JPS6058255B2 - Molded organic rubber chemicals and their manufacturing method - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION When commercializing powdered organic rubber chemicals, the present invention aims to develop a molded organic rubber in the form of small particles that has good fluidity and is improved so that it does not scatter as dust upon disintegration. It relates to drugs and their manufacturing methods.

Generally, the proportion of organic rubber chemicals used in rubber is relatively small compared to other compounding agents such as fillers, so when using them, it is necessary to uniformly disperse them in the rubber.

Therefore, when the organic rubber chemical is solid, it is desirable that it be a fine powder in order to improve its dispersibility in rubber. However, such fine powder products have no fluidity and are difficult to measure, and they also have the disadvantage that they scatter as dust, emitting bad odors, and causing chemical harm such as adhering to workers and irritating the skin. be. In order to prevent such problems, conventional methods have been to reduce scattering by adding oil to finely powdered organic rubber chemicals, granulating them with an appropriate binder, or turning them into flakes. It is taken. However, the granulated products of organic rubber chemicals manufactured by conventional methods and currently on the market are extremely soft granulated products in consideration of dispersibility in rubber, and flake products have a small shape. Due to the unevenness and corners, any form will disintegrate during transportation, creating powder, which not only obstructs automatic weighing during use, but also causes many problems in terms of work environment, health and safety due to dust. It has points.

In view of the shortcomings of the prior art, the purpose of this invention is to provide organic rubber chemicals with fluidity to facilitate automatic metering without deteriorating their performance, and to provide them with fluidity that facilitates operations such as packaging, transportation, weighing, and compounding. To provide a method for obtaining an organic rubber chemical product that does not disintegrate into dust and scatter.

As a result of intensive research to achieve the above object, the inventors dispersed a powdered organic rubber chemical in water or water containing an appropriate weight of organic solvent, and heated it at a temperature below the boiling point of water. When heated, it granulates into small particles, and the granulated product is suitable for the above purpose. Based on this knowledge, we have completed this invention.

The organic comb drug granules according to the present invention are composed of particles that are attached to each other without intervening different binders by dissolving and/or melting on the surface of powder particles of organic comb drugs that are solid at room temperature. The particle size distribution does not pass through a sieve with an opening of 0.1TWi, and the particle size distribution is 2. - The proportion of particles passing through the sieve is about 95% by weight or more.

Furthermore, the method for producing organic rubber drug granules according to the present invention includes:
In a method of granulating an organic rubber chemical that is solid at room temperature from its powder, the organic rubber chemical is dispersed in water containing O to 3 percent organic solvent, and then heated to a temperature below the boiling point of water. The method is characterized by granulating the powder particles by melting them on their surfaces and/or adhering them to each other by melting, and collecting the obtained particles. .

That is, in the molded organic rubber drug and the method for producing the same according to the present invention, the surface of the powder particles of the organic rubber drug is brought to a semi-molten state in water or in an added organic solvent, and the powder particles are aggregated and fused. It is based on a technical idea that is characterized by being coated and granulated into small particles, and also not containing any binder.

Hereinafter, the constituent elements of this invention will be described in detail and specifically.

The organic solvent contained in the water according to this invention may be any solvent as long as it can dissolve the organic com drug even to some extent.
It is also desirable that it volatilizes at the drying temperature of the molded product. Specific examples of organic solvents include methyl alcohol, ethyl alcohol, isopropyl alcohol, propyl alcohol, isobutyl alcohol, butyl alcohol, benzene, toluene, tetrahydrofuran, dioxane, acetone, methyl ethyl ketone, methyl isopropyl ketone,
Diethyl ketone, carbon tetrachloride, chloroform, dichloroethane, trichloroethylene, methylamine, dimethylamine, ethylamine, diethylamine, isopropylamine, diisopropylamine, n-butylamine,
Examples include di-n-butylamine, cyclohexylamine, dicyclohexylamine, morpholine, piperidine, pyrrolidine, aniline, toluidine, dimethylacetamide, dimethylformamide, dimethylsulfoxide, and the like. Next, examples of organic rubber chemicals to be applied in the production method according to the present invention include 2-mercaptobenzothiazole, dibenzotidyl sulfide, N-cyclohexyl-2-benzothiazolyl sulfenamide, N-
Oxydiethylene-2-benzothiazolylsulfenamide, N,. N-dicyclohexyl-2-benzothiazolylsulfenamide, N-t-butyl-2-benzothiazolylsulfenamide, N. ．． N-diisopropyl-2-benzothiazolylsulfenamide, 2-(N-oxydiethylenedithio)benzothiazolyl, 2-(
N. ．． Flux accelerators such as N-diethylthiocarbamoylthio)benzothiazolyl, tetramethylthiuram disulfide, tetramethylthiuram monosulfide, tetraethylthiuram disulfide, N,sN'-diphenyl-p-phenylene diamine, mixed diary-p-phenylene Diamine, N-phenyl N'-isopropyl p
-phenylenediamine, 2,2,4-trimethyl-1,
Antioxidants such as polymers of 2″-dihydroquinoline, 2,6-di-t-butylphenol, 2,2″-methylenebis(4-methyl-6-t-butylphenol), N-nitrosodiphenylamine, phthalic anhydride, etc. scorch inhibitors, and others.

Representative among these are tetraethylthiuram disulfide, N-oxydiethylene-2-benzothiazolylsulfenamide, N-t-butyl-2-benzothiazolylsulfenamide, and N-cyclohexyl-2-benzothiazolylsulfenamide.
-benzothiazolylsulfenamide, N-phenyl-N''-mesopropyl-p-phenylenediamine, or mixed diary-p-phenylenediamine.

Further, in the production method according to the present invention, the granulation temperature in water or in water containing an organic solvent varies depending on the type of organic rubber chemical to be applied, but may be a temperature equal to or lower than the boiling point of water. Note that the organic solvent and solid organic rubber chemical according to the present invention are not limited to the representative examples illustrated above.

Next, the embodiments of this invention are as follows.

A suitable amount of water alone or water containing an organic solvent is placed in a reaction tank equipped with a heating device, a stirrer, and a thermometer. 0.1 to 3 percent saliva.

] and a finely powdered organic rubber chemical. The amount of the organic rubber chemical to be charged is 1 to 60% by weight as a slurry based on water or water containing an organic solvent, but preferably,
It is 10-3% by weight. Next, this slurry is heated at a temperature of 40 to 90° C. for about 15 to 30 minutes while stirring to form small particles. After washing with water and drying with hot air at about 50 to 70°C, about 9 particles with a particle size in the range of 0.1wn to 2.0Tsn were removed.
5-98%. Note that the manufacturing method according to the present invention can be carried out either in a batch method or in a continuous method.

Granular organic rubber chemicals produced by conventional granulation methods are often relatively large and irregular in shape, and are extremely soft to ensure dispersibility in rubber. It has poor fluidity, and even if a binder is used, it easily disintegrates and becomes powder during transportation, making automatic weighing difficult. In addition, it has the disadvantage of causing various problems due to dust. be. On the contrary,
The molded organic rubber drug obtained by the production method according to the present invention has a small particle size in the range of 0.1 to 2.0 THIfL, so it has good fluidity and is extremely easy to automatically measure. It is easy to carry out, and even though it does not use a binder, it does not disintegrate into granules during transportation, does not impair its dispersibility in rubber, and maintains its performance as an organic rubber chemical. It has the effect of not causing any deterioration.

Hereinafter, the effects of the present invention will be explained in detail using Examples and Test Examples, but the present invention is not limited thereto.

Example 1 Into a 21 flask equipped with a stirrer and a thermometer, 25 parts of fine powder of tetraethylthiuram disulfide (Noxeler TETl melting point 69°C: product of Ouchi Shinko Kagaku Kogyo Co., Ltd.) and 75 parts of water were added. was prepared, heated in a water bath while stirring, stirred for 2 minutes at a temperature of 62 to 65°C, cooled, then overnighted, washed with water, dried with hot air at 50°C, and formed into small granules ( Hereinafter, it will be referred to as granule-like.

24 heel portions of the target object were obtained. Its melting point was 69°C. The particle size distribution ratio of the obtained target product was measured using a wire mesh sieve, and the results are as follows. In other words, the molded particles having a size in the range of 0.15 to 0.5 TIn are 97
% of the particle size distribution.

Example 2 N-oxydiethylene-2-benzothiazolylsulfenamide (Noxela MSAl melting point 8rC: product of Ouchi Shinko Kagaku Kogyo Co., Ltd.) was prepared according to the same method as in Example 1.
200 parts by weight of fine powder product and 80 parts by filtration of water were added to 74-7
After granulating the two powders by heating and stirring at 7°C, they were cooled, filtered, washed with water, and then dried with warm air at 60°C to obtain 198 parts by weight of the desired product in the form of granules.

Its melting point was 81°C. Here are the results of measuring the particle size distribution ratio of the target product obtained in the same manner as in Example 1! y is as follows. That is, the size of the shaped particles is 0.25
Those in the range of ~1.0% showed a particle size distribution ratio of 98%. Example 3 Following a method similar to Example 1, N-t-butyl-2-
Benzothiazolylsulfenamide (Noxela NS,
Melting point 105°C: 200 parts by weight of fine powder (product of Ouchi Shinko Kagaku Kogyo Co., Ltd.) and 800 parts by weight of water containing 5 parts by weight of isopropyl alcohol were heated and stirred at 80 to 83°C. After granulation, the mixture was cooled, filtered with F3, washed with water, and dried with hot air at 70°C to obtain 195 parts by weight of the desired product in the form of granules.

Its melting point was 105°C. The particle size distribution ratio of the target product obtained here was measured in the same manner as in Example 1, and the results are as follows.

0.17n or less 0%, i.e. 9 for molded particles with a size range of 0.1 to 0.57m
It showed a particle size distribution ratio of 5%.

Example 4 According to the same method as in Example 1, N-cyclohexyl-2
-Benzothiazolylsulfenamide (Noxela C4
Melting point: 98°C: produced by Ouchi Shinko Kagaku Kogyo Co., Ltd.) 20 parts of fine powder powder and 800 parts by weight of water containing 3 parts by weight of cyclohexylamine were heated and stirred at 75 to 80°C. After granulating, it was cooled, filtered with P, washed with water, and dried with warm air at 55°C to obtain 19 heel portions of the desired product in the form of granules.

Its melting point was 98°C. The particle size distribution ratio of the obtained target product was measured for 5 steps in the same manner as in Example 1, and the results are as follows.

That is, the molded particles having a size in the range of 0.15 to 1.0 m showed a particle size distribution ratio of 98%. Example 5 Following a method similar to Example 1, N-phenyl-N''-isopropyl-p-phenylenediamine (Nokrac 81
0-NA, melting point 75°C: 2 parts of fine powder product of Ouchi Shinko Chemical Industry Co., Ltd.) and 80 parts by weight of water at 68-70°C.
After granulating the two powders by heating and stirring, the mixture was cooled, filtered, washed with water, and then dried with warm air at 50°C to obtain one heel portion of the desired product in the form of granules.

Its melting point was 75°C. The particle size distribution ratio of the target product obtained here was measured in the same manner as in Example 1, and the results are as follows. That is, the size of the shaped particles is 0.15~
Those in the 1.0 size range showed a particle size distribution ratio of 98%. Example 6 (N,N-diphenyl-p-phenylenediamine, N,
N-di-0-toly-p-phenylenediamine, N,N
5 parts by weight of a fine powder product of Ouchi Shinko Kagaku Kogyo Co., Ltd. (mixture of "-di-0-toly-p-phenylenediamine), melting point 9rC: product of Ouchi Shinko Chemical Industry Co., Ltd." and 20 parts by weight of water at 80 to 85°C at 2C@ After granulating by heating and stirring for a while, the mixture was cooled, filtered, washed with water, and then dried with hot air at 60°C to obtain 4 portions of the desired product in the form of granules.

Its melting point was 91°C. The particle size distribution ratio of the target product obtained here was measured in the same manner as in Example 1, and the results are as follows. That is, the size of the shaped particles is 0.25~
1.0? Those in the range showed a particle size distribution ratio of 98%. Example 7 N-oxydiethylene-2-benzothiazolylsulfenamide (Noxel MSA, melting point 8rC: product of Ouchi Shinko Chemical Industry Co., Ltd.) was prepared according to the same method as in Example 1.
8 parts of water containing 20 parts by weight of fine powder and 5 parts by weight of morpholin.
After heating the 0 weight part for 2 minutes at 74 to 77°C, stirring and granulating it, cooling it, filtering it, washing it with water, and then heating it to 60'C.
The mixture was dried with hot air to obtain 198 parts by weight of the desired product in the form of granules.

Its melting point was 81°C. The particle size distribution ratio of the target product obtained here was measured in the same manner as in Example 1, and the results are as follows.

That is, the size of the shaped particles is 0.25 to 2.0 Wf.
! Those in the fl range showed a particle size distribution ratio of 99%. Test Example 1 Test of Molded Organic Comb Chemical (Vulcanization Accelerator) Based on the formulation table shown in Table 1, the diameter of the molded products obtained in Examples 2 and 4 and the corresponding commercial products was determined. Table 2 shows the results of a comparative test of kneading operability and dispersibility using an 8-inch rubber kneading roll machine, as well as comparative test results of performance as a vulcanization accelerator.

Test Example 2 Test of Molded Organic Comb Chemical (Anti-Aging Agent) Based on the formulation table shown in Table 3, the molded products obtained in Examples 5 and 6 and the corresponding commercial products were tested with a diameter of 8 Table 4 shows the comparative test results of kneading operability and dispersibility using an inch rubber kneading roll machine, and the comparative test results of performance as an anti-aging agent.

Claims (1)

[Scope of Claims] 1. In a granular body of an organic rubber chemical that is solid at room temperature, the granular body is dissolved and/or melted on the surface of the powder particles of the organic rubber chemical without intervening a different binder. It consists of particles that adhere to each other, and its particle size distribution does not pass through a sieve with an opening of 0.1 mm, and the opening is 2.0 mm.
An organic rubber drug granule, characterized in that the proportion of particles passing through a sieve is about 95% by weight or more. 2 Organic rubber chemicals that are solid at room temperature include tetraethylthiuram disulfide, N-oxydiethylene-2-benzothiazolylsulfenamide, N-t-butyl-2-benzothiazolylsulfenamide, and N-cyclohexyl-2
-Benzothiazolylsulfenamide, N-phenyl-
N'-isopropyl-p-phenylenediamine, and mixed diaryl-p-phenylenediamine. An organic rubber drug granule according to claim 1. 3
In a method of granulating an organic rubber chemical that is solid at room temperature from its powder, the organic rubber chemical powder is dispersed in water containing 0 to 30 weight percent of an organic solvent, and then heated to a temperature below the boiling point of water. Organic rubber drug granules, characterized in that the powder particles are granulated by adhesion to each other by dissolution and/or melting on their surfaces, and the particles obtained are recovered. How the body is manufactured.