WO2021010343A1 - Agent de réticulation pour moulage par immersion, composition pour moulage par immersion et gant - Google Patents

Agent de réticulation pour moulage par immersion, composition pour moulage par immersion et gant Download PDF

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Publication number
WO2021010343A1
WO2021010343A1 PCT/JP2020/027114 JP2020027114W WO2021010343A1 WO 2021010343 A1 WO2021010343 A1 WO 2021010343A1 JP 2020027114 W JP2020027114 W JP 2020027114W WO 2021010343 A1 WO2021010343 A1 WO 2021010343A1
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Prior art keywords
cross
linking agent
halohydrin
dip molding
weight
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PCT/JP2020/027114
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English (en)
Japanese (ja)
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憲秀 榎本
充志 森永
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ミドリ安全株式会社
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    • A—HUMAN NECESSITIES
    • A41—WEARING APPAREL
    • A41D—OUTERWEAR; PROTECTIVE GARMENTS; ACCESSORIES
    • A41D19/00—Gloves
    • A—HUMAN NECESSITIES
    • A41—WEARING APPAREL
    • A41D—OUTERWEAR; PROTECTIVE GARMENTS; ACCESSORIES
    • A41D19/00—Gloves
    • A41D19/015—Protective gloves
    • A—HUMAN NECESSITIES
    • A41—WEARING APPAREL
    • A41D—OUTERWEAR; PROTECTIVE GARMENTS; ACCESSORIES
    • A41D19/00—Gloves
    • A41D19/04—Appliances for making gloves; Measuring devices for glove-making
    • 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
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/04—Oxygen-containing compounds
    • C08K5/05—Alcohols; Metal alcoholates
    • C08K5/053—Polyhydroxylic alcohols
    • 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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins

Definitions

  • the present invention is a dip molding cross-linking agent (hereinafter, also referred to as "halohydrin cross-linking agent”) which is a compound having two or more halohydrin groups for a carboxylic acid-modified NBR latex, and a dip containing at least the dip molding cross-linking agent.
  • halohydrin cross-linking agent a dip molding cross-linking agent which is a compound having two or more halohydrin groups for a carboxylic acid-modified NBR latex, and a dip containing at least the dip molding cross-linking agent.
  • the present invention relates to a molding composition, a method for producing a glove using the dip molding composition, and a glove.
  • a water-based emulsion containing a carboxylic acid-modified acrylonitrile butadiene rubber (XNBR) as an elastomer is produced in large quantities as a material for dip molding, and synthetic rubber gloves are particularly used.
  • XNBR carboxylic acid-modified acrylonitrile butadiene rubber
  • these elastomers are further copolymerized with an unsaturated carboxylic acid monomer and used as XNBR.
  • the X indicates that an unsaturated carboxylic acid is added as a component of the copolymerization.
  • a dip molded product produced from an aqueous emulsion containing XNBR as an elastomer is formed from a crosslinked structure of covalent bonds of butadiene, sulfur and a vulcanization accelerator, and a crosslinked structure of ionic bonds of a carboxyl group and zinc. Consists of film.
  • This glove has excellent heat resistance and chemical resistance, but has a shorter molecular chain than natural rubber and isoprene / chloroprene synthetic rubber gloves, has fewer double bonds that represent the original properties of rubber, and has weak bonding strength.
  • the vulcanization accelerator used in the production of the above dip molded products is included in the "Japanese standard allergen" defined by the Japan Society for Skin Allergy and Contact Dermatitis, and allergies develop in applications such as gloves. Multiple cases have been reported. From these case reports, it is considered that the vulcanization accelerator is an allergen for delayed-type allergy (Type IV) in XNBR gloves.
  • a vulcanization accelerator is indispensable for the cross-linking reaction (vulcanization) with sulfur from the viewpoint of economy and performance, but since it is considered to be the main cause of delayed allergy, sulfur and sulfurization are widely used.
  • Cross-linking technology that does not use a sulfur accelerator is being studied and put into practical use.
  • Sulfur and vulcanization accelerator-free gloves include, for example, self-crosslinking gloves in which an organic crosslinkable compound is contained during latex polymerization, or an external crosslinking agent type that crosslinks with polycarbodiimide or an epoxy crosslinking agent having an epoxy group. Gloves etc. have been developed.
  • Patent Document 1 contains a polymer having a specific structural unit and a specific reactive group as a latex, so that it can be covalently bonded to a carboxyl group without adding a cross-linking agent. Gloves made with an elastomeric composition are disclosed.
  • Patent Document 2 discloses a glove manufactured by using an elastomer having a specific structural unit as a latex and an emulsion composition for a glove containing polycarbodiimide as a cross-linking agent.
  • Patent Document 3 discloses a glove manufactured by using an elastomer having a specific structural unit as a latex and a dip molding composition containing a trivalent or higher valent epoxy compound as a cross-linking agent.
  • a halohydrin cross-linking agent which has not been used in the field of conventional gloves of the external cross-linking agent type, is used and is excellent in tensile strength, elongation, and fatigue durability without using a vulcanization accelerator.
  • the first task was to make gloves, and the second task was to improve the weaknesses of conventional sulfur-vulcanized XNBR gloves and to make gloves with excellent stress retention and at the same time good elongation.
  • the first problem is set as a problem to be solved at least, and the second problem is set as a problem that is desired to be further solved. It is an issue.
  • the present inventors react the halohydrin with the carboxyl group present in the elastomer. It was thought that crosslinks could be formed within and / or between the elastomeric particles. Furthermore, by using halohydrin, which has a higher affinity for water than the elastomer, the halohydrin can be reacted with the carboxyl group existing on the surface of the elastomer particles to form a crosslink between the elastomer particles.
  • halohydrin which has a higher oiliness than the elastomer
  • the halohydrin can be reacted with the carboxyl group existing in the elastomer particles to form a crosslink in the elastomer particles.
  • halohydrin as a cross-linking agent for dip molding
  • the gist of the present invention is as follows.
  • a cross-linking agent for dip molding which contains a halohydrin compound having at least two halohydrin groups D represented by the following formula (I) in one molecule.
  • R 1 is a hydrogen or alkyl group
  • X is a halogen group.
  • R 1 is a hydrogen or alkyl group
  • X is a halogen group.
  • R 2 is a (k + m) -valent aliphatic hydrocarbon group having 2 to 10 carbon atoms
  • X is a halogen group
  • k and m are 2 ⁇ k ⁇ 6,0. It is an integer that satisfies ⁇ m ⁇ 4 and 2 ⁇ k + m ⁇ 6.
  • a composition for dip molding which comprises a cross-linking agent for molding.
  • [6] The composition for dip molding according to the above [4] or [5], which further contains an epoxy cross-linking agent containing an epoxy compound having at least three epoxy groups in one molecule.
  • a glove which is a cured product of the dip molding composition according to any one of the above [4] to [6].
  • a method for manufacturing a glove which comprises a curing step and performs the above steps (3) to (7) in the above order.
  • a halohydrin cross-linking agent for a carboxylic acid-modified NBR latex which is not used in the field of conventional gloves, a dip molding composition containing at least the cross-linking agent, and a glove using the dip molding composition.
  • the theme is to improve the "stress retention rate” and maintain the "elongation rate” in the XNBR gloves.
  • the compatibility of these two physical properties is an improvement of the conventional sulfur vulcanized XNBR gloves, and aims to bring the NBR synthetic rubber gloves closer to the physical properties of natural rubber and isoprene / chloroprene synthetic rubber.
  • the "stress retention rate” in this case indicates how much the stress when the glove is stretched at a predetermined elongation rate is retained after a lapse of a predetermined time, and a high stress retention rate means that the stress retention rate is high.
  • the first embodiment of the present invention is a glove having a crosslinked structure in which XNBR is crosslinked with a halohydrin crosslinking agent.
  • a second embodiment of the present invention is a glove having a structure in which XNBR is crosslinked with a halohydrin cross-linking agent and an epoxy cross-linking agent.
  • a metal cross-linking agent such as zinc is not an essential element, but it may be used in combination as a cross-linking agent.
  • a common feature of the above two embodiments is the use of a halohydrin crosslinker for dip molding of XNBR.
  • Halohydrin cross-linking agents with high hydrophilicity are relatively less inactivated than epoxy cross-linking agents and have a pot life of about 6 days in the dip solution, so they are mainly oriented to the outside of the XNBR particles. It is characterized by being able to crosslink between particles with a salt of a carboxyl group or carboxylate.
  • Such a highly hydrophilic halohydrin cross-linking agent like the polycarbodiimide cross-linking agent (hereinafter referred to as “CDI cross-linking agent”), cross-links between particles by a covalent bond with a carboxyl group, but unlike the CDI cross-linking agent, Ca and K Since it is easy to crosslink by replacing metal elements such as, it is possible to reduce the portion of ion crosslinks in gloves. In addition, since it can provide tensile strength, it may be used as a substitute for a metal cross-linking agent such as zinc.
  • a metal cross-linking agent such as zinc.
  • the present inventors believe that in XNBR gloves, performing interparticle cross-linking by covalent bonds and reducing ionic bonds leads to an increase in the stress retention rate of XNBR gloves.
  • reducing the amount of metal cross-linking agents such as zinc is considered to be suitable for clean room gloves that dislike metal elution.
  • the second embodiment is characterized in that an epoxy cross-linking agent is used in combination with the halohydrin cross-linking agent, which is intended to increase the cross-linking density by cross-linking in the elastomer particles, but has particularly high hydrophilicity.
  • the highly hydrophilic halohydrin cross-linking agent is mainly a covalent bond between the elastomer particles
  • the epoxy cross-linking agent is mainly a covalent bond within the elastomer particles, so that the XNBR is shared both within the particles and between the particles. It is characterized by binding by binding.
  • gloves that are harder to break than ionic bonds can be made, and if the crosslink density is increased, gloves with a good stress retention rate can be made.
  • a metal cross-linking agent such as zinc is not essential, and ionic bonds due to Ca derived from the coagulant, K derived from the pH adjuster, etc.
  • the halohydrin cross-linking agent can also be reduced by the halohydrin cross-linking agent.
  • the halohydrin cross-linking agent when a highly oil-rich halohydrin is used, the halohydrin cross-linking agent also easily enters the inside of the particles. Therefore, the intra-particle cross-linking by the epoxy cross-linking agent alone is not sufficient to further strengthen the intra-particle cross-linking. Can be done.
  • FIG. 1 The conceptual diagram of the cross-linked structure of the glove cross-linked with the halohydrin cross-linking agent, which is a common feature of the first embodiment and the second embodiment, is shown in FIG. 1, and the cross-linking and the prior art in the embodiment are shown below.
  • a comparison table of the characteristics of cross-linking is shown in Table 1 below.
  • Zn 2+ , Ca 2+ , and K + in Table 1 are described assuming that a metal cross-linking agent, a coagulant, and a pH adjuster containing them are added, respectively, and are essential requirements. is not. Further, in the second embodiment of the present invention, Zn 2+ is shown in parentheses because in this embodiment, gloves having desired characteristics can be easily obtained without using Zn 2+. It shows that no particular addition is required in comparison with.
  • the dip molding composition of the first embodiment of the present invention is a dip molding composition containing at least an elastomer of XNBR and a halohydrin cross-linking agent.
  • the dip molding composition of the second embodiment of the present invention is a dip molding composition containing an epoxy cross-linking agent in combination with the above materials.
  • the dip molding composition according to the first and second embodiments may contain a metal cross-linking agent such as zinc as an optional component. Further, the dip molding composition according to the first and second embodiments may contain a pH adjuster, an antioxidant, a pigment, a chelating agent and the like as other components.
  • XNBR is a polymer of structural units derived from (meth) acrylonitrile ((meth) acrylonitrile residues), structural units derived from unsaturated carboxylic acids (unsaturated carboxylic acid residues), and structural units derived from butadiene (butadiene residues). It is an elastomer contained in the main chain.
  • the XNBR elastomer usually forms particles having a particle size of about 50 to 250 nm as an aqueous emulsion in the composition. The environment inside and outside the particle is significantly different, and the inside of the particle is lipophilic because the main component is a hydrocarbon composed of butadiene residue, (meth) acrylonitrile residue, and (meth) acrylic acid.
  • the outside of the particles is composed of water and a water-soluble component (for example, a pH adjuster, etc.), the outside of the particles has hydrophilicity.
  • the pH of the composition for dip molding is usually adjusted to 9.5 to 12.0 by a pH adjuster, and the carboxyl groups around the surface of the XNBR particles (elastomer particles) are oriented outward of the particles and carboxy. It is a rat.
  • a buried carboxyl group is present in the particles. Halohydrin cross-linking agents with high lipophilicity easily enter the elastomer particles, and most of them are present in the particles.
  • the highly hydrophilic halohydrin cross-linking agent is difficult to enter into the highly lipophilic elastomer particles, and most of them are present between the elastomer particles.
  • the epoxy cross-linking agent of the second embodiment is selected so as to easily enter the lipophilic region in the particles, most of them are present in the elastomer particles.
  • Metal cross-linking agents such as zinc exist between particles in the form of complex ions. The state inside the particles and between the particles is the state when the composition for dip molding is formed, but when the XNBR particles (XNBR elastomer particles) are finally laminated to form a film, the inside of the particles is formed. And the situation between the particles is almost maintained. In-particle cross-linking and inter-particle cross-linking are used in this sense in this sense.
  • each component of the dip molding composition will be described in detail.
  • the elastomer contains at least a structural unit derived from (meth) acrylonitrile, a structural unit derived from an unsaturated carboxylic acid, and a structural unit derived from butadiene in the polymer backbone.
  • This elastomer is also referred to as "carboxylated (meth) acrylonitrile butadiene elastomer” or "XNBR”.
  • gloves obtained by using XNBR as an elastomer are also referred to as "XNBR gloves”.
  • the structural unit derived from (meth) acrylonitrile that is, 25 to 30% by weight of the (meth) acrylonitrile residue
  • the structural unit derived from unsaturated carboxylic acid that is, unsaturated carboxylic acid
  • the structural unit derived from (meth) acrylonitrile is an element that mainly gives strength to gloves. If it is too small, the strength becomes insufficient, and if it is too large, the chemical resistance increases but it becomes too hard.
  • the ratio of structural units derived from (meth) acrylonitrile in the elastomer is usually 25 to 30% by weight.
  • the ratio of the structural units derived from (meth) acrylonitrile is reduced, and the ratio of the structural units derived from butadiene is increased to increase the rubber elasticity. It is preferable to increase the number of butadiene-derived double bonds produced.
  • the ratio of the structural unit derived from (meth) acrylonitrile in the elastomer is preferably 12 to 35% by weight, more preferably 17 to 30% by weight.
  • the amount of the structural unit derived from (meth) acrylonitrile can be obtained by converting the amount of nitrile groups from the amount of nitrogen atoms obtained by elemental analysis.
  • the amount of the unsaturated carboxylic acid-derived structural unit in the elastomer is preferably 2 to 10% by weight, preferably 2 to 9% by weight, in order to maintain the physical properties of the final product, the glove, which has an appropriate crosslinked structure. It is more preferably%, and further preferably 2 to 6% by weight.
  • the amount of the structural unit derived from the unsaturated carboxylic acid can be determined by the back titration method of the carboxyl group and the quantification of the carbonyl group derived from the carboxyl group by infrared spectroscopy (IR) or the like.
  • the type of unsaturated carboxylic acid that forms a structural unit derived from unsaturated carboxylic acid is not particularly limited, and may be monocarboxylic acid or polycarboxylic acid. More specifically, acrylic acid, methacrylic acid, crotonic acid and the like can be mentioned. Among them, acrylic acid and / or methacrylic acid (hereinafter, also referred to as "(meth) acrylic acid”) is preferably used, and methacrylic acid is more preferably used.
  • Butadiene-derived structural units are elements that impart flexibility to gloves, and the amount of butadiene-derived structural units in an elastomer usually loses flexibility below 50% by weight.
  • the ratio of butadiene-derived structural units in the elastomer is typically 50-75% by weight.
  • the amount of structural units derived from butadiene can be determined by a known method. Considering only the problem of increasing the stress retention rate of the XNBR gloves of the present invention, it is preferable to increase the ratio of the structural units derived from butadiene to increase the double bond of butadiene that gives rubber elasticity. However, it is important not to impair other physical properties such as tensile strength.
  • the polymer backbone is preferably composed of structural units derived from (meth) acrylonitrile, unsaturated carboxylic acids, and butadiene, but other structural units derived from polymerizable monomers. It may be included.
  • the structural unit derived from other polymerizable monomers is preferably 30% by weight or less, more preferably 20% by weight or less, particularly preferably 15% by weight or less, and particularly sets a lower limit in the elastomer. It is not necessary to do so, and it may be 0.1% by weight or more or 1% by weight or more.
  • Preferred polymerizable monomers include aromatic vinyl monomers such as styrene, ⁇ -methylstyrene and dimethylstyrene; ethylenically unsaturated carboxylic acid amides such as (meth) acrylamide and N, N-dimethylacrylamide; (meth). ) Ethylene unsaturated carboxylic acid alkyl ester monomers such as methyl acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate; and vinyl acetate. These can be arbitrarily used by any one type or a combination of a plurality of types.
  • Elastomer preparation As the elastomer, unsaturated carboxylic acids such as (meth) acrylonitrile and (meth) acrylic acid, butadiene such as 1,3-butadiene, and other polymerizable monomers as necessary are used, and are usually used according to a general method. It can be prepared by emulsion polymerization using the above-mentioned elastomer, polymerization initiator, molecular weight modifier and the like. The water at the time of emulsion polymerization is preferably contained in an amount having a solid content of 30 to 60% by weight, and more preferably contained in an amount having a solid content of 35 to 55% by weight. The emulsion polymerization solution after the elastomer synthesis can be used as it is as an elastomer component of the composition for dip molding.
  • unsaturated carboxylic acids such as (meth) acrylonitrile and (meth) acrylic acid, butadiene such as 1,3-butadiene, and other
  • the emulsifier examples include anionic surfactants such as dodecylbenzene sulfonate and aliphatic sulfonate; and nonionic surfactants such as polyethylene glycol alkyl ether and polyethylene glycol alkyl ester, preferably anionic surfactants. Surfactants are used.
  • the type of the polymerization initiator is not particularly limited as long as it is a radical initiator, but it is an inorganic peroxide such as ammonium persulfate and potassium perphosphate; t-butyl peroxide, cumene hydroperoxide, p-menthan hydroperoxide, etc.
  • Organic peroxides such as t-butylcumyl peroxide, benzoyl peroxide, 3,5,5-trimethylhexanoyl peroxide, t-butylperoxyisobutyrate; azobisisobutyronitrile, azobis-2,4 -Azo compounds such as dimethylvaleronitrile, azobiscyclohexanecarbonitrile, and methyl azobisisobutyrate can be mentioned.
  • the molecular weight modifier examples include mercaptans such as t-dodecyl mercaptan and n-dodecyl mercaptan, and halogenated hydrocarbons such as carbon tetrachloride, methylene chloride and methylene bromide, and t-dodecyl mercaptan; n-dodecyl mercaptan.
  • mercaptans such as t-dodecyl mercaptan and n-dodecyl mercaptan
  • halogenated hydrocarbons such as carbon tetrachloride, methylene chloride and methylene bromide, and t-dodecyl mercaptan
  • n-dodecyl mercaptan n-dodecyl mercaptan.
  • Elastomer particle size The particle size of the elastomer in the composition for dip molding is not particularly limited, but it is preferable that particles having a particle size of 50 nm or more and 250 nm or less are formed as an aqueous emulsion.
  • the elastomer chain In order for a halohydrin cross-linking agent containing a halohydrin compound having a larger molecular weight than zinc or sulfur or an epoxy cross-linking agent containing an epoxy compound to easily penetrate into the elastomer chain, the elastomer chain has few branches and is linear. Elastomers are preferred. Elastomers with few branches have been devised at the time of manufacture by each latex manufacturer, but generally speaking, cold rubber (polymerization temperature 5 to 25 ° C) with a lower polymerization temperature is hot rubber (polymerization temperature 25 to 25 to 25 ° C.). 50 ° C.) is considered to be more preferable.
  • the gel fraction (MEK insoluble matter) of the elastomer is an index of branching of the elastomer chain, and the gel fraction is high in the elastomer having many branches.
  • the gel fraction of XNBR used for manufacturing gloves is in the range of 0% by weight or more and 70% by weight or less in the measurement of the insoluble content of methyl ethyl ketone (MEK). From the viewpoint of increasing the number of buried carboxyl groups in the XNBR particles, enhancing the cross-linking in the particles, increasing the cross-linking density, and increasing the stress retention rate, it is conceivable to increase the gel fraction.
  • the content of the sulfur element detected by the neutralization titration method of the combustion gas is preferably 0% by weight, but a trace amount of sulfur is contained in the raw material manufacturing process even without any addition of sulfur. There is a risk of From this viewpoint, the sulfur content is preferably 1% by weight or less based on the weight of the elastomer.
  • 0.01 g of an elastomer sample is burned in air at 1350 ° C. for 10 to 12 minutes, and the combustion gas generated is absorbed by a hydrogen peroxide solution containing a mixing indicator, and a 0.01 N NaOH aqueous solution is used. It can be carried out by the method of neutralization titration with.
  • the composition for dip molding may contain a combination of a plurality of types of elastomers.
  • the content of the elastomer in the dip molding composition is not particularly limited, but is preferably 15% by weight or more and 35% by weight or less, preferably 18% by weight or more and 30% by weight or less, based on the total amount of the dip molding composition. More preferably, it is by weight% or less.
  • Halohydrin crosslinker The characteristics when the halohydrin cross-linking agent is used in the dip molding composition for producing XNBR gloves are as described in the description of the dip molding composition.
  • Halohydrin cross-linking agents are precursors in the production of epoxy cross-linking agents, but epoxy cross-linking agents with particularly high hydrophilicity have a short pot life (pot life), whereas they have high hydrophilicity.
  • the present inventors have focused on the fact that the pot life is long, interparticle cross-linking is possible, and a covalent bond is used.
  • the halohydrin cross-linking agent is attractive in that it can crosslink instead of metal cross-linking by Ca or K and reduce ionic bonds in terms of increasing the stress retention rate.
  • the halohydrin compound is considered to react with the carboxyl group or carboxylate based on the following formula (W1) or (W2).
  • the reactivity of carboxylate is higher than that of carboxyl group.
  • the content of the halohydrin compound in the composition for dip molding is not particularly limited, but from the viewpoint of introducing a sufficient crosslinked structure between the elastomers to ensure tensile strength and fatigue durability, the epoxy in one molecule of the epoxy compound Although it depends on the number and purity of the groups, it is usually 0.1 parts by weight or more and 10 parts by weight or less, 0.3 parts by weight or more, and 5.0 parts by weight or less with respect to 100 parts by weight of the elastomer. It is preferably 0.5 parts by weight or more and more preferably 3.0 parts by weight or less.
  • the content of the halohydrin compound in the halohydrin cross-linking agent is usually 20% by weight or more, preferably 30% by weight or more, more preferably 40% by weight or more, and further preferably 50% by weight or more. It is preferably 80% by weight or more, particularly preferably 90% by weight or more, and may be 100% by weight or less.
  • the content of the halohydrin compound may be evaluated from the amount of the raw material charged, but can be measured by a known method such as GPC.
  • the dip molding cross-linking agent (hereinafter, also referred to as “dip molding cross-linking agent” or “halohydrin cross-linking agent”), which is an embodiment of the present invention, has one molecule of halohydrin group D represented by the following formula (I).
  • a cross-linking agent for dip molding containing at least two halohydrin compounds therein.
  • R 1 and X in the following formula (I) the later.
  • the wavy line in the structure of the following formula (I) represents the coupling to another structure.
  • the elastomer particles and the like are elastomer particles having a carboxyl group and / or carboxylate. If the above is true, the elastomer is not limited to the above-mentioned elastomer, and any conventionally known elastomer can be used.
  • the halohydrin cross-linking agent is a halohydrin cross-linking agent containing a compound having at least two halohydrin groups D represented by the following formula (I) in one molecule (hereinafter, also referred to as “halohydrin compound (I))).
  • R 1 is a hydrogen or alkyl group
  • X is a halogen group.
  • R 1 is not particularly limited, but from the viewpoint of steric hindrance, it is preferably hydrogen or an alkyl group having 1 to 2 carbon atoms, more preferably hydrogen or an alkyl group having 1 carbon atom, and it is hydrogen. Is preferable.
  • X is not particularly limited, it is preferably Cl or Br, and particularly preferably Cl, from the viewpoint of reactivity. The above conditions of R 1 and X are the same in the following aspects.
  • the halohydrin compound may be a halohydrin compound having at least one halohydrin group Da represented by the following formula (Ia) in one molecule as the halohydrin group D (hereinafter, also referred to as “halohydrin compound (Ia)”). preferable.
  • the wavy line in the structure of the following formula (Ia) represents the coupling to another structure.
  • R 1 is a hydrogen or alkyl group
  • X is a halogen group
  • halohydrin compound (I) is a halohydrin compound represented by the following formula (II) (hereinafter, also referred to as "halohydrin compound (II)").
  • R 2 is a (k + m) -valent aliphatic hydrocarbon group having 2 to 10 carbon atoms
  • X is a halogen group
  • k and m are 2 ⁇ k ⁇ 6,0. It is an integer that satisfies ⁇ m ⁇ 4 and 2 ⁇ k + m ⁇ 6.
  • halohydrin compound (I) is a halohydrin compound represented by the following formula (III) (hereinafter, also referred to as "halohydrin compound (III)").
  • R 3 represents a hydrogen atom or an alkyl group
  • X is a halogen group
  • n is an integer satisfying 1 ⁇ n ⁇ 50.
  • halohydrin compound (I) is a halohydrin compound represented by the following formula (IV) (hereinafter, also referred to as "halohydrin compound (IV)").
  • R 4 is an independent hydrogen atom or a halohydrin group Da, and at least two of R 4 are halohydrin groups Da, and p is an integer satisfying 1 ⁇ p ⁇ 10. is there.
  • the halohydrin compound (I) is a compound having at least two halohydrin groups Da in one molecule, which is obtained by reacting a sugar alcohol from a oligosaccharide with epihalohydrin (hereinafter, also referred to as “halohydrin compound (V)”). Can be.
  • the halohydrin compound (I) is generally a compound having at least two hydroxyl groups in the molecule (hereinafter, also referred to as “polyhydrin alcohol”) corresponding to the halohydrin compounds (II) to (V). It can be obtained by reacting epihalohydrin.
  • the above-mentioned halohydrin compound (II) can be obtained by using the above-mentioned polyhydrin alcohol represented by the following formula (II-2) and reacting it with epihalohydrin.
  • R 2 , k and m are the same as the conditions described above.
  • the above-mentioned halohydrin compound (III) can be obtained by using the above-mentioned polyhydrin alcohol represented by the following formula (III-2) and reacting it with epihalohydrin.
  • R 3 and n are the same as the conditions described above.
  • R 3 is not particularly limited, but is preferably a hydrogen atom or a methyl group, and n is preferably 1 or 2, and more preferably 2.
  • the above-mentioned halohydrin compound (IV) can be obtained by using the above-mentioned polyhydrin alcohol represented by the following formula (IV-2) and reacting it with epihalohydrin.
  • p is the same as the above-mentioned conditions. p is not particularly limited, but is preferably 1.
  • the above-mentioned halohydrin compound (V) can be obtained by reacting epihalohydrin with a sugar alcohol obtained from a oligosaccharide.
  • the polyhydric alcohol represented by the above general formula (II-2) shall contain a sugar alcohol obtained by reducing monosaccharides, and specific examples of such polyhydric alcohols are not particularly limited. However, for example, 1,2-propanediol, 1,3-propanediol, 1,2-butanediol, 1,4-butanediol, 1,6-hexanediol, ethylene glycol, glycerin, trimethylol ethane, trimethylol. Examples thereof include propane, erythritol, pentaerythritol, sorbitol, mannitol, xylitol and the like.
  • ethylene glycol, glycerin, trimethylolethane, trimethylolpropane, sorbitol, mannitol and the like are preferable, and ethylene glycol, glycerin and trimethylolpropane are preferable.
  • the polyhydric alcohol represented by the general formula (III-2) is not particularly limited, but for example, diethylene glycol, triethylene glycol, polyethylene glycol, propylene glycol, dipropylene glycol, polypropylene glycol and the like can be used. Can be mentioned. Of these, diethylene glycol or dipropylene glycol is particularly preferable.
  • polyhydric alcohol represented by the above general formula (IV-2) is not particularly limited, and examples thereof include diglycerin and polyglycerin. Of these, diglycerin is particularly preferred.
  • the sugar alcohol from the oligosaccharide used for producing the halohydrin compound (V-2) described above is not particularly limited, but is, for example, maltose, cellobiose, sucrose (sucrose), and lactose. ) And the like, sugar alcohols obtained by reducing trisaccharides such as raffinose and meletitose, and reduced maltose obtained by reducing maltose. Sugar alcohols from such oligosaccharides can be used alone or as a mixture of two or more (with, if desired, sugar alcohols from monosaccharides).
  • maltitol sucrose alcohol from maltose
  • sugar alcohol from maltose which is easily available as a commercial product, is preferably used.
  • epichlorohydrin that reacts with such a polyhydric alcohol epichlorohydrin or epibromhydrin is particularly preferably used.
  • the reaction of various polyhydric alcohols with epihalohydrin as described above is, if necessary, in a reaction solvent in the presence of a Lewis acid catalyst, preferably under heating (eg, a temperature in the range of 30-95 ° C.). ), Epihalohydrin can be added dropwise to a polyhydric alcohol and mixed.
  • a Lewis acid catalyst include, but are limited to, boron trifluoride ether complex, tin tetrafluoride, zinc borofluoride, titanium tetrachloride, zinc chloride, silica alumina, antimony trichloride, and the like. It's not a thing.
  • the reaction solvent is used as necessary for controlling the reaction, adjusting the viscosity, etc., and can be any as long as it is inactive in the reaction between the polyhydric alcohol and epihalohydrin. Good. Therefore, examples of such a reaction solvent include aromatic hydrocarbons such as toluene and xylene, aliphatic hydrocarbons such as hexane and heptane, diethyl ether, diisopropyl ether, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether and dioxane. Examples include ethers.
  • epihalohydrin is usually used in the range of 30 to 200 mol%, preferably 50 to 150 mol%, based on the amount of hydroxyl groups of the polyhydric alcohol.
  • the amount of epihalohydrin used is less than 30 mol% with respect to the amount of hydroxyl groups of the polyhydrin alcohol, the amount of halohydrin groups in the obtained polyhalohydrin compound is too low, and it is sufficient to use this as a cross-linking agent. I can't get the physical characteristics.
  • epichlorohydrin epichlorohydrin or epichlorohydrin is preferably used.
  • 1,3-dihalo-2-propanol examples include 1,3-dichloro-2-propanol, 1,3-dibromo-2-propanol and the like.
  • halohydrin cross-linking agent An example of production of the halohydrin compound contained in the halohydrin cross-linking agent is shown below.
  • a commercially available product may be used as the halohydrin cross-linking agent. Sorbitol, toluene, and a boron trifluoride ether complex as a catalyst are charged in a separable flask, heated and stirred, and epichlorohydrin is added dropwise thereto. After completion of the dropping, the mixture is further stirred for a certain period of time at the same temperature as in the case of heating and stirring, and then the disappearance of epichlorohydrin is confirmed based on the quantification of epoxy groups by titration, and the reaction is terminated.
  • the MIBK / water distribution ratio of the halohydrin cross-linking agent is not particularly limited, and the effect of the present invention can be obtained regardless of whether it is hydrophilic or lipophilic, but it is usually 100% or less. Specifically, in the case of hydrophilicity, cross-linking between elastomer particles is promoted, in the case of lipophilicity, cross-linking within elastomer particles is promoted, and in the case between these, cross-linking between elastomer particles and within elastomer particles Although the ratio changes, in any case, the formation of crosslinks by halohydrin occurs, so that desired mechanical properties can be obtained.
  • the hydrophilic halohydrin has a MIBK / water partition ratio of usually -30 to 50%, preferably -30 to 30%, and more preferably -30 to 0%.
  • the lipophilic halohydrin has a MIBK / water distribution ratio of usually 50 to 100%, preferably 60 to 90%, and more preferably 70 to 90%.
  • the MIBK / water distribution ratio can be measured by the following method. First, about 5.0 g of water, about 5.0 g of MIBK, and about 0.5 g of a halogen cross-linking agent are precisely weighed and added to a test tube. Let the weight of MIBK be M (g) and the weight of the halogen cross-linking agent be E (g). The mixture is sufficiently stirred and mixed at a temperature of 23 ° C. ⁇ 2 ° C. for 3 minutes, and then centrifuged under the condition of 1.0 ⁇ 10 3 G for 10 minutes to separate an aqueous layer and a MIBK layer. Next, the weight of the MIBK layer is measured, and this is designated as ML (g).
  • MIBK / water distribution rate (%) (ML (g) -M (g)) / E (g) x 100
  • the MIBK / water measurement method in this specification was measured based on the weight of water and MIBK, but since MIBK dissolves water slightly, minus% is obtained as an experimental value, but the measurement is performed using the same standard. Therefore, the present inventors considered that it can be adopted as a standard.
  • Epoxy crosslinker> In the second embodiment of the present invention, an epoxy cross-linking agent is used in addition to the halohydrin cross-linking agent. Since the epoxy cross-linking agent used in the present embodiment has a relatively high lipophilicity, it easily penetrates into the elastomer particles and easily reacts with the carboxyl group in the particles. Further, in the case of a halohydrin cross-linking agent having a high lipophilicity, since the halohydrin cross-linking agent also easily enters the inside of the particles, it is possible to further strengthen the intra-particle cross-linking, which was not sufficient only by the intra-particle cross-linking with the epoxy cross-linking agent.
  • cross-linking by the reaction between the epoxy cross-linking agent and the carboxyl group of XNBR tends to be an intra-particle cross-linking. Therefore, cross-linking is possible with halohydrin alone, but by using it in combination with an epoxy cross-linking agent that enables intra-particle cross-linking, in combination with highly hydrophilic halohydrin, it should be combined with the halohydrin cross-linking agent for interparticle cross-linking.
  • the epoxy cross-linking agent contains an epoxy compound having at least three epoxy groups in one molecule.
  • Epoxide compounds having three or more epoxy groups in one molecule usually have a matrix having a plurality of glycidyl ether groups and alicyclic, aliphatic or aromatic hydrocarbons (hereinafter, "trivalent or higher”). It is also called an “epoxide compound”).
  • an epoxy compound having three or more glycidyl ether groups can be preferably mentioned.
  • An epoxy compound having three or more glycidyl ether groups can usually be produced by reacting epihalohydrin with an alcohol having three or more hydroxyl groups in one molecule.
  • Examples of the epoxy cross-linking agent containing an epoxy compound having three or more epoxy groups in one molecule include polyglycidylamine, polyglycidyl ester, epoxidized polybutadiene, and epoxidized soybean oil.
  • Alcohols having three or more hydroxyl groups that form the matrix of a trivalent or higher epoxy compound include aliphatic glycerol, diglycerol, triglycerol, polyglycerol, sorbitol, sorbitan, xylitol, erythritol, trimethylolpropane, and tri. Examples include methylolethane, pentaerythritol, aromatic cresol novolac, and trishydroxyphenylmethane.
  • the epoxy compounds having a valence of 3 or more it is preferable to use polyglycidyl ether.
  • an epoxy cross-linking agent containing trimethylolpropane among which at least one selected from trimethylolpropane triglycidyl ether, pentaerythritol triglycidyl ether, glycerol triglycidyl ether, diglycerol triglycidyl ether and pentaerythritol tetraglycidyl ether. It is more preferred to use an containing epoxy cross-linking agent. Further, it is preferable to use an epoxy cross-linking agent containing an epoxy compound having no sorbitol skeleton.
  • crosslinking reaction between epoxy compound and carboxyl group of XNBR> As shown by the following formula (Y), epoxy cross-linking occurs by the following reaction.
  • the epoxy compound represented by the following formula (Y) is monovalent from the viewpoint of simplifying the explanation. It is the carboxyl group in XNBR that the epoxy compound forms a crosslink, and in order to form a crosslink with the epoxy compound, it is necessary to heat at 90 ° C. or higher in the curing step to cause a ring-opening reaction of the epoxy group. Can be mentioned.
  • the epoxy compound contained in the dip molding composition which has escaped deactivation in the lipophilic environment in the XNBR particles, becomes a cured film precursor and is heated as a whole in the curing process as a lipophilic environment. At that time, it reacts with the carboxyl group of XNBR protruding outside the particles. At this time, by selecting XNBR having excellent water separation, the crosslinking efficiency can be increased and the crosslinking temperature can be lowered.
  • the content of the epoxy cross-linking agent in the composition for dip molding is not particularly limited, but from the viewpoint of introducing a sufficient cross-linking structure between the elastomers to ensure stress retention and fatigue durability, it is contained in one molecule of the epoxy compound. Although it depends on the number and purity of the epoxy groups, it is usually 0.2 parts by weight or more and 5 parts by weight or less with respect to 100 parts by weight of the elastomer. Practically, even if it is extremely thin (2.7 g glove, film thickness is about 50 ⁇ m), it is possible to manufacture a glove having sufficient performance with 0.4 parts by weight or more with respect to 100 parts by weight of the elastomer.
  • the content of the epoxy compound in the dip molding composition is 5 parts by weight or less with respect to 100 parts by weight of the elastomer. It is preferably 3 parts by weight or less, more preferably 2 parts by weight or less, more preferably 0.3 parts by weight or more, and 0.5 parts by weight or more. Is more preferable, and it is considered that 0.7 parts by weight or more is further preferable.
  • the content of the epoxy compound in the epoxy cross-linking agent is usually 20% by weight or more, preferably 30% by weight or more, more preferably 40% by weight or more, and further preferably 50% by weight or more. It is preferably 80% by weight or more, particularly preferably 90% by weight or more, and may be 100% by weight or less.
  • the content of the epoxy compound may be evaluated from the amount of the raw material charged, but can be measured by a known method such as GPC.
  • the average number of epoxy groups of the epoxy cross-linking agent is not particularly limited, but is preferably more than 2.0, more preferably 2.3 or more, from the viewpoint of obtaining a good stress retention rate and fatigue durability of the glove. 2.5 or more is more preferable.
  • the upper limit of the average number of epoxy groups is not particularly limited, and for example, 10.0 or less can be mentioned.
  • the epoxy equivalent of the epoxy cross-linking agent is 100 g / eq. 230 g / eq. The following is preferable. Even if the epoxy equivalents are similar, the trivalent epoxy cross-linking agent tends to have a better stress retention rate than the divalent epoxy cross-linking agent.
  • the epoxy equivalent of the epoxy cross-linking agent is a value obtained by dividing the average molecular weight of the epoxy cross-linking agent by the average number of epoxy groups, and indicates the average weight per epoxy group. This value can be measured by the perchloric acid method.
  • the molecular weight of the epoxy compound contained in the epoxy cross-linking agent is preferably 150 to 1500, more preferably 175 to 1400, and even more preferably 200 to 1300.
  • ⁇ MIBK / water distribution rate> By using an epoxy cross-linking agent having a MIBK / water distribution ratio of 27% or more according to the following measuring method, it becomes easy to obtain a dip molding composition having a pot life of 3 days or more.
  • the pot life is a period from the preparation of the dip molding composition to the preparation of the cured film, and if the dip molding composition is used within that period, the obtained cured film meets a specific standard. Indicates the period during which it can be done. If the MIBK / water distribution ratio is less than 27%, the pot life tends to be less than 3 days.
  • the MIBK / water partition ratio of the epoxy cross-linking agent is preferably 30% or more in order to obtain the desired pot life of the dip molding composition.
  • An epoxy cross-linking agent having a MIBK / water distribution ratio of 50% or more tends to have a pot life of 5 days or more. Further, an epoxy cross-linking agent having a MIBK / water distribution ratio of 70% or more is preferable because a pot life of 7 days or more can be easily obtained.
  • the upper limit of the MIBK / water distribution ratio of the epoxy cross-linking agent does not need to be set in particular, but is usually 95% or less, for example.
  • MIBK / water distribution rate (%) (ML (g) -M (g)) / E (g) x 100
  • MIBK / water measurement method in this specification was measured based on the weight of water and MIBK, but since MIBK dissolves water slightly, minus% is obtained as an experimental value, but the measurement is performed using the same standard. Therefore, I thought that it could be adopted as a standard.
  • Dispersant for epoxy cross-linking agent The epoxy cross-linking agent described above needs to be kept in a uniformly dispersed state in the composition for dip molding. On the other hand, in the epoxy cross-linking agent having a MIBK / water partition ratio of 27% or more, there is a problem that the higher the MIBK / water partition ratio is, the more difficult it is to add the cross-linking agent to the latex solution and the more difficult it is to disperse.
  • the dispersant of the epoxy cross-linking agent comprises a monohydric lower alcohol, a glycol represented by the following formula (1), an ether represented by the following formula (2), and an ester represented by the following formula (3). It is preferably one or more selected from the group.
  • HO- (CH 2 CHR 1- O) n1- H (1) [In the above formula (1), R 1 represents a hydrogen or a methyl group, and n1 represents an integer of 1 to 3. ]
  • R 1 represents a hydrogen or methyl group
  • R 2 represents an aliphatic hydrocarbon group having 1 to 5 carbon atoms
  • R 3 represents hydrogen or an aliphatic hydrocarbon group having 1 to 3 carbon atoms.
  • R 1 represents a hydrogen or methyl group
  • R 2 represents an aliphatic hydrocarbon group having 1 to 5 carbon atoms
  • n 3 represents an integer of 0 to 3.
  • Examples of the monohydric lower alcohol include methanol and ethanol.
  • Examples of the glycol represented by the formula (1) include ethylene glycol, propylene glycol, diethylene glycol, dipropylene glycol, and tripropylene glycol.
  • the glycol ethers include diethylene glycol monomethyl ether, diethylene glycol monoisopropyl ether, diethylene glycol monobutyl ether, diethylene glycol monoisobutyl ether, triethylene glycol monomethyl ether, triethylene glycol monobutyl ether, and tripropylene glycol. Examples thereof include monomethyl ether and triethylene glycol dimethyl ether.
  • the ester represented by the formula (3) include diethylene glycol monoethyl ether acetate and diethylene glycol monobutyl ether acetate.
  • diethylene glycol is particularly preferable from the viewpoint of volatility and flammability. It is presumed that diethylene glycol is suitable because it has a highly hydrophilic glycol group and an ether structure, and at the same time contains a lipophilic hydrocarbon structure, and is easily dissolved in water and an elastomer.
  • the weight ratio of the epoxy cross-linking agent to the dispersant in the dip molding composition is preferably 1: 4 to 1: 1.
  • an epoxy cross-linking agent having a low water content is used when preparing the composition for dip molding, the epoxy cross-linking agent is dissolved in the dispersant of the epoxy cross-linking agent in advance, and then the composition for dip molding is added. It is preferable to mix with the constituents of.
  • the dip molding composition of the first and second embodiments may contain a metal cross-linking agent such as zinc as an optional component.
  • a metal cross-linking agent such as zinc
  • a metal cross-linking agent such as zinc
  • the XNBR gloves contain a considerable amount of ionic bonds due to Ca derived from the coagulant and K derived from the pH adjuster, and a halohydrin cross-linking agent capable of reducing these ionic cross-links is also effective in that respect. it is conceivable that.
  • the polyvalent metal compound used as a metal cross-linking agent is one that ion-crosslinks between functional groups such as unreacted carboxyl groups in an elastomer.
  • zinc oxide which is a divalent metal oxide
  • aluminum which is a trivalent metal
  • Aluminum has the smallest ionic radius among the above and is optimal for obtaining chemical resistance and tensile strength, but if too much is added, the glove becomes too hard.
  • the amount of the divalent metal oxide, for example zinc oxide, and / or the aluminum complex added can be 0.0 to 2.0 parts by weight with respect to 100 parts by weight of the elastomer in the dip molding composition.
  • aqueous solutions of citric acid, malic acid, tartaric acid, lactic acid and the like can be used as the polybasic hydroxycarboxylic acid.
  • malic acid is preferably used as a ligand from the viewpoint of tensile strength and fatigue durability of gloves
  • citric acid is preferably used as a ligand from the viewpoint of stability of an aqueous aluminum solution.
  • composition for dip molding usually contains the following components as components other than the above-mentioned elastomer, cross-linking agent and the like (hereinafter, also referred to as "other components"). Examples of other components are shown below.
  • the dip molding composition needs to be adjusted to be alkaline at the stage of the stirring step (maturation step) described later.
  • One of the reasons for making it alkaline is that -COOH is oriented outward as -COO- from the elastomer particles, and interparticle cross-linking with a halohydrin cross-linking agent is sufficiently performed. Since the metal cross-linking that can occur when a metal cross-linking agent such as zinc oxide or a coagulant containing calcium ions or the like is used is also inter-particle cross-linking, it is necessary to make it alkaline for the same reason as described above.
  • the preferable pH value is 9.5 to 12.0.
  • the pH adjuster one or more obtained from ammonia, ammonium compounds, amine compounds and alkali metal hydroxides can be used.
  • alkali metal hydroxides are preferably used because the production conditions such as pH adjustment and gelling conditions are easy, and among them, potassium hydroxide (hereinafter, also referred to as KOH) is the easiest to use.
  • the amount of the pH adjuster added can be 1.5 to 10.0 parts by weight with respect to 100 parts by weight of the elastomer in the composition for dip molding, but it is usually industrially 1.8 to 2. Use 0 parts by weight.
  • the composition for dip molding contains water, and the content of water in the composition for dip molding is set to a predetermined concentration because the latex concentration, which is a factor for adjusting the thickness of gloves, is set to this concentration. It can be changed as appropriate, but it is usually 78 to 92 parts by weight.
  • water pure water or industrial water can be used, but it is preferable to use pure water.
  • the composition for dip molding also usually contains a dispersant for dispersing each component.
  • a dispersant for dispersing each component.
  • an anionic surfactant is preferable, and for example, a carboxylate, a sulfonate, a phosphate, a polyphosphoric acid ester, a polymerized alkylarylsulfonate, a polymerized sulfonated naphthalene, and a polymerized naphthalene / formaldehyde Condensation polymers and the like are mentioned, and sulfonates are preferably used.
  • Commercially available products can be used as the dispersant.
  • "Tamol NN9104" manufactured by BASF may be used.
  • the amount used is preferably about 0.5 to 2.0 parts by weight with respect to 100 parts by weight of the elastomer in the dip molding composition.
  • the composition for dip molding usually further contains various other additives.
  • the additive include antioxidants, pigments, chelating agents and the like.
  • the antioxidant a hindered phenol type antioxidant, for example, WingstayL can be used.
  • the pigment for example, titanium dioxide is used.
  • the chelating agent sodium ethylenediaminetetraacetate or the like can be used.
  • each additive such as an elastomer, a halohydrin cross-linking agent, and if necessary, an epoxy cross-linking agent, a pH adjuster, and water is mixed by a conventional mixing means, for example, a mixer or the like. Can be made.
  • a glove manufacturing method (hereinafter, also simply referred to as “glove manufacturing method”), which is another embodiment of the present invention, is the following manufacturing method. That is, (1) Coagulant adhesion step (step of adhering coagulant to glove molding mold), (2) Stirring step (step of preparing a composition for dip molding and stirring), (3) Dip molding step (step of immersing the glove molding die in the dip molding composition), (4) Gelling step (step of gelling the film formed on the glove molding to make a cured film precursor), (5) Reaching step (step of removing impurities from the cured film precursor formed on the glove molding die), (6) Beading process (process of making a roll around the cuffs of gloves), (7) Curing step (step of heating and drying at the temperature required for the cross-linking reaction)
  • This is a method for manufacturing gloves which comprises the above steps (3) to (7) in the above order.
  • step (6') may be optionally provided between the steps (6) and (7) above.
  • step (6') Precure ring step, (step of heating and drying the cured film precursor at a lower temperature than the curing step)
  • the above-mentioned manufacturing method also includes a method of manufacturing gloves by so-called double dipping, in which the steps (3) and (4) are repeated twice.
  • the cured film precursor is a film composed of an elastomer aggregated on a glove molding by a coagulant in a dipping step, and calcium is dispersed in the film in a subsequent gelling step to gel to some extent. It is a modified film that has not been finally cured.
  • Coagulant Adhesion Step (a) Mold or former (glove molding type) is placed in a coagulant solution containing 5 to 40% by weight, preferably 8 to 35% by weight of Ca 2+ ions as a coagulant and a gelling agent. Soak.
  • the time for adhering the coagulant or the like to the surface of the mold or former is appropriately determined, and is usually about 10 to 20 seconds.
  • the coagulant calcium nitrate or chloride is used. Other inorganic salts having the effect of precipitating the elastomer may be used. Above all, it is preferable to use calcium nitrate.
  • This coagulant is usually used as an aqueous solution containing 5 to 40% by weight.
  • the solution containing the coagulant preferably contains potassium stearate, calcium stearate, mineral oil, ester-based oil, or the like as a release agent in an amount of about 0.5 to 2% by weight, for example, about 1% by weight.
  • halohydrin cross-linking agent When using a hydrophilic halohydrin cross-linking agent or an epoxy cross-linking agent with a trivalent MIBK / water distribution ratio of 27% or more, it is necessary to secure a minimum of 3 days as a mass production condition (leave it uninactivated). it can. It has been confirmed that the halohydrin cross-linking agent has a pot life of about 6 days.
  • the dip molding composition (dip liquid) according to the embodiment of the present invention that has been stirred is poured into a dip tank, and the coagulant adhering step is carried out in the dip tank.
  • This is a step of immersing the mold or former after the coagulant is attached and dried, usually for 1 to 60 seconds under a temperature condition of 25 to 35 ° C.
  • the calcium ions contained in the coagulant agglomerate the elastomer contained in the dip molding composition on the surface of the mold or former to form a film.
  • the leaching step is a step of washing and removing excess chemicals and impurities that interfere with subsequent curing such as calcium precipitated on the surface of the cured film precursor. Normally, the former is dipped in warm water at 40 to 60 ° C. for about 1.5 to 4 minutes.
  • leaching, removing the emulsifier is a film of XNBR particles in order to proceed smoothly crosslinked by curing process, -COO oriented outwardly - to return to -COOH, complex ion of metal cross-linking agent This is an important step in that it is retained in the film instead of the hydroxide that is insoluble in water, and Ca derived from the excess coagulant and K derived from the pH adjuster are removed.
  • Beading step This is a step of winding up the cuff end of the glove of the cured film precursor for which the leaching step has been completed to make a ring having an appropriate thickness and reinforcing it.
  • the adhesiveness of the roll portion is excellent.
  • Precure ring step (a) After the beading step, the cured film precursor is heated and dried at a lower temperature than the subsequent curing step. Usually, in this step, heating and drying are performed at 60 to 90 ° C. for about 30 seconds to 5 minutes. If the high-temperature curing process is performed without going through the pre-curing process, the water will evaporate rapidly and convex parts like swelling may be formed on the gloves, which may impair the quality, but without going through this process. You may move to the curing process. (B) The temperature may be raised to the final temperature of the curing step without going through this step, but if curing is performed in multiple drying furnaces and the temperature of the first-stage drying furnace is slightly lowered, this first step Dry eyes correspond to the precuring process.
  • the curing step is a step of heating and drying at a high temperature to finally complete the cross-linking and to make a cured film as a glove. It is usually heated and dried at 90 to 140 ° C. for 10 to 30 minutes, preferably about 15 to 30 minutes.
  • Double dipping As for the method of manufacturing gloves, so-called single dipping has been described above.
  • the dipping step and the gelling step may be performed twice or more, and this is usually called double dipping. Double dipping is performed for the purpose of preventing the formation of pinholes when manufacturing thick gloves (thickness of more than 200 to 300 ⁇ m) and also in the manufacturing method of thin gloves.
  • double dipping In order to aggregate XNBR in the second dipping step, it is necessary to have a sufficient time in the gelling step for sufficiently precipitating calcium to the film surface in the first gelling step. Is mentioned.
  • the glove according to the above-described embodiment of the present invention is a glove manufactured by using the above-mentioned dip molding composition, and in the first embodiment, it has a cross-linked structure of a carboxyl group of XNBR and a halohydrin cross-linking agent. It is a glove, and in the second embodiment, it is a glove having a cross-linked structure of a carboxyl group and an epoxy cross-linking agent.
  • the XNBR glove having the necessary physical characteristics of the glove can be produced by using the halohydrin cross-linking agent.
  • the tensile strength was as strong as 7N or more.
  • the intra-particle cross-linking is cross-linked with an epoxy cross-linking agent and the inter-particle cross-linking is cross-linked with a halohydrin cross-linking agent to eliminate zinc, which is an ionic cross-link, and halohydrin with high oiliness
  • the cross-linking agent it is considered that this was achieved by further strengthening the inter-particle cross-linking by covalent bond.
  • the glove can be a glove which is a cured product of the above-mentioned dip molding composition.
  • the elastomer forming the glove has a (meth) acrylonitrile-derived structural unit of 12 to 35% by weight, an unsaturated carboxylic acid-derived structural unit of 2 to 10% by weight, and the rest of which is a butadiene-derived structural unit. And other components are preferred. Further, the structural unit derived from butadiene is preferably 50 to 75% by weight.
  • the above gloves do not substantially contain sulfur and vulcanization accelerators unlike conventional XNBR gloves, and therefore, the greatest feature is that they do not cause type IV allergies. ..
  • sulfur is contained in the surfactant and the like during the production of the elastomer, a very small amount of sulfur may be detected.
  • the stress retention rate of the gloves according to the present embodiment is increased in that the cross-linking is not a sulfur cross-linking that causes a cross-linking reaction near the double bond of butadiene but a covalent bond with a carboxyl group.
  • tensile strength and elongation For the tensile strength and elongation, a JIS K6251 No. 5 dumbbell test piece was cut out from the cured film, and a TENSILON universal tensile tester RTC-1310A manufactured by A & D was used to test the test speed at 500 mm / min, the distance between chucks at 75 mm, and between the marked lines. Measured at a distance of 25 mm. As for the physical characteristics of gloves, the tensile strength is considered to be 20 MPa or more, and the elongation rate is considered to be 500% or more.
  • the stress retention rate was measured as follows. A test piece is prepared from the cured film using a punching cutter (Super Straight Cutter SK-1000-D manufactured by Dumbbell) according to the strip No. 2 specified in JIS K 6263, and the speed is 100 mm at both ends of the test piece. Tensile stress is applied in minutes, and when the test piece is stretched twice (100%), the stretching is stopped and the tensile stress M100 (0) is measured, and the tensile stress M100 (6 minutes) after elapsed as it is. 6) was measured. Then, the percentage of M100 (6) with respect to M100 (0) was defined as the stress retention rate. Since the stress retention rate of the conventional sulfur-crosslinked XNBR gloves is in the 40% range, it is considered that 50% or more is good for XNBR gloves.
  • a 120 mm long JIS K6251 No. 1 dumbbell test piece is made from a cured film, the lower part is fixed and the upper part of the test piece is pulled to a length of 60 mm while being immersed in an artificial sweat solution. It is indicated by the time required for the test piece to break by repeating stretching and relaxation between a maximum of 195 mm and a minimum of 147 mm in the direction. Elongation (195 mm) and relaxation (147 mm) are performed by repeating a cycle (1 cycle 12.8 seconds) of holding in a relaxed state for 11 seconds, then extending to 195 mm in 1.8 seconds and returning to 147 mm. Can be done.
  • a fatigue durability test can be performed using a device as shown in FIG. 2 using a dumbbell-shaped test piece as in the case of performing a tensile test of a rubber product.
  • the lower end of the test piece is fixed with a clamp, and up to 60 mm is immersed in artificial sweat liquid.
  • the upper end of the test piece is sandwiched and expanded and contracted up and down using a pneumatic piston so as to be in the relaxed state of FIG. 2 (b) ⁇ the extended state of FIG. 2 (c) ⁇ the relaxed state of FIG. 2 (b). Evaluation is made by measuring the number of cycles and the time until the bicycle breaks, with the expansion and contraction of 2 (b) ⁇ FIG. 2 (c) ⁇ FIG. 2 (b) as one cycle.
  • the photoelectric sensor reacts and the device stops.
  • part by weight indicates, in principle, the number of parts by weight with respect to 100 parts by weight of the elastomer.
  • the number of parts by weight of each additive is based on the solid content, and the number of parts by weight of the halohydrin cross-linking agent and the epoxy cross-linking agent is based on the total weight of each cross-linking agent.
  • the calibration curve was prepared from a sample in which polyacrylic acid was added as an internal standard substance to each elastomer and the amount of acrylonitrile groups was known.
  • the amount of unsaturated carboxylic acid residue was calculated from the following formula.
  • Unsaturated carboxylic acid residue amount (% by weight) [Abs (1699 cm -1 ) / Abs (2237 cm -1 )] /0.2661
  • the coefficient 0.2661 is a converted value obtained by preparing a calibration curve from a plurality of samples in which the ratio of the unsaturated carboxylic acid group amount and the acrylonitrile group amount is known.
  • MEK insoluble amount The MEK (methyl ethyl ketone) insoluble (gel) component was measured as follows. A 0.2 g XNBR latex dried product sample was placed in a weighed mesh basket (80 mesh), immersed in 80 mL of MEK solvent in a 100 mL beaker together with the basket, and the beaker was covered with Parafilm. Allowed for hours in the draft. Then, the mesh basket was taken out from the beaker, suspended in the air in the draft, and dried for 1 hour. This was dried under reduced pressure at 105 ° C. for 1 hour, then weighed, and the weight of the basket was subtracted to obtain the weight after immersion of the XNBR latex dried product.
  • the content (insoluble amount) of the MEK insoluble component was calculated from the following formula.
  • Insoluble component content (% by weight) (weight g after immersion / weight g before immersion) ⁇ 100
  • the XNBR latex dried product sample was prepared as follows. That is, after stirring the XNBR latex at a rotation speed of 500 rpm for 30 minutes in a 500 mL bottle, 14 g of the latex was weighed in a 180 ⁇ 115 mm stainless steel vat, and the latex was 23 ° C. ⁇ 2 ° C. and humidity 50 ⁇ 10 RH% for 5 days. It was dried to obtain a cast film, and the film was cut into 5 mm squares to prepare an XNBR latex dried product sample.
  • Halohydrin cross-linking agent Table 3 shows the characteristics of the halohydrin cross-linking agent used in this experimental example, such as the mother skeleton.
  • the solid content in Table 3 indicates the content of the halohydrin compound in the halogen cross-linking agent in this example.
  • a chlorohydrin cross-linking agent was used as the halohydrin cross-linking agent.
  • the chlorohydrin cross-linking agent was produced as follows.
  • Chlorohydrin cross-linking agent A (sorbitol skeleton) 182 g (1.0 mol) of sorbitol, 500 g of toluene, and 1.8 g of boron trifluoride ether complex as a catalyst are charged in a 1 L volume separable flask, and the mixture is heated and stirred to maintain the internal temperature at 70 to 90 ° C., and epichlorohydrin. 277.5 g (3.0 mol) was added dropwise. At the end of the dropping, the reaction system was a uniform solution.
  • Chlorohydrin cross-linking agent B ethylene glycol skeleton
  • 166 g (2.7 mol) of ethylene glycol, 70 g of toluene, and 0.6 g of boron trifluoride ether complex as a catalyst were charged in a 2 L volume separable flask, and the mixture was heated and stirred to keep the internal temperature at 50 ° C. 557 g (6.0 mol) of epichlorohydrin was added dropwise. At the end of the dropping, the reaction system was a uniform solution. After completion of the dropping, the mixture was further stirred at the same temperature for 2 hours, and then the disappearance of epichlorohydrin was confirmed based on the determination of epoxy groups by titration, and the reaction was terminated.
  • Chlorohydrin cross-linking agent C (glycerin skeleton) 300 g (3.3 mol) of glycerin, 150 g of toluene, and 0.6 g of boron trifluoride ether complex as a catalyst were charged in a 2 L volume separable flask, and the mixture was heated and stirred to maintain the internal temperature at 50 ° C., and 999 g of epichlorohydrin (999 g). 10.8 mol) was added dropwise. At the end of the dropping, the reaction system was a uniform solution.
  • Chlorohydrin cross-linking agent D (trimethylolpropane skeleton) 425 g (3.2 mol) of trimethylolpropane, 300 g of toluene, and 2.4 g of boron trifluoride ether complex as a catalyst are charged in a 2 L volume separable flask, and the mixture is heated and stirred to maintain the internal temperature at 50 ° C., and epichlorohydrin. 894 g (9.7 mol) was added dropwise. At the end of the dropping, the reaction system was a uniform solution.
  • Epoxy cross-linking agent The epoxy cross-linking agent used in the examples is "Denacol Ex-321" manufactured by Nagase ChemteX Corporation, and its physical characteristics are as follows. Epoxy equivalent: 140 g / eq. Average number of epoxy groups: 2.7 MIBK / water distribution rate: 87% The content of the epoxy compound in the epoxy cross-linking agent in this example is approximately 100% by weight, although impurities such as reaction by-products are contained.
  • the epoxy equivalent is a catalog value, and the average epoxy group number is an analytical value.
  • the method for measuring the MIBK / water distribution ratio is the method described in the embodiment for carrying out the invention. In the example using the epoxy cross-linking agent, when adding, it is added after mixing with the same amount of diethylene glycol.
  • the solid content concentration of 22% is the film thickness of the coagulation liquid of 20%. It can be adjusted to 80 ⁇ m.
  • the film in this example is a film that has been dipped 24 hours after the addition of the halohydrin cross-linking agent.
  • the condition is described for each Example.
  • the cured film precursor that aggregated and formed a film on a ceramic plate was dried at 80 ° C. for 2 minutes (gelling step) and leached with warm water at 50 ° C. for 2 minutes. Then, it was dried at 70 ° C. for 5 minutes and thermoset at 130 ° C. for 30 minutes.
  • the obtained cured film was peeled off cleanly from the ceramic plate and stored in an environment of 23 ° C. ⁇ 2 ° C. and a humidity of 50% ⁇ 10% until it was subjected to a physical characteristic test.
  • the condition is described for each Example.
  • a JIS K6251 No. 1 dumbbell test piece was cut out from the cured film, and this was mixed with an artificial sweat solution (20 g of sodium chloride, 17.5 g of ammonium chloride, 17.05 g of lactic acid, 5.01 g of acetic acid in 1 liter, and an aqueous sodium hydroxide solution. The pH was adjusted to 4.7), and the fatigue durability was evaluated using the above-mentioned durability test apparatus. That is, 15 mm from each of the two ends of the 120 mm long dumbbell test piece was sandwiched between the fixed chuck and the movable chuck, and 60 mm from the bottom of the test piece on the fixed chuck side was immersed in the artificial sweat solution.
  • the test piece After moving the movable chuck to the minimum position (relaxed state) of 147 mm (123%) and holding it for 11 seconds, the test piece reaches the maximum position (extended state) of 195 mm (163%) and the minimum again. It was moved to the position (relaxed state) over 1.8 seconds, and a cycle test was conducted with this as one cycle. The time of one cycle was 12.8 seconds, and the time (minutes) of fatigue durability was obtained by multiplying by the number of cycles until the test piece broke. ⁇ Stress retention rate> The stress retention rate was determined according to the above method.
  • Experimental Example 1 is a physical property of a film crosslinked only with zinc oxide as a reference example.
  • Experimental Examples 2 to 5 show the physical characteristics of the film when zinc oxide is fixed at 1.0 part by weight and chlorohydrin is changed to 0.25 to 3.0 parts by weight (chlorohydrin compound amount).
  • Experimental Examples 6 and 7 are films prepared using 1.0 part by weight of chlorohydrin and 0.5 part by weight of zinc oxide. As the pH adjuster, 6 is ammonia and 7 is the physical characteristics of the film when KOH is used. is there. The results of the experiments conducted using each film are shown in Table 4 below.
  • Experimental Examples 2 to 7 correspond to the first embodiment of the present invention, but if the amount of chlorohydrin added is 1.0 part by weight or more, the film prepared by using chlorohydrin as a cross-linking agent has the normal physical characteristics of gloves. You can see that you are satisfied. Looking at Experimental Examples 1 to 5, when zinc oxide is fixed at 1.0 part by weight and the amount of chlorohydrin is increased, the fatigue durability increases accordingly, so that chlorohydrin is surely crosslinked. It can be seen that it is contributing. Further, looking at Experimental Examples 2 to 5, it can be seen that the cross-linking reaction is proceeding even if the tensile elongation decreases as the amount of chlorohydrin increases. From these results, it was found that the film using chlorohydrin can make gloves having excellent fatigue durability, tensile strength, and tensile elongation.
  • Experimental Examples 8 to 11 are films prepared by using the chlorohydrin cross-linking agent and the epoxy cross-linking agent of the second embodiment in combination without using zinc oxide
  • Experimental Examples 12 to 15 are reference examples. This is a conventional film to which an epoxy cross-linking agent and zinc oxide are added, and the physical characteristics of each film are measured. The results of experiments conducted using each film are shown in Table 5 below. The amount of chlorohydrin in Table 5 below is the amount of the chlorohydrin compound, and the amount of epoxy is the amount of the epoxy compound.
  • Experimental Examples 8 and 12, 9 and 13, 10 and 14, 11 and 15 use the same latex, one is cross-linking with chlorohydrin and epoxy, and the other is cross-linking with epoxy and zinc oxide. .. It can be seen that the stress retention rate is higher when chlorohydrin is used instead of zinc oxide. Further, it can be seen that the stress retention rate of the epoxy cross-linking agent itself is further increased by adding chlorohydrin based on the fact that the stress retention rate is originally superior to that of the sulfur-crosslinked XNBR gloves. In Experimental Example 11, the stress retention rate is 67.8%, which is incredibly high as the stress retention rate of the XNBR gloves.
  • the value is 500% or more, and when the sulfur vulcanized XNBR gloves increase the amount of sulfur added to increase the crosslink density and increase the stress retention, the elongation increases. It's amazing considering that it's going down to the extreme. Further, in the first embodiment, fatigue durability was not obtained unless chlorohydrin was 1.0 part by weight, but when chlorohydrin and epoxy, which are the second embodiment, were used in combination, chlorohydrin was 0. It was also found that even 5 parts by weight can satisfy all the physical characteristics of gloves.
  • the fatigue durability is at a very high level of 279 minutes even when the stirring time is 6 days, and the pot life of the chlorohydrin cross-linking agent is 6 days or more even if it is water-soluble. This is a sufficient number of days even when considering actual production.
  • cross-linking agents B, C, and D have a high MIBK / water distribution ratio and are poorly soluble in water, and have strong lipophilicity, and enter the XNBR particles to form an intra-particle cross-link. Conceivable.
  • a halohydrin cross-linking agent for a carboxylic acid-modified NBR latex which is not used in the field of conventional gloves, a dip molding composition containing at least the cross-linking agent, and a glove using the dip molding composition.

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Abstract

Le premier problème abordé par la présente invention est de produire un gant ayant une excellente résistance à la traction, un excellent allongement et une excellente endurance à la fatigue à l'aide d'un agent de réticulation d'halohydrine, qui n'a pas été utilisé dans le domaine des gants de type à agent de réticulation externe classiques, tout en n'utilisant aucun accélérateur de vulcanisation. Le second problème abordé par la présente invention est de produire un gant ayant un excellent rapport de rétention de contrainte et un bon allongement en même temps, tout en améliorant les faiblesses des gants XNBR vulcanisés au soufre classiques. L'invention concerne également un agent de réticulation pour moulage par immersion, qui contient un composé halohydrine ayant au moins deux groupes halohydrine D représentés par la formule (I) dans chaque molécule. Dans la formule (I), R1 représente un atome d'hydrogène ou un groupe alkyle ; et X représente un groupe halogène.
PCT/JP2020/027114 2019-07-12 2020-07-10 Agent de réticulation pour moulage par immersion, composition pour moulage par immersion et gant WO2021010343A1 (fr)

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Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2000073367A1 (fr) * 1999-05-28 2000-12-07 Suzuki Latex Industry Co., Ltd. Produits de latex non collants
WO2015141780A1 (fr) * 2014-03-19 2015-09-24 ナガセケムテックス株式会社 Agent de réticulation de résine absorbant l'eau
WO2015146784A1 (fr) * 2014-03-24 2015-10-01 ナガセケムテックス株式会社 Composition d'agent de réticulation pour une résine absorbant l'eau
US20170099889A1 (en) * 2015-10-07 2017-04-13 Derlink Co., Ltd. High stress retention nitrile glove
JP2017082077A (ja) * 2015-10-27 2017-05-18 ナガセケムテックス株式会社 ハロヒドリン化合物及び樹脂組成物
WO2017126660A1 (fr) * 2016-01-21 2017-07-27 ミドリ安全株式会社 Gant
WO2019102985A1 (fr) * 2017-11-24 2019-05-31 ミドリ安全株式会社 Gant, composition de moulage au trempé et procédé de fabrication de gant

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2000073367A1 (fr) * 1999-05-28 2000-12-07 Suzuki Latex Industry Co., Ltd. Produits de latex non collants
WO2015141780A1 (fr) * 2014-03-19 2015-09-24 ナガセケムテックス株式会社 Agent de réticulation de résine absorbant l'eau
WO2015146784A1 (fr) * 2014-03-24 2015-10-01 ナガセケムテックス株式会社 Composition d'agent de réticulation pour une résine absorbant l'eau
US20170099889A1 (en) * 2015-10-07 2017-04-13 Derlink Co., Ltd. High stress retention nitrile glove
JP2017082077A (ja) * 2015-10-27 2017-05-18 ナガセケムテックス株式会社 ハロヒドリン化合物及び樹脂組成物
WO2017126660A1 (fr) * 2016-01-21 2017-07-27 ミドリ安全株式会社 Gant
WO2019102985A1 (fr) * 2017-11-24 2019-05-31 ミドリ安全株式会社 Gant, composition de moulage au trempé et procédé de fabrication de gant

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