JPS6259140B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to a partially crosslinkable composition for obtaining a thermoplastic elastomer by partially crosslinking the rubber component of a composition consisting of a monoolefin polymer rubber and a polyolefin resin. Thermoplastic elastomers have excellent rubber elasticity and can be molded into any shape by the same molding methods as thermoplastic resins, such as extrusion molding and injection molding, and do not require a vulcanization process. As a rubber or rubber-like material, it has been attracting attention in fields such as automobile parts, home appliance parts, footwear, electric wire coatings, and miscellaneous goods. Among them, polyolefin-based thermoplastic elastomers differ from those obtained by polymerizing hard segments and soft segments like other polystyrene-based, polyester-based, and polyurethane-based thermoplastic elastomers. For example, polypropylene) and monoolefin copolymer rubber as a soft segment are melt-kneaded, and in some cases, the rubber portion is partially cross-linked during melt-kneading. Research has focused on resins, which are being put to practical use in automobile parts and other applications, taking advantage of their relatively low cost, flexibility, heat deformation resistance, and weather resistance. Particularly, partially crosslinked polyolefin thermoplastic elastomers have excellent heat deformation resistance, rubber elasticity, etc., and are considered to be the favorite of future polyolefin thermoplastic elastomers. The production method for obtaining a partially crosslinked polyolefin thermoplastic elastomer usually uses a Banbury, kneader, etc. to produce a monoolefin copolymer rubber (e.g., ethylene, propylene/diene copolymer rubber (EPDM), ethylene/propylene copolymer rubber, etc.). A common method is to mechanically melt-knead copolymer rubber (EPM) and polypropylene, and then add a crosslinking agent to cause partial crosslinking.The method for obtaining such a thermoplastic elastomer is as follows: For example, JP-A-48-26838, JP-A-51
―No. 145553, JP-A-52-37953, JP-A-53-
Methods such as No. 145857 are known. However, these methods do not give much consideration to the method of adding the crosslinking agent, and only a method of simply adding the crosslinking agent (direct addition method) is described. This direct addition method has poor workability during addition, and in the case of production using an extruder, the direct addition method has poor addition efficiency.
In particular, powdered crosslinking agents tend to separate from granular monoolefin copolymer rubber and crystalline polypropylene resin, making it difficult to obtain products with stable quality due to poor addition accuracy. Furthermore, in production using extruders, Banbury, etc., the added crosslinking agent may adhere to equipment heated to around 200°C before it is sufficiently dispersed in the monoolefin copolymer rubber and crystalline polypropylene resin. There is a risk that the crosslinking agent (organic peroxide) may be present at an extremely high concentration locally due to the crosslinking agent (organic peroxide) being scattered. If a shock is applied to the uneven distribution of the crosslinking agent, or if foreign substances that promote decomposition (for example, reducing agents such as amines) are mixed in, there is a risk of explosion or ignition. There are many accidents like this, and there are also safety issues. On the other hand, in JP-A-54-1386, for safety reasons,
A block masterbatch of the crosslinking agent is produced by adding and kneading the monoolefin copolymer rubber at a high concentration below the decomposition temperature of the crosslinking agent using a roll, Banbury, kneader, etc., and using this, partial crosslinking is performed using a Banbury, kneader, etc. A method for obtaining thermoplastic elastomers is described. However, this method has the following problems. That is, in order to knead the crosslinking agent into the monoolefin copolymer rubber at a temperature below the decomposition temperature, it is necessary to plasticize the rubber, and on the other hand, it is necessary to knead at a temperature at which the crosslinking agent does not decompose. It is necessary to use a rubber with high viscosity and low viscosity, and a crosslinking agent with a high decomposition temperature.
Limited by both rubber and crosslinking agent. Furthermore, from the viewpoint of the method of making a masterbatch, it is preferable that the crosslinking agent used be in powder form, and liquid crosslinking agents are disadvantageous in terms of workability and precision in the amount added. Since the obtained masterbatch is in the form of a lump, when producing a thermoplastic elastomer using this masterbatch, an extruder cannot be used, but a Banbury or kneader must be used. In this case, the crosslinking agent contained in the bulk masterbatch takes time to disperse when kneading with the monoolefin copolymer rubber and crystalline polypropylene resin.
Before the crosslinking agent is sufficiently dispersed, the crosslinking agent begins to decompose, and there is a possibility that a region with a locally high crosslinking density is generated, resulting in an overdensified gel in the obtained thermoplastic elastomer. Overdense gel deteriorates the appearance and physical properties of products molded from thermoplastic elastomers, so in order to prevent the occurrence of such overdensity gel, it is necessary to include a crosslinking retarder in the crosslinking agent masterbatch. When ethylene-propylene-diene copolymer rubber (EPDM) with a high ethylene content is used as the monoolefin copolymer rubber, it is difficult to completely suppress the occurrence of overdensified gel. Another method for blending a crosslinking agent into rubber is a solution blending method. That is, this is a method in which the rubber and the crosslinking agent are dissolved in a good solvent, blended, and reprecipitated from the solution. This method requires a large amount of organic solvent, and although it is possible in the laboratory, it is not suitable for industrial production. On the other hand, a method is known in which the granular polyolefin resin is crosslinked by impregnating the granular polyolefin resin with a crosslinking agent such as an organic peroxide by heating in an aqueous medium (Japanese Patent Publication No. 52-39264, Japanese Patent Application Laid-Open No. 47-34436).
No., Japanese Patent Publication No. 48-43026). These are intended for cross-linking and foaming of polyolefin resins, and since polyolefin resins generally have high crystallinity, they are impregnated below the melting point of the polyolefin resin, and in cross-linking, the degree of impregnation of the cross-linking agent between the crystalline and non-crystalline parts of the polyolefin resin is controlled. Also, the degree of crosslinking becomes uneven, making it impossible to obtain a homogeneous crosslinked product. Therefore, the impregnation temperature needs to be raised to about the melting point of the polyolefin resin, and therefore, an anti-fusing agent such as basic zinc carbonate or tricalcium phosphate is required to prevent the polyolefin resin particles from fusing together. . However, it has been found that when a monoolefin copolymer rubber is impregnated with a crosslinking agent in an aqueous medium, such problems do not arise and a large amount of the crosslinking agent can be uniformly impregnated. Also,
When monoolefin copolymer rubber and crystalline polyolefin resin coexist in the aqueous medium, the copolymer rubber is selectively impregnated with the crosslinking agent. This also applies to a composite obtained by kneading a monoolefin copolymer rubber and a crystalline polyolefin resin, and it is possible to obtain granules in which the crosslinking agent is uniformly impregnated into the rubber component. The present invention is a composition uniformly containing a crosslinking agent in a precise amount in an undecomposed state, and depending on the crosslinking agent content, a thermoplastic elastomer can be obtained by arbitrary kneading and heating as a masterbatch. The present invention provides a partially crosslinkable composition that can be crosslinked, and a partially crosslinked product obtained therefrom. That is, the present invention contains (a) 100 parts by weight of monoolefin copolymer rubber, (b) 10 to 900 parts by weight of polyolefin resin, and (c) 0.1 to 40 parts by weight of a crosslinking agent, and (c) does not substantially decompose. This is a partially crosslinkable composition in which (c) is impregnated into granules consisting of (a) and (b) in an aqueous suspension state. Depending on the content of the crosslinking agent, this partially crosslinkable composition may be used as it is or may be mixed with a monoolefin copolymer rubber and/or a polyolefin resin to form a monoolefin polymer rubber.
A partially crosslinked product can be obtained by heating and kneading the crosslinking agent in an amount of 0.1 to 10 parts by weight per 100 parts by weight. The granular partially crosslinkable composition according to the present invention consists of the following three components. (a) Monoolefin copolymer rubber Monoolefin copolymer rubber is produced by copolymerizing two or more monoolefins (including ethylene) or further using a Ziegler-Natsuta catalyst consisting of a combination of a vanadium compound and an aluminum compound. It is an essentially amorphous random copolymer copolymerized with at least one polyene that can be used. Usually one of the monoolefins is ethylene and the other propylene, but other α-monoolefins can also be used. This monoolefin copolymer rubber may be a saturated compound such as an ethylene/propylene two-component copolymer rubber, but the copolymer may contain at least one copolymerizable polyene to make the copolymer unsaturated. You may also add gender. Typically used polyenes include 1.4hexadiene, dicyclopentadiene, methylenenorbornene, ethylidenenorbornene, propenylnorbornene, cyclooctadiene, methyltetrahydroindene, and the like. (b) Polyolefin resin Polyolefin resin is a solid high molecular weight resin-like plastic material obtained by polymerizing olefins such as ethylene, propylene, butene-1, pentene-1, and 4-methylpentene-1 by a conventional method. Polypropylene, polyethylene, (low density, medium density,
Crystalline polyolefin resins such as ethylene/propylene copolymer resins, ethylene/vinyl acetate copolymers, etc. can be used. Among them, polypropylene is a particularly preferred polyolefin resin. Polypropylene includes highly crystalline propylene homopolymer, propylene/ethylene block or random copolymer, propylene/butene-1 block or random copolymer, propylene/butene-1/ethylene ternary block or Random copolymer, propylene/hexene
1 block or random copolymer, propylene/hexene-1/ethylene tertiary block or random copolymer, propylene/4-methylpentene-1 block or random copolymer,
Includes crystalline copolymers of propylene and other linear or branched α-olefins, such as propylene/4-methylpentene-1/ethylene ternary block or random copolymers. (c) Crosslinking agent As a crosslinking agent, octanoyl peroxide,
lauroyl peroxide, benzoyl peroxide, p-chlorobenzoyl peroxide,
2,4-dichlorobenzoyl peroxide, cyclohexanone peroxide, t-butyl peroxybenzoate, methyl ethyl ketone peroxide, dicumyl peroxide, di-t-butyl peroxide, 2,5-dimethyl-2,5
-di(benzoylperoxy)hexane, 2,5
-dimethyl-2,5-di(t-butylperoxy)hexane, di-t-butyl-di-peroxyphthalate, t-butyl cumyl peroxide, diisopropylbenzene hydroperoxide, 1,3-bis-(t -butylperoxyisopropyl)benzene, t-butylperoxypiparate, 3,5,5-trimethylhexanoyl peroxide, 1,1-bis(t-butylperoxy)3,5,5-trimethylcyclohexane, 1 , 1-bis(t-butylperoxy)cyclohexane and other organic peroxides, azo compounds such as azobisisobutyronitrile, and others. Composite of component (a) and component (b) In the composition of the present invention, the amount of polyolefin resin as component (b) is 10 to 900 parts by weight per 100 parts by weight of monoolefin copolymer rubber as component (a). Part is mixed. Therefore, regarding only the blending ratio of these two components, component (a) corresponds to approximately 10 to 90 parts by weight and component (b) corresponds to approximately 90 to 10 parts by weight in 100 parts by weight of the blend. When impregnating component (c) with a crosslinking agent in an aqueous suspension, it is preferable that components (a) and (b) are composited in advance. This compounding is performed using a general melt kneading machine such as a single-screw extruder, a twin-screw extruder, a Banbury mixer, or various kneaders. The complexed formulation is 1
It is granulated into spherical, angular or cylindrical pellets with a size of ~7 mm, preferably 2-5 mm, and used for subsequent impregnation with a crosslinking agent. However, the components (a) and (b) do not necessarily need to be composited by melt-kneading, and may be a mixture of pellets of the two components, each of which is granulated. (c) Impregnation of crosslinking agent 0.1 to 40 parts by weight of the crosslinking agent, component (c), of the composition of the present invention is impregnated with respect to 100 parts by weight of the monoolefin copolymer rubber, component (a). A typical method for impregnating the composite or mixture of components (a) and (b) with a crosslinking agent in an aqueous medium is to add the crosslinking agent to an aqueous suspension of the granular material to be impregnated and stir the mixture. Alternatively, there is a method in which a granular material to be impregnated is added to an aqueous suspension of a crosslinking agent and stirred. In this case, a solution of the crosslinking agent dissolved in advance in a rubber swelling agent can be used. This impregnation operation is carried out at a temperature sufficiently lower than the decomposition temperature of the crosslinking agent used so that the crosslinking agent does not substantially decompose. The impregnation time is about 0.5 to 10 hours, and the pressure at this time is usually normal pressure to about 20 kg/cm ² G. The content of the granular material to be impregnated and the crosslinking agent in the aqueous suspension is usually about 5 to 100 parts by weight per 100 parts by weight of water. Such aqueous suspensions can be maintained in a stable dispersion state simply by sufficient stirring, but suspensions can be easily and more stably maintained by using an appropriate suspension stabilizer. Can be adjusted. As the suspension stabilizer in this case, those that can be used as a suspension stabilizer during aqueous suspension polymerization of vinyl monomers can generally be used.
Specifically, for example, water-soluble polymer substances such as polyvinyl alcohol, polyvinylpyrrolidone, methylcellulose, and hydroxycellulose, anionic surfactants such as alkylbenzene sulfonates, nonionic surfactants such as polyoxyethyl alkyl ether, or , magnesium oxide,
Water-insoluble inorganic salts such as magnesium phosphate are used alone or in combination in an amount of about 0.1 to 10% by weight based on water. In addition, when impregnating the above-mentioned material to be impregnated with a crosslinking agent, plasticizers, lubricants, ultraviolet stabilizers,
It can also be impregnated with auxiliary materials such as antioxidants, foaming agents, and crosslinking reaction retarders. After the impregnation operation, if the process of pickling, washing with water, and drying is carried out in the same manner as the post-treatment of ordinary aqueous suspension polymerization of vinyl monomers, the shape of the impregnated object is maintained as it is, and the granular partial crosslinking property is immediately obtained. A composition is obtained. Production of Partially Crosslinked Product The partially crosslinked composition obtained is used as it is or as a masterbatch in the production of a thermoplastic elastomer, depending on the content of the crosslinking agent.
In other words, the amount of crosslinking agent is
If the amount is 0.1 to 10 parts by weight per 100 parts by weight, a partially crosslinked thermoplastic elastomer can be obtained by statically raising the temperature or dynamically melt-kneading, and the amount of crosslinking agent added is also 0.1 to 10 parts by weight. For products of 10 to 40 parts by weight, a monoolefin copolymer rubber and, if necessary, a polyolefin resin are additionally mixed to make the amount of crosslinking agent to the rubber 0.1 to 10 parts by weight and melt-mixed to produce a thermoplastic elastomer. be able to. Even if the partially crosslinkable composition has a crosslinking agent content of 10 parts or less, monoolefin copolymer rubber and/or polyolefin resin can be added and melt-kneaded, if necessary. For melt-kneading, general kneading machines such as a Banbury mixer, various kneaders, and extruders can be used. When producing a thermoplastic elastomer using the partially crosslinkable composition of the present invention, there are various advantages as follows. That is, when producing a thermoplastic elastomer, there is no operation of directly adding a crosslinking agent (organic peroxide) to Banbury, etc., so the work is safe. The amount of crosslinking agent added is accurate and the addition accuracy is high. In addition, when the partially crosslinkable composition of the present invention is partially crosslinked as it is, and even when used as a master batch, the crosslinking agent is uniformly dispersed in the rubber component, so that the reaction between the crosslinking agent and the rubber component is prevented. It is uniform, has good production stability, and has little occurrence of overdense gel. Furthermore, since the crosslinking agent is selectively impregnated into the rubber component, there is little deterioration due to crosslinking or decomposition of the polyolefin resin. Therefore, an extremely homogeneous thermoplastic elastomer with excellent performance can be stably produced. In addition, when the partially crosslinkable composition of the present invention is to be partially crosslinked as it is by melt-kneading to form a thermoplastic elastomer, the following composition is suitable. (a) Monoolefin copolymer rubber: 100 parts by weight (b) Polyolefin resin: 25 to 900 parts by weight (c) Crosslinking agent: 0.1 to 10 parts by weight When used as a masterbatch, the following composition is suitable. ing. (a) Monoolefin copolymer rubber: 100 parts by weight (b) Polyolefin resin: 10 to 150 parts by weight (c) Crosslinking agent: 10 to 40 parts by weight In the following examples, the measurement methods and test methods used are as follows: It is as follows. (1) Crosslinking agent content Depending on the type and structure of the crosslinking agent, an appropriate method was used among gas chromatography and iodine titration. Generally speaking, gas chromatography is suitable for some peroxides that have a high decomposition temperature. (b) Gas chromatography method Waste liquid obtained by filtering out the impregnated particles impregnated with a crosslinking agent and the suspending agent by the aqueous suspension impregnation operation as described above.
Weigh 100g and extract it with 1Kg of purified benzene. The amount of crosslinking agent in the extract is measured using a gas chromatograph (GC7A model manufactured by Shimadzu Corporation) using normal paraffin as an internal standard substance.
At this time, operating conditions such as detector, column type, column temperature, sample injection temperature, carrier gas flow rate, etc. are selected as appropriate for each sample. This is similar to the conventional measurement operation. On the other hand, dissolve or dilute pure crosslinking agent to 100 ppm with benzene, use a gas chromatograph to determine the standard peak area, and use this as a standard to compare the previously measured values to determine the crosslinking agent concentration. From this value, calculate the amount of crosslinking agent impregnated into the product. (b) Iodine titration method (1) Precisely weigh 0.5g of product particles and replace the content with nitrogen.
Place in a 300 c.c. flask, add 100 c.c. of purified benzene, melt at a temperature below 60°C, and place on dry ice 2.
g was added to make it weakly acidic. Warm the flask to room temperature and add 3 ml of a half-saturated benzene solution of potassium iodide.
When added, the reaction occurs immediately and I ₂ is liberated within a few minutes. After standing for 30 minutes, 10 c.c. of carbonated water was added, mixed uniformly, and titrated with 0.01N thiosulfuric acid solution. The crosslinking agent content is determined from the titration amount compared to the blank. (c) Iodometric titration method (2) After extracting 100 g of suspension impregnation waste liquid with 1 kg of purified benzene in the same manner as the above gas chromatography method,
Do the following: () Add 40 ml of isopropanol, 5 ml of glacial acetic acid (depending on the type of crosslinking agent, use chloroform or titanium trichloride in place of glacial acetic acid), and 10 ml of a saturated isopropanol solution of sodium iodide to a 500 ml Erlenmeyer flask, and then purge with argon. () Add 100g of the previously extracted benzene solution to this. () Attach a reflux condenser to the Erlenmeyer flask and bring to a gentle boil on a hot plate.
Reflux is carried out for 3 minutes. Here, peroxide reacts and iodine is precipitated. () After cooling, titrate with 0.1N sodium thiosulfate and calculate the amount of crosslinking agent from the titration amount.
From this value, calculate the amount of crosslinking agent impregnated into the product. (2) Melt flow rate (MFR) (230, 190℃) ASTM-D-1238, [g/10min] (3) Mooney viscosity (M _L1+4 100℃) JIS-K-6300 (4) Gel content Rate 0.25g sample immersed in 100ml cyclohexane, 23
After standing at ℃ for 48 hours, pass through an 80-mesh wire mesh and residual insoluble matter [wt%] (5) Hardness (JIS-A) JIS-K-6301 (6) Strength at break JIS-K-6301, No. 3 dumbbell [ Kg/cm ² ] (7) Elongation at break JIS-K-6301, No. 3 dumbbell [%] Example 1 3.44 kg of pure water in an autoclave with an internal capacity of 10,
68.8 g of tricalcium phosphate as a suspending agent and sodium dodecylbenzenesulfonate as a suspending agent.
0.103g was added to make an aqueous medium. 540g of ethylene-propylene copolymer rubber (propylene content 26% by weight, Mooney viscosity 70, no third component) as monoolefin copolymer rubber and polypropylene as polyolefin resin (specific gravity 0.91, MFR 230℃)
5.0 g/10 minutes) was kneaded in a pressure kneader for 1 rubber at 170° C. for 5 minutes, sealed with a roll, and granulated with a sheet cutter. This was carried out several times, and 1000 g of the mixture was added to the above-mentioned aqueous medium and suspended by stirring. As a crosslinking agent, 360 g of 1,3-bis-(t-butylperoxyisopropyl)benzene (manufactured by Kayaku Nouri Co., Ltd., trade name: Percadox) was dissolved in 360 g of n-hexane, and this was added to the above suspension system. The 10 hour half-life temperature of this crosslinker is 127°C. After purging the inside of the autoclave with nitrogen gas, the temperature inside the system was raised to 60°C, and stirring was continued at this temperature for 5 hours to perform impregnation. Next, the system is cooled, the contents are taken out, pickled, washed with water, and dried to form a granular composite of monoolefin copolymer rubber and polyolefin resin containing a crosslinking agent.
Obtained 1360g. When the crosslinking agent content of this product was measured by gas chromatography, it was found that it was introduced almost quantitatively. Example 2 4.08Kg of pure water in an autoclave with a capacity of 10,
81.6 g of tricalcium phosphate as a suspending agent and sodium dodecylbenzenesulfonate as a suspending agent.
0.122g was added to form an aqueous medium. 540 g of ethylene propylene copolymer rubber (propylene content 28% by weight, Mooney viscosity 88, third component ethylidene norbornene) as monoolefin copolymer rubber
and 60 g of polypropylene (specific gravity 0.91 MFR 5.0 g/10 minutes at 230°C) as the polyolefin resin in Example 1.
The same granulation operation was performed several times, and eventually
1500 g was added to the above aqueous medium and suspended by stirring. 2,5-dimethyl-2,5 as a crosslinking agent
-Di(t-butylperoxy)hexane (manufactured by NOF Corporation, trade name Perhexa 25B, purity 90%) 300
g was diluted with 240 g of n-hexane and added to the above suspension system. The 10-hour half-life temperature of this cross-linking agent is
It is 118℃. After replacing the inside of the autoclave with nitrogen gas, the system temperature was raised to 60℃, and at this temperature
Impregnation was carried out by continuing stirring for a period of time. The system is then cooled, the contents are taken out, acid washed, water washed, and dried to form a granular composite of monoolefin copolymer rubber and polyolefin resin containing a crosslinking agent.
Obtained 1770g. When the content of the crosslinking agent in this product was measured by the same gas chromatography method as in Example 1, it was found that it was introduced almost quantitatively. Comparative example 1 3.8 kg of pure water in an autoclave with a capacity of 10,
76 g of tricalcium phosphate as a suspending agent and sodium dodecylbenzenesulfonate as a suspending agent.
0.114g was added to make an aqueous medium. 540g of ethylene-propylene copolymer rubber (propylene content 26% by weight, Mooney viscosity 24, no third component) as monoolefin copolymer rubber and polypropylene as polyolefin resin (specific gravity 0.91, MFR 230℃)
(5.0g/10 minutes) 60g was subjected to the same granulation operation as in Example 1 several times, and 1000g of it was added to the above-mentioned aqueous medium and suspended by stirring. 450 g of Parkadox used in Example 1 as a crosslinking agent was added to n-
It was dissolved in 450 g of hexane and added to the above suspension system. After replacing the inside of the autoclave with nitrogen gas,
The temperature inside the system was raised to 60°C, and stirring was continued at this temperature for 5 hours to carry out impregnation. The system was then cooled, the contents were taken out, washed with water, and dried to obtain 1410 g of a granular composite of monoolefin copolymer rubber and polyolefin resin containing a crosslinking agent. When the crosslinking agent content of this material was measured, it was found that only about 90% of the charged peroxide was impregnated. As can be seen from this example, when trying to introduce almost the entire amount of crosslinking agent of 40 parts by weight or more to 100 parts by weight of monoolefin copolymer rubber, it is difficult to use the impregnation method used in the present invention, and there is no efficient method. do not have. Example 3 240 g of ethylene propylene copolymer rubber (propylene content 34% by weight, Mooney viscosity 38, third component ethylidene norbornene) was used as the monoolefin copolymer rubber, and low density polyethylene (specific gravity 0.918, MFR 190°C) was used as the polyolefin resin.
45 g/10 minutes) and 360 g were granulated in the same manner as in Example 1. After doing this several times, 1500g of
The crosslinking agent was prepared in the same manner as in Example 1 using 60 g of the crosslinking agent 1,1-bis-(t-butylperoxy)-3,3,5-trimethylcyclohexane (manufactured by NOF Corporation, trade name Perhexa 3M). 1,560 g of a granular composite of a monoolefin copolymer rubber containing polyolefin resin and a polyolefin resin was obtained. When the content of the crosslinking agent in this product was measured by iodometric titration, it was found that it was introduced almost quantitatively. Example 4 Ethylene and monoolefin copolymer rubber
360 g of propylene copolymer rubber (propylene content 43% by weight, Mooney viscosity 83, third component ethylidene norbornene) and ethylene-vinyl acetate copolymer (vinyl acetate content
20% by weight, MFR 190°C, 12g/10 minutes) and 240g were granulated in the same manner as in Example 1. This was carried out several times, and a monoolefin copolymer containing a crosslinking agent was prepared in the same manner as in Example 1 using 1500g of the above and 180g of crosslinking agent dicumyl peroxide (manufactured by NOF Corporation, trade name Percumyl D). 1680 g of a granular composite of rubber and polyolefin resin was obtained. When the crosslinking agent content of this product was measured by gas chromatography, it was found that it was introduced almost quantitatively. Example 5 Ethylene and monoolefin copolymer rubber
480g of propylene copolymer rubber (propylene content 32% by weight, Mooney viscosity 50, third component dicyclopentadiene) and polypropylene as polyolefin resin (specific gravity 0.91, MFR 5.0g/10 at 230℃)
120g) was granulated in the same manner as in Example 1. This was carried out several times, and 1,860 g of a granular composite of monoolefin copolymer rubber and polyolefin resin containing a cross-linking agent was obtained in the same manner as in Example 1 using 1,500 g of the mixture and 360 g of the cross-linking agent Percadox. When the crosslinking agent content of this product was measured by gas chromatography, it was found that it was introduced almost quantitatively. Example 6 Granular ethylene/pyroprene copolymer rubber (propylene content 28
Weight%, Mooney viscosity 88, 100 parts by weight of third component (ethylidene norbornene) and polypropylene resin (specific gravity 0.91MFR230℃) as polyolefin resin
5.0 g/10 minutes) and 67 parts by weight were kneaded in a 30 mm diameter twin screw extruder (L/D17) at a set temperature of 190°C and a screw rotation speed of 200 rpm to obtain pellets. A granular composite of monoolefin copolymer rubber and polyolefin resin containing a crosslinking agent was prepared in the same manner as in Example 1 using 1500g of these pellets and 45g of benzoyl peroxide crosslinking agent (manufactured by NOF Corporation, trade name Nyper B). Obtained 1545g. When the content of the crosslinking agent in this product was measured by iodometric titration, it was found that it was introduced almost quantitatively. Example 7 Granular ethylene-propylene copolymer rubber (propylene content 28
Weight%, Mooney viscosity 88, 100 parts by weight of third component (ethylidene norbonene) and polypropylene resin (specific gravity 0.91MFR230) as polyolefin resin
5.0 g/10 minutes) and 25 parts by weight were kneaded using the same extruder as in Example 6 to obtain pellets. Using 1500 g of these pellets and 60 g of the crosslinking agent Percadox, 1560 g of a granular composite of monoolefin copolymer rubber and polyolefin resin containing a crosslinking agent was obtained in the same manner as in Example 1. When the crosslinking agent content of this material was measured using gas chromatography, it was found that
It was found that the introduction was almost quantitative. Reference example 1 Granular ethylene/propylene copolymer rubber (propylene content 28
Weight%, Mooney viscosity 88, third component ethylidene norbornene) 100 parts by weight and polyolefin resin propylene resin (specific gravity 0.91, MFR 230°C)
(5.0 g/10 minutes) and 67 parts by weight were kneaded using the same extruder as in Example 6 to obtain pellets. Example 8 1500 g of the pellets obtained in Reference Example 1 and 0.9 g of the crosslinking agent Percadox (per 100 parts by weight of the rubber component)
A granular composite of a monoolefin copolymer rubber containing a crosslinking agent and a polyolefin resin was obtained in the same manner as in Example 1. Quantitative properties were also confirmed by iodometric titration. 60 g of this crosslinking agent-containing composition was kneaded at 200° C. for 10 minutes in a 100 c.c. capacity Brabender to completely decompose the crosslinking agent and cause crosslinking. This partially crosslinked product was extracted with xylene at the boiling point for 10 hours, and the gel portion was determined to be 15% from the insoluble portion on an 80-mesh wire mesh. This gel part is entirely a crosslinked part. Comparative Example 2 A granular composite containing a crosslinking agent was obtained in the same manner as in Example 1 using 1500 g of the pellets obtained in Reference Example 1 and 0.45 g of the crosslinking agent Percadox. Furthermore, the quantitative nature of introduction of the crosslinking agent was similarly confirmed by gas chromatography. 60 g of this crosslinking agent-containing composition was kneaded at 200° C. for 10 minutes in a 100 c.c. capacity Brabender to completely decompose the crosslinking agent and cause crosslinking. The xylene-extracted gel portion of this partially crosslinked product was measured and found to be 3%. As you can see from this example, the crosslinking agent is a rubber component.
If it is less than 0.1 part by weight per 100 parts by weight, a sufficient gel content cannot be obtained, that is, crosslinking cannot be carried out satisfactorily, which is not preferable. Example 9 Granular ethylene/propylene copolymer rubber (propylene content 28
% by weight, Mooney viscosity 88, 100 parts by weight of third component (ethylidene norbornene) and polypropylene resin (specific gravity 0.91,
900 parts by weight of MFR (5.0 g/10 minutes) at 230° C. were kneaded using the same extruder as in Example 6 to obtain pellets. 2000g of these pellets and crosslinking agent Percadox
0.4g (0.2 parts by weight per 100 parts by weight of rubber component)
A granular composite containing a crosslinking agent was obtained in the same manner as in Example 1. Additionally, the quantitative nature of introduction of the crosslinking agent was confirmed using gas chromatography. Comparative Example 3 A monoolefin copolymer rubber similar to that used in Example 9 and a polyolefin resin of 100 parts by weight and 1900 parts by weight, respectively, were kneaded in the same manner as in Example 6 to obtain pellets. 2000 g of these pellets and 0.2 g of the same crosslinking agent used in Example 9 (rubber component 100 g)
A granular composite containing a crosslinking agent was obtained in the same manner as in Example 1 using 0.2 parts by weight). When the amount of crosslinking agent introduced was quantified, it was found that only 0.09 parts by weight (based on 100 parts by weight of the rubber component) was introduced into the rubber component particles. A comparison with Example 9 shows that if the proportion of polyolefin resin is significantly greater than 900 parts by weight per 100 parts by weight of rubber, it is not preferable because impregnation of the crosslinking agent into the rubber component is poor and quantitative introduction becomes impossible. Example 10 400 g of ethylene-propylene copolymer rubber (Mooney viscosity 40, propylene content 50% by weight) and crystalline polypropylene (5.0 g/10 min at MFR 230°C,
Specific gravity 0.91) 200g were melt-kneaded at 170°C for 5 minutes using a pressure kneader for rubber, then formed into a sheet using a roll, and the sheet was granulated using a sheet cutter. This was carried out three times, and 1600 g of the granular composite obtained was used. 4.8Kg of pure water in an autoclave with a capacity of 10.
As a suspension aid, 0.144 g of sodium dodecylbenzenesulfonate was added to water to prepare an aqueous medium. 1600 g of the granular composite was added to this aqueous medium and suspended by stirring. Next, 400 g of Percadox as a crosslinking agent was dissolved in 400 g of n-hexene and added to the above suspension system. After replacing the inside of the autoclave with nitrogen gas, the system temperature was raised to 60℃, and at this temperature about 5
Impregnation was carried out by continuing stirring for a period of time. Next, the system was cooled, and the contents were taken out, pickled with a 2% aqueous nitric acid solution, further washed with water, and then dried. 2000 g of a granular crosslinking agent masterbatch containing a crosslinking agent was obtained. Next, 100 parts by weight of granular ethylene-propylene copolymer rubber (propylene content 26% by weight, Mooney viscosity 88, third component ethylidene norbornene) was used as a monoolefin copolymer rubber, and the same crystalline polypropylene as above was used as a polyolefin resin.
67 parts by weight and 4.2 parts by weight of the crosslinking agent masterbatch obtained above were added to produce thermoplastic elastomers using an extruder and a pressure kneader, respectively. The manufacturing conditions for each are as follows. Extruder Model: 30φ twin screw extruder, L/D=17 Conditions: Screw rotation speed 200r.pm Extrusion temperature (setting) 190℃ Pressure kneader Model: Single pressure kneader for rubber Conditions: Rotor rotation speed 70r.pm Kneading temperature (Settings) 170°C Kneading time 10 minutes The physical properties of the obtained thermoplastic elastomer were as follows. A 2 mm thick injection molded sheet was used for physical property evaluation.

[Table] Example 11 Ethylene and monoolefin copolymer rubber
480 g of propylene copolymer rubber (Mooney viscosity 38, propylene content 33% by weight, third component ethylidene norbornene) and crystalline propylene-ethylene block copolymer resin (specific gravity 0.90, MFR 15 g/10 min at 230°C, ethylene) as polyolefin resin. 120 g (content: 8% by weight) was granulated in the same manner as in Example 10. 1500g of the granular composite obtained by repeating the operation several times and 6% of the crosslinking agent Parkadox.
1506 g of a granular composite of a monoolefin copolymer rubber containing a crosslinking agent and a polyolefin resin was obtained in the same manner as in Example 10. Using this, a thermoplastic elastomer was produced in the same manner as in Example 10 using an extruder. The physical properties of the obtained thermoplastic elastomer were as follows. For physical property evaluation, a 2 mm thick, injection molded sheet was used. Gel fraction (weight%) 73.0 Hardness (JIS-A) 68 200% modulus (Kg/cm ² ) 33 Strength at break (Kg/cm ² ) 47 Elongation at break (%) 370

Claims (1)

[Scope of Claims] 1 Contains (a) 100 parts by weight of monoolefin copolymer rubber, (b) 10 to 900 parts by weight of polyolefin resin, and (c) 0.1 to 40 parts by weight of a crosslinking agent, and (c) contains ( 1. A partially crosslinkable composition, characterized in that a granule consisting of a) and (b) is impregnated with (c) in an aqueous suspension state under conditions such that it does not substantially decompose.