viewpoint that the texture, mechanical strength and oil grip properties of the glove can be further improved.
- the fluorine atom content in the film is determined by burning the film together with an appropriate auxiliary combustor using an automatic sample combustion device, collecting the generated gas in 15 mL of an absorbing solution, and then burning the absorbing solution after burning. The value obtained by diluting as necessary and performing quantitative analysis by the following ion chromatograph is shown.
- the glove of the present invention has excellent oil grip properties. Moreover, since the water-based urethane resin composition is used, the environmental load at the time of glove manufacture is also small. Therefore, the glove of the present invention can be suitably used as an industrial glove used in various fields such as the chemical industry field, food field, and medical field.
- TDFOA 3,3,4,4,5,5,6,6,7,7,8,8,8-tridecafluorooctyl acrylate
- average repeat A monomer solution in which 60 parts by mass of polyethylene glycol monoacrylate having 10 units are dissolved in 125 parts by mass of toluene
- a radical polymerization initiator solution in which 8 parts by mass of t-butylperoxy-2-ethylhexanoate are dissolved in 20 parts by mass of toluene.
- the fluorine compound (C-1-1) had a weight average molecular weight of 7,500. Moreover, the content rate of the fluorine atom was 24 mass%.
- X is a perfluoromethylene group and a perfluoroethylene group, and an average of 7 perfluoromethylene groups and an average of 8 perfluoroethylene groups are present per molecule, and the number of fluorine atoms is (The average is 46. The number average molecular weight by GPC is 1,500.)
- X is a perfluoromethylene group and a perfluoroethylene group, and an average of 7 perfluoromethylene groups and an average of 8 perfluoroethylene groups are present per molecule, and the number of fluorine atoms is (The average is 46.)
- the fluorine compound (C-2-1) had a weight average molecular weight of 6,000. Moreover, the content rate of the fluorine atom was 11 mass%.
- Two types of dripping solutions of a radical polymerization initiator solution obtained by dissolving 8 parts by mass of butylperoxy-2-ethylhexanoate in 20 parts by mass of toluene were set in separate dripping apparatuses, respectively, while keeping the flask at 105 ° C. at the same time. It was dripped over 2 hours.
- the fluorine compound (C-1) had a weight average molecular weight of 11,200.
- the fluorine atom content was 5.9% by mass.
- urethane resin (A-1) 686.7 parts by mass of methyl ethyl ketone is added as a diluting solvent, whereby the urethane resin (A-1) is added.
- An organic solvent solution was obtained.
- 30.3 parts by mass of triethylamine as a neutralizing agent was added to the organic solvent solution of the urethane resin (A-1) and stirred, and further 4120.6 parts by mass of water (B-1) was added and stirred.
- An aqueous dispersion of urethane resin (A-1) was obtained.
- the aqueous dispersion of the urethane resin (A-1) was desolvated to obtain an aqueous urethane resin composition containing 35% by mass of water (B-1).
- Example 1 Nylon fiber knitted gloves were attached to the hand mold, dipped in a 20% by mass calcium nitrate aqueous solution for 15 seconds, and then pulled up. Next, the hand mold was dipped in the aqueous urethane resin composition (X-1) having a viscosity of 400 mPa ⁇ s (Brookfield viscometer, 30 revolutions) in advance with carboxymethyl cellulose for 0.5 minutes, and the surface of the knitted glove After forming a solidified film of the aqueous urethane resin composition (X-1), the film was pulled up. Thereafter, the hand mold was dipped in water for 60 minutes and pulled up. Subsequently, the hand mold was dried at 70 ° C.
- the knitted glove was taken out from the hand mold to obtain a glove having a film.
- membrane was 0.13 mass%.
- Example 2 Comparative Examples 1 and 2
- a glove was obtained in the same manner as in Example 1 except that the type of the aqueous urethane resin composition used was changed as shown in Table 1.
- Comparative Example 1 is an embodiment in which a fluorine compound (C) other than (C-1) and (C-2) was used, but it was found that the oil grip property was insufficient.
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Abstract
Description
カラム:東ソー株式会社製の下記のカラムを直列に接続して使用した。
「TSKgel G5000」(7.8mmI.D.×30cm)×1本
「TSKgel G4000」(7.8mmI.D.×30cm)×1本
「TSKgel G3000」(7.8mmI.D.×30cm)×1本
「TSKgel G2000」(7.8mmI.D.×30cm)×1本
検出器:RI(示差屈折計)
カラム温度:40℃
溶離液:テトラヒドロフラン(THF)
流速:1.0mL/分
注入量:100μL(試料濃度0.4質量%のテトラヒドロフラン溶液)
標準試料:下記の標準ポリスチレンを用いて検量線を作成した。
東ソー株式会社製「TSKgel 標準ポリスチレン A-500」
東ソー株式会社製「TSKgel 標準ポリスチレン A-1000」
東ソー株式会社製「TSKgel 標準ポリスチレン A-2500」
東ソー株式会社製「TSKgel 標準ポリスチレン A-5000」
東ソー株式会社製「TSKgel 標準ポリスチレン F-1」
東ソー株式会社製「TSKgel 標準ポリスチレン F-2」
東ソー株式会社製「TSKgel 標準ポリスチレン F-4」
東ソー株式会社製「TSKgel 標準ポリスチレン F-10」
東ソー株式会社製「TSKgel 標準ポリスチレン F-20」
東ソー株式会社製「TSKgel 標準ポリスチレン F-40」
東ソー株式会社製「TSKgel 標準ポリスチレン F-80」
東ソー株式会社製「TSKgel 標準ポリスチレン F-128」
東ソー株式会社製「TSKgel 標準ポリスチレン F-288」
東ソー株式会社製「TSKgel 標準ポリスチレン F-550」
測定装置:東ソー株式会社製「HLC-8220 GPC」
カラム:東ソー株式会社製ガードカラム「HHR-H」(6.0mmI.D.×4cm)+東ソー株式会社製「TSK-GEL GMHHR-N」(7.8mmI.D.×30cm)
+東ソー株式会社製「TSK-GEL GMHHR-N」(7.8mmI.D.×30cm)
+東ソー株式会社製「TSK-GEL GMHHR-N」(7.8mmI.D.×30cm)
+東ソー株式会社製「TSK-GEL GMHHR-N」(7.8mmI.D.×30cm)
検出器:ELSD(オルテック製「ELSD2000」)
データ処理:東ソー株式会社製「GPC-8020モデルIIデータ解析バージョン4.30」
測定条件:カラム温度 40℃
展開溶媒 テトラヒドロフラン(THF)
流速 1.0ml/分
試料:固形分換算で1質量%のテトラヒドロフラン溶液をマイクロフィルターでろ過したもの(100μl)。
標準試料:前記「GPC-8020モデルIIデータ解析バージョン4.30」の測定マニュアルに準拠して、分子量が既知の下記の単分散ポリスチレンを用いた。
東ソー株式会社製「A-500」
東ソー株式会社製「A-1000」
東ソー株式会社製「A-2500」
東ソー株式会社製「A-5000」
東ソー株式会社製「F-1」
東ソー株式会社製「F-2」
東ソー株式会社製「F-4」
東ソー株式会社製「F-10」
東ソー株式会社製「F-20」
東ソー株式会社製「F-40」
東ソー株式会社製「F-80」
東ソー株式会社製「F-128」
東ソー株式会社製「F-288」
東ソー株式会社製「F-550」
なお、前記皮膜中のフッ素原子の含有率は、皮膜を、適切な助燃剤と共に自動試料燃焼装置を用いて燃焼させ、発生したガスを吸収液15mLに捕集し、燃焼後、その吸収液を必要に応じて希釈し、下記のイオンクロマトグラフにより定量分析を行って得られた値を示す。
(自動試料燃焼装置)三菱化学アナリテック社製「AQF-100」
(イオンクロマトグラフ)Thermo Fisher Scientific社製「ICS-3000」
(自動試料燃焼装置)
温度;Inlet 1,000℃、Outlet 1,100℃
ガス流量;酸素400mL/min、アルゴン/酸素200mL/min、アルゴン( 送水ユニット:目盛4)150mL/min
(イオンクロマトグラフ)
分離カラム;Dicnex IonPac AS18(4mm×250mm)
ガードカラム;Dicnex IonPac AG18(4mm×50mm)
除去システム;AERS-500(エクスターナルモード)
検出器;電気伝導度検出器
溶離液;水酸化カリウム水溶液(溶離液ジェネレーターEGCiiiを使用)
溶離液流量;1mL/min
試料注入量;250μL
試料(皮膜)中の全フッ素の含有率(質量%)=(測定溶液中のF-面積-検量線切片)/検量線の傾き×吸収液量[mL]×希釈率[倍]/(試料採取量[mg]/1000)/10000
(*測定溶液=250μLの注入試料)
3リットルのフラスコに1,4-ブタンジオールを477.5質量部、アジピン酸を693.5質量部、及び、エステル化触媒としてテトライソプロポキシチタンを0.06質量部添加し、120℃でそれらを溶融した。次いで、撹拌しながら3時間~4時間かけて220℃へ昇温し10時間保持した後、100℃に冷却することによって、ポリエステルポリオール(a1-1-1)(水酸基価:62.3mgKOH/g)を調製した。
撹拌装置、コンデンサ-、滴下装置及び温度計を備えたガラスフラスコに、トルエンを200質量部入れ、窒素気流中、攪拌しながら105℃に昇温した。次いで、3,3,4,4,5,5,6,6,7,7,8,8,8-トリデカフルオロオクチルアクリレート(以下、「TDFOA」と略記する。)40質量部及び平均繰り返し単位数10のポリエチレングリコールモノアクリレート60質量部をトルエン125質量部に溶解したモノマー溶液と、t-ブチルペルオキシ-2-エチルヘキサノエート8質量部をトルエン20質量部に溶解したラジカル重合開始剤溶液の2種類の滴下液をそれぞれ別々の滴下装置にセットし、フラスコ内を105℃に保ちながら同時に2時間かけて滴下した。滴下終了後、105℃で13時間攪拌した後、減圧下で溶媒を留去することにより、フッ素化合物(C-1-1)を得た。前記フッ素化合物(C-1-1)の重量平均分子量は7,500であった。また、フッ素原子の含有率は24質量%であった。
撹拌装置、温度計、冷却管、滴下装置を備えたガラスフラスコに、下記式(w-1)で表される両末端に水酸基を有するパーフルオロポリエーテル化合物20質量部、溶媒としてジイソプロピルエーテル20質量部、重合禁止剤としてp-メトキシフェノール0.02質量部及び中和剤としてトリエチルアミン3.1質量部を仕込み、空気気流下にて攪拌を開始し、フラスコ内を10℃に保ちながらアクリル酸クロライド2.7質量部を1時間かけて滴下した。滴下終了後、10℃で1時間攪拌し、昇温して30℃で1時間撹拌した後、50℃に昇温して10時間攪拌することにより反応を行い、ガスクロマトグラフィー測定にてアクリル酸クロライドの消失が確認された。次いで、溶媒としてジイソプロピルエーテル40質量部を追加した後、イオン交換水80質量部を混合して攪拌してから静置し水層を分離させて取り除く方法による洗浄を3回繰り返した。次いで、重合禁止剤としてp-メトキシフェノール0.02質量部を添加し、脱水剤として硫酸マグネシウム8質量部を添加して1日間静置することで完全に脱水した後、脱水剤を濾別した。
撹拌装置、コンデンサ-、滴下装置及び温度計を備えたガラスフラスコに、トルエンを200質量部入れ、窒素気流中、攪拌しながら105℃に昇温した。次いで、TDFOA10質量部及び平均繰り返し単位数11のオキシエチレン部位と平均繰り返し単位数22のオキシプロピレン部位を有するポリエチレングリコールポリプロピレングリコールモノアクリレート90質量部をトルエン125質量部に溶解したモノマー溶液と、t-ブチルペルオキシ-2-エチルヘキサノエート8質量部をトルエン20質量部に溶解したラジカル重合開始剤溶液の2種類の滴下液をそれぞれ別々の滴下装置にセットし、フラスコ内を105℃に保ちながら同時に2時間かけて滴下した。滴下終了後、105℃で13時間攪拌した後、減圧下で溶媒を留去することにより、フッ素化合物(C-1)を得た。前記フッ素化合物(C-1)の重量平均分子量は11,200であった。また、フッ素原子の含有率は5.9質量%であった。
温度計、窒素ガス導入管及び撹拌機を備えた窒素置換された容器中で、前記ポリエステルポリオール(a1-1-1)を900質量部、エチレングリコールを18.6質量部、ジメチロールプロピオン酸40.2質量部、ジフェニルメタンジイソシアネート275.1質量部、及び有機溶剤としてメチルエチルケトンを824質量部の存在下、70℃で反応させた。
反応物が規定粘度に達した時点でメタノール2質量部を加えて1時間撹拌して反応を終了し、更に希釈溶剤としてメチルエチルケトンを686.7質量部追加することでウレタン樹脂(A-1)の有機溶剤溶液を得た。
次いで、前記ウレタン樹脂(A-1)の有機溶剤溶液に、中和剤としてトリエチルアミンを30.3質量部加えて攪拌し、更に水(B-1)を4120.6質量部加え撹拌することにより、ウレタン樹脂(A-1)の水分散体を得た。次いで、前記ウレタン樹脂(A-1)の水分散体を脱溶剤することにより、水(B-1)を含む不揮発分35質量%の水性ウレタン樹脂組成物を得た。
次いで、得られた水性ウレタン樹脂組成物100質量部に、合成例2で得られたフッ素化合物(C-1-1)を0.2質量部加えて30分間撹拌し、水性ウレタン樹脂組成物(X-1)を得た。
用いるフッ素化合物(C)の種類及び量を表1に示す通りに変更した以外は、調整例1と同様にして水性ウレタン樹脂組成物(X-2)~(X-4)を得た。
手型にナイロン繊維による編み手袋を装着し、20質量%硝酸カルシウム水溶液に15秒間浸漬した後、引きあげた。次いで、予めカルボキシメチルセルロースで粘度を400mPa・s(ブルックフィールド型粘度計、30回転)にした前記水性ウレタン樹脂組成物(X-1)中に該手型を0.5分間浸漬させ、編み手袋表面に水性ウレタン樹脂組成物(X-1)の凝固皮膜を形成させた後に引き上げた。その後、該手型を水に60分間浸漬させ引きあげた。ついで、該手型を70℃で20分間乾燥し、連続して120℃で30分間乾燥させた。次いで、手型から編み手袋を取り出し、皮膜を有する手袋を得た。なお、前記皮膜中のフッ素原子の含有率は、0.13質量%であった。
用いる水性ウレタン樹脂組成物の種類を表1に示す通りに変更した以外は、実施例1と同様にして手袋を得た。
15cm×7cm×2.5cmの角材の外面に離型紙(リンテック株式会社製「EK-100D」)を離型面が外側になるように貼り重量が320gになるようにした。これに、ひもで1kgのおもりを吊り下げた装置を作成した。次いで、実施例及び比較例で得られた手袋を装着した親指と人差し指とをそれぞれオイル(大澤ワックス株式会社製「BM-1K」)に浸した後、角材の上端から4cmの中央部を表側と裏側から親指と人差し指とでつまみ持ち上げる。このときおもりと一緒に角材が持ち上がればオイルグリップ性が良好であると判定した。また、角材を持ち上げた後角材がすべり落ちまでの時間(秒)を測定し、その時間が長い程オイルグリップ性に優れると判定した。
Claims (5)
- 水性ウレタン樹脂(A)、水性媒体(B)、及び、フッ素化合物(C)を含有する水性ウレタン樹脂組成物により形成された皮膜を有する手袋であって、
前記フッ素化合物(C)が、
炭素原子数4~6のフッ素化アルキル基を有する重合性単量体(c1-1)及び下記一般式(2)で表されるポリオキシエチレン構造を有する重合性単量体(c1-2)の重合物であるフッ素化合物(C-1)、又は、
ポリ(パーフルオロアルキレンエーテル)鎖の両末端に重合性不飽和基を有する重合性単量体(c2-1)及び下記一般式(4)で表されるポリオキシアルキレン構造を有する重合性単量体(c2-2)の重合物であるフッ素化合物(C-2)
であることを特徴とする手袋。
- 前記フッ素化合物(C)の含有量が、前記水性ウレタン樹脂(A)100質量部に対して、0.05~10質量部の範囲である請求項1記載の手袋。
- 前記フッ素化合物(C-1)、及び、(C-2)中のフッ素原子の含有率が、それぞれ1~40質量%の範囲である請求項1又は2記載の手袋。
- 前記フッ素化合物(C-1)、及び、(C-2)の重量平均分子量が、それぞれ2,000~100,000の範囲である請求項1~3のいずれか1項記載の手袋。
- 前記水性ウレタン樹脂(A)が、アニオン性基を有する水性ウレタン樹脂である請求項1~4のいずれか1項記載の手袋。
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JP2011080016A (ja) * | 2009-10-09 | 2011-04-21 | Mitsubishi Chemicals Corp | ポリウレタン及びその製造方法 |
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