JPH0912839A - Resin composition for rubber compounding - Google Patents

Abstract

PURPOSE: To obtain a resin compsn. for rubber compounding which is excellent in workability and aging stability and does not undergo the degradation in cross-linkability by mixing an alkylphenol resin with a general-purpose rubber. CONSTITUTION: This compsn. is prepd. by mixing 100 pts.wt. alkylphenol resin obtd. by the condensation reaction of an alkylphenol pref. having a 1-18C alkyl group (e.g. cresol, p-t-butylphenol, or amylphenol) with a formaldehyde compd. or sulfur chloride, 20-300 pts.wt. general-purpose rubber (e.g. a natural, butyl, or brominated butyl rubber), and if necessary 20-200 pts.wt. filler (e.g. carbon black, calcium, carbonate, or clay) and 1-100 pts.wt. softener (e.g. a fatty acid or a fatty acid salt) followed by sheeting or pelletizing.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a resin composition for rubber compounding. More specifically, it relates to a rubber compounding resin composition obtained by mixing an alkylphenol resin and general-purpose rubbers.

[0002]

2. Description of the Related Art In the rubber industry, a wide range of chemicals are required, and the chemicals are often added in the form of powder and have various drawbacks. That is, the powder is difficult to mix with other substances and does not easily disperse, so that a relatively long mixing time is required. Further, dust and odor are generated during the kneading work, which causes a problem of environmental pollution.

Resin compositions for rubber compounding include methylolated alkylphenol resins which require a catalyst such as Lewis acid or halogenated elastomer, brominated alkylphenol resins which can be vulcanized without a catalyst, and alkylphenol sulfide resins. These generally have a product shape such as a block shape, a flake shape, and a rough shape, and since the resin is brittle, it is partly powdered due to vibration during the packaging process or during transportation. Further, the block-like material has a problem that it is crushed when passing through a roll during kneading and dust is generated, which adheres to a hand or a face and causes discomfort. In addition, these resins have a low softening point, causing blocking during storage under high temperature and high humidity,
There was a problem such as a decrease in crosslinking performance.

[0004]

As described above, the alkylphenol resin has a problem that dust is generated in the kneading work process, and further, it is colored due to aging.
Further, the resin has a low softening point, which causes problems such as blocking during storage under high temperature and high humidity and deterioration of crosslinking performance. This means that, for example, the user stores a fraction after use in the factory and uses it after several months, which causes problems such as poor workability and lack of predetermined performance, which hinders operation. There were cases. For this reason, various methods have been tried, but a solution having a sufficient effect has not been found. Therefore, there has been a strong demand for a resin composition for rubber compounding which is excellent in workability and stability over time and which does not cause deterioration in crosslinking performance.

The inventors of the present invention have previously added a general-purpose rubber to a specific alkylphenol resin and, if necessary, added a filler, a softening agent and other additives, and kneaded them to form a so-called compound, thereby improving workability and aging. The inventors have found that a resin composition for rubber compounding having excellent stability, that is, a so-called masterbatch can be obtained, and completed the present invention.

[0006]

According to the present invention, general-purpose rubbers 20 to 30 are added to 100 parts by weight of an alkylphenol resin.
It is a resin composition for rubber compounding (so-called masterbatch), which is characterized by being mixed with 0 parts by weight.

Further, according to the present invention, 20 to 300 parts by weight of general-purpose rubbers and 20 to 200 parts by weight of a filler are mixed and kneaded with 100 parts by weight of an alkylphenol resin, and a resin composition for rubber compounding. Is. Furthermore, the present invention is based on 100 parts by weight of an alkylphenol resin, 20 to 300 parts by weight of a general-purpose rubber, and 20 to 20 parts by weight of a filler.
It is a resin composition for rubber compounding, which comprises mixing and kneading 0 parts by weight and 1 to 100 parts by weight of a softening agent.

Specific examples of the alkylphenol resin referred to in the present invention include alkylphenol resins obtained by condensation of formaldehydes with phenols having an alkyl group having 1 to 18 carbon atoms or 1 to 18 carbon atoms.
Preferred are alkylphenol resins obtained by condensation of a phenol having an alkyl group with sulfur chloride.

Specific examples of the phenols having an alkyl group having 1 to 18 carbon atoms as a raw material of the alkylphenol resin include p-cresol, i-propylphenol, pt-butylphenol and amylphenol. , P-t-octylphenol, nonylphenol, dodecylphenol, allylphenol, cyclohexylphenol, 4,6-dioctylresorcin, and the like. Among these, especially p-
T-butylphenol, amylphenol, and pt-octylphenol are preferably used. Such an alkylphenol resin can be used, for example, as a tacky roll 201.
(Trademarks manufactured by Taoka Chemical Co., Ltd.), Sumikanol-AP, Sumifine-V200 (all manufactured by Sumitomo Chemical Co., Ltd., etc.) are commercially available.

The general-purpose rubbers mixed and added to the rubber compounding resin composition of the present invention include, for example, natural rubber (NR) and styrene-butadiene rubber (SB).
R), butadiene rubber (BR), butyl rubber (II
R), brominated butyl rubber (Br-IIR), chlorinated butyl rubber (CL-IIR), chloroprene rubber (CR),
The ethylene-propylene-terpolymer (EPDM) and the like can be raised. Among these, natural rubber (NR), butyl rubber (IIR), and chlorinated butyl rubber (CL-IIR) are particularly preferably used.

If necessary, a filler or a softening agent is added to the resin composition for rubber compounding of the present invention. Usually, in order to facilitate compounding, it is preferable to use a filler or a softening agent together for other purposes.

Examples of the filler used in the present invention include carbon black, calcium carbonate, clay, silica, calcium silicate, magnesium silicate, talc, zinc oxide, magnesium oxide and titanium white.

Examples of the softening agent used in the present invention include fatty acids, fatty acid salts, naphthenic process oils, paraffinic process oils, aromatic process oils and waxes. Here, examples of the fatty acids include stearic acid and stearyl alcohol, examples of the fatty acid salts include zinc stearate, aluminum stearate, barium stearate, lithium stearate, and the like. Molex No. 2, PW-90
Examples of the paraffinic process oil include Samper 107, -115, -150, and paraffin wax as waxes.

In the rubber compounding resin composition of the present invention,
The mixing ratio of alkylphenol resin and general-purpose rubber is
General rubbers are 20 to 300 parts by weight, preferably 40 to 200 parts by weight, based on 100 parts by weight of the alkylphenol resin.

The mixing ratio of the filler, which is added if necessary, is 20 to 200 parts by weight, preferably 50 to 150 parts by weight, based on 100 parts by weight of the alkylphenol resin. Further, the mixing ratio of the softening agent to be added if necessary,
1 to 10 relative to 100 parts by weight of alkylphenol resin
It is 0 part by weight, preferably 5 to 80 parts by weight.

As the method for producing the resin composition for rubber compounding of the present invention, for example, the above-mentioned alkylphenol resin, the above-mentioned general-purpose rubbers and, if necessary, a filler, a softening agent and the like are charged into a closed kneader capable of heating and cooling, Internal temperature is 30 ~
It can be easily obtained by mixing and homogenizing while maintaining at 100 ° C., preferably 60 to 80 ° C., and putting out a sheet or pelletizing depending on the application.

The thus-obtained resin composition for rubber compounding of the present invention can be easily made into, for example, a solid plate shape or a 5 mm square pellet shape. Shortening and improvement of dispersibility are possible. In addition, the resin composition for compounding rubber has a storage condition of 40
There is no blocking even after the lapse of 6 months at ° C, the crosslinking performance is the same as immediately after production, and improved stability is shown.

The rubber compounding resin composition of the present invention is a so-called masterbatch, which is a natural rubber (NR), styrene-butadiene rubber (SBR), butadiene rubber (BR), butyl rubber (IIR), brominated butyl rubber. (Br-IIR), chlorinated butyl rubber (Cl-II
R), chloroprene rubber (CR), ethylene-propylene-terpolymer (EPDM), and other general-purpose rubbers to act as a so-called resin vulcanizing agent or to act as a tackifier, and to measure and knead It is possible to easily produce a stable vulcanized rubber product which is excellent in the prevention of dust, shortens working time, has excellent dispersibility, and has no deterioration in coloring, blocking and crosslinking performance due to aging. Further, the production of this vulcanized rubber product is carried out by an ordinary method together with the resin composition for rubber compounding of the present invention on the above-mentioned general-purpose rubber, carbon black, a filler, a softening agent or Sokushinol DM (manufactured by Sumitomo Chemical Co., Ltd.). ) And other vulcanization accelerators, etc. are added and kneaded by a known method.

[0019]

EFFECT OF THE INVENTION Using the rubber compounding resin composition of the present invention as a masterbatch, natural rubber (NR), butyl rubber (IIR), brominated butyl rubber (Br-IIR), chlorinated butyl rubber (Cl-IIR), Chloroprene rubber (C
When used as a resin vulcanizing agent and / or tackifier for general-purpose rubbers such as R), it is possible to prevent dust in the weighing and kneading work process, shorten the work time, improve the dispersibility, and change over time. It is possible to produce a stable vulcanized rubber product with no deterioration in coloring, blocking and cross-linking performance.

[0020]

EXAMPLES Next, a method for preparing a resin composition for rubber compounding according to the present invention and a rubber compounding composition using the same will be described with reference to Examples and Comparative Examples, but the present invention is not limited thereto. Absent. The middle part and% in the examples are based on weight unless otherwise specified.

Example 1 Butyl rubber (IIR; Exxon # 268) 35 was placed in a 3.5 liter kneader equipped with heating and cooling equipment.
0 parts, Tucky Roll 201 (Taoka Chemical Co., Ltd.,
Alkylphenol resin) 350 parts, magnesium silicate 250 parts, and stearic acid 50 parts are charged, and the contents are kneaded for 15 minutes while maintaining the temperature at 60 to 80 ° C. under stirring,
It was taken out on a 6-inch roll, formed into a sheet having a thickness of 5 mm, allowed to cool, and then finished into pellets of 5 mm square with a pelletizer to obtain 1000 parts of a light tan rubber-containing resin composition.

EXAMPLE 2 Chlorinated butyl rubber (HT-106 manufactured by Exxon Co., Ltd.) was placed in a 3.5 liter kneader equipped with heating and cooling equipment.
8) 375 parts, natural rubber (RSS # 1) 250 parts, Sumikanol-AP (Sumitomo Chemical Co., Ltd., registered trade name) 625 parts and stearic acid 312.5 parts were charged, and the content was 60 to 80 with stirring. Knead for 15 minutes while keeping the temperature at ℃, take out on a 6-inch roll, form a sheet with a thickness of 5 mm, allow to cool, then finish with pelletizer into a pellet of 5 mm square, a light tan rubber-containing resin composition 1
562.5 parts were obtained.

Example 3 In the same equipment as in Example 2, chlorinated butyl rubber (HT-1
068) 487.5 parts, natural rubber (RSS # 1) 26
2.5 parts, Sumifine V-200 (produced by Sumitomo Chemical Co., Ltd., registered trademark) 350 parts and stearic acid 17
5 parts were charged, the contents were kneaded for 15 minutes while maintaining the temperature at 60 to 80 ° C. with stirring, taken out on a 6 inch roll,
After making it into a sheet with a thickness of 5 mm and allowing it to cool, 5 with a pelletizer
After finishing into mm-square pellets, 1275 parts of a light yellowish-brown resin composition for rubber compounding was obtained.

Example 4 In the same equipment as in Example 3, chlorinated butyl rubber (HT-1
068) 487.5 parts, natural rubber (RSS # 1) 26
2.5 parts, Sumifine V-200 350 parts, stearic acid 175 parts and paraffin wax 87.5 parts were charged, and the contents were kept under stirring at 60 to 80 ° C for 15
Kneading for minutes, taking out on a 6-inch roll, forming a sheet with a thickness of 5 mm, allowing to cool, and finishing with a pelletizer into pellets of 5 mm square, 1362.5 parts of a light tan rubber compounding resin composition is obtained. Was given.

EXAMPLE 5 Butyl rubber (IIR; Exxon # 268) 35 was added to a 3.5 liter kneader equipped with heating and cooling equipment.
0 parts, Tucky Roll 201 (Taoka Chemical Co., Ltd.,
Alkylphenol resin) 538.5 and carbon black (HAF black) 175 parts, castor oil 13.5
Parts, kneading the contents under stirring for 15 minutes while maintaining the temperature at 60 to 80 ° C, and taking out on a 6 inch roll, 5
After making it into a mm-thick sheet and letting it cool, it is 5m with a pelletizer.
The product was finished into m square pellets to obtain 1077 parts of a rubber-black resin composition for compounding rubber.

Vulcanization Performance and Storage Stability Test To compare the storage stability of the rubber compounding resin composition obtained by the method described in Examples 1 to 5 of the present invention with a conventional alkylphenol resin alone. And both at -5 ° C and 2
The sample was stored under the conditions of 5 ° C and 40 ° C and measured after 6 months. Storage conditions -5 ℃ Use incubator 25 ℃ Use incubator 40 ℃ Use hot air circulation dryer

The cross-linking performance is shown in the following Tables 1 to 5 in order to compare the case where a conventional alkylphenol resin is added to the synthetic rubber and the case where the resin composition for rubber compounding of the present invention is added. A rubber compound was prepared for each of the comparative example and Examples 1 to 5 of the present invention by the compounding recipe of the above, and a roll temperature of 6 was used using a 6-inch test roll machine.
After kneading and homogenizing at 0 ± 5 ° C and taking out the sheet, Mooney Viscometer (SMV-200, manufactured by Shimadzu Corporation)
Type) and Toyo Seiki Seisakusho Co., Ltd. oscillating disc rheometer (ASTM-100 type)
Scorch time and vulcanization rate were measured.

The test conditions and the like are as follows. ? Scorch test: Temperature 135 ° C (for Sumikanol AP and Tacky Roll 201) Temperature 125 ° C (for Sumifine V-200) ML-5: Scorch time ML-Δ30: Vulcanization rate

Rheometer test: temperature 180 ° C., amplitude ± 1 ° (for tacky roll 201) Temperature 150 ° C., amplitude ± 3 ° (for Sumikanol AP, Sumi Fine V-200) T90: optimum vulcanization time MH: Maximum torque (crosslink density) The results are shown in Tables 1-5. The meanings of the symbols in the table are shown below.

The turned workability which was evaluated by the following criteria difficulty of kneading when introducing rubber compounding resin composition conventional alkylphenol resin or the present invention in a state of winding the rubber roll. X --- There is blocking, and the input material flies off and it is difficult to knead. Δ --- There is no blocking, but it is slightly difficult to knead. ○ ---- Kneading is relatively easy. ◎ --- Easily kneaded.

The dusting which was evaluated by the following criteria of the degree of dust at the time of introducing rubber compounding resin composition conventional alkylphenol resin or the present invention in a state of winding the rubber roll. × −−− A lot of dust. △ ---- A little dust. ○ ---- Dust is relatively small. ◎ ---- No dust at all.

The compatibility This was evaluated on the following criteria by visual inspection of the degree of kneading demon Keru compatibility with the rubber compounding resin composition of rubber and conventional alkylphenol resin or the present invention. × −−− It takes a long time to be compatible. Δ --- The time until it becomes compatible is slightly long. ○ ---- Compatible in a relatively short time. ◎ ---- Easily compatible.

Storage stability This was evaluated by the following criteria according to the vulcanization physical properties of a conventional alkylphenol resin and the resin composition for rubber compounding of the present invention before and after long-term (6 months) storage. × −−− There are major differences before and after storage. △ --- There are some differences before and after storage. ○ ---- There is no difference before and after storage.

[0034]

[Table 1-a] (Note) Figures in parentheses are included in the resin composition for rubber compounding (hereinafter the same)

[0035]

[Table-1-b]

[0036]

[Table-2-a] Sokushinol DM; Vulcanization accelerator (Sumitomo Chemical Co., Ltd., registered trademark)

[0037]

[Table-2-b]

[0038]

[Table-3-a]

[0039]

[Table-3-b]

[0040]

[Table-4-a]

[0041]

[Table-4-b]

[0042]

[Table-5-a]

[0043]

[Table-5-b]

Claims (9)

[Claims] 1. A rubber compounding resin composition comprising 20 to 300 parts by weight of a general-purpose rubber mixed with 100 parts by weight of an alkylphenol resin. 2. The alkylphenol resin has 1 to 1 carbon atoms.
The resin composition for rubber compounding according to claim 1, which is an alkylphenol resin obtained by condensing phenols having an alkyl group of 8 with formaldehydes. 3. The alkylphenol resin has 1 to 1 carbon atoms.
The resin composition for rubber compounding according to claim 1, which is an alkylphenol resin obtained by condensing a phenol having an alkyl group of 8 and sulfur chloride. 4. Phenols having an alkyl group having 1 to 18 carbon atoms include cresol, pt-butylphenol,
The resin composition for rubber compounding according to any one of claims 2 to 3, which is selected from amylphenol, nonylphenol and pt-octylphenol. 5. A filler is alkylphenol resin 100.
The resin composition for rubber compounding according to any one of claims 1 to 4, which is formed by mixing 20 to 200 parts by weight with respect to parts by weight. 6. The resin composition for rubber compounding according to claim 5, wherein the filler is selected from carbon black, calcium carbonate, clay, silica, calcium silicate, magnesium silicate, talc, zinc oxide, magnesium oxide and titanium white. Stuff. 7. A softener is an alkylphenol resin 100.
A mixture of 1 to 100 parts by weight with respect to parts by weight.
A resin composition for compounding a rubber according to claim 6. 8. The rubber compounding resin composition according to claim 7, wherein the softening agent is selected from fatty acids, fatty acid salts, naphthenic or paraffinic process oils. 9. The rubber compounding resin composition according to claim 1, wherein the general-purpose rubbers are selected from natural rubber, butyl rubber, brominated butyl rubber, chlorinated butyl rubber and chloroprene rubber.