JPWO2019159780A1 - ラテックス組成物および膜成形体 - Google Patents
ラテックス組成物および膜成形体 Download PDFInfo
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- JPWO2019159780A1 JPWO2019159780A1 JP2020500430A JP2020500430A JPWO2019159780A1 JP WO2019159780 A1 JPWO2019159780 A1 JP WO2019159780A1 JP 2020500430 A JP2020500430 A JP 2020500430A JP 2020500430 A JP2020500430 A JP 2020500430A JP WO2019159780 A1 JPWO2019159780 A1 JP WO2019159780A1
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- Prior art keywords
- weight
- acid
- latex
- metal compound
- parts
- Prior art date
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- Granted
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- 229920000126 latex Polymers 0.000 title claims abstract description 122
- 239000004816 latex Substances 0.000 title claims abstract description 122
- 239000000203 mixture Substances 0.000 title claims abstract description 88
- 238000000465 moulding Methods 0.000 title claims description 57
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims abstract description 72
- 150000002736 metal compounds Chemical class 0.000 claims abstract description 69
- 229920003244 diene elastomer Polymers 0.000 claims abstract description 37
- 229910052723 transition metal Inorganic materials 0.000 claims abstract description 16
- 150000003624 transition metals Chemical class 0.000 claims abstract description 16
- 230000000737 periodic effect Effects 0.000 claims abstract description 13
- -1 aluminum compound Chemical class 0.000 claims description 40
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 22
- 239000004408 titanium dioxide Substances 0.000 claims description 10
- MCMNRKCIXSYSNV-UHFFFAOYSA-N ZrO2 Inorganic materials O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims description 7
- 229910052782 aluminium Inorganic materials 0.000 claims description 7
- ANBBXQWFNXMHLD-UHFFFAOYSA-N aluminum;sodium;oxygen(2-) Chemical compound [O-2].[O-2].[Na+].[Al+3] ANBBXQWFNXMHLD-UHFFFAOYSA-N 0.000 claims description 7
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 claims description 7
- 229910001388 sodium aluminate Inorganic materials 0.000 claims description 7
- 238000004519 manufacturing process Methods 0.000 claims description 5
- 239000000178 monomer Substances 0.000 description 92
- 238000000034 method Methods 0.000 description 48
- 238000006116 polymerization reaction Methods 0.000 description 27
- 238000004804 winding Methods 0.000 description 26
- 229920000459 Nitrile rubber Polymers 0.000 description 25
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 24
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 24
- 239000002253 acid Substances 0.000 description 22
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- 206010020751 Hypersensitivity Diseases 0.000 description 19
- 208000026935 allergic disease Diseases 0.000 description 19
- 230000007815 allergy Effects 0.000 description 19
- 150000001993 dienes Chemical class 0.000 description 18
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 17
- 150000001875 compounds Chemical class 0.000 description 15
- 239000000701 coagulant Substances 0.000 description 13
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 12
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- 230000014759 maintenance of location Effects 0.000 description 11
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 10
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- 150000001261 hydroxy acids Chemical class 0.000 description 10
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- 239000011324 bead Substances 0.000 description 9
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 9
- 230000000052 comparative effect Effects 0.000 description 9
- 229920003048 styrene butadiene rubber Polymers 0.000 description 9
- 229910052717 sulfur Inorganic materials 0.000 description 9
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- 239000003505 polymerization initiator Substances 0.000 description 8
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- 238000010438 heat treatment Methods 0.000 description 7
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 description 7
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- SDJHPPZKZZWAKF-UHFFFAOYSA-N 2,3-dimethylbuta-1,3-diene Chemical compound CC(=C)C(C)=C SDJHPPZKZZWAKF-UHFFFAOYSA-N 0.000 description 6
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 6
- 239000007864 aqueous solution Substances 0.000 description 6
- ZCCIPPOKBCJFDN-UHFFFAOYSA-N calcium nitrate Chemical compound [Ca+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ZCCIPPOKBCJFDN-UHFFFAOYSA-N 0.000 description 6
- 239000003431 cross linking reagent Substances 0.000 description 6
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- 238000004073 vulcanization Methods 0.000 description 6
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 5
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 5
- FBPFZTCFMRRESA-FSIIMWSLSA-N D-Glucitol Natural products OC[C@H](O)[C@H](O)[C@@H](O)[C@H](O)CO FBPFZTCFMRRESA-FSIIMWSLSA-N 0.000 description 5
- FBPFZTCFMRRESA-JGWLITMVSA-N D-glucitol Chemical compound OC[C@H](O)[C@@H](O)[C@H](O)[C@H](O)CO FBPFZTCFMRRESA-JGWLITMVSA-N 0.000 description 5
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- 150000005846 sugar alcohols Chemical class 0.000 description 5
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 4
- 239000002202 Polyethylene glycol Substances 0.000 description 4
- 229910052783 alkali metal Inorganic materials 0.000 description 4
- 230000003712 anti-aging effect Effects 0.000 description 4
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- 229920001971 elastomer Polymers 0.000 description 4
- ROBFUDYVXSDBQM-UHFFFAOYSA-N hydroxymalonic acid Chemical compound OC(=O)C(O)C(O)=O ROBFUDYVXSDBQM-UHFFFAOYSA-N 0.000 description 4
- 239000012535 impurity Substances 0.000 description 4
- HEBKCHPVOIAQTA-UHFFFAOYSA-N meso ribitol Natural products OCC(O)C(O)C(O)CO HEBKCHPVOIAQTA-UHFFFAOYSA-N 0.000 description 4
- 150000002772 monosaccharides Chemical group 0.000 description 4
- 229920001223 polyethylene glycol Polymers 0.000 description 4
- 239000005060 rubber Substances 0.000 description 4
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- PMJHHCWVYXUKFD-SNAWJCMRSA-N (E)-1,3-pentadiene Chemical compound C\C=C\C=C PMJHHCWVYXUKFD-SNAWJCMRSA-N 0.000 description 3
- BJEPYKJPYRNKOW-REOHCLBHSA-N (S)-malic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O BJEPYKJPYRNKOW-REOHCLBHSA-N 0.000 description 3
- RBNPOMFGQQGHHO-UHFFFAOYSA-N -2,3-Dihydroxypropanoic acid Natural products OCC(O)C(O)=O RBNPOMFGQQGHHO-UHFFFAOYSA-N 0.000 description 3
- GLDQAMYCGOIJDV-UHFFFAOYSA-N 2,3-dihydroxybenzoic acid Chemical compound OC(=O)C1=CC=CC(O)=C1O GLDQAMYCGOIJDV-UHFFFAOYSA-N 0.000 description 3
- IGLWCQMNTGCUBB-UHFFFAOYSA-N 3-methylidenepent-1-ene Chemical compound CCC(=C)C=C IGLWCQMNTGCUBB-UHFFFAOYSA-N 0.000 description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- RBNPOMFGQQGHHO-UWTATZPHSA-N D-glyceric acid Chemical compound OC[C@@H](O)C(O)=O RBNPOMFGQQGHHO-UWTATZPHSA-N 0.000 description 3
- FEWJPZIEWOKRBE-JCYAYHJZSA-N Dextrotartaric acid Chemical compound OC(=O)[C@H](O)[C@@H](O)C(O)=O FEWJPZIEWOKRBE-JCYAYHJZSA-N 0.000 description 3
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 3
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 3
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 3
- BJEPYKJPYRNKOW-UHFFFAOYSA-N alpha-hydroxysuccinic acid Natural products OC(=O)C(O)CC(O)=O BJEPYKJPYRNKOW-UHFFFAOYSA-N 0.000 description 3
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical class [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 3
- DIZPMCHEQGEION-UHFFFAOYSA-H aluminium sulfate (anhydrous) Chemical compound [Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O DIZPMCHEQGEION-UHFFFAOYSA-H 0.000 description 3
- 239000003242 anti bacterial agent Substances 0.000 description 3
- 150000001720 carbohydrates Chemical class 0.000 description 3
- YACLQRRMGMJLJV-UHFFFAOYSA-N chloroprene Chemical compound ClC(=C)C=C YACLQRRMGMJLJV-UHFFFAOYSA-N 0.000 description 3
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- 230000000694 effects Effects 0.000 description 3
- 238000010556 emulsion polymerization method Methods 0.000 description 3
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- 239000004310 lactic acid Substances 0.000 description 3
- 235000014655 lactic acid Nutrition 0.000 description 3
- 239000001630 malic acid Substances 0.000 description 3
- 235000011090 malic acid Nutrition 0.000 description 3
- KVBGVZZKJNLNJU-UHFFFAOYSA-N naphthalene-2-sulfonic acid Chemical compound C1=CC=CC2=CC(S(=O)(=O)O)=CC=C21 KVBGVZZKJNLNJU-UHFFFAOYSA-N 0.000 description 3
- 239000003002 pH adjusting agent Substances 0.000 description 3
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 3
- 150000002978 peroxides Chemical class 0.000 description 3
- PMJHHCWVYXUKFD-UHFFFAOYSA-N piperylene Natural products CC=CC=C PMJHHCWVYXUKFD-UHFFFAOYSA-N 0.000 description 3
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- 229910052708 sodium Inorganic materials 0.000 description 3
- 229940023144 sodium glycolate Drugs 0.000 description 3
- 159000000000 sodium salts Chemical class 0.000 description 3
- JEJAMASKDTUEBZ-UHFFFAOYSA-N tris(1,1,3-tribromo-2,2-dimethylpropyl) phosphate Chemical compound BrCC(C)(C)C(Br)(Br)OP(=O)(OC(Br)(Br)C(C)(C)CBr)OC(Br)(Br)C(C)(C)CBr JEJAMASKDTUEBZ-UHFFFAOYSA-N 0.000 description 3
- MYRTYDVEIRVNKP-UHFFFAOYSA-N 1,2-Divinylbenzene Chemical compound C=CC1=CC=CC=C1C=C MYRTYDVEIRVNKP-UHFFFAOYSA-N 0.000 description 2
- OWEGMIWEEQEYGQ-UHFFFAOYSA-N 100676-05-9 Natural products OC1C(O)C(O)C(CO)OC1OCC1C(O)C(O)C(O)C(OC2C(OC(O)C(O)C2O)CO)O1 OWEGMIWEEQEYGQ-UHFFFAOYSA-N 0.000 description 2
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- 229940061720 alpha hydroxy acid Drugs 0.000 description 2
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- LUEWUZLMQUOBSB-ZLBHSGTGSA-N alpha-maltotetraose Chemical compound O[C@@H]1[C@@H](O)[C@H](O)[C@@H](CO)O[C@@H]1O[C@@H]1[C@@H](CO)O[C@H](O[C@@H]2[C@H](O[C@H](O[C@@H]3[C@H](O[C@H](O)[C@H](O)[C@H]3O)CO)[C@H](O)[C@H]2O)CO)[C@H](O)[C@H]1O LUEWUZLMQUOBSB-ZLBHSGTGSA-N 0.000 description 2
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- 238000007665 sagging Methods 0.000 description 2
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- 125000003011 styrenyl group Chemical group [H]\C(*)=C(/[H])C1=C([H])C([H])=C([H])C([H])=C1[H] 0.000 description 2
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Classifications
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- C—CHEMISTRY; METALLURGY
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- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/10—Metal compounds
- C08K3/105—Compounds containing metals of Groups 1 to 3 or of Groups 11 to 13 of the Periodic Table
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L9/00—Compositions of homopolymers or copolymers of conjugated diene hydrocarbons
- C08L9/02—Copolymers with acrylonitrile
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C41/00—Shaping by coating a mould, core or other substrate, i.e. by depositing material and stripping-off the shaped article; Apparatus therefor
- B29C41/02—Shaping by coating a mould, core or other substrate, i.e. by depositing material and stripping-off the shaped article; Apparatus therefor for making articles of definite length, i.e. discrete articles
- B29C41/14—Dipping a core
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/01—Use of inorganic substances as compounding ingredients characterized by their specific function
- C08K3/011—Crosslinking or vulcanising agents, e.g. accelerators
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- C—CHEMISTRY; METALLURGY
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
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- B29K2995/00—Properties of moulding materials, reinforcements, fillers, preformed parts or moulds
- B29K2995/0037—Other properties
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- B29L—INDEXING SCHEME ASSOCIATED WITH SUBCLASS B29C, RELATING TO PARTICULAR ARTICLES
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Abstract
Description
前記金属化合物(C)の含有量が、前記カルボキシル基含有共役ジエン系ゴム(A)100重量部に対して、0.5〜4重量部であるラテックス組成物が提供される。
本発明において、前記水溶性の金属化合物(B)が、アルミン酸ナトリウムであることが好ましい。
本発明において、前記水溶性の金属化合物(B)の含有量が、前記カルボキシル基含有共役ジエン系ゴム(A)100重量部に対して、0.1〜1.5重量部であることが好ましい。
本発明において、前記非水溶性の金属化合物(C)が、二酸化チタンまたは二酸化ジルコニウムであることが好ましい。
本発明において、前記非水溶性の金属化合物(C)の含有量が、前記カルボキシル基含有共役ジエン系ゴム(A)100重量部に対して、1.5〜3重量部であることが好ましい。
さらに、本発明によれば、上記本発明のラテックス組成物をディップ成形する工程を備えるディップ成形体の製造方法が提供される。
前記金属化合物(C)の含有量が、前記カルボキシル基含有共役ジエン系ゴム(A)100重量部に対して、0.5〜4重量部であるラテックス組成物である。
本発明で用いるカルボキシル基含有共役ジエン系ゴム(A)のラテックスは、共役ジエン単量体およびエチレン性不飽和カルボン酸単量体を少なくとも含む単量体混合物を共重合して得られる共重合体のラテックスであり、カルボキシル基含有共役ジエン系ゴム(A)としては、カルボキシル基含有ニトリルゴム(a1)、カルボキシル基含有スチレン−ブタジエンゴム(a2)およびカルボキシル基含有共役ジエンゴム(a3)から選択される少なくとも1種が好ましい。
共役ジエン単量体およびエチレン性不飽和カルボン酸単量体と共重合可能なその他のエチレン性不飽和単量体としては、たとえば、上述したカルボキシル基含有ニトリルゴム(a1)のラテックスと同様のものが挙げられる。カルボキシル基含有共役ジエンゴム(a3)中における、その他のエチレン性不飽和単量体により形成されるその他の単量体単位の含有割合は、好ましくは10重量%以下であり、より好ましくは5重量%以下、さらに好ましくは3重量%以下である。
本発明のラテックス組成物は、上述したカルボキシル基含有共役ジエン系ゴム(A)のラテックスに加えて、水溶性の金属化合物(B)を含有する。本発明のラテックス組成物において、水溶性の金属化合物(B)は、架橋剤として作用する。
本発明のラテックス組成物は、上述したカルボキシル基含有共役ジエン系ゴム(A)のラテックスおよび水溶性の金属化合物(B)に加えて、周期律表第4族遷移金属を含む非水溶性の金属化合物(C)を含有するものであり、特に、本発明のラテックス組成物は、このような周期律表第4族遷移金属を含む非水溶性の金属化合物(C)を、ラテックス中に含まれるカルボキシル基含有共役ジエン系ゴム(A)100重量部に対して、0.5〜4重量部の割合にて含有するものである。
本発明の膜成形体は、本発明のラテックス組成物からなる膜状の成形体である。本発明の膜成形体の膜厚は、好ましくは0.03〜0.50mm、より好ましくは0.05〜0.40mm、特に好ましくは0.08〜0.30mmである。
凝固剤は、通常、水、アルコール、またはそれらの混合物の溶液として使用する。凝固剤濃度は、通常、5〜50重量%、好ましくは10〜35重量%である。
実施例および比較例にて作製したディップ成形層について、手袋型から脱型する前の段階において、温度125℃で5分間の条件にて乾燥(予備キュア)を行い、手袋型から脱型する前の段階において、万能型引張試験器にてディップ成形層と手袋型との間における180°剥離試験を実施することで、ディップ成形層と手袋型との間のピール強度を測定した。剥離速度は500mm/分とした。ピール強度が小さいほど、ディップ成形層と手袋型との密着力が低く、ビーディングが巻きやすく、ビーディング加工性に優れると判断できる。
実施例および比較例にて作製したディップ成形層について、手袋型から脱型する前の段階において、温度60℃で5分間の条件にて乾燥(予備キュア)を行い、手袋型から脱型する前の段階において、手袋型に密着しているディップ成形層の端の部分を巻き上げるビーディング巻き操作を、手作業にて実施し、以下の基準で評価を行った。
なし:5回以内の巻き上げ操作で所望のビーディング巻き操作が完了した。
有り:所望のビーディング巻き操作が完了するまでに、6回以上の巻き上げ操作が必要であったか、あるいは、ビーディング巻き操作が全くできなかった。
実施例および比較例において得られた、手袋型から脱型した後のディップ成形体としてのゴム手袋から、ASTM D−412に準じてダンベル(Die−C:ダンベル社製)を用いて、ダンベル形状の試験片を作製した。次いで、得られた試験片を、引張速度500mm/分で引っ張り、破断時の引張強度を測定した。引張強度は高いほど好ましい。
実施例および比較例において得られた、手袋型から脱型した後のディップ成形体としてのゴム手袋から、ASTM D−412に準じてダンベル(Die−C:ダンベル社製)を用いて、ダンベル形状の試験片を作製し、該試験片の両端に速度500mm/分にて引張応力をかけ、該試験片の標準区間20mmが2倍(100%)に伸張した時点で伸張を止めると共に引張応力M100(0)を測定し、また、そのまま6分間経過した後の引張応力M100(6)を測定した。そして、M100(0)に対するM100(6)の百分率(すなわち、M100(6)/M100(0)の百分率)を応力保持率とした。応力保持率は大きいほど、手袋の使用に伴うへたり(緩みやたるみ)が起きにくいため好ましい。
攪拌機付きの耐圧重合反応容器に、1,3−ブタジエン63部、アクリロニトリル34部、メタクリル酸3部、連鎖移動剤としてt−ドデシルメルカプタン0.25部、脱イオン水132部、ドデシルベンゼンスルホン酸ナトリウム3部、β−ナフタリンスルホン酸ホルマリン縮合物ナトリウム1部、過硫酸カリウム0.3部、およびエチレンジアミン四酢酸ナトリウム0.005部を仕込み、重合温度を37℃に保持して重合を開始した。そして、重合転化率が70%になった時点で、重合温度を43℃に昇温し、継続して重合転化率が95%になるまで反応させ、その後、重合停止剤としてジメチルジチオカルバミン酸ナトリウム0.1部を添加して重合反応を停止した。そして、得られた共重合体のラテックスから、未反応単量体を減圧にして留去した後、固形分濃度とpHとを調整することで、固形分濃度40重量%、pH8.0のカルボキシル基含有ニトリルゴム(a1−1)のラテックスを得た。
<ラテックス組成物の調製>
まず、二酸化チタン(TiO2)4.5部、β−ナフタリンスルホン酸ホルマリン縮合物ナトリウム塩0.3部、水酸化カリウム0.0015部、および水4.5部を混合することで、二酸化チタン分散液を調製した。そして、混合容器中において、製造例1で得られたカルボキシル基含有ニトリルゴム(a1−1)のラテックス250部(カルボキシル基含有ニトリルゴム(a1−1)換算で100部)に、アルミン酸ナトリウム0.5部、ソルビトール0.75部、グリコール酸ナトリウム0.75部を水溶させた混合水溶液を加えた。次いで、これに、カルボキシル基含有ニトリルゴム(a1−1)100部に対して、二酸化チタンの添加量が1.5部となるように、上記にて調製した二酸化チタン分散液を添加した。そして、脱イオン水を加えて、固形分濃度を30重量%に調整することで、ラテックス組成物を得た。
硝酸カルシウム30部、ノニオン性乳化剤であるポリエチレングリコールオクチルフェニルエーテル0.05部および水70部を混合することにより、凝固剤水溶液を調製した。次いで、この凝固剤水溶液に、予め70℃に加温したセラミック製手袋型(表面が粗面化されたセラミック製手袋型)を5秒間浸漬し、引上げた後、温度70℃、10分間の条件で乾燥して、凝固剤を手袋型に付着させた。そして、凝固剤を付着させた手袋型を、上記にて得られたラテックス組成物に10秒間浸漬し、引上げた後、50℃の温水に90秒間浸漬して、水溶性不純物を溶出させて、手袋型にディップ成形層を形成した。
次いで、ディップ成形層を形成した手袋型について、手袋型から脱型する前の段階において、温度125℃で5分間の条件にて乾燥(予備キュア)を行った後、手袋型から脱型する前の段階において、上記した方法にしたがって、ディップ成形層と手袋型との間のピール強度の測定を行った。また、これとは別に、上記にて得られた、ディップ成形層を形成した手袋型について、手袋型から脱型する前の段階において、温度60℃で5分間の条件にて乾燥(予備キュア)を行った後、手袋型から脱型する前の段階において、上記した方法にしたがって、ディップ成形層のビーディング巻き不良の評価を行った。結果を表1に示す。
温度125℃で5分間の条件にて乾燥(予備キュア)を行ったディップ成形層について、125℃で25分間の条件で加熱処理してディップ成形層を架橋させ、架橋したディップ成形層を手袋型から剥し、ディップ成形体(ゴム手袋)を得た。そして、得られたディップ成形体(ゴム手袋)について、上記方法にしたがって、引張強度および応力保持率の各測定を行った。結果を表1に示す。
二酸化チタンの配合量を、ラテックス中に含まれるカルボキシル基含有ニトリルゴム(a1−1)100部に対して、3.0部となる量とした以外は、実施例1と同様にして、ラテックス組成物を調製し、ディップ成形層およびディップ成形体としての評価を行った。結果を表1に示す。
二酸化ジルコニウム(ZrO2)4.5部、β−ナフタリンスルホン酸ホルマリン縮合物ナトリウム塩0.3部、水酸化カリウム0.0015部、および水4.5部を混合することで、二酸化ジルコニウム分散液を調製した。そして、二酸化チタン分散液の代わりに、二酸化ジルコニウム分散液を、二酸化ジルコニウムの配合量が、ラテックス中に含まれるカルボキシル基含有ニトリルゴム(a1−1)100部に対して、1.5部となる量にて配合した以外は、実施例1と同様にして、ラテックス組成物を調製し、ディップ成形層およびディップ成形体としての評価を行った。結果を表1に示す。
二酸化チタン分散液を添加しなかった以外は、実施例1と同様にして、ラテックス組成物を調製し、ディップ成形層およびディップ成形体としての評価を行った。結果を表1に示す。
二酸化チタンの配合量を、ラテックス中に含まれるカルボキシル基含有ニトリルゴム(a1−1)100部に対して、5.0部となる量とした以外は、実施例1と同様にして、ラテックス組成物を調製し、ディップ成形層およびディップ成形体としての評価を行った。結果を表1に示す。
アルミン酸ナトリウム、ソルビトール、およびグリコール酸ナトリウムの混合水溶液の水溶液を添加しなかった以外は、実施例1と同様にして、ラテックス組成物を調製し、ディップ成形層およびディップ成形体としての評価を行った。結果を表1に示す。
また、水溶性の金属化合物(B)を配合しなかった場合には、得られるディップ成形体(ディップ成形層)は、引張強度および応力保持率に劣る結果となった(比較例3)。
Claims (8)
- カルボキシル基含有共役ジエン系ゴム(A)のラテックスと、水溶性の金属化合物(B)と、周期律表第4族遷移金属を含む非水溶性の金属化合物(C)とを含有するラテックス組成物であって、
前記金属化合物(C)の含有量が、前記カルボキシル基含有共役ジエン系ゴム(A)100重量部に対して、0.5〜4重量部であるラテックス組成物。 - 前記金属化合物(B)が、アルミニウム化合物である請求項1に記載のラテックス組成物。
- 前記金属化合物(B)が、アルミン酸ナトリウムである請求項1または2に記載のラテックス組成物。
- 前記金属化合物(B)の含有量が、前記カルボキシル基含有共役ジエン系ゴム(A)100重量部に対して、0.1〜1.5重量部である請求項1〜3のいずれかに記載のラテックス組成物。
- 前記金属化合物(C)が、二酸化チタンまたは二酸化ジルコニウムである請求項1〜4のいずれかに記載のラテックス組成物。
- 前記金属化合物(C)の含有量が、前記カルボキシル基含有共役ジエン系ゴム(A)100重量部に対して、1.5〜3重量部である請求項1〜5のいずれかに記載のラテックス組成物。
- 請求項1〜6のいずれかに記載のラテックス組成物からなる膜成形体。
- 請求項1〜7のいずれかに記載のラテックス組成物をディップ成形する工程を備えるディップ成形体の製造方法。
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JP2002161171A (ja) * | 2000-11-28 | 2002-06-04 | Suzuki Latex Co Ltd | 非粘着性ラテックス製品 |
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WO2016072835A1 (en) * | 2014-11-06 | 2016-05-12 | Top Glove Sdn. Bhd. | Latex formulation for making elastomeric products |
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MY194391A (en) * | 2016-02-25 | 2022-11-30 | Zeon Corp | Latex composition and film molded body |
CN111629621B (zh) * | 2017-07-25 | 2023-08-01 | 皮肤防护有限公司 | 弹性体手套及其生产方法 |
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2019
- 2019-02-06 CN CN201980010255.7A patent/CN111655780A/zh active Pending
- 2019-02-06 JP JP2020500430A patent/JP7351289B2/ja active Active
- 2019-02-06 EP EP19754755.7A patent/EP3753981A4/en active Pending
- 2019-02-06 US US16/968,820 patent/US20210002453A1/en not_active Abandoned
- 2019-02-06 WO PCT/JP2019/004199 patent/WO2019159780A1/ja active Application Filing
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WO2000073367A1 (fr) * | 1999-05-28 | 2000-12-07 | Suzuki Latex Industry Co., Ltd. | Produits de latex non collants |
US6492446B1 (en) * | 1999-06-21 | 2002-12-10 | Takeda Chemical Industries, Ltd. | Alatex compound for dip molding and a dip-molded product |
WO2002036665A1 (fr) * | 2000-10-30 | 2002-05-10 | Zeon Corporation | Moulages au trempe, composition destinee au moulage au trempe et procede de production associe |
JP2002161171A (ja) * | 2000-11-28 | 2002-06-04 | Suzuki Latex Co Ltd | 非粘着性ラテックス製品 |
WO2008001764A1 (fr) * | 2006-06-30 | 2008-01-03 | Four Road Research Ltd. | Agent de réticulation contenant une composition de latex et corps moulé réticulé correspondant |
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JP2016525164A (ja) * | 2013-07-16 | 2016-08-22 | スキンプロテクト コーポレイション スンディリアン ブルハド | エラストマーフィルム形成組成物、およびエラストマーフィルムから作製された物品 |
WO2015146974A1 (ja) * | 2014-03-26 | 2015-10-01 | 日本ゼオン株式会社 | ディップ成形品およびディップ成形品の製造方法 |
WO2016072835A1 (en) * | 2014-11-06 | 2016-05-12 | Top Glove Sdn. Bhd. | Latex formulation for making elastomeric products |
WO2017116227A1 (en) * | 2015-12-30 | 2017-07-06 | Top Glove International Sdn. Bhd. | Nitrile rubber article |
WO2017127862A1 (en) * | 2016-01-29 | 2017-08-03 | Skinprotect Corporation Sdn Bhd | Elastomeric articles, compositions, and methods for their production |
WO2017146240A1 (ja) * | 2016-02-25 | 2017-08-31 | 日本ゼオン株式会社 | 手袋の製造方法 |
JP2018009272A (ja) * | 2016-07-12 | 2018-01-18 | トゥーリンク スンディリアン ブルハドTwolink Sdn Bhd | 加硫促進剤を含有せず充填剤担持量の多いニトリル手袋 |
Also Published As
Publication number | Publication date |
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CN111655780A (zh) | 2020-09-11 |
EP3753981A1 (en) | 2020-12-23 |
EP3753981A4 (en) | 2021-11-03 |
JP7351289B2 (ja) | 2023-09-27 |
WO2019159780A1 (ja) | 2019-08-22 |
US20210002453A1 (en) | 2021-01-07 |
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