JPS62201947A - Additive for rubber and production thereof - Google Patents

Abstract

PURPOSE:To form an additive for rubber, which has good flow characteristics and storage stability and is excellent in dispersibility in rubber at least equal to that of as well as granulated powder even without resort to granulation, by blending at least one member selected from among conventional additives for rubber with rubber and process oil. CONSTITUTION:This additive for rubber can be obtd. by mixing at least one member selected from among conventional additives for rubber with rubber and process oil in the presence or absence of an org. solvent. It is preferred that the rubber is used in an amount of 0.1-30wt% based on that of process oil and the amount of the member selected from among conventional additives is 0.5-30wt% based on that of a compsn. consisting of rubber and process oil.

Description

[Detailed description of the invention]

<Industrial Application Field> The present invention relates to a rubber additive and a method for producing the same, and more specifically to a rubber additive whose main component is one or more selected from commonly used rubber additives. Part 6 relates to the agent and its manufacturing method. <Prior art> Insoluble sulfur is often used as a vulcanizing agent in rubber additives, but since this insoluble sulfur is a polymeric sulfur, when it is used as a vulcanizing agent, it does not add to the rubber. Must be evenly distributed. Conventionally, insoluble particles were used in the form of fine particles, which caused dust to be generated when handled and easily dissipated as dust, and the particles were significantly charged due to friction, resulting in a dust explosion-like phenomenon due to electrical discharge. Workability may cause accidents. There are many problems from the viewpoint of pollution, etc., and since insoluble sulfur cannot be said to have good fluidity, it also has the drawback of causing problems in workability during transportation and storage. Therefore, it was proposed to add process oil for rubber for the purpose of preventing insoluble sulfur dust and static electricity. Nothing satisfied me. That is, for example, in JP-A No. 49-93294, there is an example in which a treated oil, which is a mixture of process oil and a surfactant, is added to insoluble sulfur to make granules, and in US Pat.
No. 06708 discloses an example in which ethylene glycol ether, which is a nonionic activator, is added to insoluble sulfur. However, in both of these inventions, although the dispersibility of insoluble sulfur in rubber is somewhat improved,
It has the disadvantage of being expensive due to the use of an activator, and also has the disadvantage of lacking fluidity and storage stability. Also, regarding vulcanization accelerators, which are additives for rubber, workability,
From the perspective of preventing pollution, granulation is performed while trying to improve dispersibility. For example, a method using vinyl acetate as a binder (
JP-A-49-555661 and JP-A-49-9844
7, etc.), and a method using liquid rubber (Japanese Unexamined Patent Publication No. 5
1103142f'i publication, USP, NQ 45646
70 specification, etc.), and a granulation method in which ether is added (Japanese Patent Application Laid-open No. 6 O-IE8728@Publication, etc.), but these methods cannot be said to have sufficient dispersibility. <Problems to be Solved by the Invention> The present invention is directed to one or more additives selected from commonly used rubber additives, rubber process oils and rubbers that are frequently used in the rubber industry, and the necessary additives. Rubber additives and rubber additives that have excellent dispersibility in rubber equivalent to or better than granulation without using a granulation method, and can also improve fluidity and storage stability by using a suitable solvent. The purpose of this paper is to provide a method for producing the same. <Means for Solving the Problems> The rubber additive according to the present invention is characterized in that it consists of one or more selected from commonly used rubber additives, rubber and process oil. Furthermore, the composition of the above-mentioned process oil and rubber for the entire set includes one or more selected from commonly used rubber additives, in which the ratio of rubber to prohis oil is adjusted to 0.1 to 3011i1%. It is characterized by having a proportion of 0.5 to 30% by weight. In addition, the method for producing the rubber additive of the present invention includes mixing rubber and process oil with one or more selected from commonly used rubber additives in the presence or absence of an R solvent. The organic solvent is distilled off as required. That is, the present invention aims to provide a rubber additive that exhibits the same effect as granulation without using the conventional granulation method. A rubber additive obtained by surface-treating a rubber additive, which is not particularly limited as long as the rubber is mixed with professional wrestling oil in the presence or absence of an organic solvent during production. However, butyl rubber is preferred because it has particularly good solubility in process oil. or,
If necessary, it is also possible to mechanically granulate and mold. In this case as well, the dispersibility is superior to that of ordinary granulated products. Although examples are not described below, it should be understood that the present invention is not limited to the following examples. <Example> The rubber additive according to the present invention consists of one or more selected from commonly used rubber additives, rubber and process oil, and each of these materials is commonly used in the rubber industry. Since the rubber is used, there is no adverse effect on the physical properties of the unvulcanized rubber after vulcanization. In other words, the rubber used is natural rubber, butyl rubber, styrene-butadiene rubber, nitrile rubber, isoprene rubber, ethylene brobylene rubber, polybutadiene rubber, or other synthetic rubber, and the process oil used is naphthenic, paraffinic, or aromatic. One or a mixture of two or more selected from tick-based and olefin-based rubber process oils is used, and commonly used rubber additives include organic or inorganic vulcanizing agents and vulcanization accelerators. agent. Examples include anti-aging agents and fillers. Here, further antioxidants to achieve the desired purpose. A crosslinking agent, an antistatic agent, an activator, etc. may be added. An example of the inorganic vulcanizing agent is insoluble sulfur. Insoluble sulfur here refers to polymeric sulfur that is insoluble in carbon disulfide. Due to its nature, normal insoluble sulfur usually contains about 10% of soluble sulfur, but in aS for water use, this is simply referred to as insoluble sulfur. The proportion of each of these components shall be 0.1 to 30ffi 111%, and the above process will contain one or more types selected from commonly used rubber additives. The proportion of the composition consisting of oil and rubber is 0.5 to 30% by weight. In addition, in producing the rubber additive according to the present invention,
In the presence or absence of an organic solvent, the surface of the rubber and process oil is preliminarily treated with one or more selected from commonly used rubber additives. That is, it is produced by surface-treating a coating composition consisting of process oil and rubber with one or more selected from commonly used rubber additives. At this time, the rubber may be dissolved in an organic solvent and then mixed with prohys oil and one or more additives selected from commonly used rubber additives, or after the organic solvent and process oil are mixed. It may be mixed with rubber and one or more additives selected from commonly used rubber additives. In short, rubber is dissolved in process oil and/or solvent and mixed uniformly with one or more additives selected from commonly used rubber additives. In this case, other elements may be sequentially added to one or more selected from commonly used rubber additives, but it takes time to achieve uniformity. After this, normal mechanical granulation may be further performed. The organic solvent used is one or a mixture of two or more selected from carbon disulfide, aromatic hydrocarbons, aliphatic hydrocarbons, and halogenated hydrocarbons. Next, a specific example will be described. (Method for preparing coating composition) Add 0.1 to 30% by weight of rubber to a naphthenic, paraffinic, aromatic, or olefinic process oil, which is a process oil for rubber, and add the rubber while stirring. , If necessary, heat to 80°C and stir until the rubber is completely dissolved, then cool to room temperature for 2J] l.
A coating composition is synthesized. In this case, a composition using a process oil for rubber is called a coating oil composition, and a composition using A1AFJ instead of the process oil is called a coating solvent composition. (Example 1) Pure (97%
Add 850 g of powdered insoluble IA and, while stirring, dropwise drop a mixture of 150 g of a coating oil composition consisting of 70% paraffinic process oil and 30% ethylene propylene rubber and 200 g of carbon disulfide. After addition, the coating oil composition was added to the surface of the powdered insoluble IA and resin, and the mixture was further stirred. 984, a rubber additive containing 83% insoluble A content.
ggj! , : . (Example 2) 995 g of powdered insoluble sulfur with a purity of 96%, natural rubber O
11% sulfur and naphthenic process oil 99.9% by weight
Synthesis was carried out in the same manner as in Example 1 using 5 g of a coating oil composition consisting of: the result,
Additives for rubber containing 95.5% insoluble
I got 999. (Example 3) Using a coating oil composition 100Q consisting of powdered insoluble IA 900 (J) with a purity of 97%, 0.5 ffl fM% of styrene-butadiene rubber and 99.5% by weight of aromatic process oil. It was synthesized and coated in the same manner as in Example 1. As a result, 991 g of a rubber additive containing 86.4% insoluble sulfur was obtained. (Example 4) Powdered insoluble sulfur SOOG with a purity of 98%, isoprene 3% rubber and 97% naphthenic process oil
It was synthesized and coated in the same manner as in Example 1 using 200 g of a coating oil composition consisting of: As a result, 995 g of a rubber additive containing 76.8% insoluble sulfur was obtained. (Example 5) Same as Example 1 using 250 g of a coating oil composition consisting of powdered insoluble sulfur 750 (1) with a purity of 98%, 20 ffim% of nitrile butadiene rubber and 80% by weight of acomadic pro-hyde oil. As a result, 968 (11!?) rubber additives containing 72.7% insoluble sulfur were obtained. Using 300g of a coating oil composition consisting of 30% by weight of bilene diene rubber and 70% by weight of paraffinic professional wrestling oil, it was synthesized and coated in the same manner as in Example 1.As a result, the insolubility was 67.9%. 993 g of a rubber additive containing sulfur was obtained. (Example 7) 850 g of powdered insoluble sulfur with a purity of 98%, 801 t% of naphthenic process oil, and 20% by weight of butadiene rubber.
It was synthesized and coated in the same manner as in Example 1 using 150 g of a coating oil composition consisting of: As a result, 99% of the rubber additive containing 84% insoluble sulfur was
It's 0011. (Example 8) Using 100 g of a coating solvent composition consisting of powdered insoluble sulfur 900 (1) with a purity of 98%, 5% styrene butadiene rubber and 1n% by weight of toluene 95, and aromatic process oil 959. It was synthesized and coated in the same manner as in Example 1. As a result, excluding the organic solvent, the rubber additive containing 87.5% insoluble f1 sulfur was 998.7 (] 4!J. (Example 9) ) 960 grams of wet cake-like insoluble sulfur containing 22% carbon disulfide, which is in the middle of the usual synthesis of insoluble sulfur, is placed in a ribbon blender and mixed with 14 ml of ethylene propylene rubber.
．． 360 g of a coating solvent composition consisting of 51% 3i and 85.7% by weight of carbon disulfide was added dropwise and homogenized, and then 200 g of paraffinic process oil was added and mixed homogenized to coat the surface of the insoluble sulfur. coated with a solvent composition. As a result, 990 g of a rubber additive containing 74% of insoluble A content excluding carbon disulfide was obtained. (Example 10) Wet cake-like insoluble sulfur 1090Q described in Example 9, isobutylene isoprene rubber 11.11%, carbon disulfide 88.9% (fi%), and 180 g of a coating solvent assembly consisting of Seth A-Ile 13
Coating was carried out in the same manner as in Example 4 except that 0 (l) was used. As a result, 83.2% of carbon disulfide was removed.
970 g of a rubber additive containing insoluble sulfur was obtained. (Example 11) While putting the wet cake-like insoluble sulfur 12009 described in Example 9 into a ribbon blender and stirring it, naphthenic alcohol 12009 was added.
A coating oil composition consisting of 95% by weight of cocess oil and 5% by weight of natural rubber was mixed and homogenized for coating.
1001111 A rubber additive containing an insoluble portion of
Obtained. (Example 12) 1,100 ml of the wet cake-like insoluble sulfur described in Example 9 was put into a ribbon blender, and while stirring, a coating oil composition 1,500 ml consisting of 80% by weight of naphthenic process A oil and 1% of natural rubber 20fi was added. xylene 3
00g was added at the same time, mixed uniformly, and coated. As a result, 85.1% insoluble A
1003 iJ of a rubber additive containing 1. (Comparative Example 1) Synthesis was carried out in the same manner as in Example 1 using 800 g of powdered insoluble sulfur and 200 g of naphthenic process oil to obtain 990 g of insoluble sulfur coated solely with process oil. (Comparative Example 2) Wet cake-like insoluble sulfur 11009 described in Example 9, 150 g of aromatic process oil, and 300 g of 1-luene were mixed together in a ribbon blender.
After removing the organic solvent, 1002 g of insoluble sulfur coated with process oil alone was obtained. (Example 13) 20 liters of natural rubber to 2,500 cc of toluene and 180 cc of naphthenic process oil were charged into a 51 kneader equipped with a condenser, and stirred at a temperature of 40°C to 50°C to prepare a toluene-containing toluene-containing oil. A composition was obtained.To this, 800 g of tetramethyldiura l\disulfide was charged, mixed and stirred at the same temperature for 30 minutes, and then heated to a temperature of 8.
Toluene was recovered under reduced pressure at 0°C. As a result, 950 (II!V) additives for rubber containing 80% of tetramethylthiuram disulfide and 2% of natural rubber were prepared. (Example 14) 50 g of isoprene rubber and 800 cc of trichlorethylene.
and 50 g of naphthenic process oil were placed in a No. 51 kneader equipped with a condenser, and while stirring at room temperature, isoprene rubber was dissolved in trichlorethylene and process oil to obtain a coating oil composition containing 1 to 1 chlorethylene. Next, 2-mercaptoimidacillin 90
After mixing and stirring for 60 minutes, heat to a temperature of 90
The solvent was collected at °C. As a result, 950 g of a rubber additive containing 90% of 2-mercap 1 imidacillin and 5% of isoprene rubber was obtained. <Example 15) Ethylene propylene rubber 200 (l and diagonal ball tongue 3
500cc and naphthenic process oil i oog 5
Dissolve ethylene propylene rubber in 1-cole ethane and process oil while stirring at a temperature of 25°C to 35°C.

[]] An oil composition for tinging with Lulu 23 was prepared. Next, 700 g of powdered iodine was charged, mixed and stirred using an IQ Q Iff for 60 minutes, and then heated to recover dichloroethane at a temperature of 60°C. As a result, 970 g of a rubber additive containing 70% powdered sulfur and 10% ethylene propylene rubber was obtained. <Example 16> Butyl rubber 2009, Benvin 2000 cc, and naphthenic process oil ioog were charged in a 51 kneader, and the butyl rubber was dissolved in benzene and process oil while stirring at a temperature of 30°C to 40°C, and a benzene-containing coating was prepared. It was made into an oil composition. Next is zinc oxide powder 1700! Prepare II and cook at the same temperature 6
After mixing and stirring for 0 minutes, benzene was recovered under reduced pressure at a temperature of 60°C to 65°C. As a result, 190g of a rubber additive containing 85% zinc oxide and 10% butyl rubber was obtained. (Example 17) 100 g of butadiene rubber and 3000 cc of n-hex:nan
and 300 g of aromatic process oil and 6 N-phenyl-N'-isopropyl-p-phenylenediamines.
N-phenyl-N'-isopropyl-p-phenylenediamine 6 was prepared in the same manner as in Example 11 using 000.
960 CJ of rubber additive containing 0% and 10% butadiene rubber was obtained. (Rubber vulcanization test example) Formulation J in Table 1: Rinaru unvulcanized rubber was kneaded with rolls at 50°C ± 5°C and then vulcanized, and the effect on the vulcanization of the rubber additive according to the present invention was The effects were tested. Vulcanization test is JIS-63
00 (1974). The results are shown in Table 2. (Rubber dispersibility test example) Commercially available unvulcanized polybutadiene rubber 100c) was heated at 50°C±
It was wound around a roll at 5° C., 5 g of the rubber additive synthesized according to Examples 1 to 17 and Comparative Example 1.2 was gradually added over 1 minute, and cut and turned over 2 minutes. The sheet was passed through the book 5 times and the number of poorly dispersed particles was counted and judged with the naked eye. The results are shown in Table 3 below. In Comparative Example 3, 100 g of commercially available polybutadiene rubber was wound around a roll at 50°C ± 5°C, and 4 g of insoluble sulfur and 1 g of naphthenic process oil were gradually added for 1 minute. The material was cut back and threaded 5 times to make a sheet. In addition, the sample of Example 13 was granulated and designated as 8, and the sample synthesized and granulated according to Example 13 except that it did not contain rubber was designated as 8. Table 4 shows the evaluation of fluidity and rubber dispersibility of a product synthesized in the same manner and granulated under pressure, designated as C. Table 3 Table 4 0: Good Δ: Fairly good X: Fair (Example of storage stability) Since the change in the residual rate of insoluble sulfur was small when left covered at room temperature, storage stability was tested by the following method. That is, the Examples, Comparative Example 1, and untreated powdered insoluble sulfur were heated to 90° C. for a predetermined period of time to forcibly deteriorate, and then washed with carbon disulfide to measure the residual rate of insoluble sulfur. The results are shown in Table 5. Table 5 <Effects of the Invention> As is clear from the Examples and Comparative Examples below, the rubber additive according to the present invention has the same vulcanization properties for unvulcanized rubber as commercially available products. It can be seen that there is no adverse effect on the physical properties (), and that the dispersibility in unvulcanized rubber has been greatly improved.4 Furthermore, the fluidity and storage stability are superior to commercially available products. I understand that That is, the advantage of the present invention is that it can achieve effects equivalent to and better than granulation by mixing without using a granulator, and further advantages include the following: Become. Firstly, the fluidity of the powder is improved. In powder form, fluidity is extremely low due to interparticle friction, but with the treated rubber additive of the present invention, interparticle friction is reduced. Second, since the surface treatment with oil eliminates scattering properties, generation of dust can be prevented and pollution caused by handling 14 can be prevented. Thirdly, since the surface is treated with oil, the powder does not come into direct contact with the outside air, making it difficult for decomposition reactions to proceed due to light, MQ elements, etc. Fourthly, by treating the surfaces of multiple types with oil and mixing them, different particles do not come into direct contact with each other. For example, some conventional vulcanization accelerators are incompatible with mixing, and it is difficult to prepare a miscible vulcanization accelerator. For example, it has been considered impossible to mix sulfenamides, diurams, and even guanidines because they will react. However, according to the rubber additive of the present invention, a miscible vulcanization accelerator can also be easily prepared. It can be used in combinations of vulcanizing agents and vulcanization accelerators, antioxidants and vulcanizing agents, etc. Therefore, the intended purpose can be achieved.

Claims (13)

[Claims] (1) A rubber additive characterized by comprising one or more commonly used rubber additives, rubber and process oil. (2) The ratio of rubber to process oil is 0.1 to 3.
0% by weight, and the ratio of the composition consisting of the process oil and rubber to the total amount containing one or more selected from commonly used rubber additives is 0.5 to 3.
The rubber additive according to claim (1), wherein the content is 0% by weight. (3) The rubber additive according to claim (1), wherein the rubber is natural rubber and/or synthetic rubber. (4) The rubber additive according to claim (1), wherein the rubber is natural rubber and/or butyl rubber. (5) The process oil is one or a mixture of two or more selected from naphthenic, paraffinic, and aromatic rubber process oils.
The rubber additive described in section 1). (6) The rubber additive according to claim (1), wherein the commonly used rubber additives are a vulcanizing agent, a vulcanization accelerator, an anti-aging agent, and a filler. (7) The rubber additive according to claim (6), wherein the vulcanizing agent is insoluble sulfur. (8) The rubber additive according to claim 1 or 6, which is obtained by granulating a commonly used rubber additive. (9) A rubber additive characterized by mixing rubber and process oil with one or more commonly used rubber additives in the presence or absence of an organic solvent. Production method. (10) The manufacturing method according to claim (9), characterized in that the organic solvent is distilled off as necessary. (11) Claim (9) characterized in that the rubber is dissolved in an organic solvent and then mixed with one or more selected from process oil and commonly used rubber additives. Manufacturing method described in section. (12) Claim (9) characterized in that the organic solvent and process oil are mixed and then mixed with one or more selected from rubber and commonly used rubber additives. Manufacturing method described in section. (13) The organic solvent is one or a mixture of two or more selected from carbon disulfide, aromatic hydrocarbons, aliphatic hydrocarbons, and halogenated hydrocarbons.
The manufacturing method described in ).