JPS59213745A - Vulcanizable rubber composition - Google Patents

Abstract

PURPOSE:A rubber composition preventing bloom without damaging heat aging characteristics, etc., obtained by blending rubber with a specific sulfur-containing compound as a vulcanization agent, a dithiocarbamic acid compound, a sulfide, and a benzothiazyl compound as vulcanization accelerators. CONSTITUTION:Natural rubber and/or synthetic rubber is blended with a compound shown by the formula I (X is 3-6; R is group shown by the formula II; n is 5-350), a compound shown by he formula III (M is Zn, Fe, Te, Se, or Bi; R1 and R2 alkyl, or phenyl, or R1 and R2 together with other hetero atom except N may be linked through N to form heterocyclic ring; l is 2-4), a compound shwon by the formula IV (R3 and R4 are alkyl, or phenyl, or R3 and R4 together with other hetero atom except N may be linked through N to form heterocyclic ring), and a benzothiazyl compound as vulcanization accelerators. A triazine compound may be preferably added as the vulcanization agent.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to novel vulcanizable rubber compositions. More specifically, the present invention relates to a highly vulcanized rubber composition in which rubber contains a combination of a specific vulcanizing agent and a vulcanization accelerator.

In the rubber industry, vulcanizing agents are essential. Since Gutdeyer discovered sulfur in the 19th century, sulfur has been the dominant vulcanizing agent for rubber products to this day. Since such sulfur has poor dispersion into rubber, it is usually ground into fine powder and used in rubber. However, since sulfur has poor solubility in rubber, sulfur crystals are deposited on the rubber surface (plume phenomenon).

For this purpose, recently, sulfur has been modified to form an Sμ form. However, this Sμ body does not cause a bloom phenomenon on the rubber surface at a relatively low temperature of about 50 to 60°C, but due to high temperature M or heat generation during the manufacturing process of rubber products, the Sμ body transfers and causes a plume phenomenon. becomes sulfur. When tires and tubes are molded and vulcanized using compounded rubber with sulfur still in the plume, the adhesion between the rubbers and between the rubber and fibers decreases, causing the bonded parts to peel. .

Examples of organic vulcanizing agents that cause less blooming as described above include tetrabutylthiuram disulfide (TBTD),
Sulfur-donating vulcanizing agents such as tetraethylthiuram disulfide (TETD), dimorpholinyl disulfide (DTDM), and alkylphenol polysulfide have been proposed.

However, rubber products vulcanized with these organic vulcanizing agents are relatively hard in terms of heat aging resistance, but have poor flex cracking resistance. Therefore, it is not appropriate to use only these vulcanizing agents in tires and the like.

Under the current situation as described above, it is desired to develop a vulcanizing agent that has both properties of heat aging resistance and flex cracking resistance of vulcanized rubber and does not plume.

The present inventors previously discovered the following general formula (
A vulcanized rubber made by blending at least one sulfenamide vulcanization accelerator with the polysulfide polymer shown in 1) has both heat aging resistance and flex cracking resistance, and is a vulcanizing agent that does not plume. I found out that it could be (
(Japanese Patent Application No. 57-49965), and as a result of further research, it was found that at least one of the vulcanization accelerators and benzothiazyl compounds represented by the following general formulas (II) and (IN) were added to the polysulfide polymer represented by the general formula (1). Furthermore, it has been shown that when at least one vulcanization accelerator such as a triazine compound is used in combination with rubber, the physical properties of the vulcanized material are significantly improved without impairing heat aging resistance, flex cracking resistance, and plume resistance. Heading, we arrived at the present invention.

That is, the present invention comprises at least one vulcanizing agent represented by general formula (1), at least one vulcanization accelerator represented by general formula (n), a benzothiazyl compound, and a vulcanization accelerator represented by general formula l. and at least one benzothiazyl compound of the vulcanizing agent represented by the general formula (1), and at least one benzothiazyl compound of the general formula (I).
A vulcanizable product made of natural rubber and/or synthetic rubber, characterized in that it contains at least one of the vulcanization accelerators represented by [) and I in combination with at least one vulcanization accelerator of a triazine compound. The present invention provides a new rubber composition.

General formula (1) % formula % () [In the formula, X is 5 to 6, R is -(-C!H, -OH, -0 measure, C!H, -OH, -1n is 5 to 350 ] [In the formula, M represents Zn, Fe, Te, Be, Bi. R1aRz represents a furkyl group or a phenyl group.4
7'c Rs.

R2 may form a heterocycle with other heteroatoms other than the nitrogen atom via the nitrogen atom. t represents 2 to 4. ] General formula (In [Formula 13. R4 represents an alkyl group or a phenyl group.

R3v R4 may form a heterocycle with other heteroatoms other than the nitrogen atom via the nitrogen atom. ] Examples of the type of rubber in the vulcanizable rubber composition of the present invention include natural rubber and synthetic rubber, and examples of the synthetic rubber include imprene rubber (IR), butadiene rubber (BR), styrene-butadiene rubber (8BR), Acrylonitrile butadiene rubber (NBR), chloroprene rubber (CR), 7”
The formula (1) of the present invention may include chill rubber (AER), ethylene propylene terpolymer rubber (EPDM), urethane rubber (UR), etc., and these may be one type or a blend of two or more types of rubber. For example, the vulcanizing agent represented by the following formula (IV
It is obtained by reacting dithiol and sulfur chloride as in I.

nH8-R-8H+n8XC! t2-)+R-8x+z
fH+2nHOt(IV) [wherein R is +CI(2-(H
, -0-)--,0H2-OH, -1X is 1 to 4, and n is 5 to 650] Alternatively, it can be obtained by reacting dichloride and sodium polysulfide as shown in the following formula (to). .

n0Z-R-Ot+nNazS+x -+-4R-8X
Crucible + 2nNaOt(V) The vulcanizing agent represented by the formula (1) of the present invention obtained by the above synthesis method has an average degree of polymerization of n =
5 to 350, it is a pale yellow liquid to brown viscous substance, nonvolatile, and has almost no odor. Those with an average degree of polymerization n of less than 5 are unfavorable because they have poor volatility, while those with an average degree of polymerization n of more than 350 have poor compatibility with rubber.

The vulcanization accelerators shown in the formula-beating method of the present invention include, for example, zinc dimethyldithiocarbamate (ZnMDc), zinc diethyldithiocarbamate (Zn11CDO), zinc dimethylphenyldithiocarbamate (Znl!1PDo), tellurium dimethyldithiocarbamate (TθMDC), These include tellurium diethyldithiocarbamate (Tel!iDo), selenium diethyldithiocarbamate (BeEDO), bismuth dimethyldithiocarbamate (BIMDC), iron dimethyldithiocarbamate (FeMD(3)), and zinc N-pentamethylenedithiocarbamate (ZnPDO).

The vulcanization accelerators represented by the formula (button) of the present invention are, for example, tetramethylthiuram monosulfide (TMTM), tetramethylthiuram disulfide (TMTD), tetraethylthiuram disulfide (TKTD), tetrabutylthiuram disulfide (TBTD), dipentamethylene and thiuram tetrasulfide (DPTT).

The benzothiazyl compound of the present invention is a compound represented by the following general formula (D).

[In the formula, Rs represents a lower alkyl group. Y represents a hydrogen atom, an alkyl group, a cyclic alkyl group, or a phenyl group in which R6t and R7 are also hydrogen atoms. Further, RII*R9 may form a heterocycle with other heteroatoms other than the nitrogen atom via the nitrogen atom, but R8 and R9 are not hydrogen atoms at the same time. ] Examples of the compound represented by the above formula (Vl) include N,
N-dimethyl-thiocarbamoyl-2-mercaptobenzothiazole (DMTOMB), N,N-diethyl-
Thiocarbamoyl-2-mercaptobenzothiazole (
DKTOMB), 2-mercaptobenzothiazole (M
BT), benzothiazyl disulfide (MBTS), 4
-Methyl-2-mercaptobenzothiazole (M-MB
TJ, bis(4-methyl-penzothiazole disulfide (M-MBTJ, N-cyclohexyl-2-benzothiazolesulfenamide (OBB), N,N-dicyclohexyl-2-benzothiazolesulfene Amide (
DOB8), N-improvir-2-penzthiazolesulfenamide (PBS), N,N-diisoprovir-2-benzothiazolesulfenamide (DPBS)
), N-oxydiethylene-2-benzothiazolesulfenamide (OBB), 2-(4-morpholinyldithio]-penzothiazole (MDTB), N-t-butyl-2-benzothiazolesulfenamide ( BBS
), N,N-diethyl-2-benzothiazolesulfenamide, and the like.

The vulcanization accelerator for the triazine compound of the present invention is a vulcanization accelerator represented by the following general formula M).

Indicates a kill group, a phenyl group, and "10 p R11 may form a heterocycle with a hetero atom other than a nitrogen atom via a nitrogen atom, but "10 p R11 cannot be a hydrogen atom at the same time), - 8-Rsz (Rsz represents a hydrogen atom or a benzothiazyl group).

-8-Rls (R1 represents a hydrogen atom or a benzothiazyl group). 2 is -B-Rts (Rls is hydrogen) Examples of the vulcanization accelerator represented by the above formula (Sl) include 2-diethylamino-4,6-dithiol-S-triazine, 2-dibutylamino-4,6-sithio- 8
-) riazine (DBADT), 2-anilino-4,6
-dithiol-S-triazine, 2-anilino-4,6
-bis(penzthiadylthio)-S-triazine, 2-
Dibutylamino-4,6-bis(benzothiadylthiono-8-triazine, 2-morpholino-4,6-bis(benzothiadylthio)-8-triazine, 4,6-bis(
benzothiadylthio)-8-) riazine-2-thiol, 2,4.6-)lis(benzothiadylthio)-8-)
Riazine, bis-(2,4-diethylamino-8-) riazin-6-yln-disulfide, bis-(2,4-
dimethylamino-8-triazin-6-yl λ-disulfide and the like.

In the present invention, the amounts of these vulcanizing agents and vulcanization accelerators to be blended into the rubber include at least one of the vulcanizing agents represented by the general formula (1), at least one of the general rules for accelerating vulcanization represented by the general formula (1), and benzothiazyl. When containing a compound and at least one vulcanization accelerator represented by the general formula (lit) in combination, a compound of the general formula (1) per 100 parts by weight of rubber (in the following description, parts indicate parts by weight) The vulcanizing agent shown by is 0
．． 1 to 15 parts, preferably 0.5 to 10 parts, and 0.01 to 5 parts of the vulcanization accelerator represented by the general formula, preferably 0.05 parts.
~3 parts, the benzothiazyl compound and the vulcanization accelerator represented by the general formula l are [L01~15 parts, preferably 0.1~15 parts]
5 parts is good.

Further, at least one of the vulcanizing agents represented by the general formula (D), a benzothearyl compound, the general formulas (II) and (2)
When containing a combination of at least one vulcanization accelerator represented by and at least one vulcanization accelerator of a triazine compound, the vulcanization agent represented by general formula (1) is [11 to 15 parts, preferably α5 to 1
0 parts is better, benzothiazyl compound, general formula and ■
The amount of the vulcanization accelerator shown is 1101 to 15 parts, preferably 11 to 5 parts, and the amount of the triazine compound is 0.01 to 15 parts, preferably 111 to 5 parts.

However, the present invention is not limited to the vulcanization accelerators specifically exemplified above, and depending on the purpose, vulcanizing agents such as sulfur, DTDM, TMTD may be added to the above formulation of the present invention.
and vulcanization activators, such as diphenylguanidine (DPG), hexamethylenetetramine (6), etc.
More than one species can also be used together.

In addition, when manufacturing rubber products from the rubber composition of the present invention, anti-aging agents such as styrenated phenol (8P), 2,2'-methylene-bis(4-methyl-
6-tert-butylphenol) (MBMTB), N-Ingloby-N'-phenyl-P-phenylated 7-diamine (IPFD), N,N'-diphenyl-1)-phenylenediamine (pppn), 2,2.4- Trimethyl-1,2-dihydroquinoline condensate (TMDQ, )
, resinous condensate of acetone and diphenylamine (ADP
DR), octylated dienenylamine (ODPA),
2-) 1 such as lucagutobenzimidazole (MBr)
More than one species may be used together. In addition, zinc oxide, magnesium oxide, lead oxide,
12 to 20 parts, preferably 2 to 8 parts, of fatty acids and the like are used in combination with 100 parts of rubber.

The vulcanizable rubber composition of the present invention can be vulcanized under similar vulcanization conditions to conventional rubber compositions containing sulfur and a vulcanization accelerator.

Rubber products obtained by vulcanizing the vulcanizable rubber composition of the present invention include:
Compared to yellow vulcanized rubber, there is no plume, and it has excellent vulcanized physical properties and excellent aging resistance such as heat aging resistance and flex cracking resistance. Furthermore, compared to the case where a specific vulcanization accelerator is used in combination with a polysulfide polymer, the composition of the present invention in which another vulcanization accelerator is combined with the polysulfide polymer has further improved vulcanization properties, and has improved heat aging resistance and resistance. It also has excellent aging resistance such as flex cracking resistance.

Such properties indicate that the vulcanizable rubber composition of the present invention is a highly valuable rubber composition for rubber products such as tires, tubes, anti-vibration rubber, belts, hoses, etc.

Synthesis examples and examples of the vulcanizing agent of the present invention are shown below.

Synthesis example Reaction formula: %Formula% () (In a 200wIt three-neck flask, add trithiocarbonate soda
Add f and add diglycol dichloride (f) dropwise while keeping the liquid temperature at 60°C, then stir at the same temperature for about 5 hours. Cool and extract with toluene, and transfer unreacted dichloride to the toluene layer. The aqueous layer is made acidic with dilute sulfuric acid (IV)'. After that, it is extracted with toluene. The toluene is distilled off from the extract under reduced pressure, and then further distilled under reduced pressure to obtain a colorless transparent liquid (Vi. Infrared absorption spectrum 2600"'
Check with IK.

Further, dissolve this in benzene, gradually add a benzene solution of sulfur chloride (Vlλ') at a temperature of 5 to 30°C, stir at the same temperature for 24 hours, and neutralize with aqueous sodium carbonate solution.Aqueous layer is removed, and only the benzene layer is distilled to obtain a viscous pale yellow liquid (VJI)'.The structure is confirmed by 2-man spectrum, infrared absorption spectrum, and GPOlNMR.

Triglycol dichloride can be used as a raw material in a similar manner. In addition, as an alternative synthesis method, triglycol dichloride and an aqueous polysulfide sodium solution are used, and the liquid temperature is 40 to 90°C.
You can also react with

The structural formulas of the compounds synthesized by the above method are shown in Table 1 below.

Example 1 The recipe is shown in Table 2. The compounding method, procedure, and conditions are 5604 from 8R, and the physical test method for unvulcanized rubber is J-Ko 5K650.
0, respectively. The results are shown in Table 5.

Table-2 Compounded Natural Rubber - R8S$1 100 HAF Black 50 Sonic Process Oil R-5010 Zinc Oxide 5 Stearic Acid 3 Antige 3 C(1) 0.5 Vulcanizing Agent
2.0 (sulfur equivalent amount - vulcanization accelerator Table 6 Note) (1) ANDAGE 5C Niingrobil Phenylene - p-phenylenediamine Product name manufactured by Kawaguchi Chemical Co., Ltd. (2) Each rubber test item symbol is according to 5RIS3101 .

(3) Conducted in accordance with SR Engineering 85102.

(Toyo Seiki Seisakusho Vibration type vulcanization tester 0, D, R+0
From the results in Table 3, the vulcanization systems of the present invention all have a longer scorch time t5 and extremely less vulcanization when compared to the sulfur vulcanization system, which is a known vulcanization system.

Also, compared to Comparative Example 2, Example 1-1.1-2゜1-4
The torque value is extremely high, and the effect of TθEDC is clearly recognized.

Example 2 The recipe is shown in Table-4. For compounding methods, procedures, and conditions, refer to J-tech 5.
The test method for unvulcanized rubber and vulcanized rubber is based on K6385 and K6500 from J and K65 from J.
Each test was carried out in accordance with D1.

The results are shown in Table-5.

Table-4 Compounded styrene-butadiene rubber (JSR+7+2J 10
0ISAF Black 25HA
F Black 25 Sonic Process Oil R-505 Zinc oxide 6 Stearic acid 2 Vulcanizing agent
1.8 (Basic vulcanization accelerator
Table 5 From the results in Table 5, the vulcanizates of the present invention shown in Examples have excellent scorch stability and HBe M! (The IQ is high and the vulcanized physical properties are excellent.

Example 3 The recipe is shown in Table-6. The compounding method, procedure, conditions, and physical test method for unvulcanized rubber were performed in the same manner as in Example 1, and the test method for vulcanized rubber was performed in the same manner as in Example 2. The results are shown in Table-7.

Compounded natural rubber R8S 1100 HAF Black 50 Zinc oxide 5 Stearic acid 6 ANTAGE LDA (5) 1 Vulcanizing agent 5 (sulfur equivalent) Vulcanization accelerator Table 7 Note) (5 N ANTAGE LDA: Octylated diphenylamine (ODPA) Kawaguchi Kagaku Kogyo Co., Ltd. Product Name From the results in Table 7, the rubber composition of the present invention has a torque value of 0, DlR (MHRj) < 0, and has excellent vulcanized properties even when vulcanized at high temperature for a short time. Show that.

It can be seen that even when the rubber composition of the present invention was vulcanized at 140° C., the Hs% Zoo was high and the vulcanization properties were excellent.

Example 4 The recipe is shown in Table-8. The blending method, procedure, and conditions are 5RI
S5604, physical test method for unvulcanized rubber is J-K5K63
00, respectively. The results are shown in Table-9.

Compounded Natural Rubber SMR+5 100 HAF Black 50 Zinc Oxide
5 Stearic acid 1 Antige LDA I vulcanizing agent
1.5 (button equivalent) vulcanization accelerator
Table 9 From the test results in Table 9, as the sulfur content increases from OS to OS, ty, , t'c (10), t'
c The shorter the time (90), the greater the vulcanization redo. However, compared to the sulfur of the comparative example, the vulcanizate of the present invention has less vulcanization.

Also, there is little difference between O8, ~6 and 208h6.

Example 5 The recipe is shown in Table-10. The blending method, procedure, and conditions are SR.
Engineering 85604, physical test method for unvulcanized rubber is J Engineering S K
6500. Physical tests of the vulcanized rubber were conducted in accordance with J-K 5K6301. The results are shown in Table-+1.

Table-10 Compounded natural rubber RBB Su1100 HA'? black 50 zinc oxide
5 Stearic acid 1 Antige LDA I Vulcanizing agent 1.5 (sulfur equivalent λ vulcanization accelerator) , has excellent vulcanization properties,
Moreover, even when compared with Comparative Example 9, which is a known vulcanizate, the vulcanized product of the present invention has excellent vulcanized physical properties, and is also excellent in terms of heat aging resistance and bending resistance.

Example-6 The recipe is shown in Table-12. The compounding method, procedure, conditions, and procedure for making vulcanized rubber were based on Example 5, and the bloom state of the unvulcanized and vulcanized rubber surfaces was observed, and the results are shown in Table 1.
Shown in 3.

Table-12 Compounded natural rubber R8S l#11+00 HAF Bunak 50 zinc oxide
5 Stearic acid 1 Antige 50 (L5 vulcanizing agent
5.0 (sulfur equivalent) DBADT
α5 Axel DM (MBTS)
0.5 From the test results shown in Table 15, no bloom phenomenon was observed in the rubbers containing the vulcanizing agent of the present invention, regardless of whether they were unvulcanized or vulcanized.

Example-7 The recipe is shown in Table-14. The blending method, procedure, and conditions are: J
The test was conducted in accordance with IBK6585, and the test method for unvulcanized rubber and vulcanized rubber was the same as in Example 5. The results are shown in Table-15.

Compounded styrene-butadiene comb (TSRI500)
+00 engineering 8 A F black
5° Nikk process oil R-509 Zinc oxide 5 Stearic acid 2 Antage 3c (Product PPD) 0.5 Osigard G (6) 0.5 Vulcanizing agent 7.0 (Sulfur hard weight I) Vulcanization accelerator Table- Note 15) (2)
Osigard G: Ozone-resistant wax, manufactured by Kawaguchi Chemical Industry Co., Ltd. Comparative Example 15, which is a known vulcanization system from the test results in Table-15
In comparison with Example 7-5.7-4, the scorch time t5
It can be easily inferred that the process stability due to the heat history during cross-contacting is long and that the vulcanization properties are excellent.

Generally physical properties of vulcanizates (1 (81Msoo #TB)
Increasing the scorch time t5 shortens the process stability, but Example 7-1.7-2.7
As shown in 5.7-6, the vulcanization system of the present invention has excellent physical properties such that the scorch time is only slightly faster and the physical properties of the vulcanizate are high. show.

Agents: 1) Akira Agent: Ryo Hagiwara - Procedural amendment Written by Kazuo Wakasugi, Commissioner of the Patent Office1, Indication of the case: September 1, 1958, Application No. 856822, Name of the invention: Vulcanizable rubber composition 3. Relationship with the case of the person making the amendment Patent applicant f, 1Iili 2-8-4 Uchikanda, Chiyoda-ku, Tokyo
No. 4, Agent 1.1 Iili Toranomon-16-2, Minato-ku, Tokyo Chiyo 1 [1 Building] Telephone (504) 1894 Name Benko! :J: (7179)
■" Akira (and 1 other person) 5. Date of amendment order Voluntary amendment l Application subject to amendment a Contents of amendment Insert the sentence "patent application)".

(2) Insert the sentence ``Z number of inventions stated in the claims 2'' between ``1. Title of the invention'' and ``2 Inventor'' in the application.

(3) Change “2. Inventor” to “3. Inventor” in the application, “5. Patent applicant” to “4. Patent applicant”, “4. Agent” to “S agent”, and “& attachment” Change "Document List" to "& Attached Document List" and "Inventor R and agent other than those mentioned above" to "
Z Inventors and agents other than the above.''

Claims (1)

[Claims] 1. At least one vulcanizing agent represented by the general formula (I) and at least one vulcanization accelerator represented by the general formula (I);
A vulcanizable rubber composition made of natural rubber and/or synthetic rubber, characterized by containing a benzothearyl compound and at least one vulcanization accelerator represented by general formula (Jl), general formula (I) - iR-8 horse mackerel, (I) [in the formula, X is 3 to 6, R is +0H2-OH2-%OH, J
3H, , n is 5 to 350. ] General formula (II) [In the formula, M is Zn, Fe, To, Be,
Indicates Bi. R1eR: represents an alkyl group or a phenyl group. Further, R1*R-total may form a heterocycle with other heteroatoms other than the nitrogen atom via the nitrogen atom. t represents 2 to 4. General formula ■ [In the formula, "S y R4 represents an alkyl group or a phenyl group. R3 and R4 may form a heterocycle with other heteroatoms other than the nitrogen atom via the nitrogen atom.] 2 General formula At least one of the vulcanizing agents shown in (1),
A natural rubber and/=1′ bamboo characterized by containing a benzothiazyl compound, at least one vulcanization accelerator represented by the general formula (I[), and at least one vulcanization accelerator for a triazine compound. A vulcanizable rubber composition made of synthetic rubber. 5. The vulcanizable rubber composition according to claim 1, wherein the vulcanization accelerator represented by general formula (II) is tellurium dimethyldithiocarbamate or tellurium diethylditheocarbamate. 4. The triazine compound is 2-diethylamino-4#6-
Cithio-8-) riazine, 2-dibutylamino-4
, 6-sithio-8-)'j azine, and 2-anilino-4,6-sithio-8-) riazine. & Rubber 100 parts by weight, the vulcanizing agent represented by the general formula (1) is 0.1 to 15 parts by weight, and the vulcanization accelerator represented by the general formula (I[) is 0.01 to 5 parts by weight. 4. The vulcanizable rubber composition according to claim 1, wherein the benzothiazyl compound and the vulcanization accelerator represented by formula (2) are contained in an amount of 0.01 to 15 parts by weight. & 100 parts by weight of rubber, 0.1 to 15 parts by weight of a vulcanizing agent represented by the general formula (!), and 0 parts by weight of a benzothiazyl compound, a vulcanization accelerator represented by the general formula (5)
．． 01 to 15 parts by weight, and the vulcanization accelerator for the triazine compound is Q, 01 to 15 parts by weight.
Vulcanizable rubber composition according to item 1 or 4.