TW294692B - - Google Patents

Description

2046 ^ 2 A7 _ B7 V. Description of the invention (彳). The present invention relates to an auxiliary accelerator in the vulcanization of rubber compositions, which is used in combination with amides selected from sulfenic acid and sulfinic acid. The main accelerator of sezole is combined. It is important that the rubber that can be molded in the injection molding method and continuous vulcanization of the rubber article remains processable (ie, easy to flow) in both the extruder and the conveyor belt to the mold. However, the rubber should be cured as soon as possible in the model. Faster colonization can have a higher production rate. Because the viscosity of the molded rubber decreases at higher temperatures, it needs to be maintained at the extruder and conveyor belt to the mold as high as possible to avoid the risk of early vulcanization crosslinking. In fact, the maximum processing temperature in the extruder / conveyor belt is at least 30 ° C to 50 in the model. (: The following temperature (vulcanization temperature). A small increase in processing temperature and / or an extended stay in the extruder / conveyor belt 'or a certain amount exceeding a certain threshold (threshold value) leads to early vulcanization crosslinking. Its characteristics are: Scattered or "scorched" spots are on the smooth surface of a rubber article. This phenomenon is generally known as "scorch." The tendency of rubber scorch (indicated by ts2) is measurable under commercial operating conditions. The procedure is described in the International Standard ISO 6502. The Muni Coking is measured with a Muni Viscometer based on IS0 667. Printed by the Consumer Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs (please read the back page first Please pay attention to this page. The index of rubber scorch time is ts2, which is the time obtained by adding 2% of the torque difference plus the minimum torque (ML). The torque difference or the degree of crosslinking is the maximum torque (MH ) Minus the minimum torque (ML). The residence time in the model is expressed as the value of t⑽ (vulcanization time), which is the time to obtain a torque difference of 90%. Up to now, the main accelerator and auxiliary accelerator in the vulcanization of rubber The composition of the agent has Use This composition has unique advantages' only provides a more accelerators

Public Patent Application Γ Amendment Page (November 1985) Α7 Β7

Printed by the Employee Consumer Cooperative of the Central Bureau of Standards and Economics of the Ministry of Economic Affairs V. Description of the invention (2) The vulcanization is quicker to increase the production rate. However, in some applications such as injection molding, these auxiliary accelerators become worse and worse, because they also relatively reduce the scorch time (value of t s 2) and thus increase the risk of scorch in this method. Therefore, there is a need for an auxiliary accelerator in vulcanization which reduces the vulcanization time but does not produce a relatively large reduction in scorch time, thereby providing a shorter manufacturing time and improving processing safety. The present invention solves this problem. In the vulcanization of rubber, a main accelerator selected from sulfenamide and sulfonamide, such as 2-mercaptobenzopyrazole, 2-drum benzop, zinc sulfonate and disulfide disulfide Benzo Psezole is solved by using a sufficient amount of auxiliary accelerator to increase the scorch ratio. Its characteristic is that the auxiliary accelerator is a compound of formula I:

0H / \

Ri-C C-R2 'I! 丨

H-C C-H \ 丨

C!

R (I) wherein R, 1 ^ and 1? 2 are each selected from hydrogen, Cl_Cl〇 alkyl, C factory alkyl 'C2-C1Q alkenyl, C6_C1 () aryl and C7_C " alkaryl, and R , One of Ri and R2 can be composed of element, nitrogen, hydroxyl group and at least R, R1 and R2 are one of molecular formula II, thioaminomethylformyl: 5- (please read the notes on the back before filling in This page) Binding and Ordering ir Printed by the Consumer Standards Cooperation of the Central Bureau of Standards of the Ministry of Economic Affairs ^ ^ 4 6 2 A7 _____ B7 V. Description of Invention (3) S Rg

II I

Ra ^ N-C-S-C-

II r5 r7 (II) where ruler 4 and R5 are individually selected from C] -C〗 〇pit group 'C wide Ci〇 aryl burn group, C2_C10 alkenyl group, C6_C] 〇aryl group, c7-Ci〇 burn aryl group' R4 and R5 can be combined to form a Cf c7 ring pit group or heterocyclic alkyl group; 1? 6 and R7 are individually selected from hydrogen, Ci-C1Q alkyl, c7-ci0 aralkyl, C2-C1 () alkenyl, c6-c1 () aryl and c7-c1 () alkaryl, and 1? 6 and R7 can be combined to form (: 4- (: 7 cycloalkyl. The present invention also relates to vulcanized rubber composition The main accelerator and one or more compounds of formula I and about a vulcanization method, which is carried out in the presence of the main accelerator and one or more compounds of formula I. The present invention is successfully achieved in comparison with no auxiliary accelerator system With a clear improvement in vulcanization time (tgo), even compared with other auxiliary accelerators that reduce the vulcanization time by about the same, the present invention achieves a significant improvement in coking time, and thus can provide important advantages that a relatively long coking time can Shorter production time combined. Certain compounds of formula I are known from US Patent No. 2,757,174, which also It is taught that these compounds can be used as accelerators for natural and synthetic rubber. Similar disclosures are also found in British Patent No. 722, 870. Certain compounds of formula I are also known as rubbers in Japanese published patent application No. 44245/1975 Vulcanization accelerator. This patent application uses this compound as an accelerator for rubber compositions, the composition of which contains two 6-M Zhang Cai Guan Jia Pi (CN?) A4 specifications ⑺Qx29x ^ 着------ ll · --- / 衣 ------- 定 l · ----- <-< (Please read the precautions on the back before filling out this page) A7 A7 4 5. Description of invention (special or Various rubber components have significantly different vulcanization rates, and to make these compositions more compatible during vulcanization. The basic benefit guided by this patent application is that these compounds are readily soluble in each individual rubber component. Therefore From these applications, we can deduce that most of the compounds of formula〗 are effective vulcanization accelerators in rubber vulcanization. However, British Patent No. 1,04 9, 535 discloses that certain compounds of formula Π can be used in styrene / In succinic copolymer Oxidant. Even this patent describes that these compounds have special advantages' because they have some effect on rubbers that will be subjected to any vulcanization method. Therefore this announcement has the effect of the previous US Patent No. 2,757, 174 and British Patent No. 722, 870 General guidance raises doubts. Other patents such as US Patent No. 3,117,947, European Patent Application No. 278 890 and US Patent No. 5,019,611 all exemplify these types of compounds as effective stabilizers such as antioxidants or Anti-ozonant. None of the previous patent announcements suggested or suggested the use of the compound of formula I as an auxiliary accelerator in combination with the main accelerator in rubber vulcanization. Moreover, the important advantage achieved by the compound of formula I, that is, the so-called improved coking time compared to the known ones, is used in the market as an auxiliary accelerator such as thiurams, thioamine methyl sulfenylamide sulfonamide Classes, xanthates, dithiophosphates, guanidines and their mixtures, these announcements also do not guide or recommend. More specific examples of such auxiliary accelerators include tetramethylthiuram disulfide (TMTD), tetramethylthiuram monosulfide (TMTM), tetraethylthiuram disulfide (TETD), tetrabenzene disulfide Kiturum (TBzTD), tetrabutyl disulfide This paper standard is applicable to the Chinese National Standard (CNS) A4 specification (210X297 mm) (please read the precautions on the back before filling this page), clothing Printed by the Prospective Bureau Staff Consumer Cooperative 2Ό4ί) ύ2 Α7 Printed by the Ministry of Economic Affairs Central Standards Bureau Staff Consumer Cooperative B7 5. Description of the invention (5), thiuram (TBTD), diisopropyl xanthate, dialkyl di Thiophosphate, dibenzidine (DPG), dicarbamoylguanidine (DOTG), N-oxydiethyldithioaminodimethanyl-N-oxydiethyldisulfenic acid Acetamide (OTOS) and N-oxydiethylthioethylaminomethanyl-N-tert-butylsulfonamide amide. The inventors have therefore found that by replacing the known auxiliary accelerator with one or more compounds of formula I, a significant step in coking (ts2) can be achieved. This is an important advantage for special applications such as the need to shorten the time, but also requires a longer coking time such as injection molding. The present invention provides the ability to achieve a relatively long scorch time and short vulcanization time during vulcanization without adversely affecting the crosslink density. In addition, the present invention also provides an improved rubber composition whose characteristics are better stress-strain properties. The invention can be applied to all natural and synthetic rubbers containing unsaturated bonds. Examples of such rubber include but are not limited to natural rubber (NR), ethylene-propylene-diene monomer terpolymer (EPDM), styrene-butadiene rubber (sbr), acrylonitrile-butadiene Rubber (NBR), isoprene rubber (IR), butadiene rubber (BR), polypentadiene rubber (CR), halogenated isoprene-isobutadiene rubber (BIIR or CIIR) , Isoprene-isobutadiene rubber (IIR), gasified polyethylene rubber (CN / CPE) and gas sulfonated polyethylene rubber (CSM), and a combination of two or more of these rubbers and one or more of these rubbers Combination with other rubbers and / or thermoplastics. Examples of sulfur that can be used in the present invention include various types of sulfur, such as powdered sulfur, Shendian sulfur, and insoluble sulfur. There are also sulfur providers that can be used to replace or add to sulfur to provide sulfur demand during the vulcanization process. Examples of such sulfur and sulfur suppliers include, but are not limited to, tetramethylthiuram disulfide 'tetraethyl disulfide-8-This paper size is applicable to China National Standards (CNS) A4 specification (210X 297mm f please Read the precautions on the back first and then fill out this page.} Order A7 ________B7 for consumer cooperation of the Central Standards Bureau of the Ministry of Economic Affairs. V. Invention Description (6) Keturam tetrabutyl thiuram disulfide, and five times hexasulfide A Kiturum, caprolactam disulfide and their mixtures. The sulfur referenced in this article should include the supplier of sulfur and the mixture of sulfur and sulfur supplier. Even more reference is made to the amount of sulfur used in the vulcanization, when used When referring to the amount of sulfur supplier, the sulfur supplier needs to specify the same amount of sulfur. The amount of sulfur to be compounded with the rubber is 0.1 to 25 parts by weight based on 100 parts of rubber, and more preferably 0.2 to 8 parts by weight. The amount of sulfur supplier combined with the rubber is sufficient to provide the equivalent amount of sulfur itself. Some known main vulcanization accelerators can be used, and preferred vulcanization accelerators include azole and hyposulfonic acid Acetylamine accelerator. Examples of p-sezoazole accelerators are 2- Phenylpyrazole, 2-mercaptobenzyl zinc sulfonate and dibenzoxazole disulfide. The sulfenamide amide accelerator can be N-cyclohexyl-2-benzoxazole sulfenamide Amine salt, N-tert-butyl-2-benzopyrimidine sulfonic acid amide salt, N-tertyl-2-benzylpyrazole sulfosulfonamide salt, N-oxygenated secondary ethyl Benzyl-2-benzo, thiazolidinesulfonic acid amide salt and N, N-dicyclohexyl-2-benzoxazole sulfonic acid amide salt The amount of main vulcanization accelerator is based on 100 parts by weight of the rubber composition 0. 1 to 8 parts by weight ratio. More preferably, the main vulcanization accelerator contains a weight ratio of 0.3 to 6.0 parts by weight ratio of 100 parts of rubber. The vulcanization auxiliary accelerator is selected from one or more molecular formula I These compounds can be manufactured by methods known in the art as described in the examples in US Patent No. 3,658,743. The best auxiliary accelerator used in accordance with the present invention is (dipityl-viaphenyl) -Dialkyl dithiocarbamate, (dialkyl-hydroxyphenyl) -diphenyl disulfide-9-This paper scale is applicable to China National Standard (CNS) A4 specification (210X 297mm) ( Please read the notes on the back first Then fill out this page) Order No. 84106912 patent application first Chinese manual correction pages (85 November) A7 B7

Printed by the Consumer Labor Cooperative of the Central Bureau of Standards of the Ministry of Economy V. Description of the invention (7) Aminocarbamate and (dialkyl-hydroxyphenyl) -oxydiethyldithiocarbamate. Particularly preferred are compounds (3,5-di-tert-butyl-4-hydroxyphenyl) -diphenyldithioamino formate (HB-BEC is the best), (3,5 ~ di-tert Butyl-4-hydroxyphenyl) -dimethyl dithiocarbamate (HB-DMC), and (3,5-di-tert-butyl-4-hydroxyphenyl) -diethyl di Thioamine formate (HB-DEC). An example in which the heterocycloalkyl group can be attached to the dithioaminomethylamide group is nitrohexanyl. Other traditional rubber additives can also be used in their usual amounts. For example, reinforcements such as soot, silica, clay, whitening and other mineral fillers and fillers can be included in the rubber composition, and other additives such as processing oil, tackifier, wax, antioxidant, anti-ozone Agents, colors, resins, plasticizers, processing aids, vulcanized ointments, compounds and activators such as stearic acid and zinc oxide can be used in conventionally known amounts. For a more complete list of rubber additives that can be used in combination with the present invention, see _ Η 〇fma η "Rubber Technical Manual" 4th Early "and 1989 Hanser Publishers" Rubber Chemicals and Additives "No. 2 1 7-3 5 3 pages. In addition, scorch retarders such as phthalic anhydride, pyromellitic anhydride, mellitic anhydride, 4-methylphthalic anhydride, trimellitic anhydride, 4-gasphthalic acid, N -Cyclohexyl-thiophthalimide'salicylic acid, benzoic acid, maleic anhydride and N-nitrosodiphenylamine can also be used in rubber compositions in conventionally known amounts for special applications, In general, the present invention has significantly or greatly reduced the need for such scorch retarders. Finally, in specific applications, it may be necessary to use wire adhesion promoters such as alkaloids and dithiosulfate in amounts conventionally known. -10- This paper size is suitable for 297 gallbladders with medium-sized gallbladders)-^ Binding J ^ (Read the precautions on the back and then fill out this page) Employee Consumer Cooperation of the Central Bureau of Standards of the Ministry of Economic Affairs Du Printing W Qing 2 A7- ---- B7 5. Description of the invention (8) The present invention also relates to a method of vulcanization, which contains the step of vulcanizing at least one natural or synthetic rubber, with 0.1 to 25 parts by weight per 100 parts by weight of rubber Sulfur, or a sufficient amount of sulfur supplier to provide 〇. 1 _25 parts by weight equivalent sulfur, 0.1 to 8.0 parts by weight of the main vulcanization accelerator is selected from spit and secondary acid amide accelerator , And a sufficient amount of auxiliary accelerator provides the weight ratio of the main accelerator to the auxiliary accelerator from〗 〖9〇 to 9〇: J 〇, the auxiliary accelerator is selected from the compounds given above formula I This method is carried out at a temperature of 110-220X: for more than 24 hours. More preferably, this method is carried out at 120-190 ° C under an auxiliary accelerator of 0.05 to 5.0 parts by weight over 8 Hours. Even better is to use 〇.] _ 3. 〇 parts by weight of auxiliary accelerator. All before The additives mentioned above related to the rubber composition may also be included in the vulcanization method of the present invention. In a specific example of a better vulcanization method, the vulcanization is carried out at a temperature of 12 to 19 hours for more than 8 hours. Finally, the present invention also Including products such as tires containing vulcanized rubber are vulcanized in the presence of an auxiliary accelerator of molecular formula I. The present invention is further illustrated by the following examples and does not limit the direction of the invention. The scope of the invention is determined by the scope of the attached patent application. The first step of the experimental method of mixing in the example: «Hybrid type: Werner & Pf leiderer (volume 5. 0 liters, 70% load factor) Rotation speed: 30 revolutions per minute

Starting temperature: 50 ° C -11-I paper size is applicable to China National Standard (CNS) A4 specification (210X297 Gongqing) ~~ '' ~~~ —— (please read the precautions on the back before filling this page) "

, 1T V. Description of the invention (9 mixing time mixing method second step: mixing type roller friction starting temperature mixing step vulcanization method temperature time all test square Muni viscosity Muni coking rheology tensile strength elongation at break resistance Stress: 5 minutes: 0 minutes-1 minute with rubber-1/2 filler, zinc oxide and stearic acid 2 1/2 minutes-1/2 filler, oil and antioxidant 4 minutes-shaking for 5 minutes-dumping: Two roller mixers: 1 / 1.22: 40-50 ° C: ISO 2393 Pressure molding 160 C unless otherwise indicated t90 minutes

ISO R-289-ML l〇〇eC ISO R-667-MS 121 ° C Monsanto MDR 2000E-vulcanization temperature, vulcanization time 30 minutes, Fan Gu 2.5 Newton meters, arc 0.5. -ISO 6502-91 ISO 37 / 2-¾ age shape ISO 37 / 2-¾ ridge shape ISO 37 / 2-¾ bell shape A7 B7 hardness elastic hot gas aging density V. Description of invention (10 ISO 48 (IRHD) ISO 4662 ISO 188-10 (TC, 3 days ISO 2781

Example 1 and Comparative Examples A-C The rubber compositions given in Table I were combined and cured according to the steps given above. See Table 2 for rheology during vulcanization. The mechanical properties of the resulting vulcanized rubber composition are shown in Table 3. The ripening takes place at 150 C and 170. The vulcanization is matured in the mechanical attachment of wo1. From these examples, it can be seen that when used in combination with the main vulcanization accelerator of the amide salt of hypochlorous acid, it is the compound of the present invention-3, 5-di-tert-butyl-4-phenyl-diphenyldithioamino Formate (HB-BEC) has a clear improvement in curing time (τ9〇) compared to the control without auxiliary accelerator (Comparative Example A). And when compared with two commercially available auxiliary accelerators (in Comparative Example B_C), where it can be seen that the reduction vulcanization time is about the same but obtained with the compound of the present invention and the commercially available auxiliary accelerators at the coking time There are significant improvements. (Please read the precautions on the back first and then fill in this book. Clothing. Printed by the Employees ’Consumer Cooperative of the Central Bureau of Standards of the Ministry of Economic Affairs -13 A7 B7 V. Description of the invention (h Table 1 Examples of compound combinations NR SMR CV Soot N-330 Zinc stearate aromatic oil Ingralen CBS sulfur TMTD TBzTD HB-BEC NR SMR CV = natural rubber ο ο ο ο ο 5 0 2 υ 2 ο 0 2 0 2 (please read the precautions on the back before filling this page) CBS = N-cyclohexyl-2-benzopyrazole sulfenamide amide salt TMTD = tetramethylthiuram disulfide TBzTD = tetraphenylthiuram disulfide HB-BE0 3, 5-di-tert-butyl-4-hydroxyphenyl-diphenyldithiocarbamate-14- This paper scale is applicable to China National Standard (CNS) Α4 specification (210X 297 mm ) 5. Description of the invention (12 Table 2 Examples of rheological properties Coking 05 MS 121 ° C Test temperature rheometer ts2 t5 t90 ML Torque difference test temperature rheometer ts2 t5 t90 ML Torque difference Mimi meters clock ° c Chung Chung Chung Day ° c Chung Chung Chung Dayton minutes > minutes > Niu Niuniu A7 B7 A 30. 8 150 4. 2 3. 5 9. 8 0. 2 1.8 170 1.0 0.6 2.6 0. 2 1.6 B 17. 1 150 2. 8 2. 6 4. 9 0. 2 2. 0 170 0. 9 0. 8 1. 6 0. 2 1. 9 4 0 2 5 3 250 2000 101 30. 1 150 4 . 3 4. 0 7. 2 0. 2 1. 8 170 1.3 1.2 2. 2 0. 2 1.7 (please read the precautions on the back before filling out this page) Order the printed form 3 of the Staff Consumer Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs Examples of mechanical properties after curing at 150 ° C and 170 C ABC 1 Hardness IHRD 69 74 73 74 (69) (71) (73) (72) Tensile strength MPa 29.1 25.7 25.8 27.6 (27.0) (26.6) (27.2 ) (26.3) ί middle length rate% 535 425 415 475 (480) (450) (455) (480) Tensile stress 50% MPa 1.6 2.0 2.0 2.0 (1.6) (1.9) (1.9) (1.9) 100% MPa 3.0 4.2 4.0 3.9 (3.3) (3.9) (3.9) (3. 6.) 300% MPa 15.4 18.5 18.2 17.0 (16.0) (17.6) (17.6) (15. 6) Tear strength 1000 N / m 148 93 98 98 (107) (95) (95) (114) The value in parentheses is 170 ° C cooked -15- This paper scale is applicable to China National Standard (CNS) A4 specification (210X 297 mm) V. Description of invention (13 Α7 Β7 comparison Examples DF and Example 2 These examples illustrate the auxiliary accelerator of the present invention The combination of the main vulcanization accelerator of the acid amide salt has better scorch safety than the commercially available auxiliary accelerator and the known scorch retarder and the same main sulfoamide sulfonamide salt main vulcanization accelerator. . Therefore, the compound of the present invention can be used to replace the commercially available auxiliary accelerator and coking retardant combination and modify the understanding of this combination, that is, the stress-strain properties of rubber. The composition of the rubber composition is shown in Table 4. The maturation characteristics and shame are shown in Table 5. Compound examples printed by the Consumer Standardization Bureau of the Central Bureau of Standards of the Ministry of Economic Affairs 4 Examples of compounds D NR SMR CV 100 Complete smoke Ν-765 50 Stearic acid 2 Zinc oxide HS 5 Aromatic oil Ingralen® 150 5 Permanax ® TQ 1 Permanax® 699D 1 CBS 1. TMTD 0. TBzTD-HB-BEC-retarder CTP-sulfur 2. TQ = 2, 2, 4-trimethyl-1,2-dihydroquinine (please read first Note 4 ^ on the back and fill in this page] Ε ο ο 0 5 ο ο 5 ο ο 0 5. Order. 1 ο-10 2 2 5 GPPD = N-1,3-dimethylbutyl-Ν ' -Phenyl-p-phenylenediamine CTP = cyclohexylthiophthaloyl imide-16- This paper standard is applicable to China National Standard Rate (CNS) Α4 specifications (210x297 ongdong) 2ϋ4β ^ 2 Α7 B7 Description (14) Table 5 Example of data obtained by mixing at 160 ° C to obtain curing DEF 2 Temperature 160 170 160 170 160 170 160 170 Coking ts 2 minutes 1.4 0.8 1. 7 0.95 1.7 0.9 2.4 1.3 Maximum curing t 90 minutes 2.1 1.2 2.8 1. 5 2.8 1.5 3.6 1.9 Table 6 Muni coking obtained by mixing at 121 ° C

Example D t5, minute 17. 4 t35, minute 18. 6 Maturity index MU / minute 1.25 Muni viscosity, 54. 6 CML 1 + 4) 100 ° C 3 6 2 1 3 5 1--4 (please read the back first (Notes to fill out this page) .-

* 1T Table 7: Physical-mechanical properties of vulcanization and curing at t9Q time at 160 ° C. Printed example of the employee consumer cooperative of the Central Bureau of Standards of the Ministry of Economy D Density, grams / cubic centimeter 1.13 hardness, IHRD 73 rebound, (23 ° C)% 51 Tensile strength, MPa 18.8 Elongation at break% 330 Tensile stress, 50%, MPa 2.1 Tensile stress, 100%, MPa 4.3 Tensile stress, 300%, MPa 17.2 Repeated shrinkage setting,% 8 (3d / 23〇C ) Calendar: reduced setting,% 56 (ld / 100 ° C) i ΛΟ 11 oo 11 139702479 8 7— 11 12 L〇9 2 8 2 0 7 4 2 3 1—- 3 5 6 5 Standard (CNS) A4 specification (210X29 " / mm) V. Description of the invention (15 Table 8) Physical and mechanical properties of vulcanization and aging (3d / 100 ° c) at 160 ec at t90 time Tensile strength, MPa%, maintained Elongation at break,%% Retaining tensile stress, 50%, MPa% Retaining tensile stress, 100%, MPa% Retaining 0 4 5 5 lx no oo --- 357 16 4 4 4 2 0 8 17 7 4 7 8 5 0 1—-756 0 4 8 1 8 ο 1 2 Example 3 and Comparative Example G-Η In these examples, the auxiliary accelerator according to the present invention is used with the main accelerator 2- 豉Benzopyrazole (ΜΒΤ) and compared with the combination of ΤΜΤΜ and ΜΤΤ. Such formulations are typically used for tire frame composition. Vulcanization is carried out at 15 {rc and 170 ° C and the number of mechanical properties is attached to Table 1 j. The formulations are shown in Table 9 'The ripening properties are shown in Table 10 and the mechanical properties are shown in Table 11 ° The compounds of the present invention confer three important advantages over TMTM and TBzTD' No minor amine problem, improve scorch and increase Certain mechanical properties, especially stress and strain. Printed by the Ministry of Economic Affairs Central Standards Bureau Employee Consumer Cooperative -18- ^^ Standards are applicable to China National Standards (CNS) A4 specifications (210x297 director) f Please read the notes on the back before Fill this page}

A7 B7 V. Description of the invention (16 Table 9 Compound composition examples G 3 H NR SMR 10 50. 00 50. 00 50. 00 SBR Buna EM 1712 68. 75 68. 75 68. 75 N-660 43. 00 43. 00 43. 00 Stearic acid 1. 50 1. 50 1. 50 Zinc oxide, US 4. 00 4. 00 4. 00 Aromatic oil 8. 00 8. 00 8. 00 Permanax TQ 1. 50 1. 50 1. 50 Perkacit MBT c 0. 50 0. 50 0. 50 Perkacit TMTM c 1. 00--HB-BEC-1. 00-Perkacit TBzTD--1. 00 sulfur 2. 66 2. 66 2. 66 (please read first (Notes on the back and then fill in this page) " Table 10 obtains mixed ripening data at 150 ° C and 170 ° C-set example test temperature ° C XL range Newton meter coking safety, ts2, maximum ripening time in minutes, t90 minutes test temperature ° C XL range Newton meters coking safety, ts2, minutes maximum ripening time, t90, minutes printed by the Employee Consumer Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs 8 5 5 0 7 2 4 1 7 5 7 1—- 0525 2 7 7 4 7 0 6 1-14 1 7 This paper scale is applicable to the Chinese National Standard (CNS) A4 specifications (210X297 mm) 2ϋ4β ^ 2 a? Β7 5. Invention description (17) Table 11 at 150 C / 20 minutes vulcanization physical-mechanical example G 3 Η hardness, IHRD 63 56 60 tensile strength, MPa 6 '5 11.8 9. 8 Tensile stress, 50%, MPa 1.3 0. 9 1.1 Tensile stress, 100% , MPa 2.4 1. 5 2. 1 Tensile stress, 300%, MPa-6. 1 8.4 Elongation at break,% 220 465 335 Examples 4-5 and Comparative Example 1 The auxiliary accelerators according to the invention are shown in these examples It can be used as a substitute for thioamine facyl sulfenic acid amide salt. The formulation is shown in Table 12 and the mature properties are shown in Table 13. Table 12 Compound composition (please read the notes on the back before filling this page ) 'Clothes--Printed example of the employee consumer cooperative of the Central Bureau of Standards of the Ministry of Economy I 4 5 NR SMR CV 100 100 100 Ν-330 50 50 50 ZηΟ 5 5 5 Stearic acid 2 2 2 Aromatic oil 3 3 3 CBS 1 . 05 (4 millimoles) 1. 05 (4 millimoles) 1. 05 (4 millimoles) 0T0S 0.54 (2 millimoles) HB-BEC 0. 49 (1 millimoles) 0. 98 (2 mmol) Sulfur 0.5 0.5 0.5 OTOS = N-oxydiethyl-N'-oxydiethyl-thioaminomethyl sulfenylamide sulfonamide Yan-20-This paper size is applicable China National Standard (CNS) Α4 specification (210Χ297 mm) A7 B7 V. Description of the invention (18) Table 13 Example of cooked data mixed at 170 ° C I 4 5 Torque difference, Newton meters 4. 6 3. 9 4. 3 Coking time, ts2, 2. 9 2. 8 2. 7 Maximum ripening time, t90, minutes 4. 5 4. 3 4. 4 Ripening rate, RH / minute 0. 086 0. 075 0. 084 The results show HB-BEC can act as a delayed second lam, so the replacement of 0T0S is possible. 0T0S is based on nitrous oxide and it is carcinogenic to replace this component and is therefore highly needed.

Examples 6-7 and Comparative Example J In these examples, it was shown that a smaller amount of the auxiliary accelerator according to the present invention would improve the opposite resistance in the conventional mature compounds. The formulations are shown in Table 14 and the ripening properties are shown in Table 15. Table 14 Compound composition fl ^ i nm n ^ i nn m 1 ^ ^ y ^ i (Please read the notes on the back before filling in this page) Printed example of the employee consumer cooperative of the Central Bureau of Standards of the Ministry of Economy NR SMR CV N-330 ZnO Stearic acid aromatic oil CBS HB-BEC sulfur ο ο 0 5 ο ο 0 5 0 0 2 0 0 2 The paper size is applicable to the Chinese National Standard (CNS) A4 specifications (210X297 mm) A7 B7 V. Invention description (19 ) Table 15 Example of mixed ripening data obtained at 150 ° C J 6 7 Torque difference, Newton meters 1.6 1.7 1.8 Coking safety, ts2, minutes 4.3 4.7 4. 3 Maximum coking time t90, minutes 12. 0 9 . 4 8. 0% reduction rate 150 ° C 90 minutes 14 9 6 The results show that the addition of a small amount of HB-BEC in the compound will increase the resistance of the reduction rate and increase the maturation parameters. Examples 8-10 and Comparative Example K These examples illustrate the use of some more auxiliary accelerators according to the present invention and their benefits. Table 16 shows the compound composition and Table 17 is the rheology at 150 ° C. Table 16 Compound composition (please read the precautions on the back before filling this page) "

、 1T Printed example of the employee consumer cooperative of the Central Bureau of Standards of the Ministry of Economy NR SMR N-330 ZnO Stearic acid glue HB-BEC HB-DMC HB-DEC CBS Sulfur K 97. 5 45 5 3 2. 5 8 97. 5 45 5 3 2. 5 2. 0 0. 5 2. 5 ο 2 9 97. 5 45 5 3 2. 52. 0 0. 5 2. 5 10 97. 5 45 5 3 2. 5 2 0 2 -22- The paper size is applicable to the Chinese National Standard (CNS) Α4 specification (210Χ 297 mm) Κ 8 9 1. 65 2. 23 2. 14 4. 3 3. 5 3. 3 18. 4 13. 5 11. 6 2 3 0 ^^ 46 ^ 2 ΑΊ Β7 5. Description of the invention (20). Table 17 Degree of cross-linking at 150 ° C for rheological data, the longest coking time of Newton-meter coking safety, t90, minutes. The purpose is only for illustration and description and is not intended to limit the scope of the invention. The scope of the invention is determined by the scope of the patent application attached here --- I --- Τ--, one policy-- (please read the precautions on the back before filling out this page) Cooperation Du Print-23-

Claims (1)

In the Patent Application No. 84106912, the patent Fan a was requested to amend the Taxi. Scope of patent application-an accelerator composition for improving the coking ratio used in the vulcanization of rubber ', which contains a main accelerator selected from the group consisting of inferior acid acid amine salt and I »seth and a sufficient amount of auxiliary accelerator, its characteristics In every 100 parts by weight of rubber, the weight ratio of the main accelerator to the auxiliary accelerator is 0.1 to 8 parts by weight, and the weight ratio of the main accelerator to the auxiliary accelerator is 10: 9 0 to 90: 1 0 mixed and the auxiliary accelerator is the compound of formula I: 0H IC / \ Rl-C G-R2 'ϊ;! HC CH ------ Γ-(install-(please read the notes on the back first Please fill in this page again.) Printed by the Employees Consumer Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs (I) where R, Ri '1? 2 are individually selected from hydrogen, Ci-C1 () alkyl, C7-C10 aralkyl, C2 -C1 () pyridine, C6-C1Q aryl and C7-C1 () alkaryl, and one of R, 1 ^ and 1? 2 may be halogen, nitro, hydroxy, and at least R, 1 ^ and 1 ? 2 at least one is the dithioaminoformamide of formula II: S R5 1! R4-NCSC- II r5 r7 (Π) where R4 and 1? 5 are individually selected from < ^-(: 1 ( ) Alkyl, C7-C10 aralkyl, c2-cln alkenyl, c6- c1Q aryl, c7-c1 () alkaryl, and h This paper scale is applicable to China National Standard (CNS) Α4 regulation (210X297 public director) Printed A8 B8 C8 D8 'Applicable Patent The scope and design 5 can be combined to form C4-C7 cycloalkyl or heterocycloalkyl; 1? 6 and 1? 7 are gas. 2. According to the accelerator composition of item 1 of the patent application scope, wherein the auxiliary accelerator is Used in combination with sulfenamide sulfonamide accelerators. The sulfenamide sulfonamide accelerators are selected from N-cyclohexyl-2-benzoxazolyl sulfenamide amide, N-tert-butyl-2- Benzopyrazolyl sulfenamide, N-tert-pentyl-2-benzothiazolyl sulfenamide, N-oxydiethyl-2-benzobenzoxazolyl sulfinate · Amine and N, N-dicyclohexyl-2-benzopyrazolyl sulfenamide. 3. The accelerator composition according to item 1 of the patent application scope, in which the auxiliary accelerator is used with In combination with the accelerator, the thiazole accelerator is selected from the group consisting of 2-mercaptobenzopyrazole, 2-mercaptobenzoxazole zinc, and dibenzodisulfide disulfide. 4. According to the patent application 1-3 The accelerator composition of any one, wherein the amount of the auxiliary accelerator is 0.05 to 5 parts by weight per 100 parts by weight of rubber. 5. A vulcanized rubber composition, which includes the following vulcanization reaction products: ( Α) 100 parts by weight of at least one natural or synthetic rubber; (B) 0.1 to 25 parts by weight of sulfur and / or a sufficient amount of sulfur supplier to provide a comparable 0.1 to 25 parts by weight Of sulfur; (C) 0.1 to 8.0 parts by weight, selected from the main vulcanization accelerators of azole and sulfenamide amide accelerators; and (DI sufficient auxiliary accelerator to provide a weight ratio of If the main accelerator is 10: 90 to 90: 10 for the auxiliary accelerator, the auxiliary accelerator -2- This paper scale is applicable to the Chinese National Standard (CNS) A4 specification (210X297 mm) (please Read the precautions on the back of Min Min-4-fill in this page) Order. Line The range of benefits A8 B8 C8 D3 is selected from the compound of the formula i Η CR-ρ> Ί \ y c ... 1 ΪΜ R -c IH ο '⑴ ^ ^ in the jh, R2 are independently selected from 氲, Ci_Ci〇 alkyl group, c _ group = group, C2-C1G alkenyl group, today, aryl group and burnt 7 aryl and one of R'RlW2 may be ㈣, nitro, via group and at least Er R, 1 ^ and 1? 2 is the molecular formula II: r4-NCSC-1 I r5 r7 (II), middle R4 and R5 are individually selected from c10 embankment, C7_Cufang (please read the precautions on the back before filling this page). The Ministry of Education and Welfare Bureau ’s employees ’cooperation, the company ’s printing of 0-square alkyl, C, and Qigendi applied for the vulcanized rubber composition of the patent scope item 5, where the secondary acid amide accelerator is selected from N-ring Hexyl-2-benzoxazolyl sulfenamide, N-tert-butyl-2-benzoxazolyl sulfonamide, N-tertyl-2-benzylol Amine, N-oxydiethyl-2-benzene C 1 alkenyl c6-c1 () aryl, c7_Ciq alkaryl, and R 5 can combine to form C4-(: 7 cycloalkyl or heterocycloalkane Base; for the 3-sheet paper scale applicable to the Chinese National Standard (CNS) A4 regulations (210X 297 ) Ϋ́ον 2 ABCD The Ministry of Economic Affairs Central Standards Bureau employee consumer cooperative printed π, the scope of patent application and oxazolyl sulfenamide amide and Ν, Ν-dicyclohexyl-2-benzyl sulfonyl acid amine 7. The vulcanized rubber composition according to item 5 of the patent application scope, wherein the far-end accelerator is selected from the group consisting of 2-¾-benzobenzopyridine, 2-¾-benzobenzopyridine zinc, and diphenyl disulfide Phenazole. 8. The vulcanized rubber composition according to any one of items 5 to 7 of the patent application scope, which further contains one or more additives selected from anti-ozonants, antioxidants, fillers, waxes, retarders and processing Oil 9. A method of curing a vulcanizable composition, which is carried out at a temperature of 丨 〇 to 220C to 24 hours' This composition contains at least one natural or synthetic rubber, the method is from 0.1 to 2 5 parts by weight of sulfur or a sufficient amount of sulfur supplier to provide 0.1 to 25 parts by weight of sulfur per 100 parts by weight of rubber and 0 to 1 to 8 parts by weight selected from sulfinic acid It is carried out in the presence of the main accelerators of amines and tetrazole, which is characterized by It is carried out in the presence of a sufficient amount of auxiliary accelerator so that the weight ratio of the main accelerator to the auxiliary accelerator is 1 〇: 9 〇 to 9 〇: 〇〇 To improve the safety of the method, the auxiliary accelerator is a compound of formula I / -C-Η AU ..... \ \ n / Γρ »/ 1» The size of the paper is based on SS 丨 material (CNS) A4 specification (210 ^ 297 ^ ¾ ^ 9i) A8 B8 C8 D8 Patent scope where R, Ri, R2 are individually selected from hydrogen, C1_C10 alkyl, C7_C10 aryl, C2-C1 () alkenyl, C6-C1Q aryl, and C7_Cl〇alkylaryl, and R, R1, and R2 One can be halogen, nitro, hydroxy and at least one of R, R1 and R2 is diaminomethylformyl of formula II: R ^ -MCSC- " Ί s R5 R7 Ministry of Economic Affairs, Central Bureau of Economy and Technology, consumption cooperation . Social printing (II) and R5 are individually selected from Ci_G * i〇 pit group, C7-C1 () aryl pit group, J alkenyl group, c6-c1Q aryl group, c7-c1Q alkaryl group, and R4 and R5 may Combined to form (: 4- (: 7 cycloalkyl or heterocycloalkyl; R6 * R7 is gas. The method according to item 9 of the patent application scope, wherein the sulfenamide sulfonamide accelerator is selected from N-cyclohexyl-2-benzoxazolyl sulfenamide amide, N-tert-butyl-2-benzene Pyridazole-based sulfenamide, N-tertyl-2-benzopyrazolyl sulfenamide, N-oxydiethyl-2-benzoxazolyl-sulfenylamide Amine and N, N-dicyclohexyl-2-benzoxazolyl sulfenamide. U, according to the method of claim 9 of the patent application scope, wherein the p-sezoazole accelerator is selected from 2-salbenzybenzoxazole, 2-mercaptobenzoxazole zinc, and disulfide. 12- The method according to any one of the items 9 to 11 of the patent application scope, wherein the amount of the adjuvant accelerator is 0.05 to 5 parts by weight per 100 parts by weight of rubber-5-where C (please read the back Matters needing attention before filling this page) • Binding-10. Line 2d46d2 A 8 BS C8 D8 々, the scope of patent application quantity ratio. 13. The method according to any one of items 9 to 11 of the patent application range, wherein the auxiliary accelerator is selected from dialkyl-hydroxyphenyldialkyldithiocarbamate, dialkyl- Hydroxyphenyl-diphenyldithiocarbamate and dialkylcarbonylphenyl-N-oxydiethyldithiocarbamate. 14 The method according to item 13 of the scope of the patent application, wherein the auxiliary accelerator is (3,5-di-tert-butyl 4-hydroxyphenyl) -diphenyl dithioamine carboxylate 15_ The method according to item 13 of the patent application scope, wherein the auxiliary accelerator is (3,5-di-tert-butyl-4-hydroxyphenyldimethyldithiocarbamate or (3,5- Di-tert-butyl-4-benzylphenyl) -diethyldithiocarbamate. (Please read the notes on the back before filling this page) -¾ Employee Consumer Cooperative of the Central Bureau of Samples of the Ministry of Economic Affairs印 褽 -6- The paper scale is applicable to the Chinese national standard (<: Q5> Six 4 rules. Grid (210/297 mm) year / 1 ϋ “two one” milk. R 9 Supplement, 丨 No. 84106912 Supplementary Specification for Chinese Patent Application No. (November 85) Experimental Data: Examples 1 1 and 1 2 and Comparative Example L These examples illustrate the use of some more auxiliary accelerators according to the present invention and their benefits. Table A shows the composition of the compounds And Table B is the rheology at 160 ° C. Table A Compound Composition-Example 11 12 L NR SMR CV 50 50 50 BR Cariflex BR 1220 50 50 50 Carbon Black N-220 50 50 50 Sunthene Oil 4240 10 10 10 ZnO 3.0 3.0 3.0 Stearic acid 2.0 2.0 3.0 Sunolite Scan 240 240 1.0 1.0 1.0 HB-DHEC 2.0 —-HB-DSC-2.0-CBS 0.6 0.6 0.6 Sulphur 2.3 2.3 2.3 0191G.DOC / sh -1- HB-DHEC = (3,5-di-tert-butyl-4- # to phenyl) -di-2- # ethyldithiocarbamate HB-DSC = (3,5-di-tert Butyl-4-hydroxyphenyl) -distearyl dithiocarbamate Table B Example of rheological data at 160 ° C 11 12 L Torque difference, Newton meters 1.2 1.7 1.2 ts2 (min ) 3.9 3.5 3.9 t90 (minutes) 9.2 5.6 9.3 0191G. DOC / sh-2-