WO2014034889A1 - 耐薬品性に優れた手袋及び該手袋用組成物 - Google Patents
耐薬品性に優れた手袋及び該手袋用組成物 Download PDFInfo
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- WO2014034889A1 WO2014034889A1 PCT/JP2013/073411 JP2013073411W WO2014034889A1 WO 2014034889 A1 WO2014034889 A1 WO 2014034889A1 JP 2013073411 W JP2013073411 W JP 2013073411W WO 2014034889 A1 WO2014034889 A1 WO 2014034889A1
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- elastomer
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L13/00—Compositions of rubbers containing carboxyl groups
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- A—HUMAN NECESSITIES
- A41—WEARING APPAREL
- A41D—OUTERWEAR; PROTECTIVE GARMENTS; ACCESSORIES
- A41D19/00—Gloves
- A41D19/0055—Plastic or rubber gloves
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F236/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds
- C08F236/02—Copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds
- C08F236/04—Copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds conjugated
- C08F236/06—Butadiene
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F236/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds
- C08F236/02—Copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds
- C08F236/04—Copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds conjugated
- C08F236/12—Copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds conjugated with nitriles
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/0008—Organic ingredients according to more than one of the "one dot" groups of C08K5/01 - C08K5/59
- C08K5/0025—Crosslinking or vulcanising agents; including accelerators
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2203/00—Applications
- C08L2203/02—Applications for biomedical use
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
- C08L2205/025—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure
Definitions
- the present invention relates to a glove and a composition for the glove. Specifically, the present invention relates to a glove having improved chemical resistance while maintaining flexibility by being composed of a predetermined combination of elastomers, and a composition for producing the glove.
- Rubber gloves are widely used in various industrial and medical fields such as the electronic component manufacturing industry and the pharmaceutical industry.
- a glove obtained by dip molding a latex composition obtained by crosslinking a carboxylated acrylonitrile-butadiene copolymer with a sulfur vulcanization accelerator such as sulfur and thiazole as a rubber glove having excellent tensile strength and oil resistance.
- sulfur vulcanization accelerators such as sulfur and thiazole
- Patent Document 1 discloses a glove using acid-modified nitrile rubber having a high content of methyl ethyl ketone insoluble matter.
- Patent Document 2 discloses a glove using a carboxylic acid-modified nitrile copolymer containing a monomer containing a crosslinkable functional group such as a glycidyl group as a constituent unit.
- Patent Document 3 discloses a glove using a self-crosslinking carboxylated acrylonitrile butadiene.
- An object of the present invention is to provide a glove having excellent chemical resistance and flexibility and a composition for producing the glove.
- the present invention is a carboxylated acrylonitrile butadiene elastomer comprising 30 to 40% by weight of acrylonitrile residues and 3 to 8% by weight of unsaturated carboxylic acid residues of the elastomer weight, and neutralization titration of the elastomer combustion product.
- the present invention also relates to (1) a carboxylated acrylonitrile butadiene elastomer comprising 30 to 40% by weight of acrylonitrile residues and 3 to 8% by weight of unsaturated carboxylic acid residues of the elastomer weight, An elastomer having a content of elemental sulfur detected by the neutralization titration method of 1% by weight or less of the weight of the elastomer and a Mooney viscosity (ML (1 + 4) (100 ° C.)) of 100 to 220, and ( 2) Poly (acrylonitrile butadiene) having a weight average molecular weight of 7,000 to 500,000 in terms of styrene An emulsion composition comprising a weight ratio of component (1) / component (2) of 70/30 to 90/10.
- the present invention is a glove obtained from the above composition.
- the carboxylated acrylonitrile butadiene elastomer of the present invention has a non-sulfur crosslinked structure, does not cause problems such as allergies, and is excellent in chemical resistance.
- By forming the glove by combining the elastomer with poly (acrylonitrile butadiene) having a predetermined molecular weight it is possible to produce a glove having excellent chemical resistance and excellent flexibility.
- this is because the inclusion of a predetermined amount of acrylonitrile is excellent in chemical resistance, but the carboxylated acrylonitrile butadiene elastomer having relatively low flexibility has a high compatibility with the elastomer.
- carboxylated acrylonitrile butadiene elastomer (hereinafter referred to as “XNBR”) is widely used as acrylonitrile and butadiene constituting the main chain of rubber, at least one unsaturated carboxylic acid, and optionally other copolymerizable monomers.
- the elastomer containing the carboxyl group obtained by copolymerizing is included. Further, a part of the carboxyl group may be derivatized (for example, ester, amide, etc.) to form a crosslinked structure.
- XNBR contains acrylonitrile residues of 30 to 40% by weight, preferably 32 to 38% by weight of the XNBR weight.
- the amount of acrylonitrile residue in XNBR can be determined by converting the amount of nitrile groups from the amount of nitrogen atoms determined by elemental analysis.
- XNBR contains 4 to 8% by weight, preferably 4 to 6% by weight of unsaturated carboxylic acid residues of the XNBR weight.
- the content of the unsaturated carboxylic acid residue is less than 4% by weight, the crosslinking formation by divalent ions described later is not sufficient, and the crosslinking structure in XNBR is not sufficiently formed.
- it exceeds 8% by weight the cross-linked structure becomes excessive, leading to a decrease in physical properties such as tensile strength and tensile stress (modulus) of the final product, rubber gloves.
- the unsaturated carboxylic acid acrylic acid and / or methacrylic acid (hereinafter referred to as “(meth) acrylic acid”) is used, and methacrylic acid is preferably used.
- the amount of the unsaturated carboxylic acid residue in XNBR can be determined by quantifying the carboxyl group and the carbonyl group derived from the carboxyl group by infrared spectroscopy (IR) or the like.
- XNBR XNBR
- a butadiene residue and a crosslinked structure As the butadiene constituting the butadiene residue, 1,3-butadiene is preferable.
- the amount of the butadiene residue is 52 to 66% by weight, preferably 56 to 64% by weight, based on the total of the butadiene residue, the acrylonitrile residue and the unsaturated carboxylic acid residue. .
- the amount of the butadiene residue is within the range, a final product having excellent physical properties such as tensile properties and fatigue properties can be obtained.
- the crosslinked structure of XNBR is a non-sulfur crosslinked structure.
- the content of elemental sulfur detected by the neutralization titration method of the XNBR combustion gas absorption liquid can be suppressed to 1.0% by weight or less of the XNBR weight.
- the quantification method is such that a combustion gas generated by burning 0.01 g of an XNBR sample in air at 1350 ° C. for 10 to 12 minutes is absorbed in H 2 O 2 water to which a mixed indicator is added, and a 0.01 N NaOH aqueous solution is absorbed.
- the neutralization titration method is used.
- the non-sulfur crosslinked structure in the present invention is not particularly limited, for example, crosslinking between main chains by organic peroxides, oximes, etc., crosslinking between carboxyl groups such as acid anhydrides, crosslinking agents such as polyepoxides, polyols, Crosslinking between carboxyl groups using polyimide, mono and polycarbodiimide, polyisocyanate, etc., introducing a structural unit having a carboxyl group and a reactive group such as a glycidyl group into the main chain, and reacting the group with the carboxyl group And the like.
- self-crosslinking i.e., crosslinking that is stable under normal storage conditions, but formed, for example, by evaporating or heating water, or by changing pH, without the addition of a separate cross-linking agent.
- cross-linking include those by auto-oxidation of carboxyl groups, those in which n-methylolacrylamide units are introduced and self-condensed, and Michael reaction of acetoacetoxy groups and unsaturated bonds.
- XNBR can be prepared by emulsion polymerization of acrylonitrile, (meth) acrylic acid, 1,3-butadiene and, if necessary, other unsaturated monomers for forming a crosslinked structure or the like according to a conventional method.
- emulsion polymerization commonly used emulsifiers, polymerization initiators, molecular weight modifiers, and the like can be used.
- unsaturated monomers include aromatic vinyl monomers such as styrene, ⁇ -methylstyrene and dimethylstyrene; ethylenically unsaturated carboxylic acids such as (meth) acrylamide, N, N-dimethylacrylamide and N-methylolacrylamide Amide monomers; Ethylenically unsaturated carboxylic acid alkyl ester monomers such as methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate and 2-ethylhexyl (meth) acrylate; and acetic acid Vinyl etc. are mentioned.
- the emulsifier examples include anionic surfactants such as dodecylbenzene sulfonate and aliphatic sulfonate; cationic surfactants such as polyethylene glycol alkyl ether and polyethylene glycol alkyl ester; and amphoteric surfactants. Of these, an anionic surfactant is preferably used.
- the polymerization initiator is not particularly limited as long as it is a radical initiator, but inorganic peroxides such as ammonium persulfate and potassium perphosphate; t-butyl peroxide, cumene hydroperoxide, p-menthane hydroperoxide, diester Organic peroxides such as t-butyl peroxide, t-butylcumyl peroxide, dibenzoyl peroxide, 3,5,5-trimethylhexanoyl peroxide and t-butylperoxyisobutyrate; azobisisobuty Examples include azo compounds such as rhonitrile, azobis-2,4-dimethylvaleronitrile, azobiscyclohexanecarbonitrile, and methyl azobisisobutyrate.
- inorganic peroxides such as ammonium persulfate and potassium perphosphate
- t-butyl peroxide cumene hydroperoxide
- the molecular weight modifier examples include mercaptans such as t-dodecyl mercaptan and n-dodecyl mercaptan; halogenated hydrocarbons such as carbon tetrachloride, methylene chloride and methylene bromide. Of these, mercaptans are preferably used. Furthermore, a dispersing agent, a pH adjuster, etc. can be used as needed.
- the polymer obtained by emulsion polymerization is subjected to a non-sulfur crosslinking step by heating or evaporating water to obtain XNBR.
- this step may be performed simultaneously with crosslinking with divalent ions, which will be described later, or in a heating step after the ion crosslinking.
- the resulting XNBR has a molecular weight such that the Mooney viscosity (ML (1 + 4) (100 ° C.)) is from 100 to 220, preferably from 100 to 190.
- Mooney viscosity is less than 100, it is difficult to obtain a sufficient strength of XNBR.
- the upper limit is an actual measurement limit of Mooney viscosity, and if it exceeds this, the viscosity becomes high and molding processing becomes difficult.
- XNBR has a toluene weight swelling ratio of 190 to 400% by weight, preferably 200 to 400% by weight.
- the swelling ratio is less than 190% by weight, the degree of cross-linking is low, the strength when formed into a glove is insufficient, and when it exceeds 400% by weight, the flexibility of the glove is insufficient.
- the emulsion composition of the present invention is an emulsion-like composition containing poly (acrylonitrile butadiene) (hereinafter referred to as “NBR”) in addition to the above XNBR.
- NBR poly (acrylonitrile butadiene)
- the NBR has a weight average molecular weight in terms of styrene of 7,000 to 50,000, preferably 9,000 to 30,000. When the molecular weight is less than 7,000, there is a concern about bleeding that NBR moves to the surface of the glove, and when it exceeds 50,000, the flexibility of the glove may be insufficient.
- NBR contains acrylonitrile residues of 20 to 50% by weight, preferably 30 to 40% by weight of the NBR weight, and the rest is butadiene residues. This is because when the content of the acrylonitrile residue is less than 20% by weight, the chemical resistance of the glove decreases, and when it exceeds 50% by weight, the molecular chain becomes rigid and the flexibility of the glove is impaired.
- the mixing ratio of XNBR (hereinafter referred to as “component (1)”) and NBR (hereinafter referred to as “component (2)”) in the emulsion composition of the present invention is the weight ratio of component (1) / component (2). 70/30 to 90/10, preferably 70/30 to 85/15. If the weight ratio is less than 70/30, the chemical resistance of the glove is insufficient, and if it exceeds 90/10, it is difficult to achieve sufficient flexibility of the glove. As described in detail in the examples, the weight ratio can be determined by extracting component (2) by methyl ethyl ketone extraction under reflux.
- the emulsion composition contains a divalent metal oxide and a dispersant in addition to the components (1) and (2).
- the divalent metal oxide mainly ion-crosslinks between carboxyl groups in the component (1).
- Examples of the divalent metal oxide include oxides such as zinc, calcium, and magnesium. Among these, zinc oxide is preferably used.
- the content of the divalent metal oxide is 0.5 to 4.0 parts by weight, preferably 0 when the resin component, that is, the total of the components (1) and (2) is 100 parts by weight. 0.7 to 3.0 parts by weight.
- an anionic surfactant is preferable, for example, carboxylate, sulfonate, phosphate, polyphosphate ester, polymerized alkylarylsulfonate, polymerized sulfonated naphthalene and polymerized naphthalene. / Formaldehyde condensation polymer and the like, preferably sulfonate is used.
- the content of the dispersant is 0.5 to 4 parts by weight, preferably 1 to 3 parts by weight, when the total of component (1) and component (2) is 100 parts by weight.
- the emulsion composition can contain conventional additives in addition to the above components.
- the additive include a pH adjuster, a pigment, an antioxidant, a chain transfer agent, and a polymerization initiator.
- a pH adjuster potassium hydroxide is usually used.
- the amount of potassium hydroxide used is usually 0.1 to 2.0 parts by weight per 100 parts by weight of the emulsion composition.
- the pigment for example, titanium dioxide is used.
- the antioxidant a hindered phenol type antioxidant can be used.
- chain transfer agent mercaptans represented by t-dodecyl mercaptan and the like can be used.
- the polymerization initiator is not particularly limited, and inorganic peroxides such as sodium sulfate, organic peroxides such as benzoyl peroxide, and chelating agents such as sodium ethylenediaminetetraacetate can be used.
- the emulsion composition of the present invention is produced by mixing the component (1), the component (2), the divalent metal oxide, the dispersant, each additive and water with a conventional mixing means such as a mixer. Can do.
- the emulsion composition of the present invention has a solid content of 30 to 60% by weight, preferably 40 to 50% by weight, based on the total weight of the emulsion composition.
- the glove of the present invention can be produced by the following known dipping method using the above emulsion composition.
- a dip molding die (hereinafter referred to as “former”) is immersed in a coagulant solution to adhere the coagulant to the former.
- a coagulant solution any inorganic salt having an effect of precipitating the elastomer may be used.
- a 5 to 20% by weight aqueous solution of calcium chloride or magnesium chloride is used.
- the former After drying the former with the coagulant attached at 50 to 70 ° C., the former is immersed in the emulsion composition of the present invention for a period of time corresponding to the desired thickness of the glove, usually about 1 to 20 seconds.
- the former coated with the emulsion composition is heated at 80 to 120 ° C. for 20 to 70 seconds and then washed with water.
- the gloves obtained as described above are highly flexible while being resistant to chemicals such as hydrofluoric acid.
- XNBR-B was prepared in the same manner as XNBR-A except that the amount of acrylonitrile was 34 parts by weight, N-methylolacrylamide was 0.4 parts by weight, the temperature during the reaction was 30 ° C.
- XNBR-C has an acrylonitrile amount of 25 parts by weight, N-methylolacrylamide of 0.3 parts by weight, a reaction temperature of 40 ° C., a reaction time of 18 hours, and all other conditions are XNBR-A. It was prepared in the same manner as above.
- XNBR-D has an acrylonitrile amount of 34 parts by weight, N-methylolacrylamide of 0.5 parts by weight, a reaction temperature of 40 ° C., a reaction time of 24 hours, and all other conditions are the same as those of XNBR-A.
- XNBR-E had an acrylonitrile amount of 34 parts by weight, N-methylolacrylamide was not used, the reaction temperature was 50 ° C., the reaction time was 16 hours, and all other conditions were the same as for XNBR-A. Prepared.
- Unsaturated carboxylic acid residue amount (wt%) [Abs (1699 cm ⁇ 1 ) / Abs (2237 cm ⁇ 1 )] / 0.2661
- “0.2661” is a coefficient obtained by creating a calibration curve from data of a plurality of samples whose amounts of unsaturated carboxylic acid residues and acrylonitrile residues are known.
- the obtained solid rubber was taken out and stirred and washed with about 1000 ml of ion-exchanged water 10 times, then the solid rubber was squeezed and dehydrated, and vacuum dried (60 ° C., 72 hours) to prepare a rubber sample for measurement. did.
- the obtained rubber for measurement was passed through a 6-inch roll having a roll temperature of 50 ° C. and a roll gap of about 0.5 mm several times until the rubber was collected.
- JIS K6300-1 2001 “Unvulcanized rubber—physical characteristics, It was measured according to “How to Obtain Viscosity and Scorch Time Using a 1-Part Mooney Viscometer”.
- the viscosity Mooney of XNBR-D exceeded the upper limit of measurement at a measurement temperature of 100 ° C.
- aqueous ammonia pH 13.3 was added dropwise to adjust the pH of the copolymer latex to 8 or more, and the concentration was adjusted to obtain a solid.
- NBR-a having a weight average molecular weight of 19700 in terms of polystyrene was obtained at a partial concentration of 45%.
- NBR-b having a weight average molecular weight of 10900 was prepared in the same manner as above except that the amount of t-dodecyl mercaptan was changed to 0.5 parts by weight. Further, NBR-c having a weight average molecular weight of 6600 was prepared by the same method except that the amount of t-dodecyl mercaptan was changed to 0.8 parts by weight. Table 2 shows the weight average molecular weight and solid content concentration of each NBR.
- the dispersant is sodium alkylbenzene sulfonate
- the antioxidant is 2,4,6-tri-tert-butylphenol
- the colorant is Fast Green FCF.
- gloves (Examples 1 and 2 and Comparative Examples 1 to 6) were produced by the following dipping method.
- a former which is a glove
- a cleaning liquid and then with cold water and dried
- calcium nitrate as a coagulant is dissolved in water in an amount such that the Ca 2+ ion concentration is 10% by weight Soaked for 15 seconds.
- the former with the coagulant adhered was dried at 60 ° C. for about 1 minute.
- the former was immersed in an emulsion composition adjusted to 30 ° C. for 20 seconds.
- the former was removed from the emulsion composition, washed with water, and then immersed in hot water (50 ° C.) for 140 seconds.
- the former covered with the film of the emulsion composition was dried at 120 ° C. for 300 seconds and then maintained at 60 ° C. for 80 seconds, and the resulting gloves were removed from the former.
- ⁇ Toluene swelling ratio of gloves> The gloves were immersed in toluene at room temperature, and the swelling ratio (%) was determined by dividing the weight after 72 hours by the initial weight. The lower the swelling ratio of toluene, the higher the crosslink density in the glove.
- a cross-linked polymer such as gloves is immersed in a good solvent such as toluene, the good solvent dissolves and spreads the polymer chain, but the cross-linked polymer cross-links because it is suppressed by the elasticity of the cross-linked polymer network and reaches the swelling parallel.
- the density is inversely proportional to the parallel swelling rate in the good solvent.
- ⁇ Flexibility of gloves> The flexibility of the glove was evaluated by tensile properties.
- a dumbbell-shaped No. 5 test piece of JIS K6251: 2010 was cut out from the glove, and using a TENSILON universal tensile tester “RTC-1310A” manufactured by A & D Co., Ltd.
- Tensile strength (MPa), elongation at break (%), and 500% elastic modulus (MPa) were measured to evaluate the strength and flexibility of rubber gloves.
- the tensile strength indicates the strength of the rubber glove, and the larger the value, the higher the strength.
- the elongation at break indicates the flexibility of rubber gloves, and the greater the value, the higher the flexibility.
- the 500% elastic modulus indicates the flexibility of rubber gloves, and the greater the value, the lower the flexibility.
- ⁇ Chemical resistance of gloves> The chemical resistance of the gloves was examined by the following method using the amount of the drug permeating the gloves. Turn the glove over and put 10 ml of a chemical solution selected from 47% hydrofluoric acid (HF) acid, 50% sulfuric acid, physiological saline, methanol, ethanol, acetone, and N-methylpyrrolidone (NMP) into the middle finger of the glove. In this state, the middle finger portion was immersed in 30 ml of pure water, allowed to stand at room temperature for 2 hours, and then the weight (g) of each compound eluted in pure water was quantified by ion chromatography or gas chromatography. In Table 5, “ND” indicates that it was below the detection limit.
- HF hydrofluoric acid
- NMP N-methylpyrrolidone
- the gloves of the examples all had high tensile strength and elongation at break, while having a low 500% elastic modulus, and were excellent in flexibility. Further, the gloves of the examples had low permeation amount for any compound, that is, the permeation amount of each compound from the front surface to the back surface of the glove was small, and the total chemical permeation amount was also small, so that the chemical resistance was excellent .
- the gloves (Comparative Example 1) obtained from the composition containing XNBR-C having a low acrylonitrile residue amount had a higher chemical permeation amount and lower chemical resistance than the gloves of the Examples.
- a glove obtained from an emulsion composition having a low NBR content (Comparative Example 2), a glove obtained from an emulsion composition containing a low molecular weight NBR (Comparative Example 3), and an emulsion composition having a high NBR content (Comparative Example 4), a glove obtained from an emulsion composition containing XNBR-D having a high Mooney viscosity (Comparative Example 5), a glove obtained from an emulsion composition containing XNBR-E having a low Mooney viscosity (Comparative Example 4) All of Comparative Examples 6) were very inferior in tensile strength, elongation at break or tensile properties of 500% elastic modulus.
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Abstract
Description
(2)スチレン換算値の重量平均分子量が7,000~500,000のポリ(アクリロニトリルブタジエン)
を含むエマルジョン組成物であって、成分(1)/成分(2)の重量比が70/30~90/10であるエマルジョン組成物である。
本発明において、カルボキシル化アクリロニトリルブタジエンエラストマー(以下、「XNBR」という)は、広く、ゴムの主鎖を構成するアクリロニトリル及びブタジエン、少なくとも一種の不飽和カルボン酸、並びに、所望により他の共重合性モノマーを共重合させて得られるカルボキシル基を含むエラストマーを包含する。また、該カルボキシル基の一部は、誘導体化(例えばエステル、アミド等)されて架橋構造を形成していてよい。
本発明のエマルジョン組成物は、上記XNBRに加え、ポリ(アクリロニトリルブタジエン)(以下、「NBR」という)を含むエマルジョン状の組成物である。該NBRは、スチレン換算の重量平均分子量が7,000~50,000であり、好ましくは9,000~30,000である。分子量が7,000未満の場合、NBRが手袋表面へ移行するブリードが懸念され、50,000を超える場合、手袋の柔軟性が不足する場合がある。
以下、本発明を実施例により説明するが、本発明はこれらに限定されるものではない。
1)XNBRの調製
表1に示す5種類のXNBRを、以下の手順に従って調製した。
各XNBRのエマルジョンを乾燥してフィルムを作成した。該フィルムをFT-IRで測定し、1699cm-1と2237cm-1における吸光度(Abs)の比を求め、下記式から不飽和カルボン酸残基量を求めた。
不飽和カルボン酸残基量(wt%)
=[Abs(1699cm-1)/Abs(2237cm-1)]/0.2661
硝酸カルシウムと炭酸カルシウムの重量比4:1混合物の飽和水溶液200mlを室温にて攪拌し、各XNBRのエマルジョンをピペットにより滴下し、固形ゴムを析出させた。得られた固形ゴムを取り出し、イオン交換水約1000mlでの攪拌洗浄を10回繰り返した後、固形ゴムを搾って脱水し、真空乾燥(60℃、72時間)して、測定用ゴム試料を調製した。得られた測定用ゴムをロール温度50℃、ロール間隙約0.5mmの6インチロールにゴムがまとまるまで数回通したものを、JIS K6300-1:2001 「未加硫ゴム-物理特性、第1部ムーニー粘度計による粘度およびスコーチタイムの求め方」に準拠して測定した。なお、XNBR-Dの粘度ムーニーは、測定温度100℃での測定上限値を超えていた。
各XNBRのエマルジョン中の固形物0.1gを1350℃で12分間、燃焼炉で燃焼し、発生した燃焼ガスを吸収液(希硫酸を1~数滴加えたH2O2水混合液)へ吸収させた後、0.01NaOH水を用いて中和滴定して定量した。
各XNBRのエマルジョンを1g精秤し、105℃で24時間乾燥した後、残留する固形物量を計量し、固形分量とした。
攪拌機つきの耐圧重合反応器に、イオン交換水120重量部、アクリロ二トリル35重量部、1,3-ブタジエン65重量部、ドデシルベンゼンスルホン酸ナトリウム3重量部、加硫酸カリウム0.3重量部、及びエチレンジアミン四酢酸ナトリウム0.05重量部、t-ドデシルメルカプタン1.0重量部からなる乳化液を仕込み、60~80℃で5時間反応させた後、反応停止剤を添加して重合を終了させ、共重合ラテックスを得た。得られた共重合ラテックスから未反応単量体を除去した後、アンモニア水(pH 13.3)を滴下して共重合体ラテックスのpHを8以上に調整し、さらに濃度を調整して、固形分濃度45%で、ポリスチレン換算の重量平均分子量19700のNBR-aを得た。
各NBRの重量平均分子量と固形分濃度を表2に示す。
上記各エラストマーを表3に示す重量比(樹脂分)で混合し、該混合樹脂分100重量部に対して、表4の添加剤を加えて、ミキサーで攪拌し、エマルジョン組成物1~8を調製した。表3において、A~EはそれぞれXNBR-A~Eを、a~cはそれぞれNBR-a~bを表す。例えば、実施例1は、XNBR-A樹脂85重量部とNBR-a樹脂15重量部が混合されていることを示す。
上記各エマルジョン組成物を用いて、以下のディッピング法により手袋(実施例1及び2、並びに、比較例1~6)を製造した。
(1)手袋の型であるフォーマを、洗浄液、次いで冷水で洗浄して乾燥した後、凝固剤である硝酸カルシウムがCa2+イオン濃度が10重量%となる量で水に溶解されている水溶液中に15秒間浸した。
(2)凝固剤が付着したフォーマを60℃で1分程度フォーマを乾燥した。
(3)30℃に調整したエマルジョン組成物中にフォーマを20秒間浸した。
(4)フォーマをエマルジョン組成物から取り出して水で洗浄した後、熱水(50℃)中に140秒間浸した。
(5)エマルジョン組成物の膜で覆われたフォーマを120℃で300秒間乾燥した後、60℃で80秒間維持し、得られた手袋をフォーマから取り外した。
得られた手袋の諸物性を以下の方法で評価した。結果を表5に示す。
手袋をメチルエチルケトン(MEK)に浸漬し、還流下で8時間抽出した後、得られた抽出液を回収し、濃縮・乾燥後の残留物を4桁天秤で計量した。
手袋を常温でトルエンに浸漬し、72時間後の重量を初期重量で除して膨潤比率(%)求めた。トルエンの膨潤比率が低い程、手袋における架橋密度は高くなる。手袋のような架橋ポリマーをトルエンのような良溶媒中に浸漬すると、良溶媒はポリマー鎖を溶かし広げようとするが、架橋ポリマーの網目の弾力で抑えられ膨潤平行に達するため、架橋ポリマーの架橋密度は良溶媒中の平行膨潤率と逆比例の関係になる。
手袋の柔軟性を、引張り特性により評価した。
手袋からJIS K6251:2010のダンベル状5号試験片を切り出し、株式会社A&D製のTENSILON万能引張試験機「RTC-1310A」を用い、試験速度500mm/min、チャック間75mm、標線間25mmで、引張強度(MPa)、破断時伸び(%)、及び、500%弾性率(MPa)を測定し、ゴム手袋の強度及び柔軟性を評価した。引張強度は、ゴム手袋の強度を示し数値が大きい程強度が高い。また、破断時伸びは、ゴム手袋の柔軟性を示し数値が大きい程柔軟性が高い。また、500%弾性率は、ゴム手袋の柔軟性を示し数値が大きい程柔軟性が低い。
以下の方法で、手袋を透過する薬剤量により、手袋の耐薬品性を調べた。
手袋を裏返し、手袋の中指部分に47%フッ化水素(HF)酸、50%硫酸、生理食塩水、メタノール、エタノール、アセトン、及びN-メチルピロリドン(NMP)から選ばれる一種の薬液を10ml入れた状態で、該中指部分を純水30mlに浸漬し、室温で2時間放置後、純水中に溶出してきた上記各化合物の重量(g)をイオンクロマトグラフィー又はガスクロマトグラフィー等により定量した。表5において、「ND」は検出限界以下であったことを示す。
Claims (11)
- カルボキシル化アクリロニトリルブタジエンエラストマーであって、該エラストマー重量の30~40重量%のアクリロニトリル残基及び3~8重量%の不飽和カルボン酸残基を含み、該エラストマー燃焼物の中和滴定法により検出される硫黄元素の含有量が該エラストマー重量の1重量%以下であり、且つ、ムーニー粘度(ML(1+4)(100℃))が100~220である、カルボキシル化アクリロニトリルブタジエンエラストマー。
- (1)カルボキシル化アクリロニトリルブタジエンエラストマーであって、該エラストマー重量の30~40重量%のアクリロニトリル残基及び3~8重量%の不飽和カルボン酸残基を含み、エラストマー燃焼物の中和滴定法により検出される硫黄元素の含有量が該エラストマー重量の1重量%以下であり、且つムーニー粘度(ML(1+4)(100℃))が100~220である、エラストマー、及び
(2)スチレン換算値の重量平均分子量が7,000~500,000のポリ(アクリロニトリルブタジエン)
を含むエマルジョン組成物であって、成分(1)/成分(2)の重量比が70/30~90/10であるエマルジョン組成物。 - 成分(1)のムーニー粘度が100~200である、請求項2記載のエマルジョン組成物。
- 成分(2)の重量平均分子量が9,000~30,000である、請求項2又は3記載のエマルジョン組成物。
- 成分(1)/(2)の重量比が、70/30~85/15である、請求項2~4のいずれか1項記載のエマルジョン組成物。
- 成分(1)と成分(2)の合計100重量部に対して、
(3)0.5~4.0重量部の二価金属酸化物、
(4)0.5~2.0重量部の分散剤、
をさらに含む、請求項2~5のいずれか1項記載のエマルジョン組成物。 - 固形分がエマルジョン組成物の30~60重量%である、請求項2~6のいずれか1項記載のエマルジョン組成物。
- 手袋調製用の組成物である、請求項2~7のいずれか1項記載のエマルジョン組成物。
- 請求項8記載の組成物から得られる手袋。
- 還流下でのメチルエチルケトン抽出分が手袋の15~30重量%である、請求項9記載の手袋。
- 下記方法:
手袋を裏返し、手袋の中指部分に47%フッ化水素酸、メタノール、エタノール、アセトン、及びN-メチルピロリドンから選ばれる一種の薬液を10ml入れた状態で、該中指部分を純水30mlに浸漬し、室温で2時間放置後、純水中に溶出してきた該薬剤を、イオンクロマトグラフィー又はガスクロマトグラフィーにより定量する、
により測定されるフッ素イオン透過量が0.1g以下、メタノール透過量及びエタノール透過量が、夫々、0.3g以下、アセトン透過量が5.0g以下、N-メチルピロリドン透過量が0.15g以下である、請求項9又は10記載の手袋。
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EP13833395.0A EP2891668B1 (en) | 2012-08-31 | 2013-08-30 | Glove having excellent chemical resistance and composition for said glove |
CN201380045410.1A CN104768985B (zh) | 2012-08-31 | 2013-08-30 | 耐药品性优异的手套和该手套用组合物 |
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WO2017130889A1 (ja) * | 2016-01-27 | 2017-08-03 | 日本ゼオン株式会社 | ラテックス組成物 |
JP2018506592A (ja) * | 2014-12-23 | 2018-03-08 | エルジー・ケム・リミテッド | ディップ成形用ラテックス組成物及びこれから製造されたディップ成形品 |
WO2019003743A1 (ja) * | 2017-06-29 | 2019-01-03 | 日本ゼオン株式会社 | ラテックス組成物 |
KR20190019143A (ko) * | 2016-06-16 | 2019-02-26 | 미도리안젠 가부시키가이샤 | 장갑의 제조 방법, 장갑, 및 장갑용 에멀젼 조성물 |
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Citations (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2000026547A (ja) * | 1998-05-05 | 2000-01-25 | Goodyear Tire & Rubber Co:The | 乳化剤を含まないカルボキシル化ニトリルゴムラテックスゴム |
JP2007177091A (ja) | 2005-12-28 | 2007-07-12 | Nippon Zeon Co Ltd | ディップ成形用ラテックス及びディップ成形品 |
JP2009203272A (ja) * | 2008-02-26 | 2009-09-10 | Nippon Zeon Co Ltd | カルボキシル基含有ニトリルゴムの製造方法 |
JP2010144163A (ja) | 2008-12-16 | 2010-07-01 | Lg Chem Ltd | カルボン酸変性ニトリル系共重合体ラテックス、これを含むディップ成形用ラテックス組成物 |
WO2011068394A1 (en) | 2009-12-01 | 2011-06-09 | Kossan Sdn Bhd | Elastomeric rubber and rubber products without the use of vulcanizing accelerators and sulfur |
JP2011132355A (ja) * | 2009-12-24 | 2011-07-07 | Nippon Zeon Co Ltd | 接着剤用ニトリルゴムラテックスおよびその製造方法 |
WO2012043894A1 (ja) * | 2010-09-30 | 2012-04-05 | コッサン エスディーエヌ ビーエイチ ディー | 加硫促進剤及び硫黄を用いないエラストマーゴム及びエラストマーゴム製品 |
WO2012043893A1 (ja) * | 2010-09-30 | 2012-04-05 | コッサン エスディーエヌ ビーエイチ ディー | 加硫促進剤及び硫黄を用いないクリーンルーム用エラストマーゴム手袋 |
Family Cites Families (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US6846871B2 (en) | 2003-04-25 | 2005-01-25 | Milliken & Company | Antimicrobial resin cured rubber articles and prevulcanized compositions |
JP2005139300A (ja) | 2003-11-06 | 2005-06-02 | Inoac Corp | フォームラバー |
CN101020732A (zh) | 2005-09-12 | 2007-08-22 | 上海强丰合成胶有限公司 | 一种羧基丁腈胶乳的制备方法 |
JP2012191264A (ja) * | 2011-03-08 | 2012-10-04 | Kyocera Corp | 基地局システム、無線制御部及び通信制御方法 |
JP6522942B2 (ja) * | 2011-10-04 | 2019-05-29 | べシックス・バスキュラー・インコーポレイテッド | ステント内再狭窄を治療するためのシステム及び方法 |
JP2016218945A (ja) * | 2015-05-26 | 2016-12-22 | 株式会社リコー | 情報処理システム、及び表示制御方法 |
-
2013
- 2013-08-30 WO PCT/JP2013/073411 patent/WO2014034889A1/ja active Application Filing
- 2013-08-30 MY MYPI2015700599A patent/MY173046A/en unknown
- 2013-08-30 US US14/424,741 patent/US9587091B2/en active Active
- 2013-08-30 JP JP2014533130A patent/JP6078071B2/ja active Active
- 2013-08-30 CN CN201380045410.1A patent/CN104768985B/zh active Active
- 2013-08-30 EP EP13833395.0A patent/EP2891668B1/en active Active
- 2013-08-30 TW TW102131217A patent/TWI606069B/zh active
-
2016
- 2016-11-09 JP JP2016218945A patent/JP2017036459A/ja active Pending
Patent Citations (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2000026547A (ja) * | 1998-05-05 | 2000-01-25 | Goodyear Tire & Rubber Co:The | 乳化剤を含まないカルボキシル化ニトリルゴムラテックスゴム |
JP2007177091A (ja) | 2005-12-28 | 2007-07-12 | Nippon Zeon Co Ltd | ディップ成形用ラテックス及びディップ成形品 |
JP2009203272A (ja) * | 2008-02-26 | 2009-09-10 | Nippon Zeon Co Ltd | カルボキシル基含有ニトリルゴムの製造方法 |
JP2010144163A (ja) | 2008-12-16 | 2010-07-01 | Lg Chem Ltd | カルボン酸変性ニトリル系共重合体ラテックス、これを含むディップ成形用ラテックス組成物 |
WO2011068394A1 (en) | 2009-12-01 | 2011-06-09 | Kossan Sdn Bhd | Elastomeric rubber and rubber products without the use of vulcanizing accelerators and sulfur |
JP2011132355A (ja) * | 2009-12-24 | 2011-07-07 | Nippon Zeon Co Ltd | 接着剤用ニトリルゴムラテックスおよびその製造方法 |
WO2012043894A1 (ja) * | 2010-09-30 | 2012-04-05 | コッサン エスディーエヌ ビーエイチ ディー | 加硫促進剤及び硫黄を用いないエラストマーゴム及びエラストマーゴム製品 |
WO2012043893A1 (ja) * | 2010-09-30 | 2012-04-05 | コッサン エスディーエヌ ビーエイチ ディー | 加硫促進剤及び硫黄を用いないクリーンルーム用エラストマーゴム手袋 |
Non-Patent Citations (2)
Title |
---|
"Rubber, Unvulcanized - Physical Property - Part 1, Determination of Viscosity and Scorch Time with Mooney Viscometer", JIS K 6300-1, 2001 |
See also references of EP2891668A4 |
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WO2017130889A1 (ja) * | 2016-01-27 | 2017-08-03 | 日本ゼオン株式会社 | ラテックス組成物 |
JPWO2017130889A1 (ja) * | 2016-01-27 | 2018-11-22 | 日本ゼオン株式会社 | ラテックス組成物 |
US11098148B2 (en) | 2016-01-27 | 2021-08-24 | Zeon Corporation | Latex composition |
KR20190019143A (ko) * | 2016-06-16 | 2019-02-26 | 미도리안젠 가부시키가이샤 | 장갑의 제조 방법, 장갑, 및 장갑용 에멀젼 조성물 |
KR102205129B1 (ko) | 2016-06-16 | 2021-01-19 | 미도리안젠 가부시키가이샤 | 장갑의 제조 방법, 장갑, 및 장갑용 에멀젼 조성물 |
WO2019003743A1 (ja) * | 2017-06-29 | 2019-01-03 | 日本ゼオン株式会社 | ラテックス組成物 |
WO2022065491A1 (ja) * | 2020-09-25 | 2022-03-31 | ミドリ安全株式会社 | ディップ成形用組成物、及びその成形体 |
WO2022081002A2 (en) | 2020-10-12 | 2022-04-21 | Ci Technology Sdn Bhd | Method of preparing a heterogeneous composite chemical curative dispersion for making elastomeric article |
WO2022081002A3 (en) * | 2020-10-12 | 2023-03-16 | Ci Technology Sdn Bhd | Method of preparing a heterogeneous composite chemical curative dispersion for making elastomeric article |
CN114395174A (zh) * | 2022-01-19 | 2022-04-26 | 山东景元记劳保用品有限公司 | 一种耐磨防油丁腈贴片手套及其制备方法 |
CN114395174B (zh) * | 2022-01-19 | 2023-08-18 | 山东景元记劳保用品有限公司 | 一种耐磨防油丁腈贴片手套及其制备方法 |
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EP2891668A4 (en) | 2016-03-30 |
TW201420617A (zh) | 2014-06-01 |
JP6078071B2 (ja) | 2017-02-08 |
EP2891668A1 (en) | 2015-07-08 |
TWI606069B (zh) | 2017-11-21 |
US9587091B2 (en) | 2017-03-07 |
JPWO2014034889A1 (ja) | 2016-08-08 |
CN104768985B (zh) | 2017-07-28 |
JP2017036459A (ja) | 2017-02-16 |
MY173046A (en) | 2019-12-20 |
CN104768985A (zh) | 2015-07-08 |
EP2891668B1 (en) | 2017-07-26 |
US20150218352A1 (en) | 2015-08-06 |
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