JPS59100146A - Mixed vulcanization accelerator composition - Google Patents
Mixed vulcanization accelerator compositionInfo
- Publication number
- JPS59100146A JPS59100146A JP20849882A JP20849882A JPS59100146A JP S59100146 A JPS59100146 A JP S59100146A JP 20849882 A JP20849882 A JP 20849882A JP 20849882 A JP20849882 A JP 20849882A JP S59100146 A JPS59100146 A JP S59100146A
- Authority
- JP
- Japan
- Prior art keywords
- vulcanization accelerator
- vulcanization
- rubber
- weight
- mixed
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 238000004073 vulcanization Methods 0.000 title claims abstract description 90
- 239000000203 mixture Substances 0.000 title claims abstract description 48
- KUAZQDVKQLNFPE-UHFFFAOYSA-N thiram Chemical compound CN(C)C(=S)SSC(=S)N(C)C KUAZQDVKQLNFPE-UHFFFAOYSA-N 0.000 claims abstract description 17
- 229960002447 thiram Drugs 0.000 claims abstract description 16
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 claims abstract description 13
- QAZLUNIWYYOJPC-UHFFFAOYSA-M sulfenamide Chemical compound [Cl-].COC1=C(C)C=[N+]2C3=NC4=CC=C(OC)C=C4N3SCC2=C1C QAZLUNIWYYOJPC-UHFFFAOYSA-M 0.000 claims abstract description 13
- 238000003860 storage Methods 0.000 claims abstract description 11
- 238000000354 decomposition reaction Methods 0.000 claims abstract description 8
- 239000003381 stabilizer Substances 0.000 claims abstract description 6
- 229920001971 elastomer Polymers 0.000 claims description 31
- 239000003795 chemical substances by application Substances 0.000 claims description 10
- 238000002844 melting Methods 0.000 claims description 10
- 230000008018 melting Effects 0.000 claims description 10
- 238000010058 rubber compounding Methods 0.000 claims description 8
- YXIWHUQXZSMYRE-UHFFFAOYSA-N 1,3-benzothiazole-2-thiol Chemical compound C1=CC=C2SC(S)=NC2=C1 YXIWHUQXZSMYRE-UHFFFAOYSA-N 0.000 abstract description 8
- LGRFSURHDFAFJT-UHFFFAOYSA-N Phthalic anhydride Natural products C1=CC=C2C(=O)OC(=O)C2=C1 LGRFSURHDFAFJT-UHFFFAOYSA-N 0.000 abstract description 6
- JHIWVOJDXOSYLW-UHFFFAOYSA-N butyl 2,2-difluorocyclopropane-1-carboxylate Chemical compound CCCCOC(=O)C1CC1(F)F JHIWVOJDXOSYLW-UHFFFAOYSA-N 0.000 abstract description 5
- DEQZTKGFXNUBJL-UHFFFAOYSA-N n-(1,3-benzothiazol-2-ylsulfanyl)cyclohexanamine Chemical compound C1CCCCC1NSC1=NC2=CC=CC=C2S1 DEQZTKGFXNUBJL-UHFFFAOYSA-N 0.000 abstract description 5
- 239000000945 filler Substances 0.000 abstract description 4
- 229920000642 polymer Polymers 0.000 abstract description 4
- 239000004014 plasticizer Substances 0.000 abstract description 2
- 239000000654 additive Substances 0.000 abstract 1
- 239000005060 rubber Substances 0.000 description 25
- 239000000126 substance Substances 0.000 description 10
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 7
- 239000010734 process oil Substances 0.000 description 5
- ZRALSGWEFCBTJO-UHFFFAOYSA-N Guanidine Chemical compound NC(N)=N ZRALSGWEFCBTJO-UHFFFAOYSA-N 0.000 description 4
- IOJUPLGTWVMSFF-UHFFFAOYSA-N benzothiazole Chemical compound C1=CC=C2SC=NC2=C1 IOJUPLGTWVMSFF-UHFFFAOYSA-N 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 239000003921 oil Substances 0.000 description 4
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- 239000003153 chemical reaction reagent Substances 0.000 description 3
- 238000004898 kneading Methods 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 238000012545 processing Methods 0.000 description 3
- 239000000377 silicon dioxide Substances 0.000 description 3
- 229920003051 synthetic elastomer Polymers 0.000 description 3
- 239000005061 synthetic rubber Substances 0.000 description 3
- 239000004636 vulcanized rubber Substances 0.000 description 3
- UJPKMTDFFUTLGM-UHFFFAOYSA-N 1-aminoethanol Chemical compound CC(N)O UJPKMTDFFUTLGM-UHFFFAOYSA-N 0.000 description 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- 229920002943 EPDM rubber Polymers 0.000 description 2
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 2
- 239000005977 Ethylene Substances 0.000 description 2
- 244000043261 Hevea brasiliensis Species 0.000 description 2
- VQTUBCCKSQIDNK-UHFFFAOYSA-N Isobutene Chemical group CC(C)=C VQTUBCCKSQIDNK-UHFFFAOYSA-N 0.000 description 2
- CHJJGSNFBQVOTG-UHFFFAOYSA-N N-methyl-guanidine Natural products CNC(N)=N CHJJGSNFBQVOTG-UHFFFAOYSA-N 0.000 description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 2
- FZWLAAWBMGSTSO-UHFFFAOYSA-N Thiazole Chemical compound C1=CSC=N1 FZWLAAWBMGSTSO-UHFFFAOYSA-N 0.000 description 2
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Natural products NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 2
- DKVNPHBNOWQYFE-UHFFFAOYSA-N carbamodithioic acid Chemical compound NC(S)=S DKVNPHBNOWQYFE-UHFFFAOYSA-N 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- SWSQBOPZIKWTGO-UHFFFAOYSA-N dimethylaminoamidine Natural products CN(C)C(N)=N SWSQBOPZIKWTGO-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
- 239000012990 dithiocarbamate Substances 0.000 description 2
- VKYKSIONXSXAKP-UHFFFAOYSA-N hexamethylenetetramine Chemical compound C1N(C2)CN3CN1CN2C3 VKYKSIONXSXAKP-UHFFFAOYSA-N 0.000 description 2
- 229920003052 natural elastomer Polymers 0.000 description 2
- 229920001194 natural rubber Polymers 0.000 description 2
- 239000012188 paraffin wax Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 229920003048 styrene butadiene rubber Polymers 0.000 description 2
- 229910052717 sulfur Inorganic materials 0.000 description 2
- 239000011593 sulfur Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- RKQOSDAEEGPRER-UHFFFAOYSA-L zinc diethyldithiocarbamate Chemical compound [Zn+2].CCN(CC)C([S-])=S.CCN(CC)C([S-])=S RKQOSDAEEGPRER-UHFFFAOYSA-L 0.000 description 2
- JAEZSIYNWDWMMN-UHFFFAOYSA-N 1,1,3-trimethylthiourea Chemical compound CNC(=S)N(C)C JAEZSIYNWDWMMN-UHFFFAOYSA-N 0.000 description 1
- LFMQNMXVVXHZCC-UHFFFAOYSA-N 1,3-benzothiazol-2-yl n,n-diethylcarbamodithioate Chemical compound C1=CC=C2SC(SC(=S)N(CC)CC)=NC2=C1 LFMQNMXVVXHZCC-UHFFFAOYSA-N 0.000 description 1
- OWRCNXZUPFZXOS-UHFFFAOYSA-N 1,3-diphenylguanidine Chemical compound C=1C=CC=CC=1NC(=N)NC1=CC=CC=C1 OWRCNXZUPFZXOS-UHFFFAOYSA-N 0.000 description 1
- BUZICZZQJDLXJN-UHFFFAOYSA-N 3-azaniumyl-4-hydroxybutanoate Chemical compound OCC(N)CC(O)=O BUZICZZQJDLXJN-UHFFFAOYSA-N 0.000 description 1
- GIUBHMDTOCBOPA-UHFFFAOYSA-N 3h-1,3-benzothiazole-2-thione;zinc Chemical compound [Zn].C1=CC=C2SC(S)=NC2=C1 GIUBHMDTOCBOPA-UHFFFAOYSA-N 0.000 description 1
- BWGNESOTFCXPMA-UHFFFAOYSA-N Dihydrogen disulfide Chemical compound SS BWGNESOTFCXPMA-UHFFFAOYSA-N 0.000 description 1
- PDQAZBWRQCGBEV-UHFFFAOYSA-N Ethylenethiourea Chemical compound S=C1NCCN1 PDQAZBWRQCGBEV-UHFFFAOYSA-N 0.000 description 1
- FCSHMCFRCYZTRQ-UHFFFAOYSA-N N,N'-diphenylthiourea Chemical compound C=1C=CC=CC=1NC(=S)NC1=CC=CC=C1 FCSHMCFRCYZTRQ-UHFFFAOYSA-N 0.000 description 1
- UBUCNCOMADRQHX-UHFFFAOYSA-N N-Nitrosodiphenylamine Chemical compound C=1C=CC=CC=1N(N=O)C1=CC=CC=C1 UBUCNCOMADRQHX-UHFFFAOYSA-N 0.000 description 1
- AFCARXCZXQIEQB-UHFFFAOYSA-N N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical group O=C(CCNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 AFCARXCZXQIEQB-UHFFFAOYSA-N 0.000 description 1
- 229920000459 Nitrile rubber Polymers 0.000 description 1
- 239000005062 Polybutadiene Substances 0.000 description 1
- 235000021355 Stearic acid Nutrition 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000003712 anti-aging effect Effects 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- ZOUQIAGHKFLHIA-UHFFFAOYSA-L copper;n,n-dimethylcarbamodithioate Chemical compound [Cu+2].CN(C)C([S-])=S.CN(C)C([S-])=S ZOUQIAGHKFLHIA-UHFFFAOYSA-L 0.000 description 1
- 150000003946 cyclohexylamines Chemical class 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- AFZSMODLJJCVPP-UHFFFAOYSA-N dibenzothiazol-2-yl disulfide Chemical compound C1=CC=C2SC(SSC=3SC4=CC=CC=C4N=3)=NC2=C1 AFZSMODLJJCVPP-UHFFFAOYSA-N 0.000 description 1
- 150000001993 dienes Chemical class 0.000 description 1
- 235000014113 dietary fatty acids Nutrition 0.000 description 1
- VKFAUCPBMAGVRG-UHFFFAOYSA-N dipivefrin hydrochloride Chemical compound [Cl-].C[NH2+]CC(O)C1=CC=C(OC(=O)C(C)(C)C)C(OC(=O)C(C)(C)C)=C1 VKFAUCPBMAGVRG-UHFFFAOYSA-N 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 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
- 238000009472 formulation Methods 0.000 description 1
- ANSXAPJVJOKRDJ-UHFFFAOYSA-N furo[3,4-f][2]benzofuran-1,3,5,7-tetrone Chemical compound C1=C2C(=O)OC(=O)C2=CC2=C1C(=O)OC2=O ANSXAPJVJOKRDJ-UHFFFAOYSA-N 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 235000010299 hexamethylene tetramine Nutrition 0.000 description 1
- 239000004312 hexamethylene tetramine Substances 0.000 description 1
- 229920003049 isoprene rubber Polymers 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- OFHMODDLBXETIK-UHFFFAOYSA-N methyl 2,3-dichloropropanoate Chemical compound COC(=O)C(Cl)CCl OFHMODDLBXETIK-UHFFFAOYSA-N 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 230000000877 morphologic effect Effects 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- AZHYTXUTACODCW-UHFFFAOYSA-L n,n-dimethylcarbamodithioate;iron(2+) Chemical compound [Fe+2].CN(C)C([S-])=S.CN(C)C([S-])=S AZHYTXUTACODCW-UHFFFAOYSA-L 0.000 description 1
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 1
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 229920002857 polybutadiene Polymers 0.000 description 1
- 229920001083 polybutene Polymers 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000004886 process control Methods 0.000 description 1
- 238000003908 quality control method Methods 0.000 description 1
- -1 ray Chemical compound 0.000 description 1
- 239000012744 reinforcing agent Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000013040 rubber vulcanization Methods 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 239000008117 stearic acid Substances 0.000 description 1
- 238000010059 sulfur vulcanization Methods 0.000 description 1
- 229910052714 tellurium Inorganic materials 0.000 description 1
- PORWMNRCUJJQNO-UHFFFAOYSA-N tellurium atom Chemical compound [Te] PORWMNRCUJJQNO-UHFFFAOYSA-N 0.000 description 1
- 229920001897 terpolymer Polymers 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 238000004809 thin layer chromatography Methods 0.000 description 1
- SRPWOOOHEPICQU-UHFFFAOYSA-N trimellitic anhydride Chemical compound OC(=O)C1=CC=C2C(=O)OC(=O)C2=C1 SRPWOOOHEPICQU-UHFFFAOYSA-N 0.000 description 1
- 239000001993 wax Substances 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- BOXSVZNGTQTENJ-UHFFFAOYSA-L zinc dibutyldithiocarbamate Chemical compound [Zn+2].CCCCN(C([S-])=S)CCCC.CCCCN(C([S-])=S)CCCC BOXSVZNGTQTENJ-UHFFFAOYSA-L 0.000 description 1
- JRPGMCRJPQJYPE-UHFFFAOYSA-N zinc;carbanide Chemical group [CH3-].[CH3-].[Zn+2] JRPGMCRJPQJYPE-UHFFFAOYSA-N 0.000 description 1
- AUMBZPPBWALQRO-UHFFFAOYSA-L zinc;n,n-dibenzylcarbamodithioate Chemical compound [Zn+2].C=1C=CC=CC=1CN(C(=S)[S-])CC1=CC=CC=C1.C=1C=CC=CC=1CN(C(=S)[S-])CC1=CC=CC=C1 AUMBZPPBWALQRO-UHFFFAOYSA-L 0.000 description 1
- KMNUDJAXRXUZQS-UHFFFAOYSA-L zinc;n-ethyl-n-phenylcarbamodithioate Chemical compound [Zn+2].CCN(C([S-])=S)C1=CC=CC=C1.CCN(C([S-])=S)C1=CC=CC=C1 KMNUDJAXRXUZQS-UHFFFAOYSA-L 0.000 description 1
Landscapes
- Heating, Cooling, Or Curing Plastics Or The Like In General (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
Description
【発明の詳細な説明】
本発明は、スルフェンアミド系加硫促進剤，チウラム系
加硫促進剤を主成分とする混合物の分解安定剤として芳
香族酸無水物を用いることを特徴とする混合加硫促進剤
組成物に関するものである。Detailed Description of the Invention The present invention provides a mixture characterized in that an aromatic acid anhydride is used as a decomposition stabilizer for a mixture whose main components are a sulfenamide vulcanization accelerator and a thiuram vulcanization accelerator. The present invention relates to a vulcanization accelerator composition.
従来から、硫黄又は有機加硫剤を加硫剤とするゴム加硫
系において、加硫促進剤の使用は一般的であるが、未加
硫ゴムの加硫挙動及び得られた加硫ゴムの物性に種々の
特徴を持たせるために、加硫促進剤の２種以上の組合わ
せが行われている。特に、ＥＰＤＭの硫黄加硫系は、未
加硫ゴムの特徴ある加硫挙動、及び得られた加硫ゴムの
ブルーミングのため、特公昭夕乙一．２ｇ．２６Ｏ号公
報に示されているような数種の加硫促進剤の複雑な組合
わせが通常行われ、加硫促進剤の計量及び在庫管理を困
難にし、かつ未加硫ゴムの加工工程管理とともに加硫ゴ
ム製品の品質管理に著しく影響を与えている。Traditionally, in rubber vulcanization systems using sulfur or organic vulcanizing agents, the use of vulcanization accelerators has been common, but the vulcanization behavior of unvulcanized rubber and the resulting vulcanized rubber In order to provide various physical properties, two or more types of vulcanization accelerators are used in combination. In particular, the sulfur vulcanization system of EPDM is difficult to use due to the characteristic vulcanization behavior of unvulcanized rubber and the blooming of the obtained vulcanized rubber. 2g. Complicated combinations of several types of vulcanization accelerators, such as those shown in Publication No. 26O, are commonly used, making measurement and inventory control of vulcanization accelerators difficult, as well as processing process control for unvulcanized rubber. This has significantly affected the quality control of vulcanized rubber products.
これらの問題を解決するために、いくつかの混合加硫促
進剤が提案され市販されているが、未加硫ゴムの保存時
及び加工時にスコーチを起こし、ゴム製品化ができなく
なる問題があり、耐スコーチ性を充分に保持した混合加
硫促進剤は現在ゴム業界では皆無である。この理由は、
耐スコーチ性を保持させるために必要なスルフエンアミ
ド系加硫促進剤、特にＮ−シクロヘキシル−２−ベンゾ
チアジルスルフエンアミドが他の加硫促進剤、特にチウ
ラム系加硫促進剤と混合すると貯蔵中に、相互に反応し
あい１〜２日で分解反応を起こし、スルフエンアミド系
加硫促進剤と他の加硫促進剤との混合物を作製すること
は不可能に近いためである。In order to solve these problems, several mixed vulcanization accelerators have been proposed and commercially available, but they have the problem of causing scorch during storage and processing of unvulcanized rubber, making it impossible to produce rubber products. There is currently no mixed vulcanization accelerator in the rubber industry that maintains sufficient scorch resistance. The reason for this is
When sulfenamide-based vulcanization accelerators, especially N-cyclohexyl-2-benzothiazylsulfenamide, which are necessary to maintain scorch resistance, are mixed with other vulcanization accelerators, especially thiuram-based vulcanization accelerators, it may cause damage during storage. This is because they react with each other and cause a decomposition reaction in 1 to 2 days, making it nearly impossible to prepare a mixture of a sulfenamide vulcanization accelerator and other vulcanization accelerators.
本発明の目的は、スルフエンアミド系加硫促進剤と他の
加硫促進剤との混合物作製を容易に可能とするとともに
、耐スコーチ性及び貯蔵安定性に優れた混合加硫促進剤
を提供することにある。An object of the present invention is to provide a mixed vulcanization accelerator that allows easy preparation of a mixture of a sulfenamide vulcanization accelerator and other vulcanization accelerators, and has excellent scorch resistance and storage stability. It is in.
本発明者らは、鋭意研究した結果、融点が乙Ｏ℃以１−
のスルフェンアミド系加硫促進剤とチウラム系加硫促進
剤との混合物に芳香族酸無水物を混合することにより、
芳香族酸無水物がスルフェンアミド系加硫促進剤とチウ
ラム糸加硫促進剤との混合の分解安定剤として働くとと
もに、耐スコーチ性に優れ、かつ長期間の貯蔵安定性を
有する混合加硫促進剤となることを見いただした。As a result of intensive research, the present inventors found that the melting point is 1-0℃ or higher.
By mixing an aromatic acid anhydride into a mixture of a sulfenamide vulcanization accelerator and a thiuram vulcanization accelerator,
Mixed vulcanization in which aromatic acid anhydride acts as a decomposition stabilizer for the mixture of sulfenamide vulcanization accelerator and thiuram yarn vulcanization accelerator, and has excellent scorch resistance and long-term storage stability. It was found that it acts as a promoter.
更に、上記３者の混合物にスルフェンアミド系加硫促進
剤及びチウラム系加硫促進剤以外の融点乙ｏ℃以−Ｌの
加硫促進剤及び／又はその他のゴム用配合剤及び／又は
ゴム状高分子の添加混合も可能であることを見いだした
。Furthermore, a vulcanization accelerator with a melting point of 0°C or lower and/or other rubber compounding agents and/or rubber other than the sulfenamide vulcanization accelerator and the thiuram vulcanization accelerator is added to the mixture of the three above. It has been found that it is also possible to add and mix morphological polymers.
これらの知見に基づいて、この発明を完成するに至った
。Based on these findings, we have completed this invention.
この発明の要旨は、
（Ａ）融点が６００℃以上のスルフェンアミド系加硫促
進剤５〜８０重量％
（Ｂ）１種以上のチウラム糸加硫促進剤Ｓ〜ｑＯ ，ｉ
（惜％（Ｃ）芳香族酸無水物５〜２０重量％
ＬＤ）（Ａ）〜（Ｂ）以外の加硫促進剤で融点が６０℃
以上の１種以上の有機加硫促進剤０〜８０重量％
（Ｋ）（Ａ）〜（Ｄ）以外の１種以上のゴム用配合剤及
び／又はゴム状高分千０〜乙０重量％
芳香族酸無水物を分解安定剤として用いることを特徴と
する上記（Ａ）〜（Ｅ）より成る耐スコーチ性及び貯蔵
安定性に優れた混合加硫促進剤組成物。The gist of this invention is as follows: (A) 5 to 80% by weight of a sulfenamide vulcanization accelerator having a melting point of 600°C or higher (B) One or more thiuram yarn vulcanization accelerators S to qO,i
(Remaining% (C) Aromatic acid anhydride 5-20% by weight LD) Vulcanization accelerators other than (A) to (B) with a melting point of 60°C
0 to 80% by weight of one or more of the above organic vulcanization accelerators (K) 0 to 0% by weight of one or more rubber compounding agents and/or rubbery polymers other than (A) to (D) A mixed vulcanization accelerator composition having excellent scorch resistance and storage stability, comprising the above (A) to (E), characterized in that an aromatic acid anhydride is used as a decomposition stabilizer.
この発明の構成要素の詳細かつ具体的な説明を以下述べ
る。A detailed and specific explanation of the constituent elements of this invention will be described below.
本発明に係る混合加硫促進剤組成物の対象となるゴムは
、硫黄加硫可能な天然ゴム及びイソプレンゴム，ブタジ
ェンゴム，スチレン・ブタジエンゴム，アクリロニトリ
ル・ブタジエンゴム，エチレン．プロピン．ジエン三元
共重合体ゴム（ＥＰＤ１ｖｉ），イソブチレン・イソブ
レンゴムなどの合成ゴム又に天然ゴムとこれらの合成ゴ
ムとのブレンドゴム、これらの含成ゴム間のブレンドゴ
ムであって限定されるものではないが、特に好ましいも
のは、Ｅ ｝） Ｄ Ｍ：！−ＪよびＥ Ｐ Ｉ） Ｍ
とイソブチレン・イソブレンゴムとのブレンドゴムであ
る。The target rubbers for the mixed vulcanization accelerator composition according to the present invention include sulfur vulcanizable natural rubber, isoprene rubber, butadiene rubber, styrene-butadiene rubber, acrylonitrile-butadiene rubber, ethylene. Propine. Synthetic rubbers such as diene terpolymer rubber (EPD1vi), isobutylene/isobrene rubber, blend rubbers of natural rubber and these synthetic rubbers, and blend rubbers between these rubbers, but are not limited to However, particularly preferred ones are E }) DM:! -J and E P I) M
It is a blended rubber of isobutylene and isobrene rubber.
本発明に使用するＣＡ）融点がｔｏ’ｃ以上のスルフュ
ンアミドか加硫促進剤としては、Ｎ−シクロヘキシル−
２−ベンゾチアジルスルフエンアミド，Ｎ−オキシジエ
チレン−２−ベレゾチアジルスルフエンアミド，Ｎ−ｔ
ｅｒｔ−ブチル−２−ベンゾチアジルスルフエンアミド
，Ｎ，Ｎ−ジシクロへキシル−２−ベンゾチアジルスル
フエンアミドなどが拳げられるが、これらのものに限定
されるものではない。特に好ましいものは、Ｎ−シクロ
ヘキシル−２−べンゾチアジルスルフエンアミドである
。The sulfuramide or vulcanization accelerator used in the present invention is N-cyclohexyl-
2-benzothiazylsulfenamide, N-oxydiethylene-2-berezothiadylsulfenamide, N-t
Examples include, but are not limited to, ert-butyl-2-benzothiazylsulfenamide, N,N-dicyclohexyl-2-benzothiazylsulfenamide, and the like. Particularly preferred is N-cyclohexyl-2-benzothiazylsulfenamide.
本発明に係る混合加硫促進剤組成物中のこのスルフエン
アミド糸加硫促進剤成分は、５〜８０重量％であるが、
好ましくは７０〜３゛０重量％である。そのスルフエン
アミド系加硫促進剤成分が５重量％以下では充分な耐ス
コーチ性が確保できず、また８０重量％以上では貯蔵安
定性を充分に確保できないことから好ましくない。The sulfenamide yarn vulcanization accelerator component in the mixed vulcanization accelerator composition according to the present invention is from 5 to 80% by weight,
Preferably it is 70 to 30% by weight. If the sulfenamide vulcanization accelerator component is less than 5% by weight, sufficient scorch resistance cannot be ensured, and if it is greater than 80% by weight, sufficient storage stability cannot be ensured, which is not preferable.
本発明に使用する（Ｂ）チウラム系加硫促進剤としては
、テトラメチルチウラムジスルフイド，テトラエチルチ
ウラムジスルフイド，テトラール−ｎ−ブチルチウラム
ジスルフイド，テトンメチルチウラムモノスルフイド，
ジペンタメチレンチウラムヘキサスルフイドなどが挙げ
られるが、これらに限定されるものではない。特に好ま
しいものは、テトラメチルチウラムジスルフイド及びジ
ペンタメチレンへキサスルフイドである。The (B) thiuram-based vulcanization accelerator used in the present invention includes tetramethylthiuram disulfide, tetraethylthiuram disulfide, tetral-n-butylthiuram disulfide, tetramethylthiuram monosulfide,
Examples include, but are not limited to, dipentamethylene thiuram hexasulfide. Particularly preferred are tetramethylthiuram disulfide and dipentamethylene hexasulfide.
本発明に係る混合加硫促進剤組成物中のこのチウラム系
加硫促進剤成分は、５〜９０重量％であるが、好ましく
は１０〜９０重量％である。そのチウラム系加硫促進剤
成分が５重量％以下では充分な加硫促進効力を示さず、
９０重量％以上ては貯蔵安定性に欠けるとともに、充分
な耐スコ−チ性を確保できないため好ましくない。The amount of this thiuram-based vulcanization accelerator component in the mixed vulcanization accelerator composition according to the present invention is 5 to 90% by weight, preferably 10 to 90% by weight. If the thiuram-based vulcanization accelerator component is less than 5% by weight, it will not exhibit sufficient vulcanization accelerating effect,
If it exceeds 90% by weight, it is not preferable because it lacks storage stability and cannot ensure sufficient scorch resistance.
本発明に使用する（Ｃ）芳香族酸無水物としては、無水
フタル酸， ．無水トリメリット酸、無水ピロメリット
酸などが挙げられるが、これらに限定されるものではな
い。特に好ましいものは、無水フタル酸である。The aromatic acid anhydride (C) used in the present invention includes phthalic anhydride, . Examples include, but are not limited to, trimellitic anhydride and pyromellitic anhydride. Particularly preferred is phthalic anhydride.
本発明に係る混合加硫促進剤組成物中の芳香族酸無水物
成分は、５〜２０重量％であるが、好ましくは５〜１０
重量％である。その芳香族酸無水物成分が５重量％以下
では、本発明に係る混合加硫促進剤組成物の分解安定剤
としての効果が発揮できず、２０重量％以上では、芳香
族酸無水物本来の効果である加硫遅延効果を示すため好
ましくない。The aromatic acid anhydride component in the mixed vulcanization accelerator composition according to the present invention is 5 to 20% by weight, preferably 5 to 10% by weight.
Weight%. If the aromatic acid anhydride component is less than 5% by weight, the mixed vulcanization accelerator composition according to the present invention cannot exhibit its effect as a decomposition stabilizer, and if it is more than 20% by weight, the aromatic acid anhydride component This is not preferable because it exhibits a vulcanization retardation effect.
本発明に使用する（Ｄ）上記（Ａ）〜（Ｅ）以外の融点
が６０℃以上の加硫促進剤としては、次に示すチアゾー
ル系加硫促進剤，ジチオカルバミン酸塩系加硫促進剤，
アルデヒドアンモ二ア系加硫促進剤，チオウレア系加硫
促進剤及びグアニジン系加硫促進剤などが挙げられるが
、これらのものに限定されるものではない。(D) Vulcanization accelerators other than the above (A) to (E) with a melting point of 60°C or higher used in the present invention include the following thiazole-based vulcanization accelerators, dithiocarbamate-based vulcanization accelerators,
Examples include aldehyde ammonia-based vulcanization accelerators, thiourea-based vulcanization accelerators, and guanidine-based vulcanization accelerators, but are not limited to these.
すなわち、チアゾール系加硫促進剤としては、２−メル
カートベンゾチアゾール，ジベンゾチアジルジスルフイ
ド，２−メルカプトベンゾチアゾールの亜鉛’Ｍ，”Ｃ
Ｊｓｐ’−シニトロフエニルチオ）ベンゾチアゾール，
２−メルカプトベンゾチアゾールのシクロヘキシルアミ
ン塩，．２−（Ｎ，Ｎ−ジエチルチオカルバモイルチオ
）ベンゾチアゾール，２−（４′−モルホリノジチオ）
ベンゾチアゾールなどが挙げられるが、特に好ましいも
のは２−メルカブトベンゾチアゾールである。That is, as the thiazole-based vulcanization accelerator, 2-mercaptobenzothiazole, dibenzothiazyl disulfide, 2-mercaptobenzothiazole zinc'M, "C
Jsp'-sinitrophenylthio)benzothiazole,
Cyclohexylamine salt of 2-mercaptobenzothiazole, . 2-(N,N-diethylthiocarbamoylthio)benzothiazole, 2-(4'-morpholinodithio)
Examples include benzothiazole, but particularly preferred is 2-mercabutobenzothiazole.
また、ジチオカルバミン酸塩系加硫促進剤としては、ジ
メチルジヂオカルバミン酸亜鉛，ジエチルジチオカルバ
ミン酸亜鉛，ジ−ｎ−ブチルジチオカルバミン酸亜鉛，
Ｎ−エチル−Ｎ−フェニルジチオカルバミン酸亜鉛，Ｎ
−ペンタメチレンジチオカルバミン酸亜鉛，Ｎ，Ｎ−ジ
ベンジルジチオカルバミン酸亜鉛，ジメチルジチオカル
バミン酸銅，ジメチルジチオカルバミン酸鉄，ジエチル
ジオカルバミン酸テルルなどが挙げれらるが、特に好ま
しいのは、ジエチルジチオカルバミン酸亜鉛，Ｎ−エチ
ル−Ｎ−フェニルジチオカルバミン酸亜鉛である。In addition, the dithiocarbamate-based vulcanization accelerators include zinc dimethyl didiocarbamate, zinc diethyldithiocarbamate, zinc di-n-butyldithiocarbamate,
Zinc N-ethyl-N-phenyldithiocarbamate, N
-Zinc pentamethylene dithiocarbamate, zinc N,N-dibenzyldithiocarbamate, copper dimethyldithiocarbamate, iron dimethyldithiocarbamate, tellurium diethyldiocarbamate, etc., but particularly preferred are zinc diethyldithiocarbamate, N, -ethyl-N-phenyldithiocarbamate zinc.
更に、アルデヒドアンモニア系加硫促進剤，チオウレア
系加硫促進剤及びグアニジン系加硫促進剤としては、ヘ
キサメチレンテトラミン，Ｎ，Ｎ’−ジフエニルチオ尿
素，トリメチルチオ尿素，Ｎ， ’Ｎ’−ジエチルチオ
尿素，エチレンチオ尿素，１，３−ジフェニルグアニジ
ン，ジ−０−トリルグアニジン，１−０−トリルビンア
ニド，ジカテコールポレートのジ−０−トリルグアニジ
ン塩などが挙げられるが、これら３種の加硫促進剤は加
硫速度調節用として用いることができる。Furthermore, as the aldehyde ammonia-based vulcanization accelerator, thiourea-based vulcanization accelerator, and guanidine-based vulcanization accelerator, hexamethylenetetramine, N,N'-diphenylthiourea, trimethylthiourea, N,'N'-diethylthiourea, , ethylenethiourea, 1,3-diphenylguanidine, di-0-tolylguanidine, 1-0-tolyrubinanide, and di-0-tolylguanidine salt of dicatecolporate. It can be used to adjust the vulcanization rate.
本発明に係る混各加硫促進剤組成物中の上記（Ａ）〜（
Ｂ）以外の融点が６０℃以上の加硫促進剤成分は０〜８
０重量％である点が６０℃以上の加硫促進剤成分が、８
０重量％以上では耐スコーチ性の特徴を充分に発揮でき
ない場合があり好ましくない。The above (A) to (
Vulcanization accelerator components other than B) with a melting point of 60°C or higher are 0 to 8.
The vulcanization accelerator component whose temperature is 60°C or higher is 8% by weight.
If it is more than 0% by weight, the scorch resistance characteristics may not be fully exhibited, which is not preferable.
本発明に使用す（Ｅ）、上記（Ａ）で（Ｄ＞以外のゴム
用配合剤及び／又はゴム状高分子としては、次に示すも
のが挙げられるが、これらのものに限定されるものでは
ない。この（Ａ）〜（Ｄ）以外のゴム用配合剤及び／又
はゴム状高分子は、本発明に係る混合加硫促進剤組成物
の飛散防止用，成型時のバインダー用などに用いられる
。Examples of rubber compounding agents and/or rubbery polymers other than (D) in (E) and (A) above used in the present invention include, but are not limited to, the following: Rubber compounding agents and/or rubbery polymers other than these (A) to (D) may be used to prevent scattering of the mixed vulcanization accelerator composition according to the present invention, as a binder during molding, etc. It will be done.
すなわち、ゴム用配含剤としては、．炭酸カルシウム系
，レー系，シリカ系及びカーボンブラックなどの充てん
剤又は補強剤，パラフィン系，ナフテン系及びアロマ系
の加工油などの軟化剤，ポリブテン系及びエステル系の
可塑剤，ステアリン酸などの高級脂肪酸及び融点５０℃
以上のゴム用ワックスなどの滑剤，２，．２，ゲートリ
メチルー／，２−ジヒドロキノリンの重合体などの老化
防止剤が挙げられる。In other words, as a rubber compounding agent, . Fillers or reinforcing agents such as calcium carbonate, ray, silica and carbon black, softeners such as paraffin, naphthenic and aromatic processing oils, polybutene and ester plasticizers, and high grade materials such as stearic acid. Fatty acid and melting point 50℃
Lubricants such as the above rubber waxes, 2. Examples include anti-aging agents such as polymers of 2,gatelymethyl-/,2-dihydroquinoline.
また、ゴム状高分子としては、スチレン・ブタジエンゴ
ム及びエチレン．プロビレンゴム（ＥＰＤＭ又はＥｐＲ
）などの合成ゴムが挙げられる。Examples of rubbery polymers include styrene-butadiene rubber and ethylene. Probylene rubber (EPDM or EpR)
) and other synthetic rubbers.
本発明に係る混合加硫促進剤組成物中の上記（Ａ）〜（
Ｄ）以外のゴム用配合剤及び／又はゴム状高分子成分は
、０〜６０重量％であるが、好ましくはＯ〜３０重量％
である。その（Ａ）〜（Ｄ）以外のゴム用配合剤及び／
又はゴム状高分子成分が、１０重量％以上では本発明に
係る混合加硫促進剤組成物中の加硫促進剤成分が減少し
、本発明の対象となるゴムへ本発明に係る混合加硫促進
剤組成物を添加する場合、その添加量が増大し・不経済
であるため好ましくない。The above (A) to ( in the mixed vulcanization accelerator composition according to the present invention)
The rubber compounding agent and/or rubbery polymer component other than D) is 0 to 60% by weight, preferably 0 to 30% by weight.
It is. Rubber compounding agents other than (A) to (D) and/or
Or, if the rubber-like polymer component is 10% by weight or more, the vulcanization accelerator component in the mixed vulcanization accelerator composition according to the present invention decreases, and the mixed vulcanization according to the present invention is not applied to the rubber that is the object of the present invention. When an accelerator composition is added, the amount added increases and is uneconomical, which is not preferable.
次に本発明の実施の態様を述べる。Next, embodiments of the present invention will be described.
１０ｌ小型ダッシュニーダ（川一機械製作所製）にノク
セラ−０２２！；Ｏｇ，を仕込み、高速かくはんしなが
ら／クセラーＴＴ／００ｇ，，ノクセラーＭ／００ｇ，
ノクセラーＥ２．７０ｇ，スコノック ７／Ｏｆ，三菱
ＩＯライトプロセス油２ｏｏｇ，，カープレノクス乙７
７３０ｇ及びノクラック．２２≠ｓ ．．ｏｇを順に添
加し、その後５分間かくはんし、グッシュニーダかも淡
黄白色の粉末混合物９９０ｇ（収率９ｑ％）を得た。こ
の淡黄白色の粉末混合物が本発明に係る混合加硫促進剤
組成物である。Noxela-022 for 10l small dash kneader (manufactured by Kawaichi Kikai Seisakusho)! ; While preparing Og, and stirring at high speed/Kuseler TT/00g,, Noxeller M/00g,
Noxel E2.70g, Sconok 7/Of, Mitsubishi IO light process oil 2oog,, Carple Nox Otsu 7
730g and nocrack. 22≠s. ．． After that, the mixture was stirred for 5 minutes to obtain 990 g (yield: 9 q%) of a pale yellowish white powder mixture. This pale yellow-white powder mixture is the mixed vulcanization accelerator composition according to the present invention.
ノクセラーＣＺ：大内新興化学工業株式会社製Ｎ−シク
ロヘキシル−２−ベンゾチアジルスル
フエンアミドの商品名
ノクセラーＮＳ：大内新興化学工業株式会社製Ｎ−Ｐブ
チル−２−ベンゾチアジスルフェ
ンアミドの商品名
ノクセラーＴ Ｔ二大内新興化学工業株式会社製テトラ
メチルチウラムジスルフィドの商品名
スコノツク７二大内新興化学工業・株式会社製無水フタ
ル酸の商品名
三菱１０ライトプロセス油：三菱石油株式会社製パラフ
ィン系油の商品名
カーブレックス乙７：シオノギ製薬体式会社製シリカ系
充てん剤の商品名
本発明は、上記実施方法に限定されるものではない。Noxela CZ: Trade name of N-cyclohexyl-2-benzothiazylsulfenamide manufactured by Ouchi Shinko Chemical Co., Ltd. Noxel NS: N-P butyl-2-benzothiadisulfenamide manufactured by Ouchi Shinko Chemical Co., Ltd. Product name of NOCCELER T TProduct name of tetramethylthiuram disulfide manufactured by Ni-Ouchi Shinko Kagaku Kogyo Co., Ltd.Product name of phthalic anhydride manufactured by Ni-Ouchi Shinko Kagaku Kogyo Co., Ltd.Mitsubishi 10 Light process oil: Mitsubishi Oil Corporation Carbrex Otsu 7: Trade name of silica-based filler manufactured by Shionogi Pharmaceutical Co., Ltd. The present invention is not limited to the above implementation method.
以下、実施例にて、本発明に係る混合加硫促進剤組成物
の製造例及びその混合加硫促進剤組成物の効果について
詳細に示す。Hereinafter, in Examples, manufacturing examples of the mixed vulcanization accelerator composition according to the present invention and the effects of the mixed vulcanization accelerator composition will be shown in detail.
実施例１．本発明混合加硫促進剤組成物の製造例（１）
１０ｌ小型ダッシュニーダ（川越機械製作所製）にノク
セラーＣＺ／３０已を仕込み、高速かくはんしながらノ
クセラ−ＮＳ／ｊ（１＋ｇ，／クセラーＴＴ２！；Ｏｇ
．スコノックク７ノｏｏｙ，，三菱／０ライトプロセス
油ｊ０ｇ及びカーブレックス７３００ｇを順に添加し、
その後５分間かくはんし、ダッシュニーダから白色の湿
潤性粉末混合物ｑｑｏｇ（収率９ｑ％）を得た。Example 1. Production example (1) of the mixed vulcanization accelerator composition of the present invention
Pour Noxela CZ/30 into a 10l small dash kneader (manufactured by Kawagoe Kikai Seisakusho), and mix with Noxela-NS/j (1+g, /xela TT2!; Og) while stirring at high speed.
．． Add 7300g of Mitsubishi/0 light process oil and 7300g of Carbrex in order.
Thereafter, the mixture was stirred for 5 minutes, and a white wet powder mixture qqog (yield: 9q%) was obtained from a dash kneader.
この白色の湿潤性扮未混合物は本発明に係る混合加硫促
進剤組成物である。This white wettable unmixed mixture is the mixed vulcanization accelerator composition according to the present invention.
ノクセラーＣｚ：大内新興化学工業株式会社１．ｆｌＮ
−シクロヘキシル−２−べんゾチアジスルスル７エンア
ミドの商品名
ノク七ラーＮ８・大内新興化学工業株式会社製Ｓφ
ブチル−２−ベンゾチアジスルフェ
ンアミドの商品名
ノクセラーＴＴ：犬内Ｎｒ興化学工業株式会社製テ１・
ラメチルチウラムジスルフイドの商品名
スコノック７：大内新興化学］−：業林式会社製無水フ
タル酸の商品名
三菱ノ０ライトプロセスオイル：三菱百’ｔ１ｈ林式会
社裂パラフィン糸油の商品名
カープレックス６７：シオノギ製桑株式会旧戟シリカ系
充てん剤の商品名
実施例！．本発明混合加硫促進剤組成物の製造例（２）
ｒ′練りアール機に三井ＥＰＴ．ＥＯ７０２００ｇを巻
きつけ、通常のゴム混練り手法により、ノクセラーＣＺ
．２００．２，ノクセラーＴＴ２ＪＯｇ．ノクセラーＭ
／００ｇ，ノクセラーＰＸ／ｊＯｇ，スコノノク７ＳＯ
ｇ及びノクラノク２２’ｌＪＯｐ，を順に混練りして、
淡黄白色のゴム配合物９９０ｇ（収率９９％）を得た。Noxeller Cz: Ouchi Shinko Chemical Industry Co., Ltd. 1. flN
-Product name of cyclohexyl-2-benzothiadisulfenamide Nokushichilar N8 manufactured by Ouchi Shinko Kagaku Kogyo Co., Ltd.Sφ Butyl-2-benzothiadisulfenamide trade name Noxeler TT: Inunai Nr Koka Kagaku Kogyo Co., Ltd. Company made Te1・
Product name of methyl thiuram disulfide Sconoc 7: Ouchi Shinko Chemical] -: Product name of phthalic anhydride manufactured by Gyorin Shiki Company Mitsubishi no 0 light process oil: Mitsubishi Hyaku't1h Hayashi Shiki Company's cracked paraffin thread oil product Carplex 67: Shionogi Kuwa Co., Ltd. Old Geki silica-based filler product name example! ．． Production example (2) of the mixed vulcanization accelerator composition of the present invention
Mitsui EPT. Wrap 200g of EO70 and use the usual rubber kneading method to make Noxeler CZ.
．． 200.2, Noxela TT2JOg. Noxeller M
/00g, Noxel PX/jOg, Sukononoku 7SO
g and Nokranoku 22'lJOp, are kneaded in order,
990 g (yield: 99%) of a pale yellow-white rubber compound was obtained.
この淡黄白色のゴム配合物は本発明に係る混合加硫促進
剤組成物である。This pale yellow-white rubber compound is a mixed vulcanization accelerator composition according to the present invention.
Ｅ三井Ｂ： Ｐ’Ｌ’３０７ｏ：玉丼石油化学株式会ｐ
Ｉ：７７ Ｐ Ｄ ｄの商品名
ノクセラ−Ｍ＝大内新興化学工業株式会製 ２−メルカ
プトベンゾチアゾールの商品名
ノクセラーｐｘ：大内新興化学工業株式会１′Ｊ二・展
Ｎ一エチル−Ｎ−フエニルジチオカルバミン酸亜鉛の商
品名
ノクラック，２２４：大内新興化学工業林式会社製ポ１
１１（２．２Ａｌ−トリメチルー／，２−シヒドロキノ
リン）の商品名
実施例３．本発明混合加硫促進剤組成物の貯蔵安定性上
記実施例１−２の混合加硫促進剤組成物の製造例に準じ
て作製した混合物２０ｇを直径１０ｃｍガラス製シャー
レに取り、１１０℃の恒温槽にて経時変化を観察し、更
にこの混合物の経時変化物を５ｍｇサンプリングし、１
ｍｌのジクロルメタンに溶解させ、薄層クロマトグラフ
イ−（展開液振ベン夫し
ゼン：酢酸エチル−９０：／０の容積比の混合液，発色
剤２．６− ジクロルキノン−４−クロルイミドの２％
エタノール溶液）にて分解生成物の有無を表−１に示す
各有機加硫促進剤の標準物との対比で確認した。その結
果を表−１に示す。E Mitsui B: P'L'307o: Tamadon Petrochemical Co., Ltd. p
I: 77 P D d trade name Noxela-M = manufactured by Ouchi Shinko Kagaku Kogyo Co., Ltd. Trade name of 2-mercaptobenzothiazole Noxela px: Ouchi Shinko Kagaku Kogyo Co., Ltd. - Zinc phenyldithiocarbamate trade name NOCRAC, 224: Po1 manufactured by Ouchi Shinko Kagaku Kogyo Hayashiki Company
Trade name of 11 (2.2Al-trimethyl-/,2-cyhydroquinoline) Example 3. Storage stability of the mixed vulcanization accelerator composition of the present invention 20 g of the mixture prepared according to the production example of the mixed vulcanization accelerator composition of Example 1-2 above was placed in a glass petri dish with a diameter of 10 cm, and kept at a constant temperature of 110°C. Observe the change over time in the tank, and sample 5 mg of the mixture over time.
ml of dichloromethane, and thin-layer chromatography (developing solution: dichloroquinone:ethyl acetate, a mixture with a volume ratio of 90:/0, color former: 2.6-dichloroquinone-4-chloroimide, 2%).
The presence or absence of decomposition products was confirmed by comparison with the standards of each organic vulcanization accelerator shown in Table 1. The results are shown in Table-1.
ベンゼン：純正化学株式会社製試薬生１級品−１：．酸
エチル：純正化学株式会社製試部特級品ｌ）ノクセラー
Ｃｚ：大内新興化学工業株式会社商品名．２）ノクセラ
ーＮＳ；大内新幕化学工業株式会社商品名．３）ノクセ
ラーＰＢｋ：大内新興化学工業株式会社商品名，融点３
６〜乙Ｏ′ｃｌｌ）ノクセラーＴＴ．二大内新興化学工
業株式会社商品名．５）ノクセラー’Ｉ’ＲＡ：大内新
興化学工業株式会社商品名．名）ノクセラーＭ二大内新
興化学工業株式会゜社商品名．７）ノクセラーＭ−６１
）：大内新興化学工業株式会社商品名，ｔ）ノクセラー
Ｅｚ＝大内新興化学工業株式会社商品名２９）ノク．セ
．ラー．．Ｐｘ．：′大内新興化学工業株式会社商品名
．／Ｏ）ノクセラーｌｒ：大内新興化学工業株式会社商
品名．常温で液体．／／）スコノック２：大内新興化学
工業林式会社商品名．／．２）純正化学株式会社製試薬
一級品．ｌ３）純正化学株式会社製試薬一級品．ｌｌ／
．）サントガードＰＶ工：三菱モンサヒト．株式会社商
品名．ｌ５）ルナノクＳ−．２０＝花王石鹸株式会社商
品名．＃；）手，ｉｉｉ／Ｏライトプロセス油：三菱石
油株式会社商品名．ｌ７）シルバー：白石工業株式会社
商品名．．ｉ，ｒ）カープレンクス６７：シオノギ製薬
株式会社商品名．／ｔｑ’）三井Ｋ ＰＴ’３１．’０
””７’０：三井石油化学？株式会社商品名．．２ｏ）
ノクラック．（ポリ（２２ｌトリメチル／，２ジヒドロ
キノ’Ｊ＞））：大内新興化学工業株式会社商品名／流
れる：混合物が軟化し、その表面がベタ付く状態を示す
。Benzene: Reagent grade 1 product manufactured by Junsei Kagaku Co., Ltd.-1:. Ethyl acid: Special grade product manufactured by Junsei Kagaku Co., Ltd. l) Noxeler Cz: Product name of Ouchi Shinko Kagaku Kogyo Co., Ltd. 2) Noxeler NS; Ouchi Shinmaku Chemical Industry Co., Ltd. product name. 3) Noxeler PBk: Ouchi Shinko Chemical Industry Co., Ltd. trade name, melting point 3
6~O'cll) Noxeller TT. Product name of Ni-Ouchi Shinko Chemical Industry Co., Ltd. 5) Noxeler 'I'RA: Ouchi Shinko Chemical Industry Co., Ltd. product name. Name) Noxeler M Ni-Ouchi Shinko Kagaku Kogyo Co., Ltd. Product name. 7) Noxela M-61
): Ouchi Shinko Kagaku Kogyo Co., Ltd. product name, t) Noxela Ez = Ouchi Shinko Kagaku Kogyo Co., Ltd. product name 29) Noku. C. Ra. ．． Px. :'Ouchi Shinko Chemical Industry Co., Ltd. product name. /O) Noxeller lr: Ouchi Shinko Chemical Industry Co., Ltd. product name. Liquid at room temperature. //) Sconoc 2: Ouchi Shinko Chemical Industrial Forest Company product name. /． 2) First-class reagent manufactured by Junsei Kagaku Co., Ltd. l3) First-class reagent manufactured by Junsei Kagaku Co., Ltd. ll/
．． ) Santo Guard PV Engineering: Mitsubishi Monsahit. Co., Ltd. product name. l5) Lunanok S-. 20 = Kao Soap Co., Ltd. product name. #;) Hand, III/O light process oil: Mitsubishi Oil Corporation product name. l7) Silver: Shiraishi Kogyo Co., Ltd. product name. ．． i, r) Carplainx 67: Shionogi Pharmaceutical Co., Ltd. trade name. /tq') Mitsui K PT'31. '0
""7'0: Mitsui Petrochemical? Co., Ltd. product name. ．． 2o)
Nocrack. (Poly(22l trimethyl/, 2 dihydroquino'J>)): Ouchi Shinko Chemical Industry Co., Ltd. trade name/Flowing: Indicates a state in which the mixture softens and its surface becomes sticky.
実施例４．本発明混合加硫促進剤組成物のＩＩＰＤＭに
おける耐スコーチ性及び加硫促進能力
表−２に示した配合表に基づいて、ロール表面温度／０
０℃の練りロール機により通常の混練り方法で表−３に
示した熱処理有無の混合加硫促進剤を含有する混練りゴ
ムを作製した。この混練りゴムを用いて、Ｊ工ＳＫ乙３
００に準じ、１２５ ’ａにおけるスコーチタイム（ｔ
ｊ）を測定した。更に、この混練りゴムを用いて、東洋
精機製作所製レオメータ（試験温度：／乙Ｏ℃，乙ｃｐ
ｍ，ダイス：Ｊ Ｏ ｍｍ ｆ ）でＳＲ工Ｓ３７０２
／９７７（日本ゴム協会標準規格加硫試試験機による加
硫試験方法）に基づくＭＨ，（トルクの最大値）の”：
’ｃ（９（７）Ｃｑｏ％加硫時間）を加硫速度として測
定した。その結果を表−３に示す。／
表−１及び表一２の結果から、本発明に係る混合加硫促
進剤組成物（本発明品）は、比較例及び参考例（市販品
も含む）に比較して、著しく優れた耐スコーチ性及び速
い加硫速度〔ｔ’ｃ（９０） ）の特性をもつことは
明らかである（表一／）。Example 4. Scorch resistance and vulcanization accelerating ability in IIPDM of the mixed vulcanization accelerator composition of the present invention Based on the formulation shown in Table-2, roll surface temperature/0
Kneaded rubbers containing the mixed vulcanization accelerators shown in Table 3 with and without heat treatment were prepared using a conventional kneading method using a kneading roll machine at 0°C. Using this kneaded rubber, J Engineering SK Otsu 3
According to 00, the scorch time (t
j) was measured. Furthermore, using this kneaded rubber, a rheometer manufactured by Toyo Seiki Seisakusho (test temperature: /O 0℃, Otsucp
m, dice: J O mm f) SR work S3702
MH, (maximum value of torque) based on /977 (Japan Rubber Association standard vulcanization test method using vulcanization testing machine):
'c (9(7)Cqo% vulcanization time) was measured as the vulcanization rate. The results are shown in Table-3. / From the results in Tables 1 and 2, the mixed vulcanization accelerator composition according to the present invention (product of the present invention) has significantly superior durability compared to comparative and reference examples (including commercially available products). It is clear that it has the characteristics of scorchability and fast vulcanization rate [t'c(90)] (Table 1/).
更に、貯蔵安定性が著しく優れていることは明らかであ
る。Furthermore, it is clear that the storage stability is extremely good.
Claims (1)
剤５〜８０重量％′ （Ｂ）１種以上のチウラム系加硫促進剤５〜９０重量％
（Ｃ）芳香族酸無水物５−．２’Ｏ重量％（Ｄ）（Ａ）
〜（Ｂ）以外の加硫促進剤で、融点が６０℃以上の１種
以上の有機加硫促進剤 ０−８０重量％（Ｅ）（Ａ）〜
（Ｄ）以外の１種以上のゴム用配合剤及び／又１はゴム
状高分子０〜１０重量％ 芳香族酸無水物を分解安定剤として用いることを特徴と
する上記（Ａ）〜（１）より成る耐スコーチ性及び貯蔵
安定性に優れた混合加硫促進剤組成物。[Scope of Claims] (A) 5 to 80% by weight of a sulfenamide vulcanization accelerator with a melting point of 60°C or higher' (B) 5 to 90% by weight of one or more thiuram vulcanization accelerators
(C) Aromatic acid anhydride 5-. 2'O weight% (D) (A)
~One or more organic vulcanization accelerators other than (B) with a melting point of 60°C or higher 0-80% by weight (E) (A)~
(A) to (1) above, characterized in that one or more rubber compounding agents other than (D) and/or 1 is a rubbery polymer 0 to 10% by weight and an aromatic acid anhydride is used as a decomposition stabilizer. ) A mixed vulcanization accelerator composition having excellent scorch resistance and storage stability.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP20849882A JPS59100146A (en) | 1982-11-30 | 1982-11-30 | Mixed vulcanization accelerator composition |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP20849882A JPS59100146A (en) | 1982-11-30 | 1982-11-30 | Mixed vulcanization accelerator composition |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS59100146A true JPS59100146A (en) | 1984-06-09 |
| JPH0142299B2 JPH0142299B2 (en) | 1989-09-12 |
Family
ID=16557149
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP20849882A Granted JPS59100146A (en) | 1982-11-30 | 1982-11-30 | Mixed vulcanization accelerator composition |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS59100146A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2011526632A (en) * | 2008-07-03 | 2011-10-13 | ライン・ケミー・ライノー・ゲーエムベーハー | Method and device for producing crosslinkable rubber mixture |
-
1982
- 1982-11-30 JP JP20849882A patent/JPS59100146A/en active Granted
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2011526632A (en) * | 2008-07-03 | 2011-10-13 | ライン・ケミー・ライノー・ゲーエムベーハー | Method and device for producing crosslinkable rubber mixture |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0142299B2 (en) | 1989-09-12 |
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