KR102691622B1 - Coagulant for manufacturing article form, method for preparing the same and article formed using the same - Google Patents
Coagulant for manufacturing article form, method for preparing the same and article formed using the same Download PDFInfo
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- KR102691622B1 KR102691622B1 KR1020190121611A KR20190121611A KR102691622B1 KR 102691622 B1 KR102691622 B1 KR 102691622B1 KR 1020190121611 A KR1020190121611 A KR 1020190121611A KR 20190121611 A KR20190121611 A KR 20190121611A KR 102691622 B1 KR102691622 B1 KR 102691622B1
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- KR
- South Korea
- Prior art keywords
- weight
- parts
- dip
- azobis
- coagulant
- Prior art date
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- 238000004519 manufacturing process Methods 0.000 title claims abstract description 43
- 239000000701 coagulant Substances 0.000 title claims abstract description 29
- 238000000034 method Methods 0.000 title claims description 13
- 230000001112 coagulating effect Effects 0.000 claims abstract description 50
- 239000007788 liquid Substances 0.000 claims abstract description 36
- 239000003999 initiator Substances 0.000 claims abstract description 34
- LWMFAFLIWMPZSX-UHFFFAOYSA-N bis[2-(4,5-dihydro-1h-imidazol-2-yl)propan-2-yl]diazene Chemical compound N=1CCNC=1C(C)(C)N=NC(C)(C)C1=NCCN1 LWMFAFLIWMPZSX-UHFFFAOYSA-N 0.000 claims abstract description 14
- WVFLGSMUPMVNTQ-UHFFFAOYSA-N n-(2-hydroxyethyl)-2-[[1-(2-hydroxyethylamino)-2-methyl-1-oxopropan-2-yl]diazenyl]-2-methylpropanamide Chemical group OCCNC(=O)C(C)(C)N=NC(C)(C)C(=O)NCCO WVFLGSMUPMVNTQ-UHFFFAOYSA-N 0.000 claims abstract description 13
- 239000002904 solvent Substances 0.000 claims abstract description 12
- VFXXTYGQYWRHJP-UHFFFAOYSA-N 4,4'-azobis(4-cyanopentanoic acid) Chemical compound OC(=O)CCC(C)(C#N)N=NC(C)(CCC(O)=O)C#N VFXXTYGQYWRHJP-UHFFFAOYSA-N 0.000 claims abstract description 7
- BSXGCUHREZFSRY-UHFFFAOYSA-N 3-[[1-amino-2-[[1-amino-1-(2-carboxyethylimino)-2-methylpropan-2-yl]diazenyl]-2-methylpropylidene]amino]propanoic acid;tetrahydrate Chemical compound O.O.O.O.OC(=O)CCNC(=N)C(C)(C)N=NC(C)(C)C(=N)NCCC(O)=O BSXGCUHREZFSRY-UHFFFAOYSA-N 0.000 claims abstract description 6
- 239000004816 latex Substances 0.000 claims description 75
- 229920000126 latex Polymers 0.000 claims description 75
- 238000000465 moulding Methods 0.000 claims description 61
- 239000000203 mixture Substances 0.000 claims description 59
- 239000000178 monomer Substances 0.000 claims description 45
- 150000002825 nitriles Chemical class 0.000 claims description 39
- 229920001577 copolymer Polymers 0.000 claims description 38
- 238000004132 cross linking Methods 0.000 claims description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 13
- 239000002253 acid Substances 0.000 claims description 9
- 150000001993 dienes Chemical class 0.000 claims description 9
- 238000010438 heat treatment Methods 0.000 claims description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 4
- 229910002651 NO3 Inorganic materials 0.000 claims description 3
- 229910001507 metal halide Inorganic materials 0.000 claims description 3
- 150000005309 metal halides Chemical class 0.000 claims description 3
- NHNBFGGVMKEFGY-UHFFFAOYSA-N nitrate group Chemical group [N+](=O)([O-])[O-] NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 3
- NDAJNMAAXXIADY-UHFFFAOYSA-N 2-methylpropanimidamide Chemical compound CC(C)C(N)=N NDAJNMAAXXIADY-UHFFFAOYSA-N 0.000 claims description 2
- 150000001242 acetic acid derivatives Chemical class 0.000 claims description 2
- 150000002823 nitrates Chemical class 0.000 claims description 2
- 150000003467 sulfuric acid derivatives Chemical class 0.000 claims description 2
- QMEZUZOCLYUADC-UHFFFAOYSA-N hydrate;dihydrochloride Chemical compound O.Cl.Cl QMEZUZOCLYUADC-UHFFFAOYSA-N 0.000 claims 1
- LXEKPEMOWBOYRF-UHFFFAOYSA-N [2-[(1-azaniumyl-1-imino-2-methylpropan-2-yl)diazenyl]-2-methylpropanimidoyl]azanium;dichloride Chemical compound Cl.Cl.NC(=N)C(C)(C)N=NC(C)(C)C(N)=N LXEKPEMOWBOYRF-UHFFFAOYSA-N 0.000 abstract description 9
- 238000006116 polymerization reaction Methods 0.000 description 33
- -1 [2-methyl propion amidine] tetrahydrate Chemical compound 0.000 description 22
- 239000000243 solution Substances 0.000 description 16
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 12
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical group C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 12
- 230000000052 comparative effect Effects 0.000 description 12
- QYZFTMMPKCOTAN-UHFFFAOYSA-N n-[2-(2-hydroxyethylamino)ethyl]-2-[[1-[2-(2-hydroxyethylamino)ethylamino]-2-methyl-1-oxopropan-2-yl]diazenyl]-2-methylpropanamide Chemical compound OCCNCCNC(=O)C(C)(C)N=NC(C)(C)C(=O)NCCNCCO QYZFTMMPKCOTAN-UHFFFAOYSA-N 0.000 description 11
- 239000003995 emulsifying agent Substances 0.000 description 9
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 7
- 229920000642 polymer Polymers 0.000 description 7
- 229910052717 sulfur Inorganic materials 0.000 description 7
- 239000011593 sulfur Substances 0.000 description 7
- 238000004073 vulcanization Methods 0.000 description 7
- ZCCIPPOKBCJFDN-UHFFFAOYSA-N calcium nitrate Chemical compound [Ca+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ZCCIPPOKBCJFDN-UHFFFAOYSA-N 0.000 description 6
- 239000003795 chemical substances by application Substances 0.000 description 6
- WTNTZFRNCHEDOS-UHFFFAOYSA-N n-(2-hydroxyethyl)-2-methylpropanamide Chemical compound CC(C)C(=O)NCCO WTNTZFRNCHEDOS-UHFFFAOYSA-N 0.000 description 6
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 5
- 239000003505 polymerization initiator Substances 0.000 description 5
- 150000003254 radicals Chemical class 0.000 description 5
- 239000007787 solid Substances 0.000 description 5
- YAJYJWXEWKRTPO-UHFFFAOYSA-N 2,3,3,4,4,5-hexamethylhexane-2-thiol Chemical compound CC(C)C(C)(C)C(C)(C)C(C)(C)S YAJYJWXEWKRTPO-UHFFFAOYSA-N 0.000 description 4
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 4
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 description 4
- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Chemical compound CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 description 4
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 4
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 4
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 4
- 239000012190 activator Substances 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- 239000003431 cross linking reagent Substances 0.000 description 4
- 238000007654 immersion Methods 0.000 description 4
- 239000002245 particle Substances 0.000 description 4
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 4
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 3
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- 244000043261 Hevea brasiliensis Species 0.000 description 3
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 3
- 239000000654 additive Substances 0.000 description 3
- 235000011114 ammonium hydroxide Nutrition 0.000 description 3
- 229920001971 elastomer Polymers 0.000 description 3
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 3
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 3
- 229920003052 natural elastomer Polymers 0.000 description 3
- 229920001194 natural rubber Polymers 0.000 description 3
- 239000003002 pH adjusting agent Substances 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- SDJHPPZKZZWAKF-UHFFFAOYSA-N 2,3-dimethylbuta-1,3-diene Chemical compound CC(=C)C(C)=C SDJHPPZKZZWAKF-UHFFFAOYSA-N 0.000 description 2
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 description 2
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 2
- JAHNSTQSQJOJLO-UHFFFAOYSA-N 2-(3-fluorophenyl)-1h-imidazole Chemical compound FC1=CC=CC(C=2NC=CN=2)=C1 JAHNSTQSQJOJLO-UHFFFAOYSA-N 0.000 description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 2
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical class S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 2
- SNRUBQQJIBEYMU-UHFFFAOYSA-N Dodecane Natural products CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 description 2
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- AVXURJPOCDRRFD-UHFFFAOYSA-N Hydroxylamine Chemical compound ON AVXURJPOCDRRFD-UHFFFAOYSA-N 0.000 description 2
- 206010020751 Hypersensitivity Diseases 0.000 description 2
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 description 2
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 2
- GYCMBHHDWRMZGG-UHFFFAOYSA-N Methylacrylonitrile Chemical compound CC(=C)C#N GYCMBHHDWRMZGG-UHFFFAOYSA-N 0.000 description 2
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- 230000007815 allergy Effects 0.000 description 2
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 description 2
- 125000000129 anionic group Chemical group 0.000 description 2
- 239000003963 antioxidant agent Substances 0.000 description 2
- IWOUKMZUPDVPGQ-UHFFFAOYSA-N barium nitrate Chemical compound [Ba+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O IWOUKMZUPDVPGQ-UHFFFAOYSA-N 0.000 description 2
- 229940077388 benzenesulfonate Drugs 0.000 description 2
- LBSPZZSGTIBOFG-UHFFFAOYSA-N bis[2-(4,5-dihydro-1h-imidazol-2-yl)propan-2-yl]diazene;dihydrochloride Chemical compound Cl.Cl.N=1CCNC=1C(C)(C)N=NC(C)(C)C1=NCCN1 LBSPZZSGTIBOFG-UHFFFAOYSA-N 0.000 description 2
- OSGAYBCDTDRGGQ-UHFFFAOYSA-L calcium sulfate Chemical compound [Ca+2].[O-]S([O-])(=O)=O OSGAYBCDTDRGGQ-UHFFFAOYSA-L 0.000 description 2
- 230000003247 decreasing effect Effects 0.000 description 2
- LSXWFXONGKSEMY-UHFFFAOYSA-N di-tert-butyl peroxide Chemical compound CC(C)(C)OOC(C)(C)C LSXWFXONGKSEMY-UHFFFAOYSA-N 0.000 description 2
- ZQMIGQNCOMNODD-UHFFFAOYSA-N diacetyl peroxide Chemical compound CC(=O)OOC(C)=O ZQMIGQNCOMNODD-UHFFFAOYSA-N 0.000 description 2
- AUZONCFQVSMFAP-UHFFFAOYSA-N disulfiram Chemical compound CCN(CC)C(=S)SSC(=S)N(CC)CC AUZONCFQVSMFAP-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000007720 emulsion polymerization reaction Methods 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- 239000001530 fumaric acid Substances 0.000 description 2
- 230000009477 glass transition Effects 0.000 description 2
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 2
- 239000011976 maleic acid Substances 0.000 description 2
- LVHBHZANLOWSRM-UHFFFAOYSA-N methylenebutanedioic acid Natural products OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 description 2
- 150000002978 peroxides Chemical class 0.000 description 2
- 230000000704 physical effect Effects 0.000 description 2
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 description 2
- 239000001294 propane Substances 0.000 description 2
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 2
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 description 2
- 150000004685 tetrahydrates Chemical class 0.000 description 2
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 description 2
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Chemical compound [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 description 2
- PRBHEGAFLDMLAL-GQCTYLIASA-N (4e)-hexa-1,4-diene Chemical compound C\C=C\CC=C PRBHEGAFLDMLAL-GQCTYLIASA-N 0.000 description 1
- PMJHHCWVYXUKFD-SNAWJCMRSA-N (E)-1,3-pentadiene Chemical compound C\C=C\C=C PMJHHCWVYXUKFD-SNAWJCMRSA-N 0.000 description 1
- UTOVMEACOLCUCK-SNAWJCMRSA-N (e)-4-butoxy-4-oxobut-2-enoic acid Chemical compound CCCCOC(=O)\C=C\C(O)=O UTOVMEACOLCUCK-SNAWJCMRSA-N 0.000 description 1
- ZKXXLNRGNAUYHP-IHWYPQMZSA-N (z)-4-(2-hydroxypropoxy)-4-oxobut-2-enoic acid Chemical compound CC(O)COC(=O)\C=C/C(O)=O ZKXXLNRGNAUYHP-IHWYPQMZSA-N 0.000 description 1
- MJYFYGVCLHNRKB-UHFFFAOYSA-N 1,1,2-trifluoroethyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OC(F)(F)CF MJYFYGVCLHNRKB-UHFFFAOYSA-N 0.000 description 1
- AYMDJPGTQFHDSA-UHFFFAOYSA-N 1-(2-ethenoxyethoxy)-2-ethoxyethane Chemical compound CCOCCOCCOC=C AYMDJPGTQFHDSA-UHFFFAOYSA-N 0.000 description 1
- XSZYESUNPWGWFQ-UHFFFAOYSA-N 1-(2-hydroperoxypropan-2-yl)-4-methylcyclohexane Chemical compound CC1CCC(C(C)(C)OO)CC1 XSZYESUNPWGWFQ-UHFFFAOYSA-N 0.000 description 1
- FPFVPEGEWVRCGK-UHFFFAOYSA-N 1-ethenoxy-2-fluoroethane Chemical compound FCCOC=C FPFVPEGEWVRCGK-UHFFFAOYSA-N 0.000 description 1
- IGGDKDTUCAWDAN-UHFFFAOYSA-N 1-vinylnaphthalene Chemical compound C1=CC=C2C(C=C)=CC=CC2=C1 IGGDKDTUCAWDAN-UHFFFAOYSA-N 0.000 description 1
- HECLRDQVFMWTQS-RGOKHQFPSA-N 1755-01-7 Chemical compound C1[C@H]2[C@@H]3CC=C[C@@H]3[C@@H]1C=C2 HECLRDQVFMWTQS-RGOKHQFPSA-N 0.000 description 1
- XVXNNFJCCZDKGU-UHFFFAOYSA-N 2,3-dibutylphenol;methanedithioic acid Chemical compound SC=S.CCCCC1=CC=CC(O)=C1CCCC XVXNNFJCCZDKGU-UHFFFAOYSA-N 0.000 description 1
- KAYQJQYEJMZJEF-UHFFFAOYSA-N 2,3-diethylphenol;methanedithioic acid Chemical compound SC=S.CCC1=CC=CC(O)=C1CC KAYQJQYEJMZJEF-UHFFFAOYSA-N 0.000 description 1
- GSFSVEDCYBDIGW-UHFFFAOYSA-N 2-(1,3-benzothiazol-2-yl)-6-chlorophenol Chemical compound OC1=C(Cl)C=CC=C1C1=NC2=CC=CC=C2S1 GSFSVEDCYBDIGW-UHFFFAOYSA-N 0.000 description 1
- LCPVQAHEFVXVKT-UHFFFAOYSA-N 2-(2,4-difluorophenoxy)pyridin-3-amine Chemical compound NC1=CC=CN=C1OC1=CC=C(F)C=C1F LCPVQAHEFVXVKT-UHFFFAOYSA-N 0.000 description 1
- NICLKHGIKDZZGV-UHFFFAOYSA-N 2-cyanopentanoic acid Chemical compound CCCC(C#N)C(O)=O NICLKHGIKDZZGV-UHFFFAOYSA-N 0.000 description 1
- HWPFQLJNZQAOAF-UHFFFAOYSA-N 2-ethylbut-2-enedinitrile Chemical compound CCC(C#N)=CC#N HWPFQLJNZQAOAF-UHFFFAOYSA-N 0.000 description 1
- TVWBTVJBDFTVOW-UHFFFAOYSA-N 2-methyl-1-(2-methylpropylperoxy)propane Chemical compound CC(C)COOCC(C)C TVWBTVJBDFTVOW-UHFFFAOYSA-N 0.000 description 1
- AGBXYHCHUYARJY-UHFFFAOYSA-N 2-phenylethenesulfonic acid Chemical compound OS(=O)(=O)C=CC1=CC=CC=C1 AGBXYHCHUYARJY-UHFFFAOYSA-N 0.000 description 1
- BIISIZOQPWZPPS-UHFFFAOYSA-N 2-tert-butylperoxypropan-2-ylbenzene Chemical compound CC(C)(C)OOC(C)(C)C1=CC=CC=C1 BIISIZOQPWZPPS-UHFFFAOYSA-N 0.000 description 1
- KGIGUEBEKRSTEW-UHFFFAOYSA-N 2-vinylpyridine Chemical compound C=CC1=CC=CC=N1 KGIGUEBEKRSTEW-UHFFFAOYSA-N 0.000 description 1
- FRIBMENBGGCKPD-UHFFFAOYSA-N 3-(2,3-dimethoxyphenyl)prop-2-enal Chemical compound COC1=CC=CC(C=CC=O)=C1OC FRIBMENBGGCKPD-UHFFFAOYSA-N 0.000 description 1
- MNULHGQAROOBFB-UHFFFAOYSA-N 3-[(1-amino-2-methylpropylidene)amino]propanoic acid Chemical compound CC(C)C(N)=NCCC(O)=O MNULHGQAROOBFB-UHFFFAOYSA-N 0.000 description 1
- AYKYXWQEBUNJCN-UHFFFAOYSA-N 3-methylfuran-2,5-dione Chemical compound CC1=CC(=O)OC1=O AYKYXWQEBUNJCN-UHFFFAOYSA-N 0.000 description 1
- INYHZQLKOKTDAI-UHFFFAOYSA-N 5-ethenylbicyclo[2.2.1]hept-2-ene Chemical compound C1C2C(C=C)CC1C=C2 INYHZQLKOKTDAI-UHFFFAOYSA-N 0.000 description 1
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 1
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 description 1
- KXDHJXZQYSOELW-UHFFFAOYSA-M Carbamate Chemical compound NC([O-])=O KXDHJXZQYSOELW-UHFFFAOYSA-M 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- RZXLPPRPEOUENN-UHFFFAOYSA-N Chlorfenson Chemical compound C1=CC(Cl)=CC=C1OS(=O)(=O)C1=CC=C(Cl)C=C1 RZXLPPRPEOUENN-UHFFFAOYSA-N 0.000 description 1
- 201000004624 Dermatitis Diseases 0.000 description 1
- IEPRKVQEAMIZSS-UHFFFAOYSA-N Di-Et ester-Fumaric acid Natural products CCOC(=O)C=CC(=O)OCC IEPRKVQEAMIZSS-UHFFFAOYSA-N 0.000 description 1
- IEPRKVQEAMIZSS-WAYWQWQTSA-N Diethyl maleate Chemical compound CCOC(=O)\C=C/C(=O)OCC IEPRKVQEAMIZSS-WAYWQWQTSA-N 0.000 description 1
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 description 1
- 229940123973 Oxygen scavenger Drugs 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- HRJRJZNQSHFJOK-UHFFFAOYSA-M [Na+].[O-]C(=O)N1CCC=C1 Chemical compound [Na+].[O-]C(=O)N1CCC=C1 HRJRJZNQSHFJOK-UHFFFAOYSA-M 0.000 description 1
- QILXPCHTWXAUHE-UHFFFAOYSA-N [Na].NCCN Chemical compound [Na].NCCN QILXPCHTWXAUHE-UHFFFAOYSA-N 0.000 description 1
- KYIKRXIYLAGAKQ-UHFFFAOYSA-N abcn Chemical compound C1CCCCC1(C#N)N=NC1(C#N)CCCCC1 KYIKRXIYLAGAKQ-UHFFFAOYSA-N 0.000 description 1
- ZOIORXHNWRGPMV-UHFFFAOYSA-N acetic acid;zinc Chemical compound [Zn].CC(O)=O.CC(O)=O ZOIORXHNWRGPMV-UHFFFAOYSA-N 0.000 description 1
- 125000004018 acid anhydride group Chemical group 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 229910001413 alkali metal ion Inorganic materials 0.000 description 1
- 150000004996 alkyl benzenes Chemical class 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 239000013566 allergen Substances 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-N ammonia Natural products N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 1
- 239000000908 ammonium hydroxide Substances 0.000 description 1
- 229910001870 ammonium persulfate Inorganic materials 0.000 description 1
- 150000003863 ammonium salts Chemical class 0.000 description 1
- 150000008064 anhydrides Chemical class 0.000 description 1
- 230000003712 anti-aging effect Effects 0.000 description 1
- 239000002518 antifoaming agent Substances 0.000 description 1
- 230000003078 antioxidant effect Effects 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- ITHZDDVSAWDQPZ-UHFFFAOYSA-L barium acetate Chemical compound [Ba+2].CC([O-])=O.CC([O-])=O ITHZDDVSAWDQPZ-UHFFFAOYSA-L 0.000 description 1
- WDIHJSXYQDMJHN-UHFFFAOYSA-L barium chloride Chemical compound [Cl-].[Cl-].[Ba+2] WDIHJSXYQDMJHN-UHFFFAOYSA-L 0.000 description 1
- 229910001626 barium chloride Inorganic materials 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- SRSXLGNVWSONIS-UHFFFAOYSA-M benzenesulfonate Chemical compound [O-]S(=O)(=O)C1=CC=CC=C1 SRSXLGNVWSONIS-UHFFFAOYSA-M 0.000 description 1
- 235000019400 benzoyl peroxide Nutrition 0.000 description 1
- WQZGKKKJIJFFOK-VFUOTHLCSA-N beta-D-glucose Chemical compound OC[C@H]1O[C@@H](O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-VFUOTHLCSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- NTXGQCSETZTARF-UHFFFAOYSA-N buta-1,3-diene;prop-2-enenitrile Chemical compound C=CC=C.C=CC#N NTXGQCSETZTARF-UHFFFAOYSA-N 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- UTOVMEACOLCUCK-PLNGDYQASA-N butyl maleate Chemical compound CCCCOC(=O)\C=C/C(O)=O UTOVMEACOLCUCK-PLNGDYQASA-N 0.000 description 1
- VSGNNIFQASZAOI-UHFFFAOYSA-L calcium acetate Chemical compound [Ca+2].CC([O-])=O.CC([O-])=O VSGNNIFQASZAOI-UHFFFAOYSA-L 0.000 description 1
- 239000001639 calcium acetate Substances 0.000 description 1
- 235000011092 calcium acetate Nutrition 0.000 description 1
- 229960005147 calcium acetate Drugs 0.000 description 1
- 239000001110 calcium chloride Substances 0.000 description 1
- 229910001628 calcium chloride Inorganic materials 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- SKOLWUPSYHWYAM-UHFFFAOYSA-N carbonodithioic O,S-acid Chemical compound SC(S)=O SKOLWUPSYHWYAM-UHFFFAOYSA-N 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 150000001733 carboxylic acid esters Chemical class 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 239000002738 chelating agent Substances 0.000 description 1
- 230000015271 coagulation Effects 0.000 description 1
- 238000005345 coagulation Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 238000004332 deodorization Methods 0.000 description 1
- 230000001877 deodorizing effect Effects 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 239000008121 dextrose Substances 0.000 description 1
- FJBFPHVGVWTDIP-UHFFFAOYSA-N dibromomethane Chemical compound BrCBr FJBFPHVGVWTDIP-UHFFFAOYSA-N 0.000 description 1
- JBSLOWBPDRZSMB-BQYQJAHWSA-N dibutyl (e)-but-2-enedioate Chemical compound CCCCOC(=O)\C=C\C(=O)OCCCC JBSLOWBPDRZSMB-BQYQJAHWSA-N 0.000 description 1
- JBSLOWBPDRZSMB-FPLPWBNLSA-N dibutyl (z)-but-2-enedioate Chemical compound CCCCOC(=O)\C=C/C(=O)OCCCC JBSLOWBPDRZSMB-FPLPWBNLSA-N 0.000 description 1
- 235000014113 dietary fatty acids Nutrition 0.000 description 1
- 238000000113 differential scanning calorimetry Methods 0.000 description 1
- HRKQOINLCJTGBK-UHFFFAOYSA-L dioxidosulfate(2-) Chemical compound [O-]S[O-] HRKQOINLCJTGBK-UHFFFAOYSA-L 0.000 description 1
- 229940096818 dipentamethylenethiuram disulfide Drugs 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- WNAHIZMDSQCWRP-UHFFFAOYSA-N dodecane-1-thiol Chemical compound CCCCCCCCCCCCS WNAHIZMDSQCWRP-UHFFFAOYSA-N 0.000 description 1
- GVGUFUZHNYFZLC-UHFFFAOYSA-N dodecyl benzenesulfonate;sodium Chemical compound [Na].CCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 GVGUFUZHNYFZLC-UHFFFAOYSA-N 0.000 description 1
- 125000003438 dodecyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 125000005448 ethoxyethyl group Chemical group [H]C([H])([H])C([H])([H])OC([H])([H])C([H])([H])* 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000000194 fatty acid Substances 0.000 description 1
- 229930195729 fatty acid Natural products 0.000 description 1
- 150000004665 fatty acids Chemical class 0.000 description 1
- 239000011790 ferrous sulphate Substances 0.000 description 1
- 235000003891 ferrous sulphate Nutrition 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 239000010419 fine particle Substances 0.000 description 1
- 239000006260 foam Substances 0.000 description 1
- ISXSFOPKZQZDAO-UHFFFAOYSA-N formaldehyde;sodium Chemical compound [Na].O=C ISXSFOPKZQZDAO-UHFFFAOYSA-N 0.000 description 1
- 125000003055 glycidyl group Chemical group C(C1CO1)* 0.000 description 1
- 150000008282 halocarbons Chemical class 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 125000000687 hydroquinonyl group Chemical class C1(O)=C(C=C(O)C=C1)* 0.000 description 1
- NXPHCVPFHOVZBC-UHFFFAOYSA-N hydroxylamine;sulfuric acid Chemical compound ON.OS(O)(=O)=O NXPHCVPFHOVZBC-UHFFFAOYSA-N 0.000 description 1
- 238000007689 inspection Methods 0.000 description 1
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 description 1
- 229910000359 iron(II) sulfate Inorganic materials 0.000 description 1
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 229910001629 magnesium chloride Inorganic materials 0.000 description 1
- 229910052943 magnesium sulfate Inorganic materials 0.000 description 1
- 235000019341 magnesium sulphate Nutrition 0.000 description 1
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 1
- 125000004184 methoxymethyl group Chemical group [H]C([H])([H])OC([H])([H])* 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 229910017464 nitrogen compound Inorganic materials 0.000 description 1
- 150000002830 nitrogen compounds Chemical class 0.000 description 1
- ZWWQICJTBOCQLA-UHFFFAOYSA-N o-propan-2-yl (propan-2-yloxycarbothioyldisulfanyl)methanethioate Chemical compound CC(C)OC(=S)SSC(=S)OC(C)C ZWWQICJTBOCQLA-UHFFFAOYSA-N 0.000 description 1
- KZCOBXFFBQJQHH-UHFFFAOYSA-N octane-1-thiol Chemical compound CCCCCCCCS KZCOBXFFBQJQHH-UHFFFAOYSA-N 0.000 description 1
- SRSFOMHQIATOFV-UHFFFAOYSA-N octanoyl octaneperoxoate Chemical compound CCCCCCCC(=O)OOC(=O)CCCCCCC SRSFOMHQIATOFV-UHFFFAOYSA-N 0.000 description 1
- 239000012188 paraffin wax Substances 0.000 description 1
- 125000001147 pentyl group Chemical group C(CCCC)* 0.000 description 1
- JRKICGRDRMAZLK-UHFFFAOYSA-L peroxydisulfate Chemical compound [O-]S(=O)(=O)OOS([O-])(=O)=O JRKICGRDRMAZLK-UHFFFAOYSA-L 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- KNBRWWCHBRQLNY-UHFFFAOYSA-N piperidine-1-carbothioylsulfanyl piperidine-1-carbodithioate Chemical compound C1CCCCN1C(=S)SSC(=S)N1CCCCC1 KNBRWWCHBRQLNY-UHFFFAOYSA-N 0.000 description 1
- PMJHHCWVYXUKFD-UHFFFAOYSA-N piperylene Natural products CC=CC=C PMJHHCWVYXUKFD-UHFFFAOYSA-N 0.000 description 1
- 239000004800 polyvinyl chloride Substances 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- FZYCEURIEDTWNS-UHFFFAOYSA-N prop-1-en-2-ylbenzene Chemical compound CC(=C)C1=CC=CC=C1.CC(=C)C1=CC=CC=C1 FZYCEURIEDTWNS-UHFFFAOYSA-N 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 229940080264 sodium dodecylbenzenesulfonate Drugs 0.000 description 1
- CHQMHPLRPQMAMX-UHFFFAOYSA-L sodium persulfate Substances [Na+].[Na+].[O-]S(=O)(=O)OOS([O-])(=O)=O CHQMHPLRPQMAMX-UHFFFAOYSA-L 0.000 description 1
- 235000010265 sodium sulphite Nutrition 0.000 description 1
- 241000894007 species Species 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 125000000542 sulfonic acid group Chemical group 0.000 description 1
- 150000003460 sulfonic acids Chemical class 0.000 description 1
- 210000004243 sweat Anatomy 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- KUAZQDVKQLNFPE-UHFFFAOYSA-N thiram Chemical class CN(C)C(=S)SSC(=S)N(C)C KUAZQDVKQLNFPE-UHFFFAOYSA-N 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- 239000000080 wetting agent Substances 0.000 description 1
- 239000004246 zinc acetate Substances 0.000 description 1
- 239000011592 zinc chloride Substances 0.000 description 1
- 235000005074 zinc chloride Nutrition 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
- 239000004711 α-olefin Substances 0.000 description 1
Classifications
-
- 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
- C08F6/00—Post-polymerisation treatments
- C08F6/14—Treatment of polymer emulsions
- C08F6/22—Coagulation
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/02—Direct processing of dispersions, e.g. latex, to articles
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Dispersion Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Materials Engineering (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Moulding By Coating Moulds (AREA)
Abstract
본 발명은 딥 성형품 제조용 응고액에 관한 것으로, 응고제, 용매 및 수용성 개시제를 포함하고, 상기 수용성 개시제는 2,2'-아조비스[2-메틸-N-(2-하이드록시에틸)프로피온 아미드], 4,4'-아조비스(4-시아노발레릭 산), 2,2'-아조비스[2-(2-이미다졸린-2-일)프로판], 2,2'-아조비스[2-(2-이미다졸린-2-일)프로판]다이 하이드로 클로라이드, 2,2'-아조비스(2-메틸 프로피온 아미딘)다이 하이드로 클로라이드 및 2,2'-아조비스[N-(2-카복시에틸)-2-메틸 프로피온 아미딘]테트라 하이드레이트로 이루어진 군에서 선택된 1종 이상을 포함하며, 상기 수용성 개시제의 함량은 딥 성형품 제조용 응고액 전체 100 중량부에 대하여 1.5 중량부 내지 4.5 중량부인 딥 성형품 제조용 응고액을 제공한다.The present invention relates to a coagulating solution for producing dip molded products, comprising a coagulant, a solvent, and a water-soluble initiator, wherein the water-soluble initiator is 2,2'-azobis[2-methyl-N-(2-hydroxyethyl)propion amide] , 4,4'-azobis(4-cyanovaleric acid), 2,2'-azobis[2-(2-imidazolin-2-yl)propane], 2,2'-azobis[ 2-(2-imidazolin-2-yl)propane]dihydrochloride, 2,2'-azobis(2-methylpropionamidine)dihydrochloride and 2,2'-azobis[N-(2 -carboxyethyl)-2-methyl propion amidine]tetrahydrate, and the content of the water-soluble initiator is 1.5 parts by weight to 4.5 parts by weight based on 100 parts by weight of the total coagulant for producing dip molded products. Provides a coagulating liquid for manufacturing dip molded products.
Description
본 발명은 딥 성형품 제조용 응고액에 관한 것으로 보다 상세하게는 상기 딥 성형품 제조용 응고액, 이의 제조방법 및 이를 이용하여 성형된 성형품에 관한 것이다.The present invention relates to a coagulating liquid for manufacturing dip molded products, and more specifically, to a coagulating liquid for manufacturing dip molded products, a manufacturing method thereof, and a molded product using the same.
전세계적으로 의료 검사, 공항 및 소포의 검사를 위하여 사용되는 장갑의 수요가 증가하는 상황에서 이러한 용도로 사용되던 주요 원료인 폴리염화 비닐(polyvinyl chloride, PVC)과 천연 고무에 문제점이 야기되면서 새로운 원료인 아크릴로니트릴-부타디엔계 라텍스의 시장이 큰 폭으로 성장하고 있다.As the demand for gloves used for medical examination, airport and parcel inspection increases worldwide, problems arise with polyvinyl chloride (PVC) and natural rubber, the main raw materials used for these purposes, and new raw materials are needed. The market for acrylonitrile-butadiene-based latex is growing significantly.
장갑 시장의 경우 천연 고무 장갑이 피부 알러지 발생 인자를 포함하고 있는 것으로 알려지면서 장갑 시장은 점차 천연고무 장갑에서 라텍스를 딥 성형하여 만든 황 가교 장갑으로 수요가 증가되고 이에 따른 시장의 변화가 나타났다. 하지만 현재 라텍스를 딥 성형하여 만든 황 가교 장갑의 경우에도 황 가교 과정 중에 사용되는 가황 촉진제(thiuram계, carbamate계)가 알러지 유발 물질로 알려짐으로써 이를 포함하지 않는 비황 및 비가황 촉진제 장갑에 대한 관심과 수요가 증가하고 있다. In the glove market, as natural rubber gloves are known to contain skin allergy-causing factors, the demand for gloves has gradually increased from natural rubber gloves to sulfur cross-linked gloves made by dip molding latex, leading to changes in the market. However, even in the case of sulfur cross-linked gloves made by dip molding latex, the vulcanization accelerators (thiuram series, carbamate series) used during the sulfur cross-linking process are known to be allergens, so there is interest in non-sulfur and non-vulcanization accelerator gloves that do not contain them. Demand is increasing.
따라서, 상기 가황제와 가황 촉진제에 의한 부작용을 방지하기 위해 이를 이용하지 않고 고무 장갑을 만들되 라텍스의 안정성을 저하시키지 않고, 딥 성형품 제조 시 물성이 저하시키지 않는 방법에 대한 연구가 요구되고 있다.Therefore, in order to prevent the side effects caused by the vulcanizing agent and vulcanization accelerator, research is required on a method of making rubber gloves without using them, but without reducing the stability of the latex and the physical properties when manufacturing dip molded products.
본 발명에서 해결하고자 하는 과제는, 상기 발명의 배경이 되는 기술에서 언급한 문제들을 해결하기 위하여, 가황제 및 가황 촉진제를 사용하지 않고도 딥 성형품의 내구성을 향상시키는 것이다.The problem to be solved by the present invention is to improve the durability of dip molded products without using vulcanizing agents and vulcanization accelerators in order to solve the problems mentioned in the background technology of the above invention.
즉, 본 발명은 딥 성형품 제조용 응고액에 수용성 개시제를 혼합함으로써, 딥 성형용 라텍스 조성물 내 이중결합의 가교도를 높여 이를 이용하여 제조된 딥 성형품의 내구성을 향상시키는 것을 목적으로 한다.That is, the purpose of the present invention is to increase the degree of crosslinking of double bonds in the latex composition for dip molding by mixing a water-soluble initiator with the coagulating liquid for producing dip molded products, thereby improving the durability of dip molded products manufactured using the same.
상기의 과제를 해결하기 위한 본 발명의 일 실시예에 따르면, 본 발명은 응고제, 용매 및 수용성 개시제를 포함하고, 상기 수용성 개시제는 2,2'-아조비스[2-메틸-N-(2-하이드록시에틸)프로피온 아미드], 4,4'-아조비스(4-시아노발레릭 산), 2,2'-아조비스[2-(2-이미다졸린-2-일)프로판], 2,2'-아조비스[2-(2-이미다졸린-2-일)프로판]다이 하이드로 클로라이드, 2,2'-아조비스(2-메틸 프로피온 아미딘)다이 하이드로 클로라이드 및 2,2'-아조비스[N-(2-카복시에틸)-2-메틸 프로피온 아미딘]테트라 하이드레이트로 이루어진 군에서 선택된 1종 이상을 포함하며, 상기 수용성 개시제의 함량은 딥 성형품 제조용 응고액 전체 100 중량부에 대하여 1.5 중량부 내지 4.5 중량부인 딥 성형품 제조용 응고액을 제공한다.According to one embodiment of the present invention for solving the above problems, the present invention includes a coagulant, a solvent, and a water-soluble initiator, and the water-soluble initiator is 2,2'-azobis[2-methyl-N-(2- hydroxyethyl)propion amide], 4,4'-azobis(4-cyanovaleric acid), 2,2'-azobis[2-(2-imidazolin-2-yl)propane], 2 ,2'-azobis[2-(2-imidazolin-2-yl)propane]dihydrochloride, 2,2'-azobis(2-methyl propion amidine)dihydrochloride and 2,2'- It contains at least one selected from the group consisting of azobis[N-(2-carboxyethyl)-2-methyl propion amidine]tetrahydrate, and the content of the water-soluble initiator is based on 100 parts by weight of the total coagulant for manufacturing dip molded products. A coagulating solution for manufacturing dip molded products of 1.5 to 4.5 parts by weight is provided.
또한, 본 발명은 딥 성형틀에 상기 딥 성형품 제조용 응고액을 부착시키는 단계(S10); 상기 응고액이 부착된 딥 성형틀에 딥 성형용 라텍스 조성물을 침지하여 딥 성형용 라텍스 조성물 유래층을 형성시키는 단계(S20); 및 상기 딥 성형용 라텍스 조성물 유래층을 가열하여 상기 딥 성형용 라텍스 조성물을 가교시키는 단계(S30)를 포함하는 딥 성형품 제조방법을 제공한다.In addition, the present invention includes the step of attaching the coagulating liquid for manufacturing the dip molded product to the dip mold (S10); Forming a layer derived from the latex composition for dip molding by immersing the latex composition for dip molding in the dip mold to which the coagulating liquid is attached (S20); and a step (S30) of crosslinking the latex composition for dip molding by heating the layer derived from the latex composition for dip molding.
또한, 본 발명은 상기 딥 성형품 제조용 응고액을 이용하여 제조된 딥 성형품을 제공한다.Additionally, the present invention provides a dip molded product manufactured using the coagulant for manufacturing the dip molded product.
본 발명에 따른 딥 성형품 제조용 응고액은 가황제, 가황 촉진제 및 산화아연과 같은 가교제를 사용하지 않고 딥 성형용 라텍스 조성물을 가교시킴으로써, 종래의 황으로 인한 알러지 발생 위험을 감소시켰다. The coagulating solution for producing dip molded products according to the present invention crosslinks the latex composition for dip molding without using crosslinking agents such as vulcanizing agents, vulcanization accelerators, and zinc oxide, thereby reducing the risk of allergies caused by conventional sulfur.
또한, 본 발명은 딥 성형품 제조용 응고액에 수용성 개시제를 포함함으로써 황 함유 가교제를 사용하지 않고, 딥 성형용 라텍스 조성물 내 이중결합의 가교도를 증가시켜 이를 이용하여 제조된 딥 성형품의 내구성 및 인장강도를 향상시킬 수 있다.In addition, the present invention increases the degree of cross-linking of double bonds in the latex composition for dip molding without using a sulfur-containing cross-linking agent by including a water-soluble initiator in the coagulating solution for producing dip molded products, thereby improving the durability and tensile strength of dip molded products manufactured using the same. It can be improved.
본 발명의 설명 및 청구범위에서 사용된 용어나 단어는, 통상적이거나 사전적인 의미로 한정해서 해석되어서는 아니되며, 발명자는 그 자신의 발명을 가장 최선을 방법으로 설명하기 위해 용어의 개념을 적절하게 정의할 수 있다는 원칙에 입각하여, 본 발명의 기술적 사상에 부합하는 의미와 개념으로 해석되어야만 한다.Terms or words used in the description and claims of the present invention should not be construed as limited to their ordinary or dictionary meanings, and the inventor should appropriately use the concept of the term to explain his or her invention in the best way. Based on the principle of definability, it must be interpreted with meaning and concept consistent with the technical idea of the present invention.
이하, 본 발명에 대한 이해를 돕기 위하여 본 발명을 더욱 상세하게 설명한다.Hereinafter, the present invention will be described in more detail to facilitate understanding of the present invention.
본 발명에서 용어 '단량체 유래 반복단위'는 단량체로부터 기인한 성분, 구조 또는 그 물질 자체를 나타내는 것일 수 있고, 중합체의 중합 시, 투입되는 단량체가 중합 반응에 참여하여 중합체 내에서 이루는 반복단위를 의미하는 것일 수 있다.In the present invention, the term 'monomer-derived repeating unit' may refer to a component, structure, or the substance itself derived from a monomer, and refers to a repeating unit formed within the polymer by the input monomer participating in the polymerization reaction during polymerization of the polymer. It may be.
본 발명에서 용어 '라텍스'는 중합에 의해 중합된 중합체 또는 공중합체가 물에 분산된 형태로 존재하는 것을 의미할 수 있고, 구체적인 예로 유화 중합에 의해 중합된 고무 상의 중합체 또는 고무 상의 공중합체의 미립자가 콜로이드 상태로 물에 분산된 형태로 존재하는 것을 의미할 수 있다.In the present invention, the term 'latex' may mean that a polymer or copolymer polymerized by polymerization exists in a dispersed form in water, and specific examples include fine particles of a polymer on rubber or a copolymer on rubber polymerized by emulsion polymerization. This may mean that it exists in a colloidal state dispersed in water.
본 발명에서 용어 '유래층'은 중합체 또는 공중합체로부터 형성된 층을 나타내는 것일 수 있고, 구체적인 예로, 딥 성형품 제조 시, 중합체 또는 공중합체가 딥 성형틀 상에서 부착, 고정, 및/또는 중합되어 중합체 또는 공중합체로부터 형성된 층을 의미하는 것일 수 있다.In the present invention, the term 'derived layer' may refer to a layer formed from a polymer or copolymer, and as a specific example, when manufacturing a dip molded product, the polymer or copolymer is attached, fixed, and/or polymerized on the dip mold to form a polymer or It may mean a layer formed from a copolymer.
본 발명에서 용어 '알킬'은 메틸, 에틸, 프로필, 2-프로필, n-부틸, 이소-부틸, tert-부틸, 펜틸, 헥실, 도데실 등과 같이, 탄소 원자의 직쇄형 포화 1가 탄화수소를 의미할 수 있고, 비치환된 것뿐만 아니라 치환기에 의해 치환된 것도 포함하는 것을 의미할 수 있다.In the present invention, the term 'alkyl' refers to a straight-chain saturated monovalent hydrocarbon of carbon atoms, such as methyl, ethyl, propyl, 2-propyl, n-butyl, iso-butyl, tert-butyl, pentyl, hexyl, dodecyl, etc. It can mean that it includes not only unsubstituted ones but also those substituted with a substituent.
본 발명의 일 실시예에 따르면, 딥 성형품 제조용 응고액이 제공된다. 상기 딥 성형품 제조용 응고액은 응고제, 용매 및 수용성 개시제를 포함하고, 상기 수용성 개시제는 2,2'-아조비스[2-메틸-N-(2-하이드록시에틸)프로피온 아미드], 4,4'-아조비스(4-시아노발레릭 산), 2,2'-아조비스[2-(2-이미다졸린-2-일)프로판], 2,2'-아조비스[2-(2-이미다졸린-2-일)프로판]다이 하이드로 클로라이드, 2,2'-아조비스(2-메틸 프로피온 아미딘)다이 하이드로 클로라이드 및 2,2'-아조비스[N-(2-카복시에틸)-2-메틸 프로피온 아미딘]테트라 하이드레이트로 이루어진 군에서 선택된 1종 이상을 포함하며, 상기 수용성 개시제의 함량은 딥 성형품 제조용 응고액 전체 100 중량부에 대하여 0.5 중량부 내지 4.5 중량부일 수 있다.According to one embodiment of the present invention, a coagulating liquid for manufacturing dip molded products is provided. The coagulating liquid for producing the dip molded product includes a coagulant, a solvent, and a water-soluble initiator, and the water-soluble initiator is 2,2'-azobis[2-methyl-N-(2-hydroxyethyl)propion amide], 4,4' -Azobis(4-cyanovaleric acid), 2,2'-Azobis[2-(2-imidazolin-2-yl)propane], 2,2'-Azobis[2-(2- imidazolin-2-yl)propane]dihydrochloride, 2,2'-azobis(2-methyl propion amidine)dihydrochloride and 2,2'-azobis[N-(2-carboxyethyl)- It contains at least one member selected from the group consisting of [2-methyl propion amidine] tetrahydrate, and the content of the water-soluble initiator may be 0.5 parts by weight to 4.5 parts by weight based on 100 parts by weight of the total coagulation solution for producing dip molded products.
본 발명의 일 실시예에 따르면, 상기 응고액을 딥 성형품을 제조하는데 사용함으로써, 가황제 및 가황 촉진제 등의 가교제를 사용하지 않고 딥 성형품을 제조할 수 있어, 상기 가황제 및 가황 촉진제를 사용하여 제조한 딥 성형품을 사용하는 경우 알러지가 발생하는 문제를 해결하였고, 상기 응고액 내 포함된 수용성 개시제를 이용하여 딥 성형용 라텍스 조성물 내 이중결합의 가교도를 증가시켜 이를 이용하여 제조된 딥 성형품의 내구성 및 인장강도를 향상시킬 수 있다.According to one embodiment of the present invention, by using the coagulating liquid to manufacture dip molded products, dip molded products can be manufactured without using crosslinking agents such as vulcanizing agents and vulcanization accelerators, using the vulcanizing agents and vulcanization accelerators The problem of allergies occurring when using the manufactured dip molded product was solved, and the degree of cross-linking of double bonds in the latex composition for dip molding was increased using the water-soluble initiator contained in the coagulating liquid, thereby increasing the durability of the dip molded product manufactured using it. and tensile strength can be improved.
본 발명의 일 실시예에 따르면, 상기 응고제는 금속 할라이드, 질산염, 아세트산염 및 황산염으로 이루어진 군으로부터 선택된 1종 이상을 포함할 수 있다. 예를 들어, 상기 금속 할라이드는 바륨 클로라이드, 칼슘 클로라이드, 마그네슘 클로라이드 및 징크 클로라이드로 이루어진 군으로부터 선택된 1종 이상을 포함할 수 있고, 질산염은 바륨 나이트레이트, 칼슘 나이트레이트 및 징크 나이트레이트로 이루어진 군으로부터 선택된 1종 이상을 포함할 수 있고, 상기 아세트산염은 바륨 아세테이트, 칼슘 아세테이트 및 징크 아세테이트로 이루어진 군으로부터 선택된 1종 이상을 포함할 수 있으며, 상기 황산염은 칼슘 설페이트 및 마그네슘 설페이트로 이루어진 군으로부터 선택된 1종 이상을 포함할 수 있다. 구체적인 예로서, 상기 응고제는 질산염일 수 있다. 보다 구체적인 예로서, 상기 응고제는 칼슘 나이트레이트일 수 있다.According to one embodiment of the present invention, the coagulant may include one or more selected from the group consisting of metal halides, nitrates, acetates, and sulfates. For example, the metal halide may include one or more selected from the group consisting of barium chloride, calcium chloride, magnesium chloride, and zinc chloride, and the nitrate may include one or more selected from the group consisting of barium nitrate, calcium nitrate, and zinc nitrate. The acetate may include one or more selected from the group consisting of barium acetate, calcium acetate, and zinc acetate, and the sulfate may include one selected from the group consisting of calcium sulfate and magnesium sulfate. It may include more than one species. As a specific example, the coagulant may be nitrate. As a more specific example, the coagulant may be calcium nitrate.
상기 응고제의 함량은 딥 성형품 제조용 응고액 전체 100 중량부에 대하여 10 중량부 내지 50 중량부일 수 있다. 예를 들어, 상기 응고제의 함량은 딥 성형품 제조용 응고액 전체 100 중량부에 대하여 10 중량부 내지 40 중량부, 10 중량부 내지 30 중량부 또는 15 중량부 내지 25 중량부일 수 있다. 상기 범위 내로 응고제를 포함함으로써, 우수한 내구성의 딥 성형품을 제조할 수 있다.The content of the coagulant may be 10 to 50 parts by weight based on 100 parts by weight of the total coagulant for manufacturing dip molded products. For example, the content of the coagulant may be 10 to 40 parts by weight, 10 to 30 parts by weight, or 15 to 25 parts by weight, based on 100 parts by weight of the total coagulant for manufacturing dip molded products. By including the coagulant within the above range, dip molded products with excellent durability can be manufactured.
본 발명의 일 실시예에 따르면, 상기 용매는 물 및 알코올로 이루어진 군으로부터 선택된 1종 이상을 포함할 수 있다. 예를 들어, 상기 용매는 응고제를 용해시키기 위한 것일 수 있으며, 구체적인 예로서, 상기 용매는 물일 수 있다.According to one embodiment of the present invention, the solvent may include at least one selected from the group consisting of water and alcohol. For example, the solvent may be used to dissolve the coagulant, and as a specific example, the solvent may be water.
상기 용매의 함량은 딥 성형품 제조용 응고액 전체 100 중량부에 대하여 70 중량부 내지 90 중량부일 수 있다. 예를 들어, 상기 용매의 함량은 딥 성형품 제조용 응고액 전체 100 중량부에 대하여 75 중량부 내지 90 중량부, 75 중량부 내지 85 중량부 또는 78 중량부 내지 85 중량부일 수 있다. 상기 범위 내로 용매를 포함함으로써, 응고제를 효과적으로 용해시킬 수 있다.The content of the solvent may be 70 to 90 parts by weight based on 100 parts by weight of the total coagulant for manufacturing dip molded products. For example, the content of the solvent may be 75 parts by weight to 90 parts by weight, 75 parts by weight to 85 parts by weight, or 78 parts by weight to 85 parts by weight based on 100 parts by weight of the coagulating liquid for producing dip molded products. By including the solvent within the above range, the coagulant can be effectively dissolved.
본 발명의 일 실시예에 따르면, 상기 수용성 개시제는 딥 성형품 제조용 응고액에 포함됨으로써, 딥 성형용 라텍스 조성물 내 이중결합의 가교도를 증가시켜, 이를 이용하여 제조된 딥 성형품의 내구성을 향상시킬 수 있다.According to one embodiment of the present invention, the water-soluble initiator is included in the coagulating liquid for manufacturing dip molded products, thereby increasing the degree of crosslinking of double bonds in the latex composition for dip molding, thereby improving the durability of dip molded products manufactured using the same. .
상기 수용성 개시제는 2,2'-아조비스[2-메틸-N-(2-하이드록시에틸)프로피온 아미드](2,2'-Azobis[2-methyl-N-(2-hydroxyethyl)propionamide], VA-086), 4,4'-아조비스(4-시아노발레릭 산)(4,4'-Azobis(4-cyanovaleric acid), V-501), 2,2'-아조비스[2-(2-이미다졸린-2-일)프로판](2,2'-Azobis[2-(2-imidazolin-2-yl)propane], VA-061), 2,2'-아조비스[2-(2-이미다졸린-2-일)프로판]다이 하이드로 클로라이드(2,2'-Azobis[2-(2-imidazolin-2-yl)propane]dihydrochloride], VA-044), 2,2'-아조비스(2-메틸 프로피온 아미딘)다이 하이드로 클로라이드(2,2'-Azobis(2-methylpropionamidine)dihydrochloride, V-50) 및 2,2'-아조비스[N-(2-카복시에틸)-2-메틸 프로피온 아미딘]테트라 하이드레이트(2,2'-Azobis[N-(2-carboxyethyl)-2-methylpropionamidine]tetrahydrate, VA-057)로 이루어진 군으로부터 선택된 1종 이상을 포함할 수 있다.The water-soluble initiator is 2,2'-Azobis[2-methyl-N-(2-hydroxyethyl)propionamide] (2,2'-Azobis[2-methyl-N-(2-hydroxyethyl)propionamide], VA-086), 4,4'-Azobis(4-cyanovaleric acid), V-501), 2,2'-Azobis[2- (2-imidazolin-2-yl)propane](2,2'-Azobis[2-(2-imidazolin-2-yl)propane], VA-061), 2,2'-Azobis[2- (2-imidazolin-2-yl)propane]dihydrochloride (2,2'-Azobis[2-(2-imidazolin-2-yl)propane]dihydrochloride], VA-044), 2,2'- Azobis(2-methylpropionamidine)dihydrochloride (2,2'-Azobis(2-methylpropionamidine)dihydrochloride, V-50) and 2,2'-Azobis[N-(2-carboxyethyl)-2 -Methyl propion amidine] tetrahydrate (2,2'-Azobis[N-(2-carboxyethyl)-2-methylpropionamidine] tetrahydrate, VA-057).
상기 수용성 개시제의 함량은 딥 성형품 제조용 응고액 전체 100 중량부에 대하여 1.5 중량부 내지 4.5 중량부, 1.7 중량부 내지 4.5 중량부 또는 2 중량부 내지 4 중량부일 수 있다. 상기 범위 내로 수용성 개시제를 포함하는 딥 성형품 제조용 응고액을 사용하여 제조된 성형품은 인장강도 및 신율이 동시에 향상될 수 있다.The content of the water-soluble initiator may be 1.5 parts by weight to 4.5 parts by weight, 1.7 parts by weight to 4.5 parts by weight, or 2 parts by weight to 4 parts by weight based on 100 parts by weight of the total coagulating liquid for producing dip molded products. Molded products manufactured using a coagulant for manufacturing dip molded products containing a water-soluble initiator within the above range can have both tensile strength and elongation improved.
본 발명에 따르면, 상기 딥 성형품 제조용 응고액을 이용하여 딥 성형품을 제조하는 방법을 제공한다. 상기 딥 성형품 제조방법은 딥 성형틀에 본 발명에 따른 응고액을 부착시키는 단계(S10); 상기 응고액이 부착된 딥 성형틀에 딥 성형용 라텍스 조성물을 침지하여 딥 성형용 라텍스 조성물 유래층을 형성시키는 단계(S20); 및 상기 딥 성형용 라텍스 조성물 유래층을 가열하여 상기 딥 성형용 라텍스 조성물을 가교시키는 단계(S30)를 포함하는 것일 수 있다.According to the present invention, a method of manufacturing a dip molded product using the coagulating liquid for manufacturing the dip molded product is provided. The method for manufacturing a dip molded product includes attaching the coagulating liquid according to the present invention to a dip mold (S10); Forming a layer derived from the latex composition for dip molding by immersing the latex composition for dip molding in the dip mold to which the coagulating liquid is attached (S20); And it may include a step (S30) of crosslinking the latex composition for dip molding by heating the layer derived from the latex composition for dip molding.
본 발명의 일 실시예에 따르면, 상기 딥 성형품 제조방법은 딥 성형용 라텍스 조성물을 직접 침지법, 양극(anode) 응착 침지법, 티그(Teague) 응착 침지법 등에 의해 침지시키는 단계를 포함할 수 있고, 구체적인 예로 양극 응착 침지법에 의해 실시될 수 있으며, 이 경우 균일한 두께의 딥 성형품을 수득할 수 있는 이점이 있다.According to one embodiment of the present invention, the method for manufacturing a dip molded product may include the step of immersing the latex composition for dip molding by a direct immersion method, an anode adhesion immersion method, a Teague adhesion immersion method, etc. As a specific example, it can be carried out by an anodic adhesion immersion method, and in this case, there is an advantage of obtaining dip molded products of uniform thickness.
본 발명의 일 실시예에 따르면, 상기 (S10) 단계는 딥 성형틀에 본 발명에 따른 응고액을 형성시키기 위하여 딥 성형틀을 응고액에 담가 딥 성형틀의 표면에 응고액을 부착시키는 단계로, 상기 응고액의 구성 성분 및 함량은 앞서 언급한 구성 성분의 종류 및 함량으로 투입될 수 있고, 일괄 투입, 또는 연속적으로 투입할 수 있다.According to one embodiment of the present invention, the step (S10) is a step of immersing the dip molding mold in the coagulating liquid and attaching the coagulating liquid to the surface of the dip molding mold in order to form the coagulating liquid according to the present invention in the dip molding mold. , the components and content of the coagulating liquid may be added in the type and amount of the components mentioned above, and may be added all at once or continuously.
상기 (S10) 단계에서 앞서 언급한 수용성 개시제를 포함하는 응고액을 사용함으로써, (S30) 단계에서 딥 성형용 라텍스 조성물의 가교도를 향상시킬 수 있다.By using a coagulating solution containing the water-soluble initiator mentioned above in the step (S10), the degree of cross-linking of the latex composition for dip molding can be improved in the step (S30).
본 발명의 일 실시예에 따르면, 상기 (S20) 단계는 응고액이 부착된 딥 성형틀을 딥 성형용 라텍스 조성물에 침지하여 딥 성형용 라텍스 조성물 유래층을 형성시키는 단계일 수 있다. 구체적으로, 응고액을 부착시킨 딥 성형틀을 딥 성형용 라텍스 조성물에 침지하고, 그러 다음, 딥 성형틀을 꺼내 상기 딥 성형틀에 딥 성형용 라텍스 조성물 유래층, 즉 딥 성형층을 형성시킬 수 있다.According to one embodiment of the present invention, the step (S20) may be a step of forming a layer derived from the latex composition for dip molding by immersing the dip molding mold with the coagulating liquid attached into the latex composition for dip molding. Specifically, the dip molding mold to which the coagulating liquid is attached is immersed in the latex composition for dip molding, and then the dip molding mold is taken out and a layer derived from the latex composition for dip molding, that is, a dip molding layer, can be formed in the dip molding mold. there is.
본 발명의 일 실시예에 따르면, 상기 딥 성형용 라텍스 조성물은 공액디엔계 단량체 유래 반복단위, 에틸렌성 불포화 니트릴계 단량체 유래 반복단위 및 에틸렌성 불포화산 단량체 유래 반복단위를 포함하는 카르본산 변성 니트릴계 공중합체 라텍스를 포함할 수 있다.According to one embodiment of the present invention, the latex composition for dip molding is a carboxylic acid-modified nitrile-based composition containing a repeating unit derived from a conjugated diene-based monomer, a repeating unit derived from an ethylenically unsaturated nitrile-based monomer, and a repeating unit derived from an ethylenically unsaturated acid monomer. May include copolymer latex.
본 발명의 일 실시예에 따르면, 상기 공액디엔계 단량체 유래 반복단위를 형성하는 공액디엔계 단량체는 1,3-부타디엔, 2,3-디메틸-1,3-부타디엔, 2-에틸-1,3-부타디엔, 1,3-펜타디엔 및 이소프렌으로 이루어진 군으로부터 선택된 1종 이상일 수 있고, 구체적인 예로, 1,3-부타디엔 또는 이소프렌일 수 있으며, 보다 구체적인 예로, 1,3-부타디엔일 수 있다. According to one embodiment of the present invention, the conjugated diene monomer forming the repeating unit derived from the conjugated diene monomer is 1,3-butadiene, 2,3-dimethyl-1,3-butadiene, 2-ethyl-1,3 -It may be one or more selected from the group consisting of butadiene, 1,3-pentadiene, and isoprene, and as a specific example, it may be 1,3-butadiene or isoprene, and as a more specific example, it may be 1,3-butadiene.
상기 공액디엔계 단량체 유래 반복단위의 함량은 카르본산 변성 니트릴계 공중합체 라텍스 전체 함량에 대하여, 35 중량% 내지 80 중량%, 40 중량% 내지 80 중량%, 또는 40 중량% 내지 75 중량%일 수 있고, 이 범위 내에서 상기 카르본산 변성 니트릴계 공중합체를 포함하는 딥 성형용 라텍스 조성물로부터 성형된 딥 성형품이 유연하고, 촉감 및 착용감이 우수함과 동시에, 내유성 및 인장강도가 우수한 효과가 있다.The content of the repeating unit derived from the conjugated diene monomer may be 35% by weight to 80% by weight, 40% by weight to 80% by weight, or 40% by weight to 75% by weight, based on the total content of the carboxylic acid-modified nitrile-based copolymer latex. Within this range, dip molded products molded from the latex composition for dip molding containing the carboxylic acid-modified nitrile-based copolymer are flexible, have excellent touch and fit, and have excellent oil resistance and tensile strength.
또한, 본 발명의 일 실시예에 따르면, 상기 에틸렌성 불포화 니트릴계 단량체 유래 반복단위를 형성하는 에틸렌성 불포화 니트릴계 단량체는 아크릴로니트릴, 메타크릴로니트릴, 후마로니트릴, α-클로로니트릴 및 α-시아노 에틸 아크릴로니트릴로 이루어진 군으로부터 선택된 1종 이상일 수 있고, 구체적인 예로, 아크릴로니트릴 및 메타크릴로니트릴일 수 있으며, 보다 구체적인 예로, 아크릴로니트릴일 수 있다. In addition, according to one embodiment of the present invention, the ethylenically unsaturated nitrile-based monomers forming the repeating units derived from the ethylenically unsaturated nitrile-based monomers include acrylonitrile, methacrylonitrile, humaronitrile, α-chloronitrile, and α-chloronitrile. -It may be one or more types selected from the group consisting of cyano ethyl acrylonitrile, and as a specific example, it may be acrylonitrile and methacrylonitrile, and as a more specific example, it may be acrylonitrile.
상기 에틸렌성 불포화 니트릴계 단량체 유래 반복단위의 함량은 카르본산 변성 니트릴계 공중합체 라텍스 전체 함량에 대하여, 20 중량% 내지 50 중량%, 25 중량% 내지 45 중량%, 또는 25 중량% 내지 40 중량%일 수 있고, 이 범위 내에서 상기 카르본산 변성 니트릴계 공중합체를 포함하는 딥 성형용 라텍스 조성물로부터 성형된 딥 성형품이 유연하고, 촉감 및 착용감이 우수함과 동시에, 내유성 및 인장강도가 우수한 효과가 있다.The content of the repeating unit derived from the ethylenically unsaturated nitrile-based monomer is 20% to 50% by weight, 25% to 45% by weight, or 25% to 40% by weight, based on the total content of the carboxylic acid-modified nitrile-based copolymer latex. It may be, and within this range, the dip molded product molded from the latex composition for dip molding containing the carboxylic acid-modified nitrile-based copolymer is flexible, has excellent touch and fit, and has excellent oil resistance and tensile strength. .
또한, 본 발명의 일 실시예에 따르면, 상기 에틸렌성 불포화산 단량체 유래 반복단위를 형성하는 에틸렌성 불포화산 단량체는 카르복실기, 술폰산기, 산무수물기와 같은 산성기를 함유하는 에틸렌성 불포화 단량체일 수 있고, 구체적인 예로 아크릴산, 메타크릴산, 이타콘산, 말레인산 및 푸마르산 등과 같은 에틸렌성 불포화산 단량체; 무수말레산 및 무수 시트라콘산 등과 같은 폴리 카르본산 무수물; 스티렌 술폰산과 같은 에틸렌성 불포화 술폰산 단량체; 푸마르산 모노부틸, 말레인산 모노부틸 및 말레인산 모노-2-히드록시 프로필 등과 같은 에틸렌성 불포화 폴리 카르본산 부분 에스테르(partial ester) 단량체로 이루어진 군으로부터 선택된 1종 이상일 수 있고, 보다 구체적인 예로 아크릴산, 메타크릴산, 이타콘산, 말레인산 및 푸마르산으로 이루어진 군으로부터 선택된 1종 이상일 수 있으며, 더욱 구체적인 예로 메타크릴산일 수 있다. 상기 에틸렌성 불포화산 단량체는 중합 시, 알칼리 금속염 또는 암모늄염 등과 같은 염의 형태로 사용될 수 있다. In addition, according to one embodiment of the present invention, the ethylenically unsaturated acid monomer forming the repeating unit derived from the ethylenically unsaturated acid monomer may be an ethylenically unsaturated monomer containing an acidic group such as a carboxyl group, a sulfonic acid group, and an acid anhydride group, Specific examples include ethylenically unsaturated acid monomers such as acrylic acid, methacrylic acid, itaconic acid, maleic acid, and fumaric acid; polycarboxylic anhydrides such as maleic anhydride and citraconic anhydride; ethylenically unsaturated sulfonic acid monomers such as styrene sulfonic acid; It may be one or more selected from the group consisting of ethylenically unsaturated polycarboxylic acid partial ester monomers such as monobutyl fumarate, monobutyl maleate, and mono-2-hydroxypropyl maleate, and more specific examples include acrylic acid and methacrylic acid. , itaconic acid, maleic acid, and fumaric acid. A more specific example may be methacrylic acid. During polymerization, the ethylenically unsaturated acid monomer may be used in the form of a salt such as an alkali metal salt or ammonium salt.
상기 에틸렌성 불포화산 단량체 유래 반복단위의 함량은 카르본산 변성 니트릴계 공중합체 라텍스 전체 함량에 대하여, 0.1 중량% 내지 10 중량%, 0.5 중량% 내지 9 중량%, 또는 1 중량% 내지 8 중량% 일 수 있고, 이 범위 내에서 상기 카르본산 변성 니트릴계 공중합체를 포함하는 딥 성형용 라텍스 조성물로부터 성형된 딥 성형품이 유연하고, 착용감이 우수함과 동시에, 내성성 및 인장강도가 우수한 효과가 있다.The content of the repeating unit derived from the ethylenically unsaturated acid monomer is 0.1% by weight to 10% by weight, 0.5% by weight to 9% by weight, or 1% by weight to 8% by weight, based on the total content of the carboxylic acid-modified nitrile-based copolymer latex. Within this range, dip molded products molded from the latex composition for dip molding containing the carboxylic acid-modified nitrile-based copolymer are flexible, have excellent wearing comfort, and have excellent resistance and tensile strength.
본 발명의 일 실시예에 따르면, 상기 카르본산 변성 니트릴계 공중합체 라텍스는 공액디엔계 단량체 유래 반복단위, 에틸렌성 불포화 니트릴계 단량체 유래 반복단위 및 에틸렌성 불포화산 단량체 유래 반복단위 외에 에틸렌성 불포화 단량체 유래 반복단위를 선택적으로 더 포함할 수 있다.According to one embodiment of the present invention, the carboxylic acid-modified nitrile-based copolymer latex contains ethylenically unsaturated monomers in addition to repeating units derived from conjugated diene-based monomers, repeating units derived from ethylenically unsaturated nitrile-based monomers, and repeating units derived from ethylenically unsaturated acid monomers. Additional derived repeating units may optionally be included.
상기 에틸렌성 불포화 단량체 유래 반복단위를 형성하는 상기 에틸렌성 불포화 단량체는 스티렌, 아릴 스티렌, 및 비닐 나프탈렌으로 이루어진 그룹으로부터 선택된 비닐 방향족 단량체; 플루오로(fluoro) 에틸 비닐 에테르 등의 플루오로알킬비닐 에테르; (메타)아크릴아미드, N-메틸올 (메타)아크릴아미드, N,N-디메틸올(메타)아크릴아미드, N-메톡시 메틸(메타)아크릴아미드, 및 N-프로폭시 메틸(메타)아크릴아미드로 이루어진 군으로부터 선택된 에틸렌성 불포화 아미드 단량체; 비닐 피리딘, 비닐 노보넨, 디시클로 펜타디엔, 1,4-헥사디엔 등의 비공액 디엔 단량체; (메타)아크릴산 메틸, (메타)아크릴산 에틸, (메타)아크릴산 부틸, (메타)아크릴산-2-에틸헥실, (메타)아크릴산 트리 플루오로 에틸, (메타)아크릴산 테트라 플루오로 프로필, 말레인산 디부틸, 푸마르산 디부틸, 말레인산 디에틸, (메타)아크릴산 메톡시메틸, (메타)아크릴산 에톡시에틸, (메타)아크릴산 메톡시에톡시에틸, (메타)아크릴산시아노메틸, (메타)아크릴산 2-시아노에틸, (메타)아크릴산 1-시아노프로필, (메타)아크릴산 2-에틸-6-시아노헥실, (메타)아크릴산 3-시아노프로필, (메타)아크릴산 히드록시에틸, (메타)아크릴산 히드록시프로필, 글리시딜 (메타)아크릴레이트, 및 디메틸아미노 에틸(메타)아크릴레이트로 이루어진 군으로부터 선택된 에틸렌성 불포화카르본산 에스테르 단량체로 이루어진 군으로부터 선택된 1 종 이상일 수 있다.The ethylenically unsaturated monomer forming the repeating unit derived from the ethylenically unsaturated monomer may include a vinyl aromatic monomer selected from the group consisting of styrene, aryl styrene, and vinyl naphthalene; Fluoroalkyl vinyl ethers such as fluoro ethyl vinyl ether; (meth)acrylamide, N-methylol (meth)acrylamide, N,N-dimethylol(meth)acrylamide, N-methoxy methyl(meth)acrylamide, and N-propoxy methyl(meth)acrylamide An ethylenically unsaturated amide monomer selected from the group consisting of; Non-conjugated diene monomers such as vinyl pyridine, vinyl norbornene, dicyclopentadiene, and 1,4-hexadiene; Methyl (meth)acrylate, ethyl (meth)acrylate, butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, trifluoroethyl (meth)acrylate, tetrafluoropropyl (meth)acrylate, dibutyl maleate, Dibutyl fumarate, diethyl maleate, methoxymethyl (meth)acrylate, ethoxyethyl (meth)acrylate, methoxyethoxyethyl (meth)acrylate, cyanomethyl (meth)acrylate, 2-cyano (meth)acrylate. Ethyl, 1-cyanopropyl (meth)acrylic acid, 2-ethyl-6-cyanohexyl (meth)acrylic acid, 3-cyanopropyl (meth)acrylic acid, hydroxyethyl (meth)acrylic acid, hydroxy (meth)acrylic acid It may be one or more types selected from the group consisting of ethylenically unsaturated carboxylic acid ester monomers selected from the group consisting of propyl, glycidyl (meth)acrylate, and dimethylamino ethyl (meth)acrylate.
상기 에틸렌성 불포화 단량체 유래 반복단위 함량은 카르본산 변성 니트릴계 공중합체 라텍스 전체 함량에 대하여, 20 중량% 이내, 0.01 내지 20 중량%, 또는 0.01 내지 15 중량%일 수 있고, 이 범위 내에서 상기 카르본산 변성 니트릴계 공중합체를 포함하는 딥 성형용 라텍스 조성물로부터 성형된 딥 성형품의 촉감 및 착용감이 우수함과 동시에, 인장강도가 우수한 효과가 있다.The content of the repeating unit derived from the ethylenically unsaturated monomer may be within 20% by weight, 0.01 to 20% by weight, or 0.01 to 15% by weight, based on the total content of the carboxylic acid-modified nitrile-based copolymer latex, and within this range, the carboxylic acid-modified nitrile-based copolymer latex The dip molded product molded from the latex composition for dip molding containing the acid-modified nitrile-based copolymer has excellent feel and fit, and has excellent tensile strength.
또한, 본 발명의 일 실시예에 따르면, 상기 딥 성형용 라텍스 조성물은 필요에 따라, 이온성 가교제, 안료, 충전재, pH 조절제 등의 첨가제를 더 포함할 수 있다.In addition, according to one embodiment of the present invention, the latex composition for dip molding may further include additives such as ionic crosslinking agents, pigments, fillers, and pH adjusters, if necessary.
또한, 본 발명의 일 실시예에 따르면, 상기 딥 성형용 라텍스 조성물은 일례로 고형분 함량(농도)가 5 중량% 내지 40 중량%, 8 중량% 내지 35 중량%, 또는 10 중량% 내지 25 중량%일 수 있고, 이 범위 내에서 라텍스 운송의 효율이 우수하고, 라텍스 점도의 상승을 방지하여 저장 안정성이 뛰어난 효과가 있다.In addition, according to one embodiment of the present invention, the latex composition for dip molding has a solid content (concentration) of 5% by weight to 40% by weight, 8% by weight to 35% by weight, or 10% by weight to 25% by weight. Within this range, the efficiency of latex transportation is excellent, and an increase in latex viscosity is prevented, resulting in excellent storage stability.
또 다른 예로, 상기 딥 성형용 라텍스 조성물은 pH가 8 내지 12, 9 내지 11, 또는 9.3 내지 11일 수 있고, 이 범위 내에서 딥 성형품 제조 시 가공성 및 생산성이 뛰어난 효과가 있다. 상기 딥 성형용 라텍스 조성물의 pH는 앞서 기재한 pH 조절제의 투입에 의해 조절될 수 있다. 상기 pH 조절제는 일례로 1 중량% 내지 5 중량% 농도의 수산화칼륨 수용액, 또는 1 중량% 내지 5 중량% 농도의 암모니아수일 수 있다.As another example, the latex composition for dip molding may have a pH of 8 to 12, 9 to 11, or 9.3 to 11, and within this range, it has excellent processability and productivity when manufacturing dip molded products. The pH of the latex composition for dip molding can be adjusted by adding the pH adjuster described above. For example, the pH adjuster may be an aqueous solution of potassium hydroxide at a concentration of 1% to 5% by weight, or aqueous ammonia at a concentration of 1% to 5% by weight.
또한, 본 발명의 일 실시예에 따르면, 상기 카르본산 변성 니트릴계 공중합체 라텍스 내의 카르본산 변성 니트릴계 공중합체의 유리전이온도는 -50 ℃ 내지 -15 ℃, -47 ℃ 내지 -15 ℃ 또는 -45 ℃ 내지 -20 ℃일 수 있고, 상기 범위 내에서 상기 카르본산 변성 니트릴계 공중합체 라텍스를 포함하는 딥 성형용 라텍스 조성물로부터 딥 성형된 성형품의 인장 강도 등 인장 특성의 저하 및 균열 발생을 방지하면서도, 끈적임이 적어 착용감이 우수한 효과가 있다. 상기 유리전이온도는 시차 주사 열량계(Differential Scanning Calorimetry)를 이용하여 측정된 것일 수 있다.In addition, according to one embodiment of the present invention, the glass transition temperature of the carboxylic acid-modified nitrile-based copolymer in the carboxylic acid-modified nitrile-based copolymer latex is -50 ℃ to -15 ℃, -47 ℃ to -15 ℃, or - It may be 45 ℃ to -20 ℃, and within the above range, the deterioration of tensile properties such as tensile strength of the molded product dip molded from the latex composition for dip molding containing the carboxylic acid-modified nitrile-based copolymer latex and the occurrence of cracks are prevented. , It has low stickiness and provides excellent wearing comfort. The glass transition temperature may be measured using differential scanning calorimetry.
또한, 본 발명의 일 실시예에 따르면, 상기 카르본산 변성 니트릴계 공중합체 라텍스 내의 카르본산 변성 니트릴계 공중합체 입자의 평균 입경은 50 nm 내지 500 nm, 80 nm 내지 300 nm, 100 nm 내지 250 nm 또는 90 nm 내지 200 nm일 수 있다. 상기 범위 내에서 상기 카르본산 변성 니트릴계 공중합체 라텍스의 점도가 상승되지 않아 카르본산 변성 니트릴계 공중합체 라텍스를 고농도로 제조할 수 있고, 이를 포함하는 딥 성형용 라텍스 조성물로부터 딥 성형된 성형품의 인장 강도 등 인장 특성이 우수한 효과가 있다. 또한, 상기 범위 내에서 필름 형성 속도가 적정 수준으로 제어되어 시너리시스 특성이 우수한 효과가 있다. 상기 평균 입경은 레이저 분산 분석기(Laser Scattering Analyzer, Nicomp)를 이용하여 측정된 것일 수 있다.In addition, according to one embodiment of the present invention, the average particle diameter of the carboxylic acid-modified nitrile-based copolymer particles in the carboxylic acid-modified nitrile-based copolymer latex is 50 nm to 500 nm, 80 nm to 300 nm, and 100 nm to 250 nm. Or it may be 90 nm to 200 nm. Within the above range, the viscosity of the carboxylic acid-modified nitrile-based copolymer latex does not increase, so that the carboxylic acid-modified nitrile-based copolymer latex can be manufactured at a high concentration, and the tensile strength of the molded product dip molded from the latex composition for dip molding containing the same It has excellent tensile properties such as strength. In addition, the film formation speed is controlled to an appropriate level within the above range, resulting in excellent synergy characteristics. The average particle diameter may be measured using a laser scattering analyzer (Nicomp).
본 발명의 일 실시예에 따르면, 상기 (S30) 단계는 딥 성형품을 수득하기 위하여 딥 성형틀에 형성된 딥 성형용 라텍스 조성물 유래층을 가열하여 상기 딥 성형용 라텍스 조성물을 가교시켜 경화를 진행하는 단계일 수 있다. According to one embodiment of the present invention, the step (S30) is a step of curing the latex composition for dip molding by heating the layer derived from the latex composition for dip molding formed in the dip mold to crosslink the latex composition for dip molding to obtain a dip molded product. It can be.
상기 (S30) 단계는 50 ℃ 내지 150 ℃에서 수행될 수 있다. 구체적으로, (S20) 단계에서 형성된 딥 성형용 라텍스 조성물 유래층을 50 ℃ 내지 150 ℃로 가열하여 딥 성형용 라텍스 조성물에 포함되어 있는 카르본산 변성 니트릴계 공중합체 내 공액디엔계의 이중결합을 응고액에 포함된 수용성 개시제를 이용하여 가교시킬 수 있다.The step (S30) may be performed at 50°C to 150°C. Specifically, the layer derived from the latex composition for dip molding formed in step (S20) is heated to 50 ℃ to 150 ℃ to bind the double bond of the conjugated diene system in the carboxylic acid-modified nitrile-based copolymer contained in the latex composition for dip molding. Crosslinking can be done using a water-soluble initiator contained in the solid liquid.
상기 (S30) 단계는 온도가 서로 다른 조건에서 2 단계로 수행될 수 있다. 예를 들어, 상기 (S30) 단계는 50 ℃ 내지 90 ℃의 온도 조건에서 1차 가교시키고, 95 ℃ 내지 130 ℃의 온도 조건에서 2차 가교시킬 수 있다. 이 때, 상기 1차 가교 단계는 1 분 내지 5 분 동안 수행하고, 2차 가교 단계는 15 분 내지 30 분 동안 수행할 수 있다. 이와 같이, (S30) 단계를 수행함으로써, 물을 증발시키고, 딥 성형용 라텍스 조성물에 포함되어 있는 카르본산 변성 니트릴계 공중합체 내 공액디엔계의 이중결합을 가교시켜 경화가 진행될 수 있다.The step (S30) may be performed in two steps under different temperature conditions. For example, in the step (S30), primary crosslinking may be performed under temperature conditions of 50°C to 90°C, and secondary crosslinking may be performed under temperature conditions of 95°C to 130°C. At this time, the first crosslinking step may be performed for 1 to 5 minutes, and the second crosslinking step may be performed for 15 to 30 minutes. In this way, by performing step (S30), water can be evaporated and curing can proceed by crosslinking the double bonds of the conjugated diene system in the carboxylic acid-modified nitrile-based copolymer contained in the latex composition for dip molding.
본 발명에 따른 상기 딥 성형용 라텍스 조성물 제조방법은 앞서 언급한 카르본산 변성 니트릴계 공중합체를 구성하는 단량체 혼합물에 유화제, 중합 개시제, 활성화제, 분자량 조절제 및 중합 정지제 등을 첨가하여 유화 중합함으로써 제조할 수 있다. 이 때, 상기 중합에 있어서, 앞서 언급한 단량체 혼합물의 종류 및 함량으로 투입될 수 있고, 일괄 투입, 또는 연속적으로 투입할 수 있다.The method for producing the latex composition for dip molding according to the present invention involves emulsion polymerization by adding an emulsifier, a polymerization initiator, an activator, a molecular weight regulator, and a polymerization terminator to the monomer mixture constituting the aforementioned carboxylic acid-modified nitrile-based copolymer. It can be manufactured. At this time, in the polymerization, the type and amount of the monomer mixture mentioned above may be added, and may be added in batches or continuously.
상기 유화제는 중합 반응 중과 반응 이후 라텍스에 안정성을 부여하기 위하여 투입하며, 다양한 종류의 음이온계 유화제와 비이온계 유화제를 사용할 수 있다. 예를 들어, 음이온계 유화제로는 알킬 벤젠 술폰산 나트륨 등의 알킬 벤젠 술포네이트, 알코올 설페이트, 알코올 에테르 술포네이트, 알킬 페놀 에테르 술포네이트, 알파 올레핀 술포네이트, 파라핀 술포네이트, 에스테르 술포숙시네이트, 포스페이트 에스테르 등이 있으며, 비이온계 유화제로는 알킬 페놀 에톡시레이트, 페티 아민 에톡시레이트, 지방산 에톡시레이트, 알카노아미드 등을 포함할 수 있다. 이러한 유화제는 단독 또는 2종 이상을 조합시켜 이용할 수 있다. 또한, 상기 유화제는 단량체 혼합물 전체 함량 100 중량부에 대하여 0.3 중량부 내지 10 중량부, 0.8 중량부 내지 8 중량부, 또는 1.5 중량부 내지 8 중량부로 투입될 수 있고, 이 범위 내에서 중합 안정성이 우수하고, 거품 발생량이 적어 성형품의 제조가 용이한 효과가 있다.The emulsifier is added to provide stability to the latex during and after the polymerization reaction, and various types of anionic emulsifiers and nonionic emulsifiers can be used. For example, anionic emulsifiers include alkyl benzene sulfonates such as sodium alkyl benzene sulfonate, alcohol sulfate, alcohol ether sulfonate, alkyl phenol ether sulfonate, alpha olefin sulfonate, paraffin sulfonate, ester sulfosuccinate, and phosphate. Examples include esters, and nonionic emulsifiers may include alkyl phenol ethoxylate, petiamine ethoxylate, fatty acid ethoxylate, and alkanoamide. These emulsifiers can be used individually or in combination of two or more types. In addition, the emulsifier may be added in an amount of 0.3 parts by weight to 10 parts by weight, 0.8 parts by weight to 8 parts by weight, or 1.5 parts by weight to 8 parts by weight based on 100 parts by weight of the total content of the monomer mixture, and polymerization stability is within this range. It is excellent and has a low amount of foam, making it easy to manufacture molded products.
또한, 상기 카르본산 변성 니트릴계 공중합체의 중합이 중합 개시제를 포함하여 실시되는 경우, 라디칼 개시제를 사용할 수 있다. 예를 들어, 라디칼 개시제는 과황산나트륨, 과황산칼륨, 과황산암모늄, 과인산칼륨, 과산화수소 등의 무기 과산화물; t-부틸 퍼옥사이드, 큐멘 하이드로 퍼옥사이드, p-멘탄하이드로 퍼옥사이드, 디-t-부틸 퍼옥사이드, t-부틸쿠밀 퍼옥사이드, 아세틸 퍼옥사이드, 이소부틸 퍼옥사이드, 옥타노일 퍼옥사이드, 디벤조일 퍼옥사이드, 3,5,5-트리메틸헥산올 퍼옥사이드, t-부틸 퍼옥시 iso 부틸레이트 등의 유기 과산화물; 아조비스 이소부티로니트릴, 아조비스-2,4-디메틸발레로니트릴, 아조비스시클로헥산카르보니트릴, 아조비스 이소부틸산 메틸 등의 질소화합물을 포함할 수 있다. 상기 중합 개시제는 단독으로 혹은 2종 이상을 조합시켜 사용될 수 있으며, 구체적인 예로서, 상기 라디칼 개시제는 무기 과산화물이 사용될 수 있고, 보다 구체적인 예로서, 상기 라디칼 개시제는 과황산염이 사용될 수 있다. 상기 중합 개시제는 단량체 혼합물 전체 함량 100 중량부에 대하여 0.01 중량부 내지 2 중량부 또는 0.02 중량부 내지 1.5 중량부로 투입될 수 있고, 이 범위 내에서 중합 속도를 적정 수준으로 유지할 수 있는 효과가 있다.Additionally, when polymerization of the carboxylic acid-modified nitrile-based copolymer is carried out including a polymerization initiator, a radical initiator may be used. For example, the radical initiator may include inorganic peroxides such as sodium persulfate, potassium persulfate, ammonium persulfate, potassium perphosphate, and hydrogen peroxide; t-butyl peroxide, cumene hydroperoxide, p-menthane hydroperoxide, di-t-butyl peroxide, t-butylcumyl peroxide, acetyl peroxide, isobutyl peroxide, octanoyl peroxide, dibenzoyl peroxide Organic peroxides such as oxide, 3,5,5-trimethylhexanol peroxide, and t-butyl peroxy isobutyrate; It may include nitrogen compounds such as azobisisobutyronitrile, azobis-2,4-dimethylvaleronitrile, azobiscyclohexanecarbonitrile, and methyl azobisisobutyrate. The polymerization initiator may be used alone or in combination of two or more types. As a specific example, the radical initiator may be an inorganic peroxide, and as a more specific example, the radical initiator may be a persulfate. The polymerization initiator may be added in an amount of 0.01 to 2 parts by weight or 0.02 to 1.5 parts by weight based on 100 parts by weight of the total monomer mixture, and within this range, it is effective in maintaining the polymerization rate at an appropriate level.
또한, 상기 카르본산 변성 니트릴계 공중합체의 중합이 활성화제를 포함하여 실시되는 경우, 상기 활성화제는 소듐포름알데히드, 설폭실레이트, 소듐에틸렌디아민 테르라아세테이트, 황산 제1철, 덱스트로오스, 피롤린산나트륨 및 아황산나트륨으로 이루어진 군으로부터 선택된 1종 이상일 수 있다. 또한, 상기 활성화제는 단량체 혼합물 전체 함량 100 중량부에 대하여 0.01 중량부 내지 2.0 중량부, 0.02 중량부 내지 1.5 중량부, 또는 0.05 중량부 내지 1.0 중량부로 투입될 수 있고, 이 범위 내에서 중합 속도를 적정 수준으로 유지할 수 있는 효과가 있다.In addition, when the polymerization of the carboxylic acid-modified nitrile-based copolymer is carried out including an activator, the activator may be sodium formaldehyde, sulfoxylate, sodium ethylenediamine teraacetate, ferrous sulfate, dextrose, It may be one or more selected from the group consisting of sodium pyrrolinate and sodium sulfite. In addition, the activator may be added in an amount of 0.01 parts by weight to 2.0 parts by weight, 0.02 parts by weight to 1.5 parts by weight, or 0.05 parts by weight to 1.0 parts by weight based on 100 parts by weight of the total content of the monomer mixture, and the polymerization rate within this range. It has the effect of maintaining it at an appropriate level.
또한, 상기 카르본산 변성 니트릴계 공중합체의 중합이 분자량 조절제를 포함하여 실시되는 경우, 상기 분자량 조절제는 예를 들어, α-메틸스티렌다이머, t-도데실 머캅탄, n-도데실 머캅탄, 옥틸 머캅탄 등의 머캅탄류; 사염화탄소, 염화메틸렌, 브롬화 메틸렌 등의 할로겐화 탄화 수소; 테트라에틸티우람 다이설파이드, 디펜타메칠렌티우람 다이설파이드, 디이소프로필키산토겐 다이설파이드 등의 황 함유 화합물 등을 포함할 수 있다. 이러한 분자량 조절제는 단독으로 또는 2종 이상을 조합시켜 사용할 수 있다. 구체적인 예로서, 상기 분자량 조절제는 머캅탄류를 사용할 수 있고, 보다 구체적인 예로서, 상기 분자량 조절제는 t-도데실 머캅탄을 사용할 수 있다. 상기 분자량 조절제는 단량체 혼합물 전체 함량 100 중량부에 대하여 0.1 중량부 내지 2 중량부, 0.2 중량부 내지 1.5 중량부 또는 0.3 중량부 내지 1 중량부로 투입될 수 있고, 이 범위 내에서 중합 안정성이 우수하고, 중합 후 성형품 제조 시, 성형품의 물성이 뛰어난 효과가 있다.In addition, when the polymerization of the carboxylic acid-modified nitrile-based copolymer is carried out including a molecular weight regulator, the molecular weight regulator is, for example, α-methylstyrenedimer, t-dodecyl mercaptan, n-dodecyl mercaptan, Mercaptans such as octyl mercaptan; Halogenated hydrocarbons such as carbon tetrachloride, methylene chloride, and methylene bromide; It may include sulfur-containing compounds such as tetraethylthiuram disulfide, dipentamethylenethiuram disulfide, and diisopropylxanthogen disulfide. These molecular weight regulators can be used individually or in combination of two or more types. As a specific example, the molecular weight regulator may use mercaptans, and as a more specific example, the molecular weight regulator may use t-dodecyl mercaptan. The molecular weight regulator may be added in an amount of 0.1 to 2 parts by weight, 0.2 to 1.5 parts by weight, or 0.3 to 1 part by weight based on 100 parts by weight of the total monomer mixture, and within this range, polymerization stability is excellent. , When manufacturing molded products after polymerization, the physical properties of the molded products are excellent.
또한, 상기 카르본산 변성 니트릴계 공중합체의 중합이 중합 정지제를 포함하여 실시되는 경우, 상기 중합 정지제는, 예를 들어, 히드록실 아민(Hydroxyl Amine), 히드록시 아민(Hydroxy Amine) 황산염, 디에틸 히드록시 아민(Diethylhydroxy Amine), 히드록시 아민 술폰산 및 그 알칼리 금속 이온, 소듐 디메틸 디티오 카바메이트, 하이드로 퀴논 유도체, 히드록시 디에틸 벤젠 디티오 카르본산, 히드록시 디부틸 벤젠 디티오 카르본산 등의 방향족 히드록시 디티오 카르본산 등을 포함할 수 있다. 상기 중합 정지제는 단량체 혼합물 전체 함량 100 중량부에 대하여 0.1 중량부 내지 2 중량부로 투입될 수 있다. In addition, when the polymerization of the carboxylic acid-modified nitrile-based copolymer is carried out including a polymerization terminator, the polymerization terminator is, for example, hydroxyl amine, hydroxy amine sulfate, Diethylhydroxy Amine, hydroxy amine sulfonic acid and its alkali metal ion, sodium dimethyl dithio carbamate, hydroquinone derivative, hydroxy diethyl benzene dithiocarboxylic acid, hydroxy dibutyl benzene dithiocarboxylic acid. It may include aromatic hydroxy dithio carboxylic acid, etc. The polymerization terminator may be added in an amount of 0.1 to 2 parts by weight based on 100 parts by weight of the total monomer mixture content.
또한, 본 발명의 일 실시예에 따르면, 상기 카르본산 변성 니트릴계 공중합체의 중합은 매질로서 물, 구체적인 예로 탈이온수에서 실시될 수 있고, 중합 용이성 확보를 위해, 필요에 따라 킬레이트제, 분산제, pH 조절제, 탈산소제, 입경 조절제, 노화 방지제 및 산소 포착제 등과 같은 첨가제를 더 포함하여 실시될 수 있다.In addition, according to one embodiment of the present invention, the polymerization of the carboxylic acid-modified nitrile-based copolymer may be carried out in water as a medium, specifically deionized water, and to ensure ease of polymerization, chelating agents, dispersants, and It may be carried out by further including additives such as pH adjusters, deoxidizers, particle size adjusters, anti-aging agents, and oxygen scavengers.
본 발명의 일 실시예에 따르면, 상기 유화제, 중합 개시제, 분자량 조절제, 첨가제 등은 상기 단량체 혼합물과 같이 중합 반응기에 일괄 투입, 또는 분할 투입될 수 있고, 각 투입 시 연속적으로 투입될 수도 있다.According to one embodiment of the present invention, the emulsifier, polymerization initiator, molecular weight regulator, additives, etc. may be added to the polymerization reactor as a lump or divided portion, like the monomer mixture, or may be added continuously during each addition.
또한, 본 발명의 일 실시예에 따르면, 상기 카르본산 변성 니트릴계 공중합체의 중합은 10 ℃ 내지 90 ℃, 20 ℃ 내지 80 ℃, 또는 25 ℃ 내지 75 ℃의 중합 온도에서 실시될 수 있고, 이 범위 내에서 라텍스 안정성이 뛰어난 효과가 있다.In addition, according to one embodiment of the present invention, polymerization of the carboxylic acid-modified nitrile-based copolymer may be carried out at a polymerization temperature of 10 ℃ to 90 ℃, 20 ℃ to 80 ℃, or 25 ℃ to 75 ℃, Latex stability is excellent within the range.
한편, 본 발명의 일 실시예에 따르면, 상기 라텍스 딥 성형용 라텍스 조성물 제조방법은 중합 반응을 종료하여 카르본산 변성 니트릴계 공중합체 라텍스를 수득할 수 있다. 상기 카르본산 변성 니트릴계 공중합체의 중합 반응의 종료는 중합 전환율이 90% 이상, 91% 이상 또는 92% 내지 99.9%인 시점에서 실시될 수 있고, 중합 정지제, pH 조절제 및 산화방지제의 첨가에 의해 실시될 수 있다. 또한, 상기 라텍스 조성물 제조방법은, 상기 반응 종료 후, 탈취 농축공정에 의한 미반응 단량체 제거 단계를 더 포함할 수 있다.Meanwhile, according to one embodiment of the present invention, the method for producing a latex composition for latex dip molding can obtain carboxylic acid-modified nitrile-based copolymer latex by completing the polymerization reaction. Termination of the polymerization reaction of the carboxylic acid-modified nitrile-based copolymer may be carried out when the polymerization conversion rate is 90% or more, 91% or more, or 92% to 99.9%, and the addition of a polymerization terminator, pH adjuster, and antioxidant It can be carried out by: In addition, the method for producing the latex composition may further include a step of removing unreacted monomers by a deodorizing concentration process after completion of the reaction.
본 발명에 따르면, 상기 응고액을 이용하여 제조된 딥 성형품을 제공한다. 보다 구체적으로, 상기 딥 성형품 제조 방법에 있어서, (S30) 단계에서 가열 처리에 의해 가교된 딥 성형용 라텍스 조성물 유래층을 딥 성형틀로부터 벗겨냄으로써 딥 성형품을 수득할 수 있다.According to the present invention, a dip molded article manufactured using the above coagulating liquid is provided. More specifically, in the method for manufacturing a dip molded product, a dip molded product can be obtained by peeling the layer derived from the latex composition for dip molding crosslinked by heat treatment in step (S30) from the dip mold.
본 발명의 일 실시예에 따르면, 상기 성형품은 수술용 장갑, 검사용 장갑, 산업용 장갑 및 가정용 장갑 등과 같은 장갑, 콘돔, 카테터, 또는 건강 관리용품일 수 있다.According to one embodiment of the present invention, the molded article may be a glove such as surgical gloves, examination gloves, industrial gloves, and household gloves, condoms, catheters, or health care products.
이하, 실시예에 의하여 본 발명을 더욱 상세하게 설명하고자 한다. 그러나, 하기 실시예는 본 발명을 예시하기 위한 것으로 본 발명의 범주 및 기술사상 범위 내에서 다양한 변경 및 수정이 가능함은 통상의 기술자에게 있어서 명백한 것이며, 이들 만으로 본 발명의 범위가 한정되는 것은 아니다.Hereinafter, the present invention will be described in more detail through examples. However, the following examples are intended to illustrate the present invention, and it is obvious to those skilled in the art that various changes and modifications are possible within the scope and spirit of the present invention, and the scope of the present invention is not limited to these alone.
실시예Example
실시예 1 Example 1
<카르본산 변성 니트릴계 공중합체 라텍스 제조> <Manufacture of carboxylic acid-modified nitrile-based copolymer latex>
중합 반응기에 아크릴로니트릴 30.0 중량%, 1,3-부타디엔 57.7 중량% 및 메타크릴산 6.3 중량%로 구성되는 단량체 혼합물과 상기 단량체 혼합물 99 중량부에 대하여 t-도데실머캅탄 0.55 중량부, 소듐 도데실 벤젠설포네이트 2.1 중량부, 과황산칼륨 0.5 중량부, 물 140 중량부를 넣은 후 37 ℃의 온도에서 중합을 개시하였다. 그런 다음, 중합 전환율이 75%인 시점에 1,3-부타디엔 6.0 중량%, t-도데실 머캅탄 0.055 중량%, 소듐 도데실벤젠 설포네이트 0.4 중량%를 첨가하였다.In the polymerization reactor, a monomer mixture consisting of 30.0% by weight of acrylonitrile, 57.7% by weight of 1,3-butadiene, and 6.3% by weight of methacrylic acid, 0.55 parts by weight of t-dodecyl mercaptan, and sodium dodecyl based on 99 parts by weight of the monomer mixture. After adding 2.1 parts by weight of benzenesulfonate, 0.5 parts by weight of potassium persulfate, and 140 parts by weight of water, polymerization was started at a temperature of 37°C. Then, when the polymerization conversion rate was 75%, 6.0% by weight of 1,3-butadiene, 0.055% by weight of t-dodecyl mercaptan, and 0.4% by weight of sodium dodecylbenzene sulfonate were added.
그런 다음, 중합 전환율이 94%에 이르렀을 때 수산화암모늄 0.3 중량부를 첨가하여 중합을 정지시켰다. 그 후 탈취 공정을 통하여 미반응물을 제거하고 암모니아수, 산화방지제, 소포제를 첨가하여 고형분 농도 45%, pH 8.5의 카르본산 변성 니트릴계 공중합체 라텍스를 수득하였다.Then, when the polymerization conversion rate reached 94%, 0.3 parts by weight of ammonium hydroxide was added to stop the polymerization. Afterwards, unreacted substances were removed through a deodorization process, and ammonia water, antioxidants, and antifoaming agents were added to obtain carboxylic acid-modified nitrile-based copolymer latex with a solid content of 45% and pH 8.5.
<딥 성형용 라텍스 조성물 제조><Manufacture of latex composition for dip molding>
상기 제조된 카르본산 변성 니트릴계 공중합체 라텍스 100 중량부(고형분 기준)에 수산화칼륨 용액 2.5 중량부, 티타늄옥사이드 1.2 중량부 및 2차 증류수를 더하여 고형분 농도 20%, pH 10의 딥 성형용 라텍스 조성물을 얻었다. A latex composition for dip molding with a solids concentration of 20% and pH 10 was prepared by adding 2.5 parts by weight of potassium hydroxide solution, 1.2 parts by weight of titanium oxide, and secondary distilled water to 100 parts by weight (based on solid content) of the carboxylic acid-modified nitrile-based copolymer latex prepared above. got it
<딥 성형품 제조><Manufacture of deep molded products>
18 중량부의 칼슘 나이트레이트, 81.9 중량부의 물, 0.1 중량부의 습윤제(wetting agent, Teric 320 produced by Huntsman Corporation,Australia), 3.0 중량부의 2,2'-아조비스[2-메틸-N-(2-하이드록시에틸)프로피온 아미드(VA-086)를 혼합하여 딥 성형품 제조용 응고액을 만들었다. 상기 응고액에 손 모양의 세라믹 딥 성형틀을 10초간 담그고, 끄집어 낸 후 80 ℃에서 4 분간 건조하여 응고제를 손 모양의 딥 성형틀에 도포하였다.18 parts by weight calcium nitrate, 81.9 parts by weight water, 0.1 part by weight wetting agent (Teric 320 produced by Huntsman Corporation, Australia), 3.0 parts by weight 2,2'-azobis[2-methyl-N-(2- Hydroxyethyl)propion amide (VA-086) was mixed to create a coagulating solution for manufacturing dip molded products. The hand-shaped ceramic dip mold was immersed in the coagulant for 10 seconds, pulled out, dried at 80°C for 4 minutes, and the coagulant was applied to the hand-shaped dip mold.
다음에, 응고액이 도포된 딥 성형틀을 상기 딥 성형용 라텍스 조성물에 10 초 간 담그고, 끌어 올린 뒤, 80 ℃에서 2 분간 건조한 후 물 또는 온수에 30 초간 담가 리칭(leaching)을 하였다. 그런 다음, 다시 딥 성형틀을 110 ℃에서 20 분간 가교시켰다. 가교된 딥 성형층을 손 모양의 딥 성형틀로부터 벗겨내어 장갑 형태의 딥 성형품을 얻었다.Next, the dip molding mold coated with the coagulating solution was dipped into the latex composition for dip molding for 10 seconds, pulled up, dried at 80°C for 2 minutes, and then leached by immersing it in water or warm water for 30 seconds. Then, the dip mold was crosslinked again at 110°C for 20 minutes. The cross-linked dip molding layer was peeled off from the hand-shaped dip molding mold to obtain a glove-shaped dip molding product.
실시예 2 Example 2
상기 실시예 1에서, 응고액 제조 시, 2,2'-아조비스[2-메틸-N-(2-하이드록시에틸)프로피온 아미드(VA-086) 대신 4,4'-아조비스(4-시아노발레릭 산)(V-501)을 투입한 것을 제외하고는 상기 실시예 1과 동일한 방법으로 장갑 형태의 딥 성형품을 수득하였다.In Example 1, when preparing the coagulating solution, 4,4'-azobis (4-) was used instead of 2,2'-azobis[2-methyl-N-(2-hydroxyethyl)propion amide (VA-086) A dip molded product in the form of a glove was obtained in the same manner as in Example 1, except that cyanovaleric acid (V-501) was added.
실시예 3 Example 3
상기 실시예 1에서, 응고액 제조 시, 2,2'-아조비스[2-메틸-N-(2-하이드록시에틸)프로피온 아미드(VA-086) 대신 2,2'-아조비스[2-(2-이미다졸린-2-일)프로판](VA-061)을 투입한 것을 제외하고는 상기 실시예 1과 동일한 방법으로 장갑 형태의 딥 성형품을 수득하였다.In Example 1, when preparing the coagulating solution, 2,2'-azobis[2- A dip molded product in the form of a glove was obtained in the same manner as Example 1, except that (2-imidazolin-2-yl)propane] (VA-061) was added.
실시예 4 Example 4
상기 실시예 1에서, 응고액 제조 시, 2,2'-아조비스[2-메틸-N-(2-하이드록시에틸)프로피온 아미드(VA-086) 대신 2,2'-아조비스[N-(2-카복시에틸)-2-메틸 프로피온 아미딘]테트라 하이드레이트(VA-057)을 투입한 것을 제외하고는 상기 실시예 1과 동일한 방법으로 장갑 형태의 딥 성형품을 수득하였다.In Example 1, when preparing the coagulating solution, 2,2'-azobis[N- was used instead of 2,2'-azobis[2-methyl-N-(2-hydroxyethyl)propion amide (VA-086). A dip molded product in the form of a glove was obtained in the same manner as Example 1, except that (2-carboxyethyl)-2-methyl propion amidine]tetrahydrate (VA-057) was added.
실시예 5 Example 5
상기 실시예 1에서, 응고액 제조 시, 2,2'-아조비스[2-메틸-N-(2-하이드록시에틸)프로피온 아미드(VA-086) 대신 2,2'-아조비스(2-메틸 프로피온 아미딘)다이 하이드로 클로라이드(V-50)을 투입한 것을 제외하고는 상기 실시예 1과 동일한 방법으로 장갑 형태의 딥 성형품을 수득하였다.In Example 1, when preparing the coagulating solution, 2,2'-azobis(2- A dip molded product in the form of a glove was obtained in the same manner as in Example 1, except that methyl propion amidine) dihydrochloride (V-50) was added.
실시예 6 Example 6
상기 실시예 1에서, 응고액 제조 시, 2,2'-아조비스[2-메틸-N-(2-하이드록시에틸)프로피온 아미드(VA-086) 대신 2,2'-아조비스[2-(2-이미다졸린-2-일)프로판]다이 하이드로 클로라이드(VA-044)을 투입한 것을 제외하고는 상기 실시예 1과 동일한 방법으로 장갑 형태의 딥 성형품을 수득하였다.In Example 1, when preparing the coagulating solution, 2,2'-azobis[2- A dip molded product in the form of a glove was obtained in the same manner as in Example 1, except that (2-imidazolin-2-yl)propane] dihydrochloride (VA-044) was added.
비교예Comparative example
비교예 1 Comparative Example 1
상기 실시예 1에서, 응고액 제조 시, 2,2'-아조비스[2-메틸-N-(2-하이드록시에틸)프로피온 아미드(VA-086)를 투입하지 않은 것을 제외하고는 상기 실시예 1과 동일한 방법으로 장갑 형태의 딥 성형품을 수득하였다.In Example 1, except that 2,2'-azobis[2-methyl-N-(2-hydroxyethyl)propion amide (VA-086) was not added when preparing the coagulating solution. A glove-shaped dip molded product was obtained in the same manner as in 1.
비교예 2 Comparative Example 2
상기 실시예 1에서, 응고액 제조 시, 2,2'-아조비스[2-메틸-N-(2-하이드록시에틸)프로피온 아미드(VA-086)를 3 중량부 투입하는 대신 1 중량부 투입한 것을 제외하고는 상기 실시예 1과 동일한 방법으로 장갑 형태의 딥 성형품을 수득하였다. In Example 1, when preparing the coagulating solution, 1 part by weight of 2,2'-azobis[2-methyl-N-(2-hydroxyethyl)propion amide (VA-086) was added instead of 3 parts by weight. A dip molded product in the form of a glove was obtained in the same manner as in Example 1 except for one thing.
비교예 3Comparative Example 3
상기 실시예 1에서, 응고액 제조 시, 2,2'-아조비스[2-메틸-N-(2-하이드록시에틸)프로피온 아미드(VA-086)를 3 중량부 투입하는 대신 5 중량부 투입한 것을 제외하고는 상기 실시예 1과 동일한 방법으로 장갑 형태의 딥 성형품을 수득하였다. In Example 1, when preparing the coagulating solution, 5 parts by weight of 2,2'-azobis[2-methyl-N-(2-hydroxyethyl)propion amide (VA-086) was added instead of 3 parts by weight. A dip molded product in the form of a glove was obtained in the same manner as in Example 1 except for one thing.
실험예Experiment example
실험예 1Experimental Example 1
상기 실시예 1 내지 6 및 비교예 1 내지 3에서 제조된 딥 성형품의 인장강도, 신율, 신율 300%에서의 응력(모듈러스) 신율 500%에서의 응력(모듈러스) 및 내구성에 대해 하기 조건으로 측정하여 하기 표 1에 나타내었다. The tensile strength, elongation, stress (modulus) at 300% elongation, stress (modulus) at 500% elongation, and durability of the dip molded products manufactured in Examples 1 to 6 and Comparative Examples 1 to 3 were measured under the following conditions. It is shown in Table 1 below.
* 인장강도(MPa), 신율(%), 신율 300%에서의 응력(MPa) 및 신율 500%에서의 응력(MPa): 각 실시예 및 비교예에서 수득한 딥 성형품에 대해서, ASTM D638 방법에 의하여, 테스트 기기인 U,T,M(제조사; Instron, 모델명; 4466)을 이용하여 크로스헤드 스피드를 500 mm/min으로 당긴 후, 신율이 각각 300%, 500% 일 때의 응력, 파단시의 신율 및 인장강도를 측정하였다.* Tensile strength (MPa), elongation (%), stress at 300% elongation (MPa) and stress at 500% elongation (MPa): For dip molded products obtained in each example and comparative example, according to ASTM D638 method After pulling the crosshead speed to 500 mm/min using test devices U, T, M (manufacturer; Instron, model name: 4466), the stress and fracture at elongation were 300% and 500%, respectively. Elongation and tensile strength were measured.
* 내구성: 상기 제조된 딥 성형품을 갈지자 모양의 시편으로 제조하여 인공적으로 만든 땀용액에 담궈 200% 신장시키는 것을 반복하면서 시편이 끊어질 때의 횟수를 측정하였다.* Durability: The above-mentioned dip molded product was manufactured into a rib-shaped specimen, immersed in an artificial sweat solution, stretched 200%, and repeatedly stretched to 200%, and the number of times the specimen broke was measured.
상기 표 1을 참조하면, 실시예 1 내지 6의 딥 성형품의 경우 응고액으로서 수용성 개시제를 3 중량부 포함함으로써, 인장강도, 신율 및 내구성이 동시에 향상된 것을 확인할 수 있었다. 보다 구체적으로, 실시예 1의 경우, 다른 실시예 대비 신율은 향상되었으며, 인장 강도는 다소 저하된 것을 확인할 수 있다. 또한, 실시예 6은 다른 실시예 대비 신율은 다소 저하되었으나, 인장강도는 우수한 것을 확인할 수 있다. 이는 수용성 개시제의 라디칼 생성 온도가 낮을수록 장갑의 가교도가 높아져 이러한 결과가 나타났음을 알 수 있다.Referring to Table 1, it was confirmed that in the case of the dip molded products of Examples 1 to 6, tensile strength, elongation, and durability were simultaneously improved by including 3 parts by weight of a water-soluble initiator as a coagulating liquid. More specifically, in the case of Example 1, it can be seen that the elongation was improved and the tensile strength was somewhat decreased compared to the other examples. In addition, it can be seen that Example 6 had slightly lower elongation compared to other Examples, but had excellent tensile strength. This shows that the lower the radical generation temperature of the water-soluble initiator, the higher the degree of crosslinking of the glove, resulting in this result.
이와 비교하여, 응고액으로서 수용성 개시제를 포함하고 있지 않은 비교예 1의 경우, 응고액 내 수용성 개시제의 부재로 인해 딥 성형품의 가교도가 낮아, 인장강도 및 내구성 저하된 것을 확인할 수 있었다.In comparison, in the case of Comparative Example 1, which did not contain a water-soluble initiator as the coagulating liquid, it was confirmed that the degree of cross-linking of the dip molded product was low due to the absence of a water-soluble initiator in the coagulating liquid, resulting in a decrease in tensile strength and durability.
또한, 응고액으로서 수용성 개시제를 포함하나, 본 발명에 따른 수용성 개시제 함량보다 적은 양을 투입한 비교예 2의 경우, 딥 성형품의 가교도가 낮아, 인장강도 및 내구성 저하된 것을 확인할 수 있었다.In addition, in the case of Comparative Example 2, which included a water-soluble initiator as a coagulating liquid but added a smaller amount than the water-soluble initiator content according to the present invention, it was confirmed that the degree of cross-linking of the dip molded product was low and the tensile strength and durability were reduced.
또한, 응고액으로서 수용성 개시제를 포함하나, 본 발명에 따른 수용성 개시제 함량보다 많은 양을 투입한 비교예 3의 경우, 신율이 저하된 것을 확인할 수 있었다.In addition, in the case of Comparative Example 3, which included a water-soluble initiator as the coagulating liquid but added an amount greater than that of the water-soluble initiator according to the present invention, it was confirmed that the elongation was decreased.
Claims (10)
상기 수용성 개시제는 2,2'-아조비스[2-메틸-N-(2-하이드록시에틸)프로피온 아미드], 4,4'-아조비스(4-시아노발레릭 산), 2,2'-아조비스[2-(2-이미다졸린-2-일)프로판], 2,2'-아조비스[2-(2-이미다졸린-2-일)프로판]다이 하이드로 클로라이드, 2,2'-아조비스(2-메틸 프로피온 아미딘)다이 하이드로 클로라이드 및 2,2'-아조비스[N-(2-카복시에틸)-2-메틸 프로피온 아미딘]테트라 하이드레이트로 이루어진 군에서 선택된 1종 이상을 포함하며,
상기 수용성 개시제의 함량은 딥 성형품 제조용 응고액 전체 100 중량부에 대하여 1.5 중량부 내지 4.5 중량부인 딥 성형품 제조용 응고액.Contains a coagulant, a solvent and a water-soluble initiator,
The water-soluble initiator is 2,2'-azobis[2-methyl-N-(2-hydroxyethyl)propion amide], 4,4'-azobis(4-cyanovaleric acid), 2,2' -Azobis[2-(2-imidazolin-2-yl)propane], 2,2'-Azobis[2-(2-imidazolin-2-yl)propane]dihydrochloride, 2,2 At least one selected from the group consisting of '-azobis(2-methyl propion amidine) dihydrochloride and 2,2'-azobis[N-(2-carboxyethyl)-2-methyl propion amidine] tetrahydrate Includes,
The content of the water-soluble initiator is 1.5 parts by weight to 4.5 parts by weight based on the total 100 parts by weight of the coagulating liquid for manufacturing dip molded products.
상기 수용성 개시제의 함량은 딥 성형품 제조용 응고액 전체 100 중량부에 대하여 2 중량부 내지 4 중량부인 딥 성형품 제조용 응고액.According to paragraph 1,
The content of the water-soluble initiator is 2 parts by weight to 4 parts by weight based on the total 100 parts by weight of the coagulating liquid for manufacturing dip molded products.
상기 응고제는 금속 할라이드, 질산염, 아세트산염 및 황산염으로 이루어진 군으로부터 선택된 1종 이상을 포함하는 것인 딥 성형품 제조용 응고액.According to paragraph 1,
The coagulant is a coagulant for manufacturing dip molded products, wherein the coagulant includes at least one selected from the group consisting of metal halides, nitrates, acetates, and sulfates.
상기 응고제는 질산염인 딥 성형품 제조용 응고액.According to paragraph 3,
The coagulant is a nitrate coagulant for manufacturing dip molded products.
상기 응고제의 함량은 딥 성형품 제조용 응고액 전체 100 중량부에 대하여 10 중량부 내지 50 중량부인 딥 성형품 제조용 응고액.According to paragraph 1,
The content of the coagulant is 10 parts by weight to 50 parts by weight based on the total 100 parts by weight of the coagulant for manufacturing dip molded products.
상기 용매는 물 및 알코올로 이루어진 군으로부터 선택된 1종 이상을 포함하는 것인 딥 성형품 제조용 응고액.According to paragraph 1,
The coagulating liquid for manufacturing dip molded products, wherein the solvent includes at least one selected from the group consisting of water and alcohol.
상기 용매의 함량은 딥 성형품 제조용 응고액 전체 100 중량부에 대하여 70 중량부 내지 90 중량부인 딥 성형품 제조용 응고액.According to paragraph 1,
The content of the solvent is 70 parts by weight to 90 parts by weight based on the total 100 parts by weight of the coagulating liquid for manufacturing dip molded products.
상기 응고액이 부착된 딥 성형틀에 딥 성형용 라텍스 조성물을 침지하여 딥 성형용 라텍스 조성물 유래층을 형성시키는 단계(S20); 및
상기 딥 성형용 라텍스 조성물 유래층을 가열하여 상기 딥 성형용 라텍스 조성물을 가교시키는 단계(S30)를 포함하는 딥 성형품 제조방법.Attaching the coagulating liquid according to any one of claims 1 to 7 to a dip mold (S10);
Forming a layer derived from the latex composition for dip molding by immersing the latex composition for dip molding in the dip mold to which the coagulating liquid is attached (S20); and
A method for manufacturing a dip molded product comprising the step (S30) of crosslinking the latex composition for dip molding by heating the layer derived from the latex composition for dip molding.
상기 딥 성형용 라텍스 조성물은 공액디엔계 단량체 유래 반복단위, 에틸렌성 불포화 니트릴계 단량체 유래 반복단위 및 에틸렌성 불포화산 단량체 유래 반복단위를 포함하는 카르본산 변성 니트릴계 공중합체 라텍스를 포함하는 것인 딥 성형품 제조방법.According to clause 8,
The latex composition for dip molding is a dip comprising a carboxylic acid-modified nitrile-based copolymer latex containing a repeating unit derived from a conjugated diene-based monomer, a repeating unit derived from an ethylenically unsaturated nitrile-based monomer, and a repeating unit derived from an ethylenically unsaturated acid monomer. Molded product manufacturing method.
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| KR20110038992A (en) * | 2009-10-09 | 2011-04-15 | 주식회사 엘지화학 | Carboxylated nitrile based copolymer latex, latex composition for dip-forming comprising the same, and the product thereof |
| KR101192276B1 (en) * | 2009-11-12 | 2012-10-18 | 주식회사 엘지화학 | Carboxylic acid modified-nitrile based copolymer latex for dip-forming, latex composition for dip-forming comprising the same |
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