WO2024070750A1 - Procédé de production d'un objet formé par immersion, et objet formé par immersion - Google Patents

Procédé de production d'un objet formé par immersion, et objet formé par immersion Download PDF

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Publication number
WO2024070750A1
WO2024070750A1 PCT/JP2023/033643 JP2023033643W WO2024070750A1 WO 2024070750 A1 WO2024070750 A1 WO 2024070750A1 JP 2023033643 W JP2023033643 W JP 2023033643W WO 2024070750 A1 WO2024070750 A1 WO 2024070750A1
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mold
rubber latex
latex composition
rubber
water
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PCT/JP2023/033643
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English (en)
Japanese (ja)
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晃平 澤田
聖司 西岡
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住友精化株式会社
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    • 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
    • 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
    • B29C41/34—Component parts, details or accessories; Auxiliary operations
    • B29C41/36—Feeding the material on to the mould, core or other substrate
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L1/00—Compositions of cellulose, modified cellulose or cellulose derivatives
    • C08L1/08—Cellulose derivatives
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L21/00—Compositions of unspecified rubbers
    • C08L21/02—Latex
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L5/00—Compositions of polysaccharides or of their derivatives not provided for in groups C08L1/00 or C08L3/00

Definitions

  • the present invention relates to a method for producing a dip-molded body, a dip-molded body, etc. More specifically, the present invention relates to a method for producing a dip-molded body by dip molding using rubber latex, and a dip-molded body that can be produced by the method.
  • dip molded articles using rubber latex is widely practiced, and examples of such products include gloves, sacks, catheters, and balloons. These products are manufactured by dipping a mold of the desired shape (also called a molding mold or membrane mold) into rubber latex, adhering rubber particles to the mold until the desired thickness is reached, and then vulcanizing the rubber attached to the mold as necessary.
  • a mold of the desired shape also called a molding mold or membrane mold
  • Patent Document 1 discloses a method for producing a dip-molded body from latex using a coagulating liquid containing calcium chloride.
  • Patent Document 2 discloses a method for producing a dip-molded body from natural rubber latex containing a heat-sensitizing agent and an anodic coagulant.
  • Patent Document 3 discloses a method for producing a dip-molded body from nitrile rubber latex containing a specific polysaccharide, using alcohol as a coagulant.
  • Patent Document 4 discloses a method for producing a dip-molded body by immersing a mold to which calcium ions are attached in chlorosulfonated polyethylene latex containing sodium alginate.
  • the object of the present invention is to provide a method for stably producing a relatively thick molded product by the dip molding method.
  • Another object of the present invention is to provide a relatively thick, practical dip molded product.
  • the present invention provides a method for producing a dip-molded body and a dip-molded body, for example, as described in the following sections.
  • Section A-1 A mold having a surface temperature of 30° C. or more and less than 100° C. is immersed in a rubber latex composition containing a water-soluble polymer having an acidic functional group and a rubber, thereby adhering the rubber latex composition to the surface of the mold; and gelling the water-soluble polymer in the rubber latex composition attached to the mold;
  • a method for producing a dip-molded body comprising the steps of: Section A-2.
  • the rubber latex composition is a latex composition containing a water-soluble polymer having an acidic functional group and a chlorosulfonated polyolefin.
  • Section A-9 Prior to depositing the rubber latex composition on the surface of the mold, The method according to any one of items A-1 to A-8, further comprising attaching a coagulant to the mold. Section A-10. After applying the rubber latex composition to the surface of the mold, The method according to any one of items A-1 to A-9, comprising attaching a coagulant to a mold having the rubber latex composition attached to its surface. Section A-11.
  • a dip-molded article comprising a water-soluble polymer having an acidic functional group and a rubber, the thickness of the membrane being greater than 0.3 mm, and the thickness unevenness calculated as follows being 50% or less.
  • Section B-1 A mold having a surface temperature of 30° C. or more and less than 100° C. is immersed in a rubber latex composition containing a water-soluble polymer having an acidic functional group (excluding sodium alginate) and rubber, thereby adhering the rubber latex composition to the surface of the mold; and gelling the water-soluble polymer in the rubber latex composition attached to the mold;
  • Section B-3 The method according to item B-2, wherein the polyvalent ion is at least one metal ion selected from the group consisting of calcium ion, magnesium ion, aluminum ion, zinc ion, iron ion, copper ion, cobalt ion, nickel ion, and barium ion.
  • Section B-4 The method according to any one of Items B-1 to B-3, wherein the mold is immersed in the rubber latex composition for 15 seconds or more.
  • Section B-5 The manufacturing method according to any one of Items B-1 to B-4, wherein the rubber latex composition contains 0.1 parts by mass or more of a water-soluble polymer having an acidic functional group per 100 parts by mass of rubber.
  • Section B-6 The manufacturing method according to any one of Items B-1 to B-4, wherein the rubber latex composition contains 0.1 parts by mass or more of a water-soluble polymer having an acidic functional group per 100 parts by mass of rubber.
  • Section B-7 The method according to any one of Items B-1 to B-5, wherein the water-soluble polymer having an acidic functional group is an acidic polysaccharide.
  • Section B-7 The method according to Item B-6, wherein the acidic polysaccharide is at least one selected from the group consisting of LM pectin, xanthan gum, ⁇ -carrageenan, ⁇ -carrageenan, and carboxymethylcellulose.
  • Section B-8. The production method according to any one of Items B-1 to B-7, wherein the rubber latex composition is a latex composition containing a water-soluble polymer having an acidic functional group and a chlorosulfonated polyolefin. Section B-9.
  • the present invention makes it possible to stably manufacture relatively thick dip-molded bodies using various types of rubber latex while suppressing thickness variations, entrapment of air bubbles, and loss of latex, thereby providing relatively thick, practical dip-molded bodies.
  • the present invention preferably includes a method for producing a dip-molded body, which includes immersing a mold (also called a molding mold or a film-molding mold) in a rubber latex composition containing a water-soluble polymer having an acidic functional group, and a dip-molded body that can be produced by the method, but is not limited to these, and the present invention includes all of the embodiments disclosed in this specification that can be recognized by a person skilled in the art.
  • the method for producing a dip-molded product included in the present invention includes immersing a mold (also called a molding mold or a film-molding mold) in a rubber latex composition containing a water-soluble polymer having an acidic functional group and rubber, and adhering the rubber latex composition to the surface of the mold, and further includes gelling the water-soluble polymer in the rubber latex composition that has been adhered to the mold. As a result, a rubber film is formed on the surface of the mold, and a dip-molded product can be obtained.
  • This production method is sometimes referred to as the production method of the present invention.
  • this rubber latex composition is sometimes referred to as the latex composition of the present invention.
  • the latex composition of the present invention contains a water-soluble polymer and rubber having an acidic functional group.
  • the rubber latex constituting the latex composition of the present invention is not particularly limited, and examples of the rubber latex that can be used include natural rubber latex, polybutadiene rubber latex, polyisoprene rubber latex, acrylonitrile-butadiene rubber latex, hydrogenated acrylonitrile-butadiene rubber latex, styrene-butadiene rubber latex, hydrogenated styrene-butadiene rubber latex, acrylic rubber latex, ethylene-propylene-diene rubber latex, chloroprene rubber latex, butyl rubber latex, chlorinated polyolefin rubber latex, chlorosulfonated polyolefin rubber latex, fluororubber latex, epichlorohydrin rubber latex, silicone rubber latex, and urethane rubber latex. These may be used alone or in combination of two or more. In particular, the present invention is particularly effective with chlorosulfonated polyolefin rubber latex, which is difficult to
  • the latex composition of the present invention has been described from the viewpoint of the rubber latex that can be used to form the latex composition of the present invention, but it can also be described from the viewpoint of the rubber contained in the latex composition of the present invention as follows. That is, examples of the rubber contained in the latex composition of the present invention include natural rubber, polybutadiene rubber, polyisoprene rubber, acrylonitrile-butadiene rubber, hydrogenated acrylonitrile-butadiene rubber, styrene-butadiene rubber, hydrogenated styrene-butadiene rubber, acrylic rubber, ethylene-propylene-diene rubber, chloroprene rubber, butyl rubber, chlorinated polyolefin rubber, chlorosulfonated polyolefin rubber, fluororubber, epichlorohydrin rubber, silicone rubber, and urethane rubber.
  • Chlorosulfonated polyolefin is a polymer having a structure in which a chlorosulfone group (-SO 2 Cl) and chlorine are bonded to a polyolefin main chain. Chlorosulfonated polyolefin can be obtained by chlorosulfonating and chlorinating polyolefin.
  • Polyolefins are polymers that contain 50% or more by mass of monomer units derived from olefins, such as ethylene, propylene, 1-butene, 1-pentene, 1-hexene, 4-methyl-1-pentene, 1-octene, and 1-decene.
  • olefins such as ethylene, propylene, 1-butene, 1-pentene, 1-hexene, 4-methyl-1-pentene, 1-octene, and 1-decene.
  • the polyolefin is preferably a polyolefin having at least ethylene and/or propylene as a monomer unit.
  • a homopolymer of ethylene or propylene or a copolymer of ethylene and/or propylene is preferable, and more preferably, for example, polyethylene, polypropylene, ethylene- ⁇ -olefin copolymer, ethylene-vinyl compound copolymer, etc.
  • the ⁇ -olefin include propylene, 1-butene, 1-pentene, 1-hexene, 4-methyl-1-pentene, 1-octene, 1-decene, etc.
  • vinyl compound examples include vinyl acetate, vinyl alcohol, acrylic acid, methyl methacrylate, vinyl chloride, acrylonitrile, styrene, vinylcyclohexane, N-isopropylacrylamide, acrolein, vinylene carbonate, maleic anhydride, etc.
  • the polyolefin may be copolymerized with other polymerizable components.
  • other polymerizable components include linear dienes such as 1,3-butadiene, isoprene, 1,4-hexadiene, 1,6-octadiene, 2-methyl-1,5-hexadiene, 6-methyl-1,5-heptadiene, and 7-methyl-1,6-octadiene; and cyclic dienes such as 1,3-cyclohexadiene, 1,4-cyclohexadiene, dicyclopentadiene, 5-vinyl-2-norbornene, 5-ethylidene-2-norbornene, 5-methylene-2-norbornene, and 5-isopropylidene-2-norbornene.
  • Chlorosulfonated polyolefins can be produced by reacting polyolefins with chlorine and sulfurous acid gas, or by reacting polyolefins with sulfuryl chloride in the presence of an amine.
  • the chlorine content in the chlorosulfonated polyolefin is not particularly limited, but from the viewpoint of solubility in a solvent when emulsifying the chlorosulfonated polyolefin and productivity, it is preferably 5 to 60 mass%, more preferably 10 to 50 mass%, and particularly preferably 20 to 40 mass%.
  • the sulfur content in the chlorosulfonated polyolefin is not particularly limited, but it is preferably 0.1 to 5 mass%, more preferably 0.4 to 3 mass%, and particularly preferably 0.6 to 2 mass%.
  • the chlorine content and sulfur content can be calculated by elemental analysis.
  • various methods can be used, such as polymerizing rubber-making monomers emulsified in water using an emulsifier and forming the latex as is, or dissolving solid rubber in an organic solvent, inverting the phases to emulsify and disperse the rubber in water, and then removing the organic solvent to form the latex.
  • the emulsifier used in the production of rubber latex is not particularly limited as long as it can emulsify the monomers used in rubber production.
  • anionic surfactants include aliphatic carboxylates, alkyl ether carboxylates, rosinates, alkyl sulfonates, alkyl benzene sulfonates, and alkyl phosphates.
  • nonionic surfactants include polyoxyalkylene ethers, polyoxyalkylene esters, polyhydric alcohol fatty acid esters, sugar fatty acid esters, and alkyl polyglycosides.
  • anionic-nonionic surfactants include polyoxyalkylene alkyl sulfates, polyoxyalkylene alkyl ether sulfates, and polyoxyalkylene alkyl phenyl ether sulfates. These may be used alone or in combination of two or more.
  • the solids (i.e. rubber) concentration of the rubber latex is preferably 20 to 70% by mass, more preferably 25 to 65% by mass, and particularly preferably 30 to 60% by mass.
  • the solids concentration can be measured in accordance with JIS K 6387-2:2011.
  • the particle size of the rubber in the rubber latex is not particularly limited, but the median particle size measured with a laser diffraction particle size distribution analyzer is preferably 0.05 to 10 ⁇ m, more preferably 0.1 to 5 ⁇ m, and particularly preferably 0.2 to 2.5 ⁇ m. A particle size within this range can result in a more stable rubber latex.
  • the particle size of the rubber can be adjusted by the type and amount of emulsifier, the amount of water used, the operating conditions of the emulsification device, etc.
  • the latex composition of the present invention is a rubber latex composition containing a water-soluble polymer having an acidic functional group and rubber, and can be prepared, for example, by adding a water-soluble polymer having an acidic functional group to the rubber latex.
  • the water-soluble polymer having an acidic functional group may have a part of the acidic functional group neutralized. Even if an attempt is made to neutralize the acidic functional group of a polymer having an acidic functional group, it may be difficult to neutralize all of the acidic functional groups, and commercially available products with the notation of salt are usually "water-soluble polymers having acidic functional groups" in which a part of the acidic functional groups has been neutralized.
  • water-soluble polymers having acidic functional groups polymers having carboxylic acid (salt) groups, sulfonic acid (salt) groups, sulfuric acid (salt) groups, phosphoric acid (salt) groups, phosphonic acid (salt) groups, phenol groups, etc. are preferred.
  • polymers that are soluble in 100 g of water at 50° C. at a rate of 1% by mass or more are preferred.
  • carboxylic acid (salt) and similar notations mean “carboxylic acid” and/or “carboxylate salt”.
  • sodium alginate may be excluded from the water-soluble polymer having an acidic functional group.
  • a rubber latex composition containing sodium alginate is easy to obtain a relatively thin dip-molded product, and therefore the present invention can exert a particularly remarkable effect on a rubber latex containing a "water-soluble polymer having an acidic functional group" other than sodium alginate.
  • water-soluble polymers having acidic functional groups include unsaturated carboxylic acid polymers, unsaturated sulfonic acid polymers, polyamino acids (polypeptides), acidic polysaccharides, etc.
  • Unsaturated carboxylic acid polymers include poly(meth)acrylic acid (salt), ethylene-(meth)acrylic acid (salt) copolymer, poly(styrene-maleic anhydride) copolymer, etc.
  • (meth)acrylic means "methacrylic” and/or "acrylic”.
  • unsaturated sulfonic acid polymers include polystyrene sulfonic acid (salt), polyvinyl sulfonic acid (salt), and poly(2-acrylamido-2-methyl-1-propanesulfonic acid (salt)).
  • polypeptides examples include polyglutamic acid (salt), polyaspartic acid (salt), gelatin, and water-soluble collagen.
  • the acidic polysaccharide may be a naturally occurring acidic polysaccharide or a processed naturally occurring acidic polysaccharide.
  • it may be a naturally occurring acidic polysaccharide that has been deesterified or deacylated, or a naturally occurring acidic polysaccharide that has been chemically modified.
  • it may be a naturally occurring neutral polysaccharide that has been chemically modified to add an acid structure.
  • naturally occurring acidic polysaccharides or processed versions thereof include polysaccharides having uronic acid structures such as galacturonic acid, glucuronic acid, mannuronic acid, and guluronic acid, or sulfated sugar structures.
  • examples of such naturally occurring acidic polysaccharides include pectin (LM pectin, HM pectin), xanthan gum, gellan gum (LA gellan gum, HA gellan gum), algin, gum arabic, ⁇ -carrageenan, ⁇ -carrageenan, tragacanth gum, glucomannan, tremel gum, fucoidan, heparin, hyaluronic acid, rhamsan gum, and diutan gum.
  • pectin LM pectin, HM pectin
  • xanthan gum gellan gum
  • LA gellan gum HA gellan gum
  • algin gum arabic
  • ⁇ -carrageenan ⁇ -carrageenan
  • tragacanth gum glucomannan
  • tremel gum fucoidan
  • fucoidan heparin
  • hyaluronic acid rhamsan gum
  • diutan gum examples of such naturally occurring acidic polys
  • Pectin includes low methoxyl pectin (LM pectin) and high methoxyl pectin (HM pectin).
  • Pectin structure can be broadly classified into two types based on the ratio of galacturonic acid to galacturonic acid methyl ester. It is classified according to the proportion of galacturonic acid methyl ester in the entire pectin molecule (degree of esterification: DE), and when the DE is 50% or more, it is called HM pectin (High Methoxyl Pectin), and when it is less than 50%, it is called LM pectin (Low Methoxyl Pectin).
  • DE degree of esterification
  • HM pectin High Methoxyl Pectin
  • LM pectin Low Methoxyl Pectin
  • pectin found in nature is HM pectin
  • LM pectin is prepared by deesterification treatment.
  • Gellan gum is a natural polysaccharide obtained by fermentation, and is a linear heteropolysaccharide consisting of a repeating structure of four sugars: two glucose units, one glucuronic acid unit, and one rhamnose unit.
  • Gellan gum obtained from fermentation is high acyl gellan gum (HA gellan gum), which has one acyl group on every other repeating unit on the glucose.
  • Low acyl gellan gum (LA gellan gum) can be obtained by removing the acyl groups from the fermentation product (deacylation process).
  • Chemically modified naturally occurring acidic polysaccharides include cationized xanthan gum and amidated pectin.
  • Naturally occurring polysaccharides that have been chemically modified to add an acid structure include carboxymethylcellulose, cellulose succinate, sulfonated cellulose, phosphorylated cellulose, maleic acid modified starch, etc.
  • Acidic polysaccharides can be used alone or in combination of two or more.
  • acidic polysaccharides which have an appropriate amount of acidic functional groups and are prone to gelation
  • the content of the water-soluble polymer having an acidic functional group in the rubber latex composition is preferably 0.1 parts by mass or more per 100 parts by mass of the solids (i.e., rubber) in the rubber latex, and more preferably 0.1 to 5 parts by mass.
  • the upper or lower limit of the range may be, for example, 0.1, 0.2, 0.3, 0.4, 0.5, 0.6, 0.7, 0.8, 0.9, 1, 1.1, 1.2, 1.3, 1.4, 1.5, 1.6, 1.7, 1.8, 1.9, 2, 2.1, 2.2, 2.3, 2.4, 2.5, 2.6, 2.7, 2.8, 2.9, 3, 3.1, 3.2, 3.3, 3.4, 3.5, 3.6, 3.7, 3.8, 3.9, 4, 4.1, 4.2, 4.3, 4.4, 4.5, 4.6, 4.7, 4.8, or 4.9 parts by mass.
  • the range is more preferably 0.2 to 4 parts by mass, and particularly preferably 0.3 to 3 parts by mass.
  • the water-soluble polymer having an acidic functional group may be added during or after the rubber latex is produced. From the viewpoint of the efficiency of rubber latex production, it is preferable to add the water-soluble polymer after the rubber latex is produced.
  • the water-soluble polymer having an acidic functional group may be added as is, as an aqueous solution, or dispersed in alcohol or the like.
  • the rubber latex composition may contain known additives such as antioxidants, defoamers, pH adjusters, chelating agents, vulcanizing agents, vulcanization accelerators, vulcanization accelerator assistants, acid acceptors, film-forming assistants, plasticizers, thickeners, fillers, pigments, etc., within the scope of the present invention.
  • additives such as antioxidants, defoamers, pH adjusters, chelating agents, vulcanizing agents, vulcanization accelerators, vulcanization accelerator assistants, acid acceptors, film-forming assistants, plasticizers, thickeners, fillers, pigments, etc.
  • antioxidants examples include phenol-based antioxidants such as dibutylhydroxytoluene, 2,2'-methylenebis(4-ethyl-6-tert-butylphenol), and 2,5-di-tert-butylhydroquinone; amine-based antioxidants such as N-phenyl-1-naphthylamine and di(4-octylphenyl)amine; phosphorus-based antioxidants such as tris(nonylphenyl)phosphite; sulfur-based antioxidants such as dilauryl thiodipropionate, 2-mercaptobenzimidazole, and nickel dibutyldithiocarbamate; and bisphenol A epoxy resins.
  • phenol-based antioxidants such as dibutylhydroxytoluene, 2,2'-methylenebis(4-ethyl-6-tert-butylphenol), and 2,5-di-tert-butylhydroquinone
  • defoamers examples include oil-based defoamers, mineral oil-based defoamers, silicone-based defoamers, polyether-based defoamers, etc.
  • pH adjusters include sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, ammonia, triethylamine, triethanolamine, tetrabutylammonium hydroxide, hydrochloric acid, sulfuric acid, phosphoric acid, citric acid, acetic acid, etc.
  • Chelating agents include ethylenediaminetetraacetic acid, nitrilotriacetic acid, trans-1,2-diaminocyclohexanetetraacetic acid, diethylenetriaminepentaacetic acid, bis(aminoethyl)glycol ether-N,N,N',N'-tetraacetic acid, N-(2-hydroxyethyl)ethylenediamine-N,N',N'-triacetic acid, dihydroxyethylglycine, 1-hydroxyethane-1,1-diphosphonic acid, gluconic acid, citric acid, malic acid, and tartaric acid.
  • Vulcanizing agents include sulfur such as powdered sulfur, sulfur flowers, precipitated sulfur, and colloidal sulfur; organic peroxides such as di-tert-butyl peroxide and dicumyl peroxide; maleimide compounds such as N,N'-m-phenylene bismaleimide; quinoid compounds such as p-quinone dioxime and p,p'-dibenzoylquinone dioxime; metal compounds such as magnesium oxide and lead oxide; and polyhydric alcohol compounds such as pentaerythritol, dipentaerythritol, sorbitol, and trimethylolpropane.
  • sulfur such as powdered sulfur, sulfur flowers, precipitated sulfur, and colloidal sulfur
  • organic peroxides such as di-tert-butyl peroxide and dicumyl peroxide
  • maleimide compounds such as N,N'-m-phenylene bismaleimide
  • quinoid compounds such as p-quinone dioxime and p,
  • Vulcanization accelerators include diethyldithiocarbamic acid, dibutyldithiocarbamic acid, diphenyldithiocarbamic acid, sodium diethyldithiocarbamate, sodium dibutyldithiocarbamate, sodium diphenyldithiocarbamate, zinc diethyldithiocarbamate, zinc dibutyldithiocarbamate, zinc diphenyldithiocarbamate, 2-mercaptobenzothiazole, zinc 2-mercaptobenzothiazole, di-2-benzothiazolyl disulfide, 2-(4'-morpholinyl) Nodithio)benzothiazole, trimethylthiourea, N,N'-diethylthiourea, 1,3-diphenylguanidine, 1,3-di-o-tolylguanidine, N-cyclohexyl-2-benzothiazolylsulfenamide, N-oxyd
  • vulcanization accelerators examples include metal oxides such as zinc oxide and magnesium oxide, and fatty acids such as stearic acid and palmitic acid.
  • Acid acceptors include metal oxides such as lead oxide, magnesium oxide, zinc oxide, and calcium oxide; metal hydroxides such as magnesium hydroxide, calcium hydroxide, and aluminum hydroxide; clay minerals such as hydrotalcite; and epoxy compounds such as phenyl glycidyl ether, epoxidized soybean oil, epoxidized castor oil, epoxidized polybutadiene, and polyglycidyl methacrylate.
  • film-forming aids include propylene glycol, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monoisopropyl ether, ethylene glycol mono n-butyl ether, ethylene glycol mono isobutyl ether, ethylene glycol mono tert-butyl ether, ethylene glycol monophenyl ether, diethylene glycol monoethyl ether, diethylene glycol monopropyl ether, diethylene glycol monoisopropyl ether, diethylene glycol mono n-butyl ether, diethylene glycol mono isobutyl ether, diethylene glycol mono tert-butyl ether, diethylene glycol monophenyl ether, diethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether, triethylene glycol mono
  • Plasticizers include phthalates such as dibutyl phthalate and dioctyl phthalate, aliphatic dibasic acid esters such as dioctyl adipate and dioctyl sebacate, glycerin fatty acid esters such as glycerin diacetomonolaurate, polyesters such as polyethylene adipate and polyhexamethylene succinate, and polyethers such as polyethylene glycol and polyethylene glycol laurate.
  • phthalates such as dibutyl phthalate and dioctyl phthalate
  • aliphatic dibasic acid esters such as dioctyl adipate and dioctyl sebacate
  • glycerin fatty acid esters such as glycerin diacetomonolaurate
  • polyesters such as polyethylene adipate and polyhexamethylene succinate
  • polyethers such as polyethylene glycol and polyethylene glycol laurate.
  • Thickening agents include neutral polysaccharides such as methylcellulose, hydroxyethylcellulose, guar gum, curdlan, and pullulan, and water-soluble polymers such as polyvinyl alcohol, polyethylene oxide, and polyvinylpyrrolidone.
  • Fillers include carbon fiber, cellulose fiber, carbon black, silica, talc, clay, calcium carbonate, titanium oxide, barium sulfate, etc.
  • Pigments include carbon black, titanium oxide, chromium oxide, iron blue, amber, nickel titanium yellow, viridian, cobalt blue, phthalocyanine blue, phthalocyanine green, molybdenum orange, chrome yellow, anthraquinone, quinacridone, etc.
  • the amount of additive is not particularly limited, but is preferably 5 to 30 parts by mass per 100 parts by mass of the solid content (i.e., rubber) in the rubber latex.
  • the viscosity of the latex composition of the present invention at 25°C is preferably 80 mPa ⁇ s or more and 4000 mPa or less, more preferably 90 mPa ⁇ s or more and 3000 mPa ⁇ s or less, and even more preferably 100 mPa ⁇ s or more and 2000 mPa ⁇ s or less.
  • the viscosity of the composition is measured under the following conditions.
  • the measurement spindle may be appropriately selected from LV-1 to LV-4 depending on the viscosity.
  • the measurement rotation speed may be appropriately set if it is outside the range in which viscosity can be measured.
  • Measurement device Brookfield viscometer (DV-II+, manufactured by BROOKFIELD) Measuring spindle: LV-1 to LV-4 Measurement temperature: 25°C Measurement speed: 60 rpm
  • the production method of the present invention includes a step of immersing a mold having a surface temperature of 30° C. or more and less than 100° C. in the latex composition of the present invention to adhere the rubber latex to the surface of the mold.
  • This step is also called a immersion step.
  • the mold for producing the dip-molded body (also called a molding mold or a membrane mold) can be a mold corresponding to the desired three-dimensional shape made of ceramic, metal, glass, plastic, etc.
  • the surface of the mold can be finished with a matte finish or provided with other materials such as fibers or other types of rubber coatings depending on the purpose of the dip-molded body.
  • the temperature of the mold during immersion is 30°C or higher and lower than 100°C.
  • the upper or lower limit of the range (30°C or more and less than 100°C) may be, for example, 31, 32, 33, 34, 35, 36, 37, 38, 39, 40, 41, 42, 43, 44, 45, 46, 47, 48, 49, 50, 51, 52, 53, 54, 55, 56, 57, 58, 59, 60, 61, 62, 63, 64, 65, 66, 67, 68, 69, 70, 71, 72, 73, 74, 75, 76, 77, 78, 79, 80, 81, 82, 83, 84, 85, 86, 87, 88, 89, 90, 91, 92, 93, 94, 95, 96, 97, 98, or 99°C.
  • the temperature of the mold during immersion may be 32 to 90° C., 35 to 90° C., 40 to 85° C., 50 to 85° C., 60 to 85° C., 65 to 85° C., 40 to 80° C., 50 to 80° C., 60 to 80° C., 65 to 80° C., or 70 to 80° C.
  • the temperature is preferably 45 to 85° C., more preferably 55 to 85° C., and particularly preferably 62 to 83° C.
  • the temperature of the mold here refers to the surface temperature immediately before immersion, and is measured with a radiation thermometer. More specifically, the temperature of the mold is measured with an infrared radiation thermometer (e.g., infrared radiation thermometer AD-5611A manufactured by A&D Corporation) with emissivity set to 0.95, from a position 20 cm away from the surface of the mold. The time from measurement to immersion is within 3 seconds.
  • infrared radiation thermometer e.g., infrared radiation thermometer AD-5611A manufactured by A&D Corporation
  • emissivity set to 0.95
  • the temperature of the mold can be adjusted using a hot air heater, infrared heater, microwave heater, high frequency heater, etc., and it is preferable to set the heating temperature taking into consideration the cooling time before immersion. It may also be adjusted by combining it with a cooling means such as a cold air blower.
  • the temperature of the rubber latex composition when immersed is not particularly limited, but in the present invention, it is preferable that the temperature of the rubber latex composition when immersed is lower than the temperature of the mold when immersed. Therefore, the temperature of the rubber latex composition when immersed is preferably [the temperature of the mold when immersed - 5] ° C or less, more preferably [the temperature of the mold when immersed - 7] ° C or less, even more preferably [the temperature of the mold when immersed - 20] ° C or less, and particularly preferably [the temperature of the mold when immersed - 30] ° C or less.
  • the temperature of the rubber latex composition when immersed is preferably 10 to 70 ° C, more preferably 15 to 60 ° C, even more preferably 20 to 50 ° C, and particularly preferably 20 to 30 ° C.
  • the temperature of the rubber latex composition during immersion is 10 to 70°C, 15 to 60°C, 20 to 50°C, or 20 to 30°C, and is preferably equal to or lower than [the temperature of the mold during immersion - 5]°C, more preferably equal to or lower than [the temperature of the mold during immersion - 7]°C, even more preferably equal to or lower than [the temperature of the mold during immersion - 20]°C, and particularly preferably equal to or lower than [the temperature of the mold during immersion - 30]°C.
  • the rubber latex composition is at such a temperature during immersion, it is possible to ensure appropriate fluidity and storage stability.
  • the time for immersing the mold in the rubber latex composition can be set so that the resulting film has the desired thickness (preferably, for example, thicker than 0.3 mm). For example, 15 seconds or more is preferable, 20 seconds or more is more preferable, and 30 seconds or more is even more preferable. Also, for example, 15 to 300 seconds is preferable, 20 to 200 seconds is more preferable, and 30 to 150 seconds is even more preferable.
  • the manufacturing method of the present invention includes a step of gelling the water-soluble polymer having an acidic functional group contained in the rubber latex composition that was attached to the mold in the immersion step. This causes a film to form on the surface of the mold. This step is also called the film formation step.
  • Various methods can be used to gel water-soluble polymers having acidic functional groups, depending on the type of water-soluble polymer having acidic functional groups used. Examples include a method of gelling by chemical cross-linking through a chemical reaction, a method of gelling by ionic cross-linking through ionic bonds, and a method of gelling by physical cross-linking through aggregation, crystallization, etc. of polymer chains.
  • a component that causes gelling can be used.
  • a component is also called a coagulant.
  • the coagulant may be, for example, a crosslinking agent for forming chemical crosslinks, or an ion-containing substance for forming ionic crosslinks.
  • a polyfunctional crosslinking agent is preferable as a crosslinking agent for forming chemical crosslinks, and more specifically, for example, ethylene glycol diglycidyl ether, pentaerythritol tetraglycidyl ether, etc.
  • a polyvalent ion-containing substance for example, a polyvalent ion-containing substance is preferable, and more specifically, for example, a substance containing a polyvalent cation such as calcium ion, magnesium ion, aluminum ion, zinc ion, iron ion, copper ion, cobalt ion, nickel ion, barium ion, etc. is preferable.
  • the method of gelling the water-soluble polymer includes reacting the polymer with a multifunctional crosslinking agent such as ethylene glycol diglycidyl ether or pentaerythritol tetraglycidyl ether (for example, reacting at 80°C) to gel the polymer through chemical crosslinking, or contacting the polymer with a multivalent ion to gel the polymer through ionic crosslinking.
  • a multifunctional crosslinking agent such as ethylene glycol diglycidyl ether or pentaerythritol tetraglycidyl ether
  • an acidic polysaccharide When an acidic polysaccharide is used as a water-soluble polymer having an acidic functional group, various methods can be used to gel the acidic polysaccharide depending on the type of acidic polysaccharide used.
  • LM pectin, algin, carboxymethylcellulose (CMC), ⁇ -carrageenan, ⁇ -carrageenan, etc. can be gelled by contacting them with polyvalent ions at a temperature of, for example, 30°C or higher to form ionic crosslinks.
  • Xanthan gum or ⁇ -carrageenan can be gelled by mixing with locust bean gum, heating (for example, 60°C), and then cooling.
  • LA gellan gum can be gelled by contacting it with cations after heating (for example, 40°C). This is because when the sugar chains lose water of hydration due to heating, they change from a random coil to a double helix when cooled, and the charge of the carboxyl groups is neutralized by cations, causing the double helices to associate with each other through hydrogen bonds.
  • HA gellan gum can be gelled by heating (e.g. 80°C) and then cooling. This is because the glyceryl groups in the double helix stabilize the double helix through interaction. Other methods that can be used include gelling by reaction with acids or bases or by contact with alcohol.
  • the method of gelling by contact with polyvalent ions is preferred from the viewpoint of fast gelling speed and strong gel strength.
  • gelling by contact with polyvalent ions it is preferable to gel the water-soluble polymer having acidic functional groups in the rubber latex composition attached to the mold by contacting it with a polyvalent ion-containing substance.
  • the polyvalent ion-containing substance can be said to act as a component that solidifies the water-soluble polymer having acidic functional groups.
  • the polyvalent ion is not particularly limited as long as it is a cation having a valence of two or more, but is preferably at least one metal ion selected from calcium ions, magnesium ions, aluminum ions, zinc ions, iron ions, copper ions, cobalt ions, nickel ions, and barium ions.
  • metal salts containing these ions e.g., halides, sulfates, nitrates, carbonates, acetates, alum, etc.
  • metal salts that are soluble at a concentration of 20 g or more per 100 g of water at 25°C being particularly preferred.
  • salts of potassium ions or sodium ions polysaccharides such as locust bean gum, acids, or polyol compounds can also be used as coagulants.
  • a gelation method using at least one acidic polysaccharide selected from the group consisting of LM pectin, xanthan gum, ⁇ -carrageenan, ⁇ -carrageenan, and carboxymethylcellulose, and a polyvalent ion-containing substance is preferred, and a gelation method using LM pectin and calcium ions is more preferred.
  • the origin of LM pectin is not particularly limited, and it may be derived from apples or citrus fruits, for example.
  • the degree of esterification (DE) of LM pectin is preferably 5 to 45%, more preferably 20 to 40%.
  • the degree of esterification can be measured by titration using an alkaline solution.
  • the degree of esterification can be adjusted by hydrolysis with an acid or alkali.
  • the coagulant may be applied to the mold in advance.
  • a coagulant application step of applying the coagulant to the surface of the mold may be provided before the immersion step.
  • the immersion step and the film formation step proceed simultaneously in parallel while the mold is immersed in the rubber latex composition.
  • the method of attaching the coagulant to the mold in advance is not particularly limited, but includes immersing the mold wetted with a solvent as necessary in the coagulant, spraying the coagulant onto the mold wetted with a solvent as necessary, immersing the mold in a solution of the coagulant (hereinafter also referred to as the coagulant liquid), applying the coagulant liquid to the mold, spraying the coagulant liquid onto the mold, etc.
  • the method of immersing the mold in the coagulant liquid is preferred from the viewpoint of uniform attachment.
  • the solvent used to prepare the coagulation liquid is not particularly limited as long as it can dissolve or disperse the coagulant uniformly, and examples include water, alcohol, etc. From the viewpoint of ease of dissolution, it is preferable to use water.
  • the concentration of the coagulant in the coagulation liquid is not particularly limited, but is preferably 5 to 50% by mass, more preferably 10 to 40% by mass, and particularly preferably 15 to 35% by mass.
  • the immersion time in the coagulant or coagulation liquid is not particularly limited, but is usually preferably 1 to 300 seconds, and more preferably 5 to 100 seconds.
  • the solvent may be removed by drying.
  • the drying temperature can be set appropriately depending on the solvent used, and is preferably 60 to 200°C, and more preferably 90 to 160°C. In this specification, the drying temperature refers to the temperature set in the drying device. There are no particular limitations on the drying time, but it is preferably 1 to 600 seconds, and more preferably 5 to 300 seconds. Drying at a high temperature for a short period of time makes it easier to create a state in which the coagulating agent is uniformly attached to the mold surface.
  • the mold may be immersed in the rubber latex composition, and after the rubber latex composition is adhered, the mold may be brought into contact with the coagulant.
  • the immersion step and the film formation step are carried out sequentially.
  • the mold to which the rubber latex composition is attached may be immersed in the coagulation liquid, or the coagulation liquid may be sprayed onto the mold to which the rubber latex composition is attached. From the viewpoint of obtaining sufficient gel strength, the method of immersing the mold to which the rubber latex composition is attached in the coagulation liquid is preferred.
  • the immersion time in the coagulation liquid is not particularly limited, but is usually preferably 1 to 300 seconds, and more preferably 5 to 100 seconds.
  • the rubber latex composition contains the above-mentioned thickener.
  • a water-soluble polymer having an acidic functional group may be used as a thickener.
  • the drying temperature is not particularly limited, but is preferably 50 to 200°C, more preferably 70 to 180°C, and particularly preferably 90 to 160°C.
  • the drying time is not particularly limited, but is preferably 1 to 120 minutes, more preferably 10 to 100 minutes, and particularly preferably 20 to 60 minutes.
  • the rubber latex composition may be one that has been aged in advance (also called pre-vulcanization).
  • the maturation temperature is not particularly limited, but is preferably 10 to 70°C, and more preferably 20 to 50°C.
  • the temperature here refers to the temperature of the rubber latex composition.
  • the maturation time is not particularly limited, but is preferably 4 to 120 hours, more preferably 10 to 72 hours, and particularly preferably 24 to 48 hours.
  • a rubber latex composition containing additives for vulcanization When a rubber latex composition containing additives for vulcanization is used, it is preferable to vulcanize the rubber component contained in the rubber latex composition by heating after forming a film. Vulcanization may be carried out simultaneously with drying after forming the aforementioned film.
  • the heating temperature for vulcanization is preferably 60 to 200°C, more preferably 80 to 180°C, and particularly preferably 100 to 160°C. By keeping the heating temperature within this range, it is possible to achieve a moderate vulcanization speed and suppress deterioration of the rubber components caused by excessive heating.
  • the heating time for vulcanization can be selected appropriately depending on the heating temperature, and is usually 5 to 120 minutes.
  • washing can be performed by immersing the film in a cleaning solution at 20 to 100°C for about 1 to 60 minutes, which can remove water-soluble impurities (e.g., emulsifiers, water-soluble polymers with acidic functional groups, coagulants, etc.).
  • a cleaning solution at 20 to 100°C for about 1 to 60 minutes, which can remove water-soluble impurities (e.g., emulsifiers, water-soluble polymers with acidic functional groups, coagulants, etc.).
  • Any cleaning solution that can remove water-soluble impurities can be used, such as water, saline, saturated sodium bicarbonate water, and aqueous solutions of chelating agents.
  • chelating agents that can be used here include citric acid, trisodium citrate, gluconic acid, ethylenediaminetetraacetic acid, and sodium tripolyphosphate.
  • Such a cleaning treatment may be carried out before or after the vulcanization. From the viewpoint of more efficient removal of water-soluble impurities, it is preferable to carry out the cleaning treatment before vulcanization.
  • drying may be performed.
  • the drying temperature and drying time are not particularly limited, but can be the same as those in the drying step after the film formation step described above.
  • the dip-molded body can be obtained by removing it from the mold.
  • Methods for removing it include peeling it off by hand, or by using water pressure or compressed air pressure.
  • the immersion molding Before or after the immersion molding is removed from the mold, it may be subjected to a heating treatment or a cleaning treatment.
  • the inner and outer surfaces of the immersion molding may be subjected to a surface treatment such as a chlorination treatment or a coating treatment.
  • the film thickness of the immersion molded article thus obtained can be freely controlled by the amount of the water-soluble polymer having an acidic functional group added, the viscosity of the rubber latex composition, the amount of the coagulant, the immersion time, etc.
  • the manufacturing method of the present invention is more effective and useful when manufacturing a relatively thick immersion molded article, so the film thickness is preferably thicker than 0.3 mm, more preferably more than 0.30 mm and not more than 2.00 mm, or more preferably 0.35 mm to 2.00 mm, and particularly preferably 0.40 mm to 1.00 mm.
  • the immersion molded body obtained in this manner has small unevenness in the film thickness, which is preferable.
  • the unevenness in thickness within the same molded body is preferably less than 50%, more preferably less than 40% or less than 30%, and particularly preferably less than 20%.
  • the thickness and unevenness of the coating are evaluated as follows.
  • the coating of the immersion molded article is divided into approximately thirds in the longitudinal direction, and the thickness is measured at three locations in each of the upper, middle, and lower areas (total of nine locations), and the average thickness of the nine locations is taken as the coating thickness.
  • the unevenness of thickness is evaluated as the difference between the maximum and minimum thicknesses of the nine locations divided by the coating thickness (average thickness of the nine locations) (see formula (1) below). The smaller this value, the smaller the unevenness of thickness, which is preferable.
  • Thickness unevenness (%) (maximum thickness - minimum thickness) / average thickness value x 100 (I)
  • the manufacturing method of the present invention makes it possible to prepare a dip-molded body having a relatively large thickness (preferably greater than 0.30 mm) as described above, while suppressing thickness variation, air bubble entrapment, and latex shedding.
  • the immersion molded product of the present invention is an immersion molded product that contains a water-soluble polymer having an acidic functional group and a rubber, and preferably has a film thickness of more than 0.3 mm and/or a thickness unevenness calculated as described above of 50% or less.
  • the explanation of the manufacturing method of the present invention and the latex composition of the present invention is applicable to the immersion molded product of the present invention.
  • the various characteristics (properties, structures, functions, etc.) described for each embodiment of the present invention above may be combined in any way to specify the present invention.
  • the present invention includes all subject matter consisting of all combinations of each of the combinable constituent elements described in this specification.
  • parts by mass represent the amount relative to 100 parts by mass of the solid content in the rubber latex (i.e. rubber; more specifically, chlorosulfonated polyethylene, hydrogenated nitrile rubber, chloroprene rubber, or styrene butadiene rubber).
  • rubber latex i.e. rubber; more specifically, chlorosulfonated polyethylene, hydrogenated nitrile rubber, chloroprene rubber, or styrene butadiene rubber.
  • all of the compounds used as coagulants were reagents manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.
  • Example 1 Preparation of Rubber Latex Composition> One part by mass of sodium polyacrylate (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd., reagent) was added to chlorosulfonated polyethylene latex (manufactured by Sumitomo Seika Chemicals, trade name "Seporex CSM", solid content concentration 40 mass%) and stirred until completely dissolved to obtain a rubber latex composition.
  • sodium polyacrylate manufactured by Fujifilm Wako Pure Chemical Industries, Ltd., reagent
  • chlorosulfonated polyethylene latex manufactured by Sumitomo Seika Chemicals, trade name "Seporex CSM", solid content concentration 40 mass
  • the ceramic mold was immersed in a 15% by mass aqueous solution of potassium aluminum sulfate for 5 seconds, and then dried in a 100°C air dryer for 300 seconds. The mold was then cooled to 60°C and immersed in the rubber latex composition maintained at 30°C for 30 seconds. The mold was removed from the latex composition and dried in a 100°C air dryer for 60 minutes, and then cooled to room temperature. The film was then peeled off from the mold to obtain a dip-molded body. The obtained dip-molded body was evaluated according to the following criteria.
  • the ceramic mold used was a rectangular thin plate of 20 cm x 8 cm, and the above-mentioned operation using half the length of this mold yielded two rectangular rubber films (dip-molded bodies) of about 10 cm x 8 cm (one on the front and one on the back of the mold).
  • the same operation was also performed on a ceramic mold in the shape of a boat (length 10 cm x width 1.5 cm x height 1 cm) shown in Figure 1, and the ability to follow a complex shape was evaluated.
  • the dip-molded bodies prepared using a ceramic boat-shaped mold were used only for the evaluation of conformability.
  • the thickness was measured at three locations in the upper, middle, and lower areas of the film when the film was divided into three in the longitudinal direction (total of nine locations), and the average thickness of the nine locations was taken as the film thickness.
  • the thickness unevenness was evaluated by dividing the difference between the maximum thickness and the minimum thickness by the film thickness (average thickness of the nine locations) (see formula (1) below), with A being less than 20%, B being 20% or more but less than 40%, C being 40% or more but less than 50%, and D being 50% or more.
  • Thickness unevenness (%) (maximum thickness - minimum thickness) / average thickness value x 100 (I)
  • Examples 2 to 4 Comparative Examples 1 to 4
  • Example 1 The same procedure as in Example 1 was carried out except that the conditions were changed as shown in Table 1, to obtain a dip-molded body.
  • the polyvinyl alcohol used in Comparative Example 4 was a reagent manufactured by Tokyo Chemical Industry Co., Ltd.
  • Example 5 Chlorosulfonated polyethylene latex (manufactured by Sumitomo Seika Chemicals, product name "Seporex CSM", solid content concentration 40 mass%) was added with 15 parts by mass of epoxidized polybutadiene (manufactured by Nippon Soda Co., Ltd., product name "NISSO-PB JP100”) as an acid acceptor, and mixed for 1 hour at 12000 rpm using a homomixer (T.K. Robomix, manufactured by Primix Corporation).
  • a homomixer T.K. Robomix, manufactured by Primix Corporation
  • a ceramic mold was immersed in a 35% by mass aqueous solution of calcium nitrate for 5 seconds, and then dried for 300 seconds in a blast dryer at 160° C. The mold was then allowed to cool to 74° C. and immersed for 30 seconds in the rubber latex composition maintained at 25° C. The mold was removed from the latex composition, dried for 20 minutes in a blast dryer at 100° C., and then heated for another 20 minutes at 160° C. After cooling to room temperature, the film was peeled off from the mold to obtain a dip-molded product.
  • Examples 6 to 23, Comparative Examples 5 to 9 The same operations as in Example 5 were carried out using the ingredients, amounts of ingredients, and immersion method shown in Table 2 to obtain immersion molded bodies.
  • the following commercially available water-soluble polymers were used.
  • Xanthan gum Tokyo Chemical Industry Co., Ltd.
  • Reagent CMC Tokyo Chemical Industry Co., Ltd.
  • Reagent ⁇ -carrageenan Sansho Co., Ltd.
  • product name "GENUVISCO carrageenan type PJ-JPE” Ammonium alginate: Fujifilm Wako Pure Chemical Industries, Ltd.
  • Reagent HA Gellan Gum Sumitomo Pharma Food & Chemical Co., Ltd.
  • Product name "Kelcogel HM" LA Gellan Gum Product name "Kelcogel” manufactured by Sumitomo Pharma Food & Chemical Co., Ltd.
  • Sodium alginate Reagent manufactured by Tokyo Chemical Industry Co., Ltd.
  • Examples 24 to 26 The same procedure as in Example 7 was carried out, except that the LM pectin used was changed to the following LM pectin, to obtain a dip-molded product.
  • the results are shown in Table 3.
  • LM pectin could be gelled under the same conditions as in Example 5, regardless of origin or degree of esterification, and a clean, thick film could be obtained.
  • Example 27 to 29 The same operation as in Example 1 was carried out using the types, compounding ingredients, and compounding amounts of rubber latex shown in Table 4 to obtain dip-molded bodies.
  • the following commercially available rubber latex was used.
  • Hydrogenated nitrile rubber latex Zeon Corporation, product name "Zetpol 2230LX”: listed as HNBR in Table 4.
  • Chloroprene rubber latex manufactured by Tosoh Corporation, product name "Skyprene LA-410”: listed as CR in Table 4.
  • Styrene butadiene rubber latex trade name "Nalstar SR-104" manufactured by Nippon A&L Co., Ltd.: listed as SBR in Table 4.
  • the method of the present invention has the same effect on rubber latex other than chlorosulfonated polyethylene latex, and a clean, thick coating can be obtained with any rubber latex.
  • Example 30 Chlorosulfonated polyethylene latex (manufactured by Sumitomo Seika Chemicals, product name "Seporex CSM", solid content concentration 40 mass%) was added with 15 parts by mass of epoxidized polybutadiene (manufactured by Nippon Soda, product name "NISSO-PB JP100”) as an acid acceptor, and mixed for 1 hour at 12000 rpm using a homomixer (T.K. Robomix, manufactured by Primix Corporation).
  • a homomixer T.K. Robomix, manufactured by Primix Corporation
  • a ceramic mold was heated to 40° C. and immersed in the rubber latex composition maintained at 25° C. for 10 seconds, and then removed from the latex composition.
  • the mold with the latex composition attached was immersed in a coagulation liquid (aqueous solution of 15% by mass of potassium aluminum sulfate) for 30 seconds, and then immersed in warm water at 60° C. for 10 minutes for cleaning.
  • the mold was dried in a 100° C. air dryer for 20 minutes, and then heated at 160° C. for 20 minutes. After cooling to room temperature, the film was peeled off from the mold to obtain a dip-molded product.
  • Example 31 The same procedure as in Example 4 was carried out using the ingredients, amounts thereof, and coagulation liquid shown in Table 5 to obtain dip-molded bodies.
  • a clean, thick coating was also obtained by immersing the mold with the latex composition in a coagulating liquid to cause it to gel.

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Abstract

L'invention concerne un procédé de production d'un objet formé par immersion, le procédé consistant à : tremper un modèle ayant une température de surface de 30 à 100 °C, à l'exclusion de 100 °C, dans une composition de latex de caoutchouc comprenant un caoutchouc et un polymère soluble dans l'eau ayant un groupe fonctionnel acide pour permettre à la composition de latex de caoutchouc d'adhérer à la surface du modèle ; et amener le polymère soluble dans l'eau dans la composition de latex de caoutchouc adhérant au modèle à se gélifier. Ce procédé de production peut produire un objet formé par immersion relativement épais tout en inhibant l'irrégularité d'épaisseur, l'inclusion de bulles et le décollement de latex.
PCT/JP2023/033643 2022-09-26 2023-09-15 Procédé de production d'un objet formé par immersion, et objet formé par immersion WO2024070750A1 (fr)

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Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2009197149A (ja) * 2008-02-22 2009-09-03 Nippon A&L Inc ディップ成形用共重合体ラテックス、ディップ成形用組成物およびディップ成形品
WO2016047418A1 (fr) * 2014-09-26 2016-03-31 日本ゼオン株式会社 Procédé de fabrication d'article moulé par immersion, et article moulé par immersion
JP2016141691A (ja) * 2015-01-29 2016-08-08 日本ゼオン株式会社 ディップ成形用組成物およびディップ成形体
JP2016157121A (ja) * 2015-02-24 2016-09-01 地方独立行政法人青森県産業技術センター 脈管モデル成形具及び脈管モデルの製造方法
JP2020503401A (ja) * 2016-12-15 2020-01-30 シントマー スンディリアン ブルハド ゴム製品製造用の硬化性ポリマーラテックス組成物
JP7033242B1 (ja) * 2021-10-19 2022-03-09 白石カルシウム株式会社 膜成形体の製造方法

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2009197149A (ja) * 2008-02-22 2009-09-03 Nippon A&L Inc ディップ成形用共重合体ラテックス、ディップ成形用組成物およびディップ成形品
WO2016047418A1 (fr) * 2014-09-26 2016-03-31 日本ゼオン株式会社 Procédé de fabrication d'article moulé par immersion, et article moulé par immersion
JP2016141691A (ja) * 2015-01-29 2016-08-08 日本ゼオン株式会社 ディップ成形用組成物およびディップ成形体
JP2016157121A (ja) * 2015-02-24 2016-09-01 地方独立行政法人青森県産業技術センター 脈管モデル成形具及び脈管モデルの製造方法
JP2020503401A (ja) * 2016-12-15 2020-01-30 シントマー スンディリアン ブルハド ゴム製品製造用の硬化性ポリマーラテックス組成物
JP7033242B1 (ja) * 2021-10-19 2022-03-09 白石カルシウム株式会社 膜成形体の製造方法

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