WO2017006385A1 - Composition de moulage par immersion et objet moulé par immersion - Google Patents

Composition de moulage par immersion et objet moulé par immersion Download PDF

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Publication number
WO2017006385A1
WO2017006385A1 PCT/JP2015/069270 JP2015069270W WO2017006385A1 WO 2017006385 A1 WO2017006385 A1 WO 2017006385A1 JP 2015069270 W JP2015069270 W JP 2015069270W WO 2017006385 A1 WO2017006385 A1 WO 2017006385A1
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Prior art keywords
dip
weight
latex
conjugated diene
carboxyl group
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PCT/JP2015/069270
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English (en)
Japanese (ja)
Inventor
直広 伊賀利
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日本ゼオン株式会社
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Priority to PCT/JP2015/069270 priority Critical patent/WO2017006385A1/fr
Publication of WO2017006385A1 publication Critical patent/WO2017006385A1/fr

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Classifications

    • A—HUMAN NECESSITIES
    • A41—WEARING APPAREL
    • A41D—OUTERWEAR; PROTECTIVE GARMENTS; ACCESSORIES
    • A41D19/00—Gloves
    • A41D19/0055—Plastic or rubber gloves
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C41/00—Shaping by coating a mould, core or other substrate, i.e. by depositing material and stripping-off the shaped article; Apparatus therefor
    • B29C41/02—Shaping by coating a mould, core or other substrate, i.e. by depositing material and stripping-off the shaped article; Apparatus therefor for making articles of definite length, i.e. discrete articles
    • B29C41/14—Dipping a core
    • 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
    • C08F236/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds
    • C08F236/02—Copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds
    • C08F236/04—Copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds conjugated
    • C08F236/06—Butadiene
    • 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
    • C08K5/16—Nitrogen-containing compounds
    • C08K5/29—Compounds containing one or more carbon-to-nitrogen double bonds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L13/00—Compositions of rubbers containing carboxyl groups
    • C08L13/02—Latex

Definitions

  • the present invention relates to a dip-molding composition and a dip-molded article. More specifically, the dip-molding is excellent in storage stability and suitable for applications such as gloves, has excellent wearing durability, hardly discolors, and has low odor.
  • the present invention relates to a dip-molding composition that gives a product, and a dip-molded product obtained by using such a dip-molding composition.
  • Rubber gloves are widely used in various industrial and medical applications such as housework, food industry and electronic component manufacturing. However, these various types of rubber gloves do not have enough durability to wear, so if they are torn during the work or if you continue to work while moving your fingers while wearing them, micro cracks will occur in the crotch part of the fingers In some cases, the problem of end up occurring.
  • Patent Document 1 discloses dip molding from a dip molding composition containing a specific amount of an acrylonitrile-butadiene copolymer latex containing a carboxyl group, a small amount of zinc oxide, a relatively large amount of sulfur and a vulcanization accelerator.
  • a rubber glove is disclosed. However, when such a glove is worn and the operation is continued, the glove itself may be colored to significantly reduce its commercial value, and the odor due to residual sulfur may be a problem.
  • the present invention has been made in view of such a situation, and is a dip-molded product that is excellent in storage stability and suitable for applications such as gloves, has excellent wearing durability, is resistant to discoloration, and has little odor. It is an object to provide a composition for dip molding. Another object of the present invention is to provide a dip-molded product obtained using such a dip-molding composition.
  • the present inventors have found that a dip molding composition containing a latex of a carboxyl group-containing conjugated diene rubber whose residual carboxylic acid amount is controlled to a specific amount or less, and a carbodiimide compound.
  • the present inventors have found that the above object can be achieved and have completed the present invention.
  • a dip-molding composition comprising a carboxyl group-containing conjugated diene rubber (A) latex and a carbodiimide compound (B), wherein the carboxyl group-containing conjugated diene rubber (A) is in a latex.
  • the amount of residual carboxylic acid is 2200 ppm by weight or less, and a dip molding composition is provided.
  • the carboxyl group-containing conjugated diene rubber (A) latex comprises 30 to 89.5% by weight of a conjugated diene monomer, 10 to 50% by weight of an ethylenically unsaturated nitrile monomer, and an ethylenically unsaturated carboxylic acid monomer. Obtained by polymerizing a monomer mixture containing 0.5 to 20% by weight of a monomer and 0 to 20% by weight of another ethylenically unsaturated monomer copolymerizable with these monomers. Copolymer latex.
  • a dip-molded product obtained by dip-molding the dip-molding composition described above is provided, and the dip-molded product is preferably a glove.
  • ADVANTAGE OF THE INVENTION According to this invention, it is excellent in storage stability and suitable for uses, such as a glove, It provides the dip molding composition which gives the dip molding product which is excellent in wearing durability, is hard to discolor, and has few odors. it can. Moreover, according to the present invention, a dip-molded product obtained using such a dip-molding composition can be provided.
  • the dip molding composition of the present invention contains a latex of carboxyl group-containing conjugated diene rubber (A) and a carbodiimide compound (B), and the amount of residual carboxylic acid in the latex of the carboxyl group-containing conjugated diene rubber (A). Is 2200 ppm by weight or less.
  • Latex of carboxyl group-containing conjugated diene rubber (A) Latex of carboxyl group-containing conjugated diene rubber (A) used in the dip molding composition of the present invention is a copolymer of a conjugated diene monomer and an ethylenically unsaturated carboxylic acid monomer.
  • the latex of the copolymer thus obtained has a residual carboxylic acid content of 2200 ppm by weight or less.
  • conjugated diene monomer examples include conjugated diene monomers having 4 to 6 carbon atoms such as 1,3-butadiene, isoprene, 2,3-dimethyl-1,3-butadiene, 1,3-pentadiene, and chloroprene. 1,3-butadiene and isoprene are more preferred, and 1,3-butadiene is particularly preferred.
  • the conjugated diene monomer may be used alone or in combination of two or more.
  • the amount of the conjugated diene monomer used is preferably such that the content of the conjugated diene monomer unit in the carboxyl group-containing conjugated diene rubber (A) is 30 to 89.5% by weight, more preferably The amount is 40 to 84% by weight, more preferably 50 to 78% by weight. If this amount is too small, the resulting dip-molded product is inferior in texture, whereas if it is too much, the tensile strength tends to be inferior.
  • the ethylenically unsaturated carboxylic acid monomer is not particularly limited, and examples thereof include ethylenically unsaturated monocarboxylic acid monomers such as acrylic acid and methacrylic acid; ethylenic unsaturated carboxylic acid monomers such as itaconic acid, maleic acid, and fumaric acid.
  • Saturated polyvalent carboxylic acid monomers ethylenically unsaturated polyvalent carboxylic acid partial ester monomers such as monobutyl fumarate, monobutyl maleate and mono-2-hydroxypropyl maleate; Since a carboxyl group is generated by this, ethylenically unsaturated polyvalent carboxylic acid anhydrides such as maleic anhydride and citraconic anhydride are also ethylenically unsaturated carboxylic acid monomers.
  • the ethylenically unsaturated monocarboxylic acid monomer is preferred and the ethylenically unsaturated carboxylic acid monomer having 3 to 10 carbon atoms because the effects of the present invention become more remarkable.
  • Monocarboxylic acid monomers are more preferred, acrylic acid and methacrylic acid are more preferred, and methacrylic acid is particularly preferred.
  • ethylenically unsaturated carboxylic acid monomers can also be used as alkali metal salts or ammonium salts.
  • these ethylenically unsaturated carboxylic acid monomers may be used alone or in combination of two or more.
  • the amount of the ethylenically unsaturated carboxylic acid monomer used is such that the content of the ethylenically unsaturated carboxylic acid monomer unit in the carboxyl group-containing conjugated diene rubber (A) is 0.5 to 20% by weight.
  • the amount is preferably 1 to 15% by weight, and more preferably 2 to 10% by weight. If this amount is too small, the resulting dip-molded product tends to be inferior in tensile strength, and conversely if it is too much, the texture and the durability of the adhesive state tend to be inferior.
  • the latex of the carboxyl group-containing conjugated diene rubber (A) used in the dip molding composition of the present invention is preferably a copolymer obtained by further copolymerizing an ethylenically unsaturated nitrile monomer from the viewpoint of improving the tensile strength.
  • ethylenically unsaturated nitrile monomer examples include acrylonitrile, methacrylonitrile, fumaronitrile, ⁇ -chloroacrylonitrile, ⁇ -cyanoethylacrylonitrile and the like. Acrylonitrile and methacrylonitrile are preferable, and acrylonitrile is particularly preferable. These ethylenically unsaturated nitrile monomers may be used alone or in combination of two or more.
  • the amount of the ethylenically unsaturated nitrile monomer used is preferably such that the content of the ethylenically unsaturated nitrile monomer unit in the carboxyl group-containing conjugated diene rubber (A) is 10 to 50% by weight.
  • the amount is more preferably 15 to 45% by weight, and still more preferably 20 to 40% by weight. If the amount is too small, the resulting dip-molded product may be inferior in tensile strength.
  • carboxyl group-containing conjugated diene rubber (A) latex used in the dip-molding composition of the present invention is not limited to other ethylenic copolymers that can be copolymerized with the above-mentioned monomers as long as the effects of the present invention are not impaired.
  • Saturated monomers may be copolymerized.
  • examples of such other copolymerizable ethylenically unsaturated monomers include aromatic vinyl monomers, ⁇ , ⁇ -ethylenically unsaturated monocarboxylic acid ester monomers, and ⁇ , ⁇ -ethylenic monomers.
  • Unsaturated monocarboxylic amide, vinyl acetate, vinyl pyrrolidone, vinyl pyridine and the like can be mentioned.
  • the amount of such other copolymerizable monomer used is such that the content of other copolymerizable monomer units in the carboxyl group-containing conjugated diene rubber (A) is 0 to 20% by weight.
  • the amount is 0 to 10% by weight, more preferably 0% by weight.
  • aromatic vinyl monomer examples include styrene, ⁇ -methylstyrene, monochlorostyrene, vinyltoluene and the like.
  • ⁇ , ⁇ -ethylenically unsaturated monocarboxylic acid ester monomers include methyl acrylate, methyl methacrylate, ethyl acrylate, butyl acrylate, ⁇ -hydroxyethyl acrylate, ⁇ -hydroxypropyl acrylate, Examples thereof include ⁇ -hydroxyethyl methacrylate, glycidyl acrylate, glycidyl methacrylate, N, N-dimethylaminoethyl (meth) acrylate, and the like.
  • Examples of the ⁇ , ⁇ -ethylenically unsaturated monocarboxylic acid amide monomer include (meth) acrylamide, N-methylol (meth) acrylamide and the like. These monomers may be used alone or in combination of two or more.
  • the carboxyl group-containing conjugated diene rubber (A) latex used in the dip molding composition of the present invention has a residual carboxylic acid content in the latex of 2200 ppm by weight or less, preferably 2100 ppm by weight or less, more preferably 2000 ppm by weight or less.
  • the storage stability can be appropriately improved by setting the amount of residual carboxylic acid in the latex within the above range.
  • the residual carboxylic acid amount is free carboxylic acid that is not copolymerized with the carboxyl group-containing conjugated diene rubber (A), and is usually ethylene used to obtain a latex of the carboxyl group-containing conjugated diene rubber (A).
  • the unsaturated carboxylic acid monomer constitutes the residual carboxylic acid.
  • the residual carboxylic acid in the latex may be a carboxylic acid salt.
  • the carboxylic acid salt is also a residual carboxylic acid. Include in quantity. However, in that case, the amount of residual carboxylic acid is calculated
  • an aqueous hydrochloric acid solution may be added to the latex to convert the carboxylic acid salt into a carboxylic acid, and then measured by gas chromatography.
  • the latex of the carboxyl group-containing conjugated diene rubber (A) used in the present invention is a copolymer latex obtained by polymerizing a monomer mixture containing the above-mentioned monomers. What is obtained is preferred.
  • a conventionally well-known method can be employ
  • polymerization auxiliary materials such as an emulsifier, a polymerization initiator, and a molecular weight modifier can be used.
  • the method for adding these polymerization auxiliary materials is not particularly limited, and any method such as an initial batch addition method, a divided addition method, or a continuous addition method may be used.
  • the emulsifier is not particularly limited, and an anionic emulsifier, a nonionic emulsifier, a cationic emulsifier, and the like can be used.
  • anionic emulsifiers include salts of fatty acids such as myristic acid, palmitic acid, oleic acid and linolenic acid; alkylbenzene sulfonates such as sodium dodecylbenzenesulfonate; higher alcohol sulfates; alkylsulfosuccinates; etc. Can be mentioned.
  • the salt in these anionic emulsifiers include alkali metal salts and ammonium salts.
  • specific examples of the nonionic emulsifier include polyoxyethylene alkyl ether, polyoxyethylene alkylphenol ether, polyoxyethylene alkyl ester, polyoxyethylene sorbitan alkyl ester and the like.
  • the cationic emulsifier examples include alkyltrimethylammonium chloride, dialkylammonium chloride, benzylammonium chloride and the like.
  • the amount of the emulsifier used is usually 0.5 to 10 parts by weight, preferably 1 to 8 parts by weight, more preferably 2 to 5 parts by weight with respect to 100 parts by weight of the total monomers used.
  • the polymerization initiator is not particularly limited, and examples thereof include inorganic peroxides such as sodium persulfate, potassium persulfate, ammonium persulfate, potassium perphosphate, and hydrogen peroxide; t-butyl peroxide, cumene hydroperoxide, p-menthane hydroperoxide, di-t-butyl peroxide, t-butylcumyl peroxide, acetyl peroxide, isobutyryl peroxide, octanoyl peroxide, dibenzoyl peroxide, 3,5,5-trimethylhexanoyl Organic peroxides such as peroxide and t-butylperoxyisobutyrate; azo compounds such as azobisisobutyronitrile, azobis-2,4-dimethylvaleronitrile, azobiscyclohexanecarbonitrile, methyl azobisisobutyrate; etc.
  • inorganic peroxides
  • Raised Rukoto can be used alone or in combination of two or more.
  • the peroxide can be used as a redox polymerization initiator in combination with a reducing agent such as sodium bisulfite.
  • a reducing agent such as sodium bisulfite.
  • the polymerization initiator inorganic or organic peroxides are preferable, inorganic peroxides are more preferable, and sodium persulfate and potassium persulfate are particularly preferably used.
  • the amount of the polymerization initiator used is preferably 0.01 to 2 parts by weight, more preferably 0.05 to 1.5 parts by weight with respect to 100 parts by weight of the total monomers used.
  • a molecular weight adjusting agent in order to adjust the methyl ethyl ketone insoluble matter of the carboxyl group-containing conjugated diene rubber (A).
  • the molecular weight modifier include mercaptans such as n-butyl mercaptan and t-dodecyl mercaptan, sulfides such as tetraethylthiuram sulfide and dibentamethylenethiuram hexasulfide, ⁇ -methylstyrene dimer, carbon tetrachloride and the like. Can be mentioned.
  • mercaptans are preferable, and t-dodecyl mercaptan is more preferable. These can be used alone or in combination of two or more.
  • the amount of the molecular weight modifier used may be appropriately determined so that the methyl ethyl ketone insoluble content of the carboxyl group-containing conjugated diene rubber (A) is within a desired range, but is preferably based on 100 parts by weight of all monomers used. 0.3 to 0.8 part by weight.
  • the amount of water used for emulsion polymerization is preferably 80 to 600 parts by weight, particularly preferably 100 to 200 parts by weight, based on 100 parts by weight of all monomers used.
  • Examples of the monomer addition method include a method of adding monomers to be used in a reaction vessel all at once, a method of adding continuously or intermittently as the polymerization proceeds, and a part of the monomer is added. And a method in which the remaining monomer is continuously or intermittently added and polymerized, and any method may be employed.
  • the composition of the mixture may be constant or may be changed.
  • Each monomer may be added to the reaction vessel after previously mixing various monomers to be used, or may be added separately to the reaction vessel.
  • polymerization auxiliary materials such as a chelating agent, a dispersant, a pH adjuster, an oxygen scavenger, and a particle size adjuster can be used, and these are not particularly limited in type and amount used.
  • the polymerization temperature at the time of emulsion polymerization is usually 0 to 95 ° C., and the polymerization time is about 5 to 40 hours.
  • the monomer is emulsion-polymerized, and when the predetermined polymerization conversion rate is reached, the polymerization reaction is stopped by cooling the polymerization system or adding a polymerization terminator.
  • the polymerization conversion rate when stopping the polymerization reaction is preferably 95% by weight or more, more preferably 96% by weight or more.
  • the upper limit of the polymerization conversion rate is not particularly limited, but is preferably 99% by weight or less. In the present invention, by setting the polymerization conversion rate within such a range, among the monomers used for the polymerization, unreacted monomers, specifically, unreacted ethylenically unsaturated carboxylic acid monomers.
  • the amount of the monomer can be reduced, whereby the amount of residual carboxylic acid in the latex of the resulting carboxyl group-containing conjugated diene rubber (A) can be reduced to the above-described range.
  • the polymerization conversion rate is too high, there is a possibility that defects such as cracks during molding and the texture of the resulting dip-molded product may be inferior.
  • polymerization of about 92% by weight is performed. The polymerization was stopped at the conversion rate.
  • unreacted monomers may be removed by a vacuum recovery method or the like. Part of the mass can be removed. However, in such a method, a certain amount of unreacted monomer remains, and in particular, the ethylenically unsaturated carboxylic acid monomer that constitutes the residual carboxylic acid is taken into the polymer particles. In addition, the boiling point is high, so that it is difficult to remove by vacuum recovery. For this reason, it is actually difficult to remove a small amount of residual ethylenically unsaturated carboxylic acid monomer by such a method.
  • the amount of unreacted ethylenically unsaturated carboxylic acid monomer is reduced by setting the polymerization conversion rate within the above predetermined range when the polymerization reaction is stopped, and the residual The amount of carboxylic acid can be appropriately reduced to the above-described range.
  • the polymerization terminator is not particularly limited as long as it is usually used in emulsion polymerization. Specific examples thereof include hydroxylamine, hydroxyamine sulfate, diethylhydroxyamine, hydroxyaminesulfonic acid and alkali metals thereof.
  • Hydroxyamine compounds such as salts; sodium dimethyldithiocarbamate; hydroquinone derivatives; catechol derivatives; aromatic hydroxydithiocarboxylic acids such as hydroxydimethylbenzenethiocarboxylic acid, hydroxydiethylbenzenedithiocarboxylic acid, hydroxydibutylbenzenedithiocarboxylic acid, and alkali metal salts thereof
  • Aromatic hydroxydithiocarboxylic acid compounds such as;
  • the amount of the polymerization terminator used is not particularly limited, but is usually 0.05 to 2 parts by weight with respect to 100 parts by weight of the total monomers used.
  • the unreacted monomer is removed if necessary, and the latex of the carboxyl group-containing conjugated diene rubber (A) is obtained by adjusting the solid content concentration and pH.
  • the latex of the carboxyl group-containing conjugated diene rubber (A) used in the present invention may be appropriately added with an anti-aging agent, an antiseptic, an antibacterial agent, a dispersant, an ultraviolet absorber, a pH adjuster, and the like as necessary. .
  • the number average particle diameter of the latex of the carboxyl group-containing conjugated diene rubber (A) used in the present invention is preferably 60 to 300 nm, more preferably 80 to 150 nm.
  • this particle diameter can be adjusted to a desired value by a method of adjusting the usage-amount of an emulsifier and a polymerization initiator.
  • Carbodiimide compound (B) The dip molding composition of the present invention contains a carbodiimide compound (B) in addition to the latex of the carboxyl group-containing conjugated diene rubber (A) described above.
  • the carbodiimide compound (B) used in the present invention may be a compound having a carbodiimide group in the molecule, but is preferably a compound having a carbon-carbon double bond in addition to the carbodiimide group.
  • Specific examples of the carbodiimide compound (B) include 1-vinyl-3-ethyl-carbodiimide, 1-vinyl-3-propyl-carbodiimide, 1-vinyl-3-methoxypropyl-carbodiimide, 1-vinyl-3-isobutyl- A carbodiimide having a vinyl group having 5 to 20 carbon atoms such as carbodiimide; 1-propenyl-3-ethyl-carbodiimide, 1-propenyl-3-propyl-carbodiimide, 1-propenyl-3-methoxypropyl-carbodiimide, 1-propenyl- And carbodiimide having a propenyl group having 5 to 20 carbon atoms such as 3-is
  • the carbodiimide compound (B) used in the present invention includes a carbodiimide polymer obtained by polymerizing a compound having a carbodiimide group and a carbon-carbon double bond alone, or a carbodiimide polymer obtained by copolymerizing two or more kinds. Further, a carbodiimide polymer obtained by copolymerizing a compound and a compound having a carbodiimide group and a carbon-carbon double bond and a copolymerizable monomer may be used.
  • copolymerizable monomers examples include aromatic vinyl monomers such as styrene, ⁇ -methylstyrene, monochlorostyrene, vinyltoluene; methyl acrylate, methyl methacrylate, ethyl acrylate, butyl acrylate, ⁇ , ⁇ -ethylenically unsaturated monocarboxylic acid ester monomers such as ⁇ -hydroxyethyl acrylate, ⁇ -hydroxypropyl acrylate, ⁇ -hydroxyethyl methacrylate, glycidyl acrylate, glycidyl methacrylate, etc. Styrene, butyl acrylate and methyl methacrylate are preferred.
  • the content ratio of the carbodiimide monomer unit in the carbodiimide polymer is preferably 5 to 80 mol%, more preferably 10%, based on the total monomer units, since the effects of the present invention become more remarkable. It is ⁇ 70 mol%, particularly preferably 15 to 60 mol%.
  • the weight average molecular weight of the carbodiimide polymer is preferably 500 to 1,000,000, more preferably 1,000 to 500,000.
  • dip molding composition of the present invention comprises the latex of the carboxyl group-containing conjugated diene rubber (A) and the carbodiimide compound (B).
  • the compounding amount of the carbodiimide compound (B) in the dip molding composition of the present invention is such that the effect of the present invention becomes more prominent, so that the carboxyl group-containing conjugated diene rubber (A) in the dip molding composition is 100 weights.
  • the amount is preferably 0.01 to 20 parts by weight, more preferably 0.1 to 10 parts by weight, and particularly preferably 0.5 to 5 parts by weight with respect to parts.
  • the carbodiimide compound (B) is crosslinked with the carboxyl group-containing conjugated diene rubber (A) to form a crosslinked structure.
  • the dip molding composition of the present invention may contain a vulcanizing agent, a vulcanization accelerator and zinc oxide. From the viewpoint of improving odor due to residual sulfur, the vulcanizing agent and the vulcanization accelerator. It is preferable not to add zinc oxide.
  • the dip molding composition of the present invention may be blended with a pH adjuster, a thickener, an anti-aging agent, a dispersant, a pigment, a filler, a softener and the like, which are usually blended.
  • a pH adjuster e.g., sodium bicarbonate
  • a thickener e.g., sodium bicarbonate
  • an anti-aging agent e.g., sodium bicarbonate
  • a dispersant e.g., sodium bicarbonate, sodium bicarbonate, sodium bicarbonate, sodium bicarbonate, sodium bicarbonate, sodium bicarbonate, sodium bicarbonate, sodium bicarbonate, sodium bicarbonate, sodium bicarbonate, sodium bicarbonate, sodium bicarbonate, sodium bicarbonate, sodium bicarbonate, sodium bicarbonate, sodium bicarbonate, sodium bicarbonate, sodium bicarbonate, sodium bicarbonate, sodium bicarbonate, sodium bicarbonate, sodium bicarbonate, sodium bicarbonate, sodium bicarbonate, sodium bicarbonate, sodium bicarbonate, sodium
  • the solid concentration of the dip molding composition of the present invention is preferably 10 to 50% by weight, more preferably 15 to 45% by weight.
  • the pH of the dip molding composition of the present invention is usually in the range of 7 to 12, preferably 8 to 11.
  • dip-molded product of the present invention is formed by dip-molding the dip-molding composition of the present invention.
  • a normal method may be employed, and examples thereof include a direct dipping method, an anode adhesion dipping method, and a teag adhesion dipping method.
  • the anode coagulation dipping method is preferred because a dip-molded product having a uniform thickness is easily obtained.
  • a dip-molding mold is immersed in a coagulant solution, the coagulant is attached to the surface of the mold, and then the dip-molding composition is immersed in the dip-molding composition.
  • a dip-formed layer is formed on the substrate.
  • the coagulant examples include metal halides such as barium chloride, calcium chloride, magnesium chloride, zinc chloride, and aluminum chloride; nitrates such as barium nitrate, calcium nitrate, and zinc nitrate; acetic acid such as barium acetate, calcium acetate, and zinc acetate. Salts; sulfates such as calcium sulfate, magnesium sulfate, and aluminum sulfate; and the like. Of these, calcium chloride and calcium nitrate are preferable.
  • These coagulants are usually used as a solution of water, alcohol, or a mixture thereof. The concentration of the coagulant is usually 5 to 50% by weight, preferably 10 to 30% by weight.
  • the obtained dip-molded layer is usually subjected to heat treatment to be crosslinked.
  • water-soluble impurities for example, excess emulsifier and coagulant
  • water-soluble impurities may be removed by immersing in water, preferably warm water of 30 to 70 ° C., for about 1 to 60 minutes. This operation may be performed after heat-treating the dip-molded layer, but is preferably performed before the heat treatment from the viewpoint that water-soluble impurities can be more efficiently removed.
  • the dip-molded layer thus obtained is subjected to a heat treatment at a temperature of 80 to 150 ° C. for 10 to 120 minutes for crosslinking.
  • a heating method external heating using infrared rays or hot air or internal heating using high frequency can be employed. Of these, heating with hot air is preferred.
  • the dip-molded product is obtained by detaching the crosslinked dip-molded layer from the dip-molding die.
  • the desorption method it is possible to adopt a method of peeling from the mold by hand, or peeling by water pressure or compressed air pressure.
  • a heat treatment may be performed at a temperature of 60 to 120 ° C. for 10 to 120 minutes.
  • the dip-molded product may further have a surface treatment layer formed on the inner and / or outer surfaces thereof.
  • the dip-molded product of the present invention is obtained by using the above-described dip-molding composition of the present invention, and is suitable for applications such as gloves, is excellent in wearing durability, hardly discolored, and has little odor. is there.
  • the dip molding composition of the present invention described above is excellent in storage stability, according to the present invention, a dip molded product having the above characteristics can be obtained stably regardless of the length of storage period. be able to.
  • Such a dip-formed product of the present invention can have a thickness of about 0.03 to about 3 mm, and can be suitably used for a thin product having a thickness of 0.05 to 0.3 mm.
  • medical supplies such as nipples for baby bottles, syringes, conduits, and water pillows; toys and exercise equipment such as balloons, dolls, and balls; industrial articles such as pressure forming bags and gas storage bags; Examples include household, agricultural, fishery and industrial gloves; finger sack. It is particularly suitable for thin surgical gloves.
  • the amount of residual methacrylic acid latex (about 5 g weight (F)) and ethylene glycol (about 20 ⁇ l weight (G)) were weighed accurately, and these were then added to 1.8 wt% polyoxyethylene alkylene ether (trade name “Emulgen 1150S- 60 "(manufactured by Kao Corporation) in addition to 90 ml of an aqueous solution, and then 1 ml of 0.1 M aqueous hydrochloric acid solution was added and stirred for 15 minutes or more to obtain a sample for measuring the amount of residual methacrylic acid.
  • polyoxyethylene alkylene ether trade name “Emulgen 1150S- 60 "(manufactured by Kao Corporation
  • the correction coefficient (E) is obtained as follows.
  • correction coefficient (E) (p ⁇ r1) / (r ⁇ p1)
  • test subjects wear rubber gloves (dip molded products) obtained from odor, perform light work of keyboard input operation for 1 hour, count the number of people who feel discomfort due to odor after 1 hour work, It was evaluated according to the criteria. None: The number of people who felt discomfort was zero. Yes: One or more people felt uncomfortable.
  • Wearing rubber gloves (dip molded products) obtained by wearing were worn by 10 test subjects, and a light work of keyboard input operation was performed. Every time 10 minutes have passed since the work was started, the crotch portion of the finger of the rubber glove was observed to confirm the presence or absence of microcracks.
  • the wearing endurance time was obtained by arithmetically averaging 8 data (data of 8 people) excluding the shortest and longest time. The wearing durability test was conducted up to 240 minutes. It can be determined that the longer the wearing durability time is, the better the wearing durability is.
  • Wear durability after storage for 7 days and storage for 14 days (storage stability)
  • the wearing durability time was determined in the same manner as above except that the obtained rubber gloves after 7 days storage (dip-molded product) and rubber gloves after 14 days storage (dip-molded product) were used. It can be determined that the longer the wearing durability time, the better the storage stability as a dip molding composition in addition to the wearing durability.
  • Production Example 1 In a polymerization reactor, 29 parts of acrylonitrile, 64 parts of 1,3-butadiene, 7 parts of methacrylic acid, 0.5 part of t-dodecyl mercaptan, 132 parts of ion-exchanged water, 3 parts of sodium dodecylbenzenesulfonate, ⁇ -naphthalenesulfonic acid Formalin condensate sodium salt 0.5 part, potassium persulfate 0.3 part and ethylenediaminetetraacetic acid sodium salt 0.05 part were charged, and the polymerization temperature was maintained at 37 ° C. to initiate the polymerization.
  • the amount of residual methacrylic acid was measured and found to be 2000 ppm by weight. Further, the content ratio of each monomer unit constituting the carboxyl group-containing conjugated diene rubber (a1) was measured and found to be equal to the charged amount (the same applies to Production Examples 2 to 7 described later).
  • Production Example 2 A latex of carboxyl group-containing conjugated diene rubber (a2) having a solid content concentration of 45 wt% and a pH of 8 was obtained in the same manner as in Production Example 1 except that the reaction was carried out until the polymerization conversion reached 98 wt%. With respect to the obtained latex of carboxyl group-containing conjugated diene rubber (a2), the amount of residual methacrylic acid was measured and found to be 1500 ppm by weight.
  • Production Example 3 Except for changing the blending amount of 1,3-butadiene from 64 parts to 65 parts and the blending amount of methacrylic acid from 7 parts to 6 parts, respectively, in the same manner as in Production Example 1, the solid content concentration was 40% by weight, A latex of carboxyl group-containing conjugated diene rubber (a3) having a pH of 8 was obtained. With respect to the obtained latex of carboxyl group-containing conjugated diene rubber (a3), the amount of residual methacrylic acid was measured and found to be 1800 ppm by weight.
  • Production Example 4 A latex of carboxyl group-containing conjugated diene rubber (a4) having a solid concentration of 45% by weight and a pH of 8 was obtained in the same manner as in Production Example 3, except that the reaction was carried out until the polymerization conversion reached 98% by weight. When the amount of residual methacrylic acid was measured about the obtained latex of carboxyl group-containing conjugated diene rubber (a4), it was 1100 ppm by weight.
  • Production Example 5 The solid content concentration was 45% by weight in the same manner as in Production Example 1, except that the amount of 1,3-butadiene was changed from 64 parts to 66 parts and the amount of methacrylic acid was changed from 7 parts to 5 parts.
  • a latex of carboxyl group-containing conjugated diene rubber (a5) having a pH of 8 was obtained. With respect to the obtained latex of the carboxyl group-containing conjugated diene rubber (a5), the amount of residual methacrylic acid was measured and found to be 1600 ppm by weight.
  • Production Example 6 The amount of acrylonitrile was changed from 29 parts to 30 parts, the amount of 1,3-butadiene was changed from 64 parts to 65 parts, the amount of methacrylic acid was changed from 7 parts to 5 parts, and the polymerization reaction was changed.
  • a latex of carboxyl group-containing conjugated diene rubber (a6) having a solid content concentration of 45% by weight and a pH of 8 was obtained in the same manner as in Production Example 1 except that the polymerization conversion was terminated when the polymerization conversion reached 94% by weight. With respect to the obtained latex of carboxyl group-containing conjugated diene rubber (a6), the amount of residual methacrylic acid was measured and found to be 2300 ppm by weight.
  • Production Example 7 Similar to Production Example 6, except that the amount of acrylonitrile was changed from 30 parts to 29 parts and the amount of methacrylic acid was changed from 7 parts to 6 parts, respectively, a carboxyl group having a solid content concentration of 45% by weight and a pH of 8 A latex of the conjugated diene rubber (a7) was obtained. With respect to the obtained latex of carboxyl group-containing conjugated diene rubber (a7), the amount of residual methacrylic acid was measured and found to be 2500 ppm by weight.
  • Example 1 Preparation of Dip Molding Composition
  • carboxyl group-containing conjugated diene rubber (a1) obtained in Production Example 1 carbodiimide compound (B) (trade name “Carbodilite V-02-L2”, manufactured by Nisshinbo Chemical Co., Ltd.) was added.
  • an aqueous ammonia solution and ion-exchanged water were further added to adjust the pH to 10.0 and the solid content concentration to 30% by weight, and the mixture was stirred and uniformly dispersed at a temperature of 20 ° C. to obtain a dip molding composition. It was.
  • the polymer having a carbodiimide structure was added to 2 parts with respect to 100 parts of the carboxyl group-containing conjugated diene rubber (a1) in the latex of the carboxyl group-containing conjugated diene rubber (a1).
  • a rubber glove (dip molded product) was produced by the following method. First, a coagulant aqueous solution in which 20 parts of calcium nitrate, 0.05 part of polyethylene glycol octylphenyl ether and 80 parts of water were mixed was prepared. Next, the glove mold was immersed in this coagulant aqueous solution for 5 seconds, pulled up, and then dried under conditions of a temperature of 50 ° C. for 10 minutes to attach the coagulant to the glove mold. And after immersing the glove mold to which the coagulant is adhered in the dip molding composition obtained above for 8 seconds and then immersing in warm water at 40 ° C.
  • the film was dried at a temperature of 50 ° C. for 10 minutes to form a dip-molded layer in a glove mold. Then, the glove mold on which the dip-molded layer was formed was dried at a temperature of 70 ° C. for 10 minutes, and subsequently the dip-molded layer was crosslinked by heat treatment at a temperature of 125 ° C. for 20 minutes. The dip-molded layer was peeled from the glove mold to obtain a rubber glove (dip-molded product) having a thickness of 0.08 mm. The obtained rubber gloves (dip molded products) were evaluated for copper ion discoloration, odor, and wearing durability by the above methods. The results are shown in Table 1.
  • Example 2 The same procedure as in Example 1 was conducted except that the carboxyl group-containing conjugated diene rubber (a2) latex obtained in Production Example 2 was used instead of the carboxyl group-containing conjugated diene rubber (a1) latex obtained in Production Example 1. Then, a dip molding composition and each rubber glove (dip molded product) were obtained and evaluated in the same manner. The results are shown in Table 1.
  • Example 3 The same procedure as in Example 1 was performed except that the carboxyl group-containing conjugated diene rubber (a3) latex obtained in Production Example 3 was used instead of the carboxyl group-containing conjugated diene rubber (a1) latex obtained in Production Example 1. Then, a dip molding composition and each rubber glove (dip molded product) were obtained and evaluated in the same manner. The results are shown in Table 1.
  • Example 4 The same procedure as in Example 1 was performed except that the carboxyl group-containing conjugated diene rubber (a4) latex obtained in Production Example 4 was used instead of the carboxyl group-containing conjugated diene rubber (a1) latex obtained in Production Example 1. Then, a dip molding composition and each rubber glove (dip molded product) were obtained and evaluated in the same manner. The results are shown in Table 1.
  • Example 5 The same procedure as in Example 1 was performed except that the carboxyl group-containing conjugated diene rubber (a5) latex obtained in Production Example 5 was used instead of the carboxyl group-containing conjugated diene rubber (a1) latex obtained in Production Example 1. Then, a dip molding composition and each rubber glove (dip molded product) were obtained and evaluated in the same manner. The results are shown in Table 1.
  • Comparative Example 1 The same procedure as in Example 1 was performed except that the carboxyl group-containing conjugated diene rubber (a6) latex obtained in Production Example 6 was used instead of the carboxyl group-containing conjugated diene rubber (a1) latex obtained in Production Example 1. Then, a dip molding composition and each rubber glove (dip molded product) were obtained and evaluated in the same manner. The results are shown in Table 1.
  • Comparative Example 2 The same procedure as in Example 1 was performed except that the carboxyl group-containing conjugated diene rubber (a7) latex obtained in Production Example 7 was used instead of the carboxyl group-containing conjugated diene rubber (a1) latex obtained in Production Example 1. Then, a dip molding composition and each rubber glove (dip molded product) were obtained and evaluated in the same manner. The results are shown in Table 1.
  • Comparative Example 3 1 part of sulfur, 0.5 part of zinc dibutylcarbamate, 0.1 part of ⁇ -naphthalenesulfonic acid formalin condensate sodium salt, 0.03 part of potassium hydroxide, and 1.63 parts of water are mixed to give a vulcanizing agent A dispersion was prepared. To the carboxyl group-containing conjugated diene rubber (a1) latex obtained in Production Example 1, the vulcanizing agent dispersion prepared above was added, and then an aqueous ammonia solution and ion-exchanged water were further added to pH 10.0, After adjusting the solid content concentration to 30%, the mixture was stirred and dispersed uniformly at a temperature of 20 ° C. for 24 hours to obtain a dip-molding composition.
  • Comparative Example 4 Except for not blending 2 parts of the polymer having a carbodiimide structure as the carbodiimide compound (B), in the same manner as in Example 1, a dip molding composition and each rubber glove (dip molded product) were obtained. Evaluation was performed in the same manner. The results are shown in Table 1.
  • a dip-molding composition comprising a carboxyl group-containing conjugated diene rubber latex having a residual methacrylic acid amount (residual carboxylic acid amount) of 2200 ppm by weight or less, and a carbodiimide compound added thereto.
  • the dip-molded product obtained by using the dip-molding product is suppressed in discoloration (discoloration due to copper ions), has no odor, and has excellent wearing durability.
  • the dip-molding composition has a temperature of 50 ° C. Even after 7 days of storage under storage and 14 days after storage at 50 ° C., a dip-molded product excellent in wearing durability could be provided, and the storage stability was excellent (Examples 1 to 5).

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Mechanical Engineering (AREA)
  • Textile Engineering (AREA)
  • Gloves (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

L'invention concerne une composition de moulage par immersion contenant un latex d'un caoutchouc (A) de diène conjugué contenant un groupe carboxyle et un composé carbodiimide (B), la composition de moulage par immersion étant caractérisée en ce que la teneur en acide carboxylique résiduel dans le latex du caoutchouc (A) de diène conjugué contenant un groupe carboxyle n'est pas supérieure à 2200 ppm en poids.
PCT/JP2015/069270 2015-07-03 2015-07-03 Composition de moulage par immersion et objet moulé par immersion WO2017006385A1 (fr)

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WO2019159779A1 (fr) * 2018-02-16 2019-08-22 日本ゼオン株式会社 Procédé de production d'article moulé par immersion
EP3473121A4 (fr) * 2016-06-16 2019-11-27 Midori Anzen Co., Ltd. Procédé de fabrication de gants, gant, et composition d'émulsion pour gants

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EP3473121A4 (fr) * 2016-06-16 2019-11-27 Midori Anzen Co., Ltd. Procédé de fabrication de gants, gant, et composition d'émulsion pour gants
US11179908B2 (en) 2016-06-16 2021-11-23 Midori Anzen Co., Ltd. Method of manufacturing gloves, glove, and emulsion composition for gloves
WO2019159779A1 (fr) * 2018-02-16 2019-08-22 日本ゼオン株式会社 Procédé de production d'article moulé par immersion
US20210001521A1 (en) * 2018-02-16 2021-01-07 Zeon Corporation Production method for dip-molded article
JPWO2019159779A1 (ja) * 2018-02-16 2021-01-28 日本ゼオン株式会社 ディップ成形体の製造方法
JP7238879B2 (ja) 2018-02-16 2023-03-14 日本ゼオン株式会社 ディップ成形体の製造方法

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