JPH04180944A - Halogenated butyl rubber composition - Google Patents
Halogenated butyl rubber compositionInfo
- Publication number
- JPH04180944A JPH04180944A JP30712390A JP30712390A JPH04180944A JP H04180944 A JPH04180944 A JP H04180944A JP 30712390 A JP30712390 A JP 30712390A JP 30712390 A JP30712390 A JP 30712390A JP H04180944 A JPH04180944 A JP H04180944A
- Authority
- JP
- Japan
- Prior art keywords
- formula
- group
- carbon atoms
- butyl rubber
- compd
- 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.)
- Pending
Links
- 229920005555 halobutyl Polymers 0.000 title claims abstract description 16
- 239000000203 mixture Substances 0.000 title claims abstract description 16
- 238000004073 vulcanization Methods 0.000 claims abstract description 29
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 claims abstract description 18
- 229960002447 thiram Drugs 0.000 claims abstract description 17
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 14
- 229910052751 metal Inorganic materials 0.000 claims abstract description 13
- 239000002184 metal Substances 0.000 claims abstract description 13
- KUAZQDVKQLNFPE-UHFFFAOYSA-N thiram Chemical compound CN(C)C(=S)SSC(=S)N(C)C KUAZQDVKQLNFPE-UHFFFAOYSA-N 0.000 claims abstract description 12
- DKVNPHBNOWQYFE-UHFFFAOYSA-N carbamodithioic acid Chemical compound NC(S)=S DKVNPHBNOWQYFE-UHFFFAOYSA-N 0.000 claims abstract description 10
- 239000012990 dithiocarbamate Substances 0.000 claims abstract description 10
- 125000003118 aryl group Chemical group 0.000 claims abstract description 8
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 claims abstract description 8
- 125000004817 pentamethylene group Chemical group [H]C([H])([*:2])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[*:1] 0.000 claims abstract description 6
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims abstract description 6
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 claims abstract description 3
- 229910052802 copper Inorganic materials 0.000 claims abstract description 3
- 229910052742 iron Inorganic materials 0.000 claims abstract description 3
- 229910052745 lead Inorganic materials 0.000 claims abstract description 3
- 229910052725 zinc Inorganic materials 0.000 claims abstract description 3
- -1 thiuram compound Chemical class 0.000 claims description 21
- 125000004432 carbon atom Chemical group C* 0.000 claims description 12
- 150000001875 compounds Chemical class 0.000 claims description 9
- 150000003839 salts Chemical class 0.000 claims description 9
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 6
- 150000004657 carbamic acid derivatives Chemical class 0.000 claims description 3
- 125000002947 alkylene group Chemical group 0.000 claims description 2
- 239000000126 substance Substances 0.000 claims 4
- 239000002253 acid Substances 0.000 claims 1
- KXDHJXZQYSOELW-UHFFFAOYSA-M Carbamate Chemical compound NC([O-])=O KXDHJXZQYSOELW-UHFFFAOYSA-M 0.000 abstract 1
- 150000001408 amides Chemical class 0.000 abstract 1
- 150000004985 diamines Chemical class 0.000 abstract 1
- MTNDZQHUAFNZQY-UHFFFAOYSA-N imidazoline Chemical compound C1CN=CN1 MTNDZQHUAFNZQY-UHFFFAOYSA-N 0.000 abstract 1
- 229920001971 elastomer Polymers 0.000 description 11
- 239000005060 rubber Substances 0.000 description 11
- 230000000694 effects Effects 0.000 description 7
- XLSZMDLNRCVEIJ-UHFFFAOYSA-N 4-methylimidazole Chemical compound CC1=CNC=N1 XLSZMDLNRCVEIJ-UHFFFAOYSA-N 0.000 description 6
- DLFVBJFMPXGRIB-UHFFFAOYSA-N Acetamide Chemical compound CC(N)=O DLFVBJFMPXGRIB-UHFFFAOYSA-N 0.000 description 6
- NAQMVNRVTILPCV-UHFFFAOYSA-N hexane-1,6-diamine Chemical compound NCCCCCCN NAQMVNRVTILPCV-UHFFFAOYSA-N 0.000 description 6
- XFNJVJPLKCPIBV-UHFFFAOYSA-N trimethylenediamine Chemical compound NCCCN XFNJVJPLKCPIBV-UHFFFAOYSA-N 0.000 description 6
- 238000000034 method Methods 0.000 description 5
- 230000002265 prevention Effects 0.000 description 5
- LLPKQRMDOFYSGZ-UHFFFAOYSA-N 2,5-dimethyl-1h-imidazole Chemical compound CC1=CN=C(C)N1 LLPKQRMDOFYSGZ-UHFFFAOYSA-N 0.000 description 4
- 239000003795 chemical substances by application Substances 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 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 4
- XSQHUYDRSDBCHN-UHFFFAOYSA-N 2,3-dimethyl-2-propan-2-ylbutanenitrile Chemical compound CC(C)C(C)(C#N)C(C)C XSQHUYDRSDBCHN-UHFFFAOYSA-N 0.000 description 3
- LXBGSDVWAMZHDD-UHFFFAOYSA-N 2-methyl-1h-imidazole Chemical compound CC1=NC=CN1 LXBGSDVWAMZHDD-UHFFFAOYSA-N 0.000 description 3
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 3
- 229920005549 butyl rubber Polymers 0.000 description 3
- QLNJFJADRCOGBJ-UHFFFAOYSA-N propionamide Chemical compound CCC(N)=O QLNJFJADRCOGBJ-UHFFFAOYSA-N 0.000 description 3
- 229940080818 propionamide Drugs 0.000 description 3
- KXDAEFPNCMNJSK-UHFFFAOYSA-N Benzamide Chemical compound NC(=O)C1=CC=CC=C1 KXDAEFPNCMNJSK-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
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 2
- ZHNUHDYFZUAESO-UHFFFAOYSA-N Formamide Chemical compound NC=O ZHNUHDYFZUAESO-UHFFFAOYSA-N 0.000 description 2
- VHRGRCVQAFMJIZ-UHFFFAOYSA-N cadaverine Chemical compound NCCCCCN VHRGRCVQAFMJIZ-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
- 239000011133 lead Substances 0.000 description 2
- KIDHWZJUCRJVML-UHFFFAOYSA-N putrescine Chemical compound NCCCCN KIDHWZJUCRJVML-UHFFFAOYSA-N 0.000 description 2
- 229920003051 synthetic elastomer Polymers 0.000 description 2
- 239000005061 synthetic rubber Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 description 2
- 239000004636 vulcanized rubber Substances 0.000 description 2
- 239000011787 zinc oxide Substances 0.000 description 2
- 235000014692 zinc oxide Nutrition 0.000 description 2
- PWGJDPKCLMLPJW-UHFFFAOYSA-N 1,8-diaminooctane Chemical compound NCCCCCCCCN PWGJDPKCLMLPJW-UHFFFAOYSA-N 0.000 description 1
- PQAMFDRRWURCFQ-UHFFFAOYSA-N 2-ethyl-1h-imidazole Chemical compound CCC1=NC=CN1 PQAMFDRRWURCFQ-UHFFFAOYSA-N 0.000 description 1
- YTWBFUCJVWKCCK-UHFFFAOYSA-N 2-heptadecyl-1h-imidazole Chemical compound CCCCCCCCCCCCCCCCCC1=NC=CN1 YTWBFUCJVWKCCK-UHFFFAOYSA-N 0.000 description 1
- ZCUJYXPAKHMBAZ-UHFFFAOYSA-N 2-phenyl-1h-imidazole Chemical compound C1=CNC(C=2C=CC=CC=2)=N1 ZCUJYXPAKHMBAZ-UHFFFAOYSA-N 0.000 description 1
- LSBDFXRDZJMBSC-UHFFFAOYSA-N 2-phenylacetamide Chemical compound NC(=O)CC1=CC=CC=C1 LSBDFXRDZJMBSC-UHFFFAOYSA-N 0.000 description 1
- LLEASVZEQBICSN-UHFFFAOYSA-N 2-undecyl-1h-imidazole Chemical compound CCCCCCCCCCCC1=NC=CN1 LLEASVZEQBICSN-UHFFFAOYSA-N 0.000 description 1
- CPGFMWPQXUXQRX-UHFFFAOYSA-N 3-amino-3-(4-fluorophenyl)propanoic acid Chemical compound OC(=O)CC(N)C1=CC=C(F)C=C1 CPGFMWPQXUXQRX-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
- TYOXIFXYEIILLY-UHFFFAOYSA-N 5-methyl-2-phenyl-1h-imidazole Chemical compound N1C(C)=CN=C1C1=CC=CC=C1 TYOXIFXYEIILLY-UHFFFAOYSA-N 0.000 description 1
- JQEVCCUJHLRAEY-UHFFFAOYSA-N 5-methyl-2-undecyl-1h-imidazole Chemical compound CCCCCCCCCCCC1=NC=C(C)N1 JQEVCCUJHLRAEY-UHFFFAOYSA-N 0.000 description 1
- ULKLGIFJWFIQFF-UHFFFAOYSA-N 5K8XI641G3 Chemical compound CCC1=NC=C(C)N1 ULKLGIFJWFIQFF-UHFFFAOYSA-N 0.000 description 1
- 244000043261 Hevea brasiliensis Species 0.000 description 1
- 241001441571 Hiodontidae Species 0.000 description 1
- 229920000459 Nitrile rubber Polymers 0.000 description 1
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 1
- 239000005062 Polybutadiene Substances 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 235000021355 Stearic acid Nutrition 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- FZWLAAWBMGSTSO-UHFFFAOYSA-N Thiazole Chemical compound C1=CSC=N1 FZWLAAWBMGSTSO-UHFFFAOYSA-N 0.000 description 1
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Natural products NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 1
- RDQQCSOIXMZZQR-UHFFFAOYSA-N [methyl(phenyl)carbamothioyl]sulfanyl n-methyl-n-phenylcarbamodithioate Chemical compound C=1C=CC=CC=1N(C)C(=S)SSC(=S)N(C)C1=CC=CC=C1 RDQQCSOIXMZZQR-UHFFFAOYSA-N 0.000 description 1
- 230000003712 anti-aging effect Effects 0.000 description 1
- 229920005557 bromobutyl Polymers 0.000 description 1
- DNSISZSEWVHGLH-UHFFFAOYSA-N butanamide Chemical compound CCCC(N)=O DNSISZSEWVHGLH-UHFFFAOYSA-N 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 229920005556 chlorobutyl Polymers 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 238000007906 compression Methods 0.000 description 1
- 230000006835 compression Effects 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 239000010949 copper 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
- YQLZOAVZWJBZSY-UHFFFAOYSA-N decane-1,10-diamine Chemical compound NCCCCCCCCCCN YQLZOAVZWJBZSY-UHFFFAOYSA-N 0.000 description 1
- PGAXJQVAHDTGBB-UHFFFAOYSA-N dibutylcarbamothioylsulfanyl n,n-dibutylcarbamodithioate Chemical compound CCCCN(CCCC)C(=S)SSC(=S)N(CCCC)CCCC PGAXJQVAHDTGBB-UHFFFAOYSA-N 0.000 description 1
- 235000014113 dietary fatty acids Nutrition 0.000 description 1
- 229940116901 diethyldithiocarbamate Drugs 0.000 description 1
- LMBWSYZSUOEYSN-UHFFFAOYSA-N diethyldithiocarbamic acid Chemical compound CCN(CC)C(S)=S LMBWSYZSUOEYSN-UHFFFAOYSA-N 0.000 description 1
- 229930195729 fatty acid Natural products 0.000 description 1
- 239000000194 fatty acid Substances 0.000 description 1
- 150000004665 fatty acids Chemical class 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- REEPJBYQLCWOAR-UHFFFAOYSA-N heptadecanamide Chemical compound CCCCCCCCCCCCCCCCC(N)=O REEPJBYQLCWOAR-UHFFFAOYSA-N 0.000 description 1
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 1
- 238000004898 kneading 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
- QGTHALAWFUFVCU-UHFFFAOYSA-L n,n-dimethylcarbamodithioate;lead(2+) Chemical compound [Pb+2].CN(C)C([S-])=S.CN(C)C([S-])=S QGTHALAWFUFVCU-UHFFFAOYSA-L 0.000 description 1
- RLRHPCKWSXWKBG-UHFFFAOYSA-N n-(2-azaniumylethyl)carbamate Chemical compound NCCNC(O)=O RLRHPCKWSXWKBG-UHFFFAOYSA-N 0.000 description 1
- 229920003052 natural elastomer Polymers 0.000 description 1
- 229920001194 natural rubber Polymers 0.000 description 1
- SXJVFQLYZSNZBT-UHFFFAOYSA-N nonane-1,9-diamine Chemical compound NCCCCCCCCCN SXJVFQLYZSNZBT-UHFFFAOYSA-N 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
- UEICEJLUNGARHQ-UHFFFAOYSA-N pentane-1,4-diamine Chemical compound CC(N)CCCN UEICEJLUNGARHQ-UHFFFAOYSA-N 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 238000013031 physical testing Methods 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 229920002857 polybutadiene Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000012744 reinforcing agent Substances 0.000 description 1
- 238000010058 rubber compounding Methods 0.000 description 1
- 238000010057 rubber processing Methods 0.000 description 1
- 230000035939 shock Effects 0.000 description 1
- 239000008117 stearic acid Substances 0.000 description 1
- 229920003048 styrene butadiene rubber Polymers 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 238000010059 sulfur vulcanization Methods 0.000 description 1
- XSOKHXFFCGXDJZ-UHFFFAOYSA-N telluride(2-) Chemical compound [Te-2] XSOKHXFFCGXDJZ-UHFFFAOYSA-N 0.000 description 1
- 229910052714 tellurium Inorganic materials 0.000 description 1
- 238000009864 tensile test Methods 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 239000011701 zinc Substances 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
- 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
- DUBNHZYBDBBJHD-UHFFFAOYSA-L ziram Chemical compound [Zn+2].CN(C)C([S-])=S.CN(C)C([S-])=S DUBNHZYBDBBJHD-UHFFFAOYSA-L 0.000 description 1
Landscapes
- Compositions Of Macromolecular Compounds (AREA)
Abstract
Description
【発明の詳細な説明】 （産業上の利用分野） 本発明はハロゲン化ブチルゴム組成物に関する。[Detailed description of the invention] (Industrial application field) The present invention relates to halogenated butyl rubber compositions.
更に詳しくは、ハロゲン化ブチルゴムに加硫促進剤とし
てチウラム化合物又はジチオカルバミン酸金属塩を用い
た場合の耐スコーチ性を改善したハロゲン化ブチルゴム
組成物に関する。More specifically, the present invention relates to a halogenated butyl rubber composition with improved scorch resistance when a thiuram compound or a dithiocarbamate metal salt is used as a vulcanization accelerator in the halogenated butyl rubber.
（従来の技術）
ハロゲン化ブチルゴムは、ブチルゴムの欠点である加硫
速度の遅延性を改良した速加硫性をもち、かつブチルゴ
ムの持つ特性（気体不透過性、耐熱性、耐オゾン性、高
衝撃吸収性等）を兼ね備えたポリマ〜である。その用途
としては、タイヤのインナーライナー、自動車部品、そ
の他工業部品等に使用されている。(Prior art) Halogenated butyl rubber has rapid vulcanization that improves the retardation of vulcanization rate, which is a disadvantage of butyl rubber, and has the characteristics of butyl rubber (gas impermeability, heat resistance, ozone resistance, high It is a polymer that also has shock absorbing properties, etc. Its applications include tire inner liners, automobile parts, and other industrial parts.
ハロゲン化ブチルゴムに用いる一般的な加硫系としては
、亜鉛華加硫、チウラム加硫、チウラム・チアゾール加
硫、イオウ加硫、チオ尿素加硫、Ｐｅ ｒｍａ Ｉ ｕ
ｘ７Ｊ［］＠、ジエチルジチオカルバミン酸亜鉛加硫
等が知られ、その特徴については長野早男著「合成ゴム
加工技術全書■ ブチルゴム」、■大成社、昭和５８年
９月３０日発行、Ｐ、１０１〜１０８に記載されている
。Common vulcanization systems used for halogenated butyl rubber include zinc white vulcanization, thiuram vulcanization, thiuram/thiazole vulcanization, sulfur vulcanization, thiourea vulcanization, and PermaIu vulcanization.
x7J[]@, zinc diethyldithiocarbamate vulcanization, etc. are known, and their characteristics are described in Hayao Nagano, "Synthetic Rubber Processing Techniques Complete Guide ■Butyl Rubber," ■Taiseisha, published September 30, 1980, p. 101 -108.
これらの加硫系のうち、テトラメチルチウラムジスルフ
ィドで代表されるチウラム加硫系、ジエチルジチオカル
バミン酸亜鉛で代表されるジチオカルバミン酸金属塩加
硫系は、高速加硫であり、かつ圧縮永久歪が小ざく、耐
熱性が優れているという特徴を有し、工業的に有利な加
硫系である。Among these vulcanization systems, thiuram vulcanization systems, represented by tetramethylthiuram disulfide, and dithiocarbamate metal salt vulcanization systems, represented by zinc diethyldithiocarbamate, have high-speed vulcanization and low compression set. It is an industrially advantageous vulcanization system that is characterized by excellent heat resistance.
しかしながら、これらの加硫系は、耐スコーチ性が劣り
、加工工程でスコーチ（焼け）を起こす欠点があるにも
かかわらず、このスコーチを防ぐ良好なスコーチ防止方
法は未だ見出されていない。However, although these vulcanization systems have the disadvantage of poor scorch resistance and scorch (burning) during the processing process, no good scorch prevention method has yet been found to prevent this scorch.
このスコーチ防止方法が見出されれば、高速加硫性能を
有する加硫系であることから省エネルギーに繋がり、経
済的に有利であるため、工業化実施可能と考えられる。If this scorch prevention method is found, it is thought that it can be commercialized because it is an economically advantageous vulcanization system that has high-speed vulcanization performance, leading to energy savings.
（発明が解決しようとする問題点）
ハロゲン化ブチルゴムに用いる加硫系のうち、テトラメ
チルチウラムジスルフィドで代表されるチウラム加硫系
又はジエチルジチオカルバミン酸亜鉛で代表されるジチ
オカルバミン酸金属塩加硫系に対する良好な耐スコーチ
性を有するハロゲン化ブチルゴム組成物を斯界に提供す
ることである。(Problems to be Solved by the Invention) Among the vulcanization systems used for halogenated butyl rubber, thiuram vulcanization systems represented by tetramethylthiuram disulfide or dithiocarbamate metal salt vulcanization systems represented by zinc diethyldithiocarbamate are It is an object of the present invention to provide a halogenated butyl rubber composition having good scorch resistance.
（問題点を解決するための手段）
本発明者らは、上記の問題点を解決するために鋭意研究
した結果、加硫促進剤としてチウラム化合物又はジチオ
カルバミン酸金属塩と共に、［ただし、式中、Ｒ１、Ｒ
２、Ｒ３は水素原子、炭素数１〜１８のアルキル基、ベ
ンジル基又はアリール基を示す。］
で表されるイミダゾール化合物、
■−一般式１］
［ただし、式中、Ｒ４、Ｒ５、Ｒ６は水素原子、炭素数
１〜１８のアルキル基又はアリール基を示す。］
で表されるイミダシリン化合物、
■一般式［■］Ｏ
Ｒ７０ＮＨ２［Ｉ［１］
［ただし、式中、Ｒ７は水素原子、炭素数１〜１８のア
ルキル基、ベンジル基又はアリール基を示す。］
で表されるアミド化合物、
■一般式［ＩＶ］
Ｈ２Ｎ Ｒ８ＮＨ２［ＩＶ］
［ただし、式中、Ｒ８は炭素数１〜１２のアルキレン基
を示す。コ
で表される脂肪族ジアミン及びこれらの脂肪族ジアミン
からなるカーバメイト化合物、
上記の０〜０項記載の化合物中から選択された１種又は
２種以上の化合物をハロゲン化ブチルゴム配合物に添加
すると、驚くことにスコーチ防止効果が著しく改良され
ることが見出され、この知見に基づき本発明を完成させ
る至った。(Means for Solving the Problems) As a result of intensive research in order to solve the above problems, the present inventors found that together with a thiuram compound or a dithiocarbamate metal salt as a vulcanization accelerator, [wherein R1, R
2. R3 represents a hydrogen atom, an alkyl group having 1 to 18 carbon atoms, a benzyl group, or an aryl group. ] An imidazole compound represented by (1)-General formula 1] [wherein R4, R5, and R6 represent a hydrogen atom, an alkyl group having 1 to 18 carbon atoms, or an aryl group. ] An imidacilline compound represented by (1) general formula [■] O R70NH2[I[1] [wherein R7 represents a hydrogen atom, an alkyl group having 1 to 18 carbon atoms, a benzyl group, or an aryl group. ] An amide compound represented by (1) General formula [IV] H2N R8NH2 [IV] [wherein R8 represents an alkylene group having 1 to 12 carbon atoms. When one or more compounds selected from among the aliphatic diamines represented by and the carbamate compounds consisting of these aliphatic diamines and the compounds described in items 0 to 0 above are added to a halogenated butyl rubber compound, It was surprisingly found that the scorch prevention effect was significantly improved, and based on this finding, the present invention was completed.
本発明に係るイミダゾール化合物は、イミダゾール、２
−メチルイミダゾール、２−エチルイミダゾール、２−
ウンデシルイミダゾール、２−ヘプタデシルイミダゾー
ル、２−フェニルイミダゾール、４−メチルイミダゾー
ル、２，４−ジメチルイミダゾール、２−エチル−４−
メチルイミダゾール、２−ウンデシル−４−メチルイミ
ダゾール、２−フェニル−４−メチルイミダゾール、２
−イソプロビルイミダゾール等が挙げられるが、これら
に限定されるものではない。The imidazole compound according to the present invention includes imidazole, 2
-Methylimidazole, 2-ethylimidazole, 2-
Undecylimidazole, 2-heptadecyl imidazole, 2-phenylimidazole, 4-methylimidazole, 2,4-dimethylimidazole, 2-ethyl-4-
Methylimidazole, 2-undecyl-4-methylimidazole, 2-phenyl-4-methylimidazole, 2
-isoprobylimidazole and the like, but are not limited to these.
本発明に係るイミダシリン化合物は、イミダシリン、２
−メチルイミダシリン、２−ペンタデシルイミダシリン
、２−フェニルイミダシリン、２−エチル−４−メチル
イミダシリン等が挙げられるが、これらに限定されるも
のではない。The imidacillin compound according to the present invention is imidacillin, 2
Examples include, but are not limited to, -methylimidacillin, 2-pentadecyl imidacilline, 2-phenylimidacillin, 2-ethyl-4-methylimidacillin, and the like.
本発明に係るアミド化合物は、ホルムアミド、アセトア
ミド、プロピオンアミド、ブチロアミド、ヘプタデカン
アミド、ベンズアミド、フエナセトアミド等が挙げられ
るが、こけらに限定されるものではない。The amide compound according to the present invention includes, but is not limited to, formamide, acetamide, propionamide, butyroamide, heptadecanamide, benzamide, phenacetamide, and the like.
本発明に係る脂肪族ジアミン及びこれらの脂肪族ジアミ
ンからなるカーバメイト化合物は、エチレンジアミン、
トリメチレンジアミン、テトラメチレンジアミン、ペン
タメチレンジアミン、ヘキサメチレンジアミン、１，７
−ジアミノへブタン、１．８−ジアミノオクタン、１，
９−ジアミノノナン、１．１０−ジアミノデカン、１，
１２−ジアミノドデカン、１−メチルテトラメチレンジ
アミン、２．２．４−トリメチルへキサメチレンジアミ
ン、エチレンジアミンカーバメイト、ヘキサメチレンジ
アミンカーバメイト等が挙げられるが、これらに限定さ
れるものではない。The aliphatic diamines and carbamate compounds comprising these aliphatic diamines according to the present invention include ethylenediamine,
Trimethylene diamine, tetramethylene diamine, pentamethylene diamine, hexamethylene diamine, 1,7
-Diaminohebutane, 1,8-diaminooctane, 1,
9-diaminononane, 1.10-diaminodecane, 1,
Examples include, but are not limited to, 12-diaminododecane, 1-methyltetramethylenediamine, 2.2.4-trimethylhexamethylenediamine, ethylenediamine carbamate, hexamethylenediamine carbamate and the like.
本発明に係るチウラム化合物は、一般式［Ｖ］［ただし
、式中、Ｒ９、Ｒｈｏは炭素数１〜４のアルキル基、フ
ェニル基を、又はＲ９とＲ１０が環化したペンタメチレ
ン基を示し、ｎは１〜６の整数を示す。］
で表されるチウラムスルフィドであり、具体例としては
、テトラメチルチウラムモノスルフィド、テトラメチル
チウラムジスルフィド、テトラエチルチウラムジスルフ
ィド、テトラブチルチウラムジスルフィド、Ｎ、Ｎ’−
ジメチル−Ｎ、Ｎ’ −ジフェニルチウラムジスルフィ
ド、ジペンタメチレンチウラムテトラスルフィド、ジペ
ンタメチレンチウラムへキサスルフィド等が挙げられる
が、これらに限定されるものではない。The thiuram compound according to the present invention has the general formula [V] [wherein R9 and Rho represent an alkyl group having 1 to 4 carbon atoms, a phenyl group, or R9 and R10 represent a cyclized pentamethylene group, n represents an integer of 1 to 6. ] It is a thiuram sulfide represented by, and specific examples include tetramethylthiuram monosulfide, tetramethylthiuram disulfide, tetraethylthiuram disulfide, tetrabutylthiuram disulfide, N, N'-
Examples include, but are not limited to, dimethyl-N,N'-diphenylthiuram disulfide, dipentamethylenethiuram tetrasulfide, dipentamethylenethiuram hexasulfide, and the like.
本発明に係るジチオカルバミン酸金属塩は、−般式［Ｖ
１］
［ただし、式中、Ｒｉｉ、Ｒ１２は炭素数１〜５のアル
キル基、フェニル基、ベンジル基を、又はＲ１１とＲ１
２が環化したペンタメチレン基を示し、ＭはＺｎ、Ｐｂ
、Ｃｕ、Ｆｅ、Ｔｅを示し、ｍ ハ金属の原子価を示す
。］で表されるジアルキルジチオカルバミン酸金属塩で
あり、具体例としては、ジメチルジチオカルバミン酸亜
鉛、ジエチルジチオカルバミン酸亜鉛、ジブチルジチオ
カルバミン酸亜鉛、ジメチルジチオカルバミンＭ鉛、シ
アミルジチオカルバミン酸鉛、ジベンジルジチオカルバ
ミン
ン酸亜鉛、エチルフエニルジチオカルバミン酸亜鉛、ジ
エチルジチオカルバミン酸テルルルジチオカルバミン酸
第二鉄、ジメチルジチオカルバミン酸銅等が挙げられる
が、これらに限定されるものではない。The dithiocarbamate metal salt according to the present invention has the general formula [V
1] [In the formula, Rii and R12 are an alkyl group having 1 to 5 carbon atoms, a phenyl group, a benzyl group, or R11 and R1
2 represents a cyclized pentamethylene group, M is Zn, Pb
, Cu, Fe, and Te, and m represents the valence of the metal. ], and specific examples include zinc dimethyldithiocarbamate, zinc diethyldithiocarbamate, zinc dibutyldithiocarbamate, lead dimethyldithiocarbamate M, lead cyamyldithiocarbamate, and zinc dibenzyldithiocarbamate. , zinc ethyl phenyl dithiocarbamate, diethyldithiocarbamate, ferric telluride dithiocarbamate, copper dimethyldithiocarbamate, but are not limited to these.
本発明に係るハロゲン化ブチルゴム組成物の対象となる
ゴムは、クロロブチルゴム又はブロモブチルゴムであり
、更にこれらのゴムと天然ゴムあるいはスチレン・ブタ
ジェンゴム、ブタジェンゴム、アクリロニトリル・ブタ
ジェンゴム、エチレン・プロピレン・ジエン共重合ゴム
等の合成ゴムとのブレンドゴムも本発明に包含されるも
のとする。The target rubber of the halogenated butyl rubber composition according to the present invention is chlorobutyl rubber or bromobutyl rubber, and furthermore, these rubbers and natural rubber, styrene-butadiene rubber, butadiene rubber, acrylonitrile-butadiene rubber, ethylene-propylene-diene copolymer rubber Blend rubbers with synthetic rubbers such as the following are also included in the present invention.
本発明に係る上記の■〜■項記載の化合物中から運択さ
れた１種又は２種以上の化合物の添加量は、ゴム１００
重量部に対して０．０１〜１．０重量部、好ましくは０
．１〜０．５重量部である。The amount of one or more compounds selected from the compounds described in items 1 to 2 above according to the present invention is
0.01 to 1.0 parts by weight, preferably 0
．． It is 1 to 0.5 parts by weight.
その添加量が０．０１重量部未満の場合は、その効果が
ほとんどなく、また１．０重量部を超える量では、スコ
ーチ防止効果がですぎる上に、加硫物物性、特に引張応
力の低下に影響を与えることから実用上不用である。If the amount added is less than 0.01 part by weight, there is almost no effect, and if the amount exceeds 1.0 part by weight, the scorch prevention effect is too great and the physical properties of the vulcanizate, especially tensile stress, are reduced. It is practically unnecessary because it affects the
本発明に係るハロゲン化ブチルゴム組成物には、必要に
応じて通常のゴム用配合剤であるステアリン酸などの脂
肪酸類、カーボンブラック、ホワイトカーボンなどの補
強剤、炭酸カルシウム、クレーなどの充填剤、硫黄など
の加硫剤、酸化亜鉛、老化防止剤、軟化剤、可塑剤、顔
料、その他のゴム用配合剤を適宜に配合せしめることが
できる。The halogenated butyl rubber composition according to the present invention may optionally contain fatty acids such as stearic acid, which are common compounding agents for rubber, reinforcing agents such as carbon black and white carbon, fillers such as calcium carbonate and clay, Vulcanizing agents such as sulfur, zinc oxide, anti-aging agents, softeners, plasticizers, pigments, and other rubber compounding agents can be blended as appropriate.
次に本発明の効果を実施例に説明するが、本発明の範囲
は実施例の態様に限定されるものではない。Next, the effects of the present invention will be explained with reference to Examples, but the scope of the present invention is not limited to the embodiments.
（実施例） 実施例１。(Example) Example 1.
表−１記載の配合に基づいて、ロールミルで公知の混練
り操作により本発明例及び比較例の未加硫ゴム組成物を
作製し、ＪＩＳ Ｋ ６３００−１９７４（未加硫
ゴム物理試験方法）に準拠してムーニースコーチ試験［
ＭＬ−１，ａｔ １２５℃］を行った。更に、これら
の未加硫ゴム組成物をプレスにて、１６０’ＣＸ１ ５
分の加硫条件で加硫し、本発明例及び比較例の加硫ゴム
組成物を作製し、ＪＩＳ Ｋ ６３０１−１９７５
（加硫ゴム物理試験方法）に準拠して引張試験を行い、
それぞれの試験結果を表−１に示した。Based on the formulations listed in Table 1, unvulcanized rubber compositions of the present invention examples and comparative examples were prepared by a known kneading operation using a roll mill, and the unvulcanized rubber compositions were prepared according to JIS K 6300-1974 (unvulcanized rubber physical testing method). In accordance with the Mooney Scorch test [
ML-1, at 125°C]. Furthermore, these unvulcanized rubber compositions were pressed to 160'CX1 5
Vulcanized rubber compositions of the present invention examples and comparative examples were prepared by vulcanization under the same vulcanization conditions as JIS K 6301-1975.
(Vulcanized rubber physical test method)
The results of each test are shown in Table-1.
（効果）
表−１の結果から本発明に係るイミダゾール、２−メチ
ルイミダゾール、４−メチルイミダゾール、２，４−ジ
メチルイミダゾール、イミダシリン、２−メチルイミダ
シリン、アセトアミド、プロピオンアミド、エチレンシ
アミン、トリメチレンジアミン、ヘキサメチレンジアミ
ン及びヘキサメチレンジアミンカーバメイトをそれぞれ
所定量を添加した本発明例は、比較例と比較して著しい
スコーチ防止効果［ｔ５］が認められる。(Effect) From the results in Table 1, imidazole, 2-methylimidazole, 4-methylimidazole, 2,4-dimethylimidazole, imidacillin, 2-methylimidacillin, acetamide, propionamide, ethylenecyamine, The present invention examples in which predetermined amounts of trimethylene diamine, hexamethylene diamine, and hexamethylene diamine carbamate were added each have a remarkable scorch prevention effect [t5] compared to the comparative examples.
しかるに、本発明に係るイミダゾール、２−メチルイミ
ダゾール、４−メチルイミダゾール、２゜４−ジメチル
イミダゾール、イミダシリン、２−メチルイミダシリン
、アセトアミド、プロピオンアミド、エチレンジアミン
、トリメチレンジアミン、ヘキサメチレンジアミン及び
ヘキサメチレンジアミンカーバメイトは、ハロゲン化ブ
チルゴムのチウラム加硫系又はジチオカルバミン酸金属
塩加硫系において引張試験で、比較例との対比で全く影
響が認められず、スコーチのみの改良が明白に認めら→
るごとから、ゴム工業界において有用なものど鷹えられ
る。However, imidazole, 2-methylimidazole, 4-methylimidazole, 24-dimethylimidazole, imidacillin, 2-methylimidacillin, acetamide, propionamide, ethylenediamine, trimethylenediamine, hexamethylenediamine and hexa Methylenediamine carbamate showed no effect at all in a tensile test on thiuram vulcanization system or dithiocarbamate metal salt vulcanization system of halogenated butyl rubber in comparison with comparative examples, and an improvement only in scorch was clearly observed →
As a result, there are many useful products in the rubber industry.
Claims (3)
バミン酸金属塩と共に、 〔１〕一般式［ I ］ ▲数式、化学式、表等があります▼［ I ］ ［ただし、式中、Ｒ＿１、Ｒ＿２、Ｒ＿３は水素原子、
炭素数１〜１８のアルキル基、ベンジル基又はアリール
基を示す。］ で表されるイミダゾール化合物、 〔２〕一般式［II］ ▲数式、化学式、表等があります▼［II］ ［ただし、式中、Ｒ＿４、Ｒ＿５、Ｒ＿６は水素原子、
炭素数１〜１８のアルキル基又はアリール基を示す。］ で表されるイミダゾリン化合物、 〔３〕一般式［III］ ▲数式、化学式、表等があります▼［III］ ［ただし、式中、Ｒ＿７は水素原子、炭素数１〜１８の
アルキル基、ベンジル基又はアリール基を示す。］ で表されるアミド化合物、 〔４〕一般式［IV］ Ｈ＿２Ｎ−Ｒ＿８−ＮＨ＿２［IV］ ［ただし、式中、Ｒ＿８は炭素数１〜１２のアルキレン
基を示す。］ で表される脂肪族ジアミン及びこれらの脂肪族ジアミン
からなるカーバメイト化合物、 上記の〔１〕〜〔４〕項記載の化合物中から選択された
１種又は２種以上の化合物を添加してなることを特徴と
するハロゲン化ブチルゴム組成物。(1) Together with a thiuram compound or dithiocarbamate metal salt as a vulcanization accelerator, hydrogen atom,
It represents an alkyl group, benzyl group, or aryl group having 1 to 18 carbon atoms. ] Imidazole compound represented by [2] General formula [II] ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ [II] [However, in the formula, R_4, R_5, R_6 are hydrogen atoms,
It represents an alkyl group or an aryl group having 1 to 18 carbon atoms. ] Imidazoline compound represented by [3] General formula [III] ▲ Numerical formula, chemical formula, table, etc. ▼ [III] [However, in the formula, R_7 is a hydrogen atom, an alkyl group having 1 to 18 carbon atoms, benzyl group or aryl group. ] [4] General formula [IV] H_2N-R_8-NH_2[IV] [In the formula, R_8 represents an alkylene group having 1 to 12 carbon atoms. ] Aliphatic diamines represented by and carbamate compounds consisting of these aliphatic diamines, added with one or more compounds selected from the compounds described in items [1] to [4] above A halogenated butyl rubber composition.
アルキル基、フェニル基を、又はＲ＿９とＲ＿１＿０が
環化したペンタメチレン基を示し、ｎは１〜６の整数を
示す。］ で表されるチウラムスルフィドである特許請求の範囲第
（１）項記載のハロゲン化ブチルゴム組成物。(2) The thiuram compound has the general formula [V] ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ [V] [However, in the formula, R_9 and R_1_0 are an alkyl group having 1 to 4 carbon atoms, a phenyl group, or R_9 R_1_0 represents a cyclized pentamethylene group, and n represents an integer of 1 to 6. ] The halogenated butyl rubber composition according to claim (1), which is thiuram sulfide represented by:
、化学式、表等があります▼［VI］ ［ただし、式中、Ｒ＿１＿１、Ｒ＿１＿２は炭素数１〜
５のアルキル基、フェニル基、ベンジル基を、又はＲ＿
１＿１とＲ＿１＿２が環化したペンタメチレン基を示し
、ＭはＺｎ、Ｐｂ、Ｃｕ、Ｆｅ、Ｔｅを示し、ｍは金属
の原子価を示す。］ で表されるジアルキルジチオカルバミン酸金属塩である
特許請求の範囲第（１）項記載のハロゲン化ブチルゴム
組成物。(3) Dithiocarbamate metal salt has the general formula [VI] ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ [VI] [However, in the formula, R_1_1 and R_1_2 have 1 to 1 carbon atoms.
5 alkyl group, phenyl group, benzyl group, or R_
1_1 and R_1_2 represent a cyclized pentamethylene group, M represents Zn, Pb, Cu, Fe, or Te, and m represents the valence of the metal. ] The halogenated butyl rubber composition according to claim (1), which is a dialkyldithiocarbamic acid metal salt represented by:
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP30712390A JPH04180944A (en) | 1990-11-15 | 1990-11-15 | Halogenated butyl rubber composition |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP30712390A JPH04180944A (en) | 1990-11-15 | 1990-11-15 | Halogenated butyl rubber composition |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH04180944A true JPH04180944A (en) | 1992-06-29 |
Family
ID=17965311
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP30712390A Pending JPH04180944A (en) | 1990-11-15 | 1990-11-15 | Halogenated butyl rubber composition |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH04180944A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6380237B1 (en) | 1998-07-16 | 2002-04-30 | Bayer Aktiengesellschaft | Diphenylimidazolines |
| US10000623B2 (en) | 2013-11-12 | 2018-06-19 | Robinson Brothers Limited | Accelerator compositions and methods |
-
1990
- 1990-11-15 JP JP30712390A patent/JPH04180944A/en active Pending
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6380237B1 (en) | 1998-07-16 | 2002-04-30 | Bayer Aktiengesellschaft | Diphenylimidazolines |
| US10000623B2 (en) | 2013-11-12 | 2018-06-19 | Robinson Brothers Limited | Accelerator compositions and methods |
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