CN100366669C - Thermoplastic elastomer composition and process for producing the same - Google Patents

Thermoplastic elastomer composition and process for producing the same Download PDF

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CN100366669C
CN100366669C CNB2005100779562A CN200510077956A CN100366669C CN 100366669 C CN100366669 C CN 100366669C CN B2005100779562 A CNB2005100779562 A CN B2005100779562A CN 200510077956 A CN200510077956 A CN 200510077956A CN 100366669 C CN100366669 C CN 100366669C
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rubber
mass
olefin
parts
thermoplastic elastomer
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CN1693353A (en
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森川明彦
鼎健太郎
中西英雄
前田稔
冈本隆浩
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JSR Corp
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L23/10—Homopolymers or copolymers of propene
    • C08L23/14—Copolymers of propene
    • C08L23/142—Copolymers of propene at least partially crystalline copolymers of propene with other olefins
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L23/16—Elastomeric ethene-propene or ethene-propene-diene copolymers, e.g. EPR and EPDM rubbers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
    • C08L2205/035—Polymer mixtures characterised by other features containing three or more polymers in a blend containing four or more polymers in a blend
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2207/00—Properties characterising the ingredient of the composition
    • C08L2207/04—Thermoplastic elastomer
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L23/04—Homopolymers or copolymers of ethene
    • C08L23/08—Copolymers of ethene
    • C08L23/0846—Copolymers of ethene with unsaturated hydrocarbons containing other atoms than carbon or hydrogen atoms
    • C08L23/0869—Acids or derivatives thereof
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L23/10—Homopolymers or copolymers of propene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
    • C08L33/04—Homopolymers or copolymers of esters
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L53/00—Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
    • C08L53/02—Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers of vinyl-aromatic monomers and conjugated dienes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L83/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon only; Compositions of derivatives of such polymers
    • C08L83/04—Polysiloxanes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L9/00—Compositions of homopolymers or copolymers of conjugated diene hydrocarbons
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L91/00—Compositions of oils, fats or waxes; Compositions of derivatives thereof

Abstract

A thermoplastic elastomer composition of the invention, formed by dynamically crosslinking a polymer composition including a rubber and an olefinic resin and having an average particle size of rubber particles within a specific range, shows an excellent balance of mechanical properties such as flexibility and elastic recovery, and a moldability. Also an inclusion of a (meth)acrylate resin and a hydrogenated diene polymer provides a composition particularly excellent in scratch resistance. Also an inclusion of a maleimide compound provides a composition particularly excellent in injection fusibility. Also an inclusion of an undenatured organopolysiloxane of a specific viscosity and a denatured organopolysiloxane provides a composition particularly excellent in initial slidability and durable slidability.

Description

Thermoplastic elastomer composition and method for producing same
The present application is a divisional application of application No. 02818331.2, application date 2002, 6/27, entitled "thermoplastic elastomer composition and method for producing the same".
Technical Field
The present invention relates to a thermoplastic elastomer composition and a method for producing the same. More specifically, it relates to a thermoplastic elastomer composition having an excellent balance between mechanical properties such as flexibility and rebound resilience and moldability, and a process for producing the same. Further, the present invention relates to a thermoplastic elastomer composition excellent in flexibility, scratch resistance, mechanical properties, rubber elasticity, and the like, and a method for producing the same. Further, the present invention relates to a thermoplastic elastomer composition having excellent injection weldability and a process for producing the same. Further, the present invention relates to a thermoplastic elastomer composition which is excellent in initial sliding properties, durable sliding properties, abrasion resistance, heat fusion properties and molding processability and gives a molded article having a good molded appearance and good hand, and a process for producing the same.
Background
The thermoplastic elastomer composition comprising the rubber and the olefin resin dynamically heat-treated in the presence of the crosslinking agent does not require a vulcanization step, and can be easily molded into a molded article by a usual molding method for a thermoplastic resin, for example, injection molding, profile extrusion molding, calendering, blow molding, and the like.
However, these olefin-based dynamically crosslinked thermoplastic elastomers are inferior in resilience to vulcanized rubbers. In order to improve the rebound resilience, for example, an increase in the crosslinking density and an increase in the mooney level of the rubber have been studied. By these methods, the resilience is increased, but the flowability of the thermoplastic elastomer composition is significantly reduced. Further, there is a method of blending a peroxide decomposition type olefin rubber in order to improve moldability, but there is a problem that rebound resilience is lowered by using this method. Thus, it has been difficult to obtain a thermoplastic elastomer composition having a good balance between the rebound resilience and the moldability by the conventional method.
In recent years, thermoplastic elastomers which do not require a vulcanization step and have moldability equivalent to that of thermoplastic resins have been attracting attention and used as rubber-like soft materials in the fields of automobile parts, household electric appliance parts, medical treatment, food machine parts, electric wires, sundry goods, and the like. Various elastomers such as polyolefin-based, polystyrene-based, polyurethane-based, polyester-based, and polyvinyl chloride-based elastomers have been developed and commercially available as such thermoplastic elastomers. Among these elastomers, a blend mainly composed of an olefin resin and an ethylene- α -olefin random copolymer rubber, or an olefin dynamic crosslinking thermoplastic elastomer which is partially crosslinked with a crosslinking agent and mainly composed of an olefin resin and an ethylene- α -olefin random copolymer rubber is particularly useful. They are excellent in heat resistance, weather resistance, cold resistance and moldability, and are relatively inexpensive. Therefore, in the field of automobile parts and the like in particular, attention is being paid to a material alternative to metal parts mainly aiming at weight reduction, a material alternative to RIM polyurethane parts mainly aiming at improvement of the life of parts and reduction of cost, a material alternative to vulcanized rubber mainly aiming at simplification of a processing process, recyclability and reduction of cost, a material alternative to soft polyvinyl chloride mainly aiming at improvement of the life of parts and improvement of contamination, and the like, and the demand therefor is increasing year by year.
However, olefin-based dynamically crosslinked thermoplastic elastomers have poor surface scratch resistance (scratch resistance), and have a problem when used for molded articles required to have scratch resistance, such as skin materials for interior panels and rack cases.
The olefin-based dynamically crosslinked thermoplastic elastomer is excellent in heat resistance, ozone resistance, weather resistance and the like, and has the same rubber elasticity as vulcanized rubber, while having substantially the same moldability as olefin-based thermoplastic resins such as polyethylene and polypropylene. This can be utilized as a molded article requiring rubber elasticity, for example, a bumper of an automobile, a trim for exterior trim, a weather strip for window sealing, a weather strip for door sealing, a weather strip for trunk sealing, a roof side rafter (roofsidel), a emblem, an interior skin material, and the like. Further, it can be used as various weather strips for building materials. Among these applications, olefin-based dynamically crosslinked thermoplastic elastomers used for, in particular, weather strips for window sealing, door sealing, body sealing, and the like of automobiles, building material sealing, and the like, which require rubber elasticity, can be produced by increasing the content of the ethylene- α -olefin-based copolymer rubber component as compared with olefin-based dynamically crosslinked thermoplastic elastomers used for other applications.
However, the olefin-based dynamically crosslinked thermoplastic elastomer thus obtained has low flowability in molding, and it is difficult to directly produce a complicated-shaped weather strip for automobiles and a weather strip for building materials by injection molding. On the other hand, conventional processes for molding these weatherstrips are complicated and have long working times as described below, and improvement is strongly desired from the viewpoint of labor saving, improvement in productivity, and the like.
In the molding step of weatherstrips, for example, in the case of ordinary vulcanized rubber, a straight line portion of a weatherstrip is produced by profile extrusion of unvulcanized rubber, and after vulcanizing the profile extrusion molded product, a curved joint portion between end portions of the molded product is fitted into a mold opening and vulcanized and joined. However, this method requires 2 vulcanization steps. In order to simplify the process and shorten the working time, a method of replacing the joint portion between the end portions of the vulcanized profile extrusion molded product with an olefin-based dynamically crosslinked thermoplastic elastomer which does not require vulcanization, and a method of replacing the profile extrusion molded product of the straight portion with an olefin-based dynamically crosslinked thermoplastic elastomer are also considered, and the former method is desired in practical use. In the method of replacing the junction between the ends of the profile extrusion molded article with the olefin-based dynamically crosslinked thermoplastic elastomer, the profile extrusion molded article is placed in a split mold, and the olefin-based dynamically crosslinked thermoplastic elastomer is injected into the junction to melt-bond the ends. However, in many cases, it is difficult to melt-bond with practical adhesion strength. For example, japanese patent application laid-open No. 61-53933 proposes a method of improving the adhesion strength by preheating the adherend at the time of bonding between extrusion molded articles of olefin-based dynamically crosslinked thermoplastic elastomer. In addition, japanese patent application laid-open No. 59-221347 proposes a method of improving the adhesive strength without preheating by using an olefin-based dynamically crosslinked thermoplastic elastomer containing crystalline poly-1-butene in the same bonding. However, in these methods, sufficient effects cannot be obtained particularly when the adherend is an olefin-based vulcanized rubber. Therefore, when the adherend is either an olefin vulcanized rubber or an olefin dynamically crosslinked thermoplastic elastomer, there is a strong demand for the development of an olefin thermoplastic elastomer composition having excellent injection weldability.
Further, olefin-based dynamically crosslinked thermoplastic elastomers have flexibility, have excellent rubber properties, and do not require a vulcanization step, and therefore can be produced into molded articles by ordinary thermoplastic resin molding methods such as injection molding, profile extrusion molding, calendering, blow molding, and the like. Therefore, in recent years, from the viewpoint of energy saving, resource saving, and recycling, there is an increasing demand for use as a substitute material for vulcanized rubber or vinyl chloride resin in automobile parts, industrial products, electric and electronic parts, building materials, and the like.
However, automotive parts such as glass run channels and window shields have problems of poor sliding properties with respect to window glass and low durability.
In order to improve the sliding properties, japanese patent application laid-open No. 2000-26668 discloses an olefin-based thermoplastic elastomer composition containing an organopolysiloxane (organopolysiloxane) and an aliphatic amide in an olefin-based dynamically crosslinked thermoplastic elastomer. Further, japanese patent application laid-open No. 2000-143884 discloses an olefinic thermoplastic elastomer composition in which an acrylic-modified organopolysiloxane and a higher fatty acid or a higher fatty acid amide are blended with an olefinic dynamic crosslinking thermoplastic elastomer, and a combination of these is used.
However, the sliding property is not satisfactory, and the fatty acid amide precipitates, which causes a problem of poor appearance.
Further, japanese patent application laid-open No. 2000-959000 discloses a polyolefin-based dynamically crosslinked thermoplastic elastomer used in combination with a compounding viscosity of 10 to less than 10 6 Organic polysiloxane of cSt, viscosity 10 6 ～10 8 cSt organopolysiloxane and fluoropolymer.
However, since a large amount of organopolysiloxane is blended, although the sliding properties are good, there is a problem that organopolysiloxane having low compatibility with the olefin-based dynamically crosslinked thermoplastic elastomer precipitates and feels sticky when in contact with the surface, which is undesirable, and there is a strong demand for the development of an olefin-based dynamically crosslinked thermoplastic elastomer having excellent sliding properties without precipitation.
Disclosure of Invention
In view of the above circumstances, an object of the present invention is to provide a thermoplastic elastomer composition having an excellent balance between mechanical properties such as flexibility and rebound resilience and moldability, and a method for producing the same.
It is another object of the present invention to provide a thermoplastic elastomer composition having the characteristics of conventional olefin-based dynamically crosslinked thermoplastic elastomers and excellent scratch resistance, and a method for producing the same.
It is another object of the present invention to provide a thermoplastic elastomer composition which has excellent injection weldability, high adhesion strength to both adherends composed of olefin-based vulcanized rubbers and adherends composed of olefin-based dynamically crosslinked thermoplastic elastomers, improved surface scratch properties, and is particularly useful for applications requiring hot melt adhesion, and a method for producing the same.
It is another object of the present invention to provide a thermoplastic elastomer composition which is excellent in initial sliding properties, durable sliding properties, abrasion resistance, hot-melt adhesion, molding processability and the like, and which gives a molded article having a good molded appearance and good hand, and a process for producing the same.
The present invention is as follows.
1. A thermoplastic elastomer composition comprising a polymer composition containing a rubber and an olefin resin, which is dynamically heat-treated in the presence of a crosslinking agent, characterized in that: the thermoplastic elastomer composition contains a rubber having a gel fraction of 80% or more, rubber particles contained in the thermoplastic elastomer composition have a number-average particle diameter (dn) of 3 [ mu ] m or less, and the ratio (dv/dn) of the volume-average particle diameter (dv) to the number-average particle diameter (dn) is 1.5 or less.
2. The thermoplastic elastomer composition according to the above 1, wherein said gel fraction is 95% or more, and said dn is 2 μm or less.
3. The thermoplastic elastomer composition according to the above 1, wherein the rubber is 20 to 95 parts by mass, the olefinic resin is 5 to 80 parts by mass, and the crosslinking agent is 0.05 to 10 parts by mass, per 100 parts by mass of the total of the rubber and the olefinic resin.
4. The thermoplastic elastomer composition according to the above 1, wherein the rubber is an ethylene- α -olefin copolymer rubber having an intrinsic viscosity [. Eta. ] measured at 135 ℃ using decalin as a solvent, of 2.0 to 6.8dl/g.
5. A thermoplastic elastomer composition characterized by: the rubber composition is formed by dynamically heat-treating a polymer composition containing a rubber, an olefin resin, a (meth) acrylate resin, and a hydrogenated diene polymer in the presence of a crosslinking agent.
6. The thermoplastic elastomer composition according to claim 5, wherein the hydrogenated diene polymer is obtained by hydrogenating a copolymer having a polymer block mainly composed of a vinyl aromatic unit and a polymer block mainly composed of a conjugated diene unit.
7. The thermoplastic elastomer composition according to the above 5, wherein the rubber is 20 to 95% by mass, the olefin resin is 3 to 70% by mass, the (meth) acrylic resin is 1 to 20% by mass, and the hydrogenated diene polymer is 1 to 10% by mass, based on 100 parts by weight of the total of the rubber, the olefin resin, the (meth) acrylic resin, and the hydrogenated diene polymer.
8. The thermoplastic elastomer composition according to the above 5, wherein the rubber is an ethylene- α -olefin copolymer rubber having an intrinsic viscosity [ η ] of 2.0 to 6.8dl/g as measured at 135 ℃ using decalin as a solvent.
9. A thermoplastic elastomer composition characterized by: the polymer composition is obtained by dynamically heat-treating a polymer composition containing a rubber, an olefin resin, a softener, and a maleimide compound in the presence of a crosslinking agent, wherein the olefin resin is 5 to 36% by weight when the total of the rubber, the olefin resin, and the softener is 100% by mass, and the maleimide compound is 0.3 to 10 parts by mass when the total of the rubber, the olefin resin, and the softener is 100 parts by mass.
10. The thermoplastic elastomer composition according to 9, wherein the rubber is 20 to 85 mass% and the softener is 10 to 75 mass% when the total of the rubber, the olefin-based resin, and the softener is 100 mass%.
11. A thermoplastic elastomer composition characterized by: the polymer composition is formed by dynamically treating a polymer composition containing rubber, olefin resin, softener, (meth) acrylate resin and maleimide compound in the presence of a crosslinking agent, wherein when the rubber, the olefin resin and the softener are added to 100 parts by mass, the maleimide compound is 0.3-10 parts by mass, and the (meth) acrylic resin is 1-30 parts by mass.
12. The thermoplastic elastomer composition according to claim 11, wherein the polymer composition further contains a hydrogenated diene polymer, and a mass ratio of the hydrogenated diene polymer to the (meth) acrylic resin is 0.1 to 1.
13. A thermoplastic elastomer composition characterized by: the polymer composition is formed by dynamically heat treating a polymer composition containing an ethylene-alpha-olefin copolymer rubber, an olefin resin, a softener and a maleimide compound in the presence of a crosslinking agent, wherein the intrinsic viscosity [ eta ] of the ethylene-alpha-olefin copolymer rubber measured at 135 ℃ using decalin as a solvent is 2.0 to 6.8dl/g, and the maleimide compound is 0.3 to 10 parts by mass when the rubber, the olefin resin and the softener are 100 parts by mass in total.
14. A thermoplastic elastomer composition characterized by: the polymer composition is formed by dynamically heat treating a polymer composition containing rubber, olefin resin, softener, low viscosity unmodified organopolysiloxane with viscosity of less than 10000cSt measured at 25 ℃ according to JIS K2283, high viscosity unmodified organopolysiloxane with viscosity of 10000cSt or more measured at 25 ℃ according to JIS K2283, and modified organopolysiloxane in the presence of crosslinking agent.
15. The thermoplastic elastomer composition according to claim 14, wherein the rubber is 20 to 69 parts by mass, the olefin resin is 1 to 50 parts by mass, and the softener is 20 to 79 parts by mass, based on 100 parts by mass of the total of the rubber, the olefin resin, and the softener.
16. The thermoplastic elastomer composition according to claim 14, wherein the low-viscosity unmodified organopolysiloxane is 1 to 10 parts by mass, the high-viscosity unmodified organopolysiloxane is 1 to 10 parts by mass, and the modified organopolysiloxane is 0.2 to 20 parts by mass, based on 100 parts by mass of the total of the rubber, the olefin-based resin, and the softener.
17. A thermoplastic elastomer composition characterized by: the polymer composition is obtained by dynamically heat treating a polymer composition containing an oil-extended rubber, an olefin resin, an optional post-addition softener, an unmodified organopolysiloxane having a viscosity of less than 10000cSt measured at 25 ℃ in accordance with JIS K2283, an unmodified organopolysiloxane having a viscosity of 10000cSt or more measured at 25 ℃ in accordance with JIS K2283, and a modified organopolysiloxane in the presence of a crosslinking agent, wherein the oil-extended rubber is bonded with a rubber and a softener, and the rubber is 30 to 70% by mass and the softener is 30 to 70% by mass when the total of the rubber and the softener is 100% by mass.
18. The thermoplastic elastomer composition according to claim 17, wherein the oil-extended rubber is 30 to 99 parts by mass, the olefinic resin is 1 to 50 parts by mass, and the post-addition softener is 50 parts by mass or less (including 0 part by mass) per 100 parts by mass of the total of the oil-free rubber, the olefinic resin, and the post-addition softener.
19. The thermoplastic elastomer composition according to claim 17, wherein the low-viscosity unmodified organopolysiloxane is 1 to 10 parts by mass, the high-viscosity unmodified organopolysiloxane is 1 to 10 parts by mass, and the modified organopolysiloxane is 0.2 to 20 parts by mass, based on 100 parts by mass of the total of the oil-free rubber, the olefin-based resin, and the post-addition softener.
20. The thermoplastic elastomer composition according to 14 or 17, wherein the rubber is an ethylene- α -olefin copolymer rubber having an intrinsic viscosity [. Eta. ] measured at 135 ℃ in the presence of decalin as a solvent, of 2.0 to 6.8dl/g.
21. A method for producing a thermoplastic elastomer composition, characterized in that: a polymer composition containing rubber and an olefin resin and other additives not containing a crosslinking agent, or a polymer composition containing rubber and an olefin resin, at least a part of a crosslinking agent and other additives not containing a crosslinking agent are melt-kneaded by an internal mixer to form a melt-kneaded product, and then the melt-kneaded product or the melt-kneaded product and additives containing at least a crosslinking agent are supplied to a continuous extruder to perform dynamic heat treatment.
22. A method for producing a thermoplastic elastomer composition, characterized in that: a crosslinking agent is mixed with a polymer composition containing a rubber and an olefin resin, and then the mixture is supplied to a plurality of continuous kneaders connected to each other and dynamically heat-treated.
23. A method for producing a thermoplastic elastomer composition, characterized in that: a polymer composition containing a rubber and an olefin resin is supplied from a raw material introducing part of a continuous counter-rotating twin-screw extruder of an extrusion apparatus in which an upstream continuous counter-rotating twin-screw kneader and a downstream co-rotating twin-screw kneader are arranged in series, the polymer composition is kneaded by the continuous counter-rotating twin-screw kneader, and the kneaded product is supplied to the co-rotating twin-screw extruder while keeping the temperature of the kneaded product at the outlet of the continuous counter-rotating twin-screw kneader at 250 ℃ or lower, thereby dynamically crosslinking the polymer composition.
24. A method for producing a thermoplastic elastomer composition, characterized in that: a polymer composition containing a rubber, an olefin resin and an organic peroxide is supplied from a raw material introducing part of a continuous counter-rotating twin-screw extruder of an extrusion apparatus in which an upstream continuous counter-rotating twin-screw kneader and a downstream co-rotating twin-screw kneader are arranged in series, the polymer composition is kneaded by the continuous counter-rotating twin-screw kneader, and the temperature (t) of the kneaded product at the outlet of the continuous counter-rotating twin-screw kneader is controlled while the polymer composition is kneaded by the continuous counter-rotating twin-screw kneader a ) Control at T h -30≤t a ≤T h In the range of +30 (DEG C), the kneaded mixture is fed to the co-rotating twin-screw extruder and dynamic crosslinking is carried out, wherein the melting point of the olefin resin is T m 1 minute half-life temperature T of organic peroxide h (. Degree. C.) at T m ≤T h ≤T m A range of +50 (. Degree. C.).
According to the present invention, the following effects can be obtained.
According to the present invention, a thermoplastic elastomer composition having excellent balance between mechanical properties such as flexibility and rebound resilience and moldability can be obtained by dynamically crosslinking a polymer composition comprising a rubber, an olefin resin and the like. Further, if the composition is used, it can be easily processed by injection molding, extrusion molding, hollow molding, compression molding, vacuum molding, lamination molding, calender molding, or the like.
In addition, the olefin-based thermoplastic elastomer composition can be particularly excellent in scratch resistance, and is particularly useful for automobile weather strips, sponges, laces and other interior and exterior parts, molded products such as housings of electric appliances, belt plate products requiring scratch resistance, and the like, in which the olefin-based thermoplastic elastomer is used for the outside.
In addition, can also be used as injection welding excellent thermoplastic elastomer composition, especially in addition to having injection welding part of various composite processing products, can be widely used in general processing products. For example, the present invention can be used for bumpers, exterior trims, window seal beads, door seal beads, body seal beads, roof side rails, emblems, and interior and exterior skin materials of automobiles, and also for sealing materials for airplanes and ships or interior and exterior skin materials, sealing materials for civil engineering and construction, interior and exterior skin materials, waterproof sealing materials, and the like, sealing materials for general machines and devices, gaskets and covers of weak electric parts, miscellaneous goods for daily use, sporting goods, and the like.
Further, the thermoplastic elastomer composition is excellent in initial sliding properties, durable sliding properties, abrasion resistance and the like, and can give molded articles having good molded appearance and good hand feeling, and can be used as automobile parts such as glass slide rails and window lace.
[1] Thermoplastic elastomer composition containing rubber particles having specific particle diameter
The thermoplastic elastomer composition of the present invention is characterized in that: the polymer composition is formed by dynamically heat-treating a polymer composition containing rubber and an olefin resin in the presence of a crosslinking agent. Specifically, the thermoplastic elastomer composition is obtained by subjecting a polymer composition containing a rubber and an olefin resin to dynamic heat treatment in the presence of a crosslinking agent (hereinafter referred to as "specific-particle-diameter rubber particle-containing composition [ A ]"), wherein the specific-particle-diameter rubber particles contain a rubber contained in the composition [ A ] and have a gel fraction of 80% or more, the specific-particle-diameter rubber particles contain a rubber particle contained in the composition [ A ] and have a number-average particle diameter (dn) of 3 μm or less, and the ratio (dv/dn) of the volume-average particle diameter (dv) to the number-average particle diameter (dn) is 1.5 or less.
(1) Rubber composition
(1) Kind of rubber
The rubber is not particularly limited, and examples thereof include isoprene rubber, butadiene rubber, styrene-butadiene rubber, natural rubber, chloroprene rubber, butyl rubber, nitrile rubber, hydrogenated nitrile rubber, norbornene rubber, ethylene- α -olefin copolymer rubber, acrylic rubber, ethylene-acrylate rubber, fluororubber, chlorosulfonated polyethylene rubber, epichlorohydrin rubber, silicone rubber, urethane rubber, polysulfide rubber, phosphazene rubber, 1,2-polybutadiene, and the like. Among these, ethylene- α -olefin copolymer rubbers are preferable. Only 1 type of these rubbers may be used, or 2 or more types may be used in combination.
(2) Ethylene-alpha-olefin copolymer rubber
An ethylene- α -olefin copolymer rubber (hereinafter, may be simply referred to as "copolymer rubber") is a rubber having an ethylene unit and an α -olefin unit containing no ethylene as main constituent units. When the total amount of the copolymer rubber is taken as 100 mol%, the total amount of the ethylene unit and the α -olefin unit is preferably 90 mol% or more.
The α -olefin used for producing the copolymer rubber may, for example, be an α -olefin having 3 to 12 carbon atoms such as propylene, 1-butene, 1-pentene, 3-methyl-1-butene, 1-hexene, 3-methyl-1-pentene, 4-methyl-1-pentene, 3-ethyl-1-pentene, 1-octene, 1-decene or 1-undecene. Among them, propylene and 1-butene are preferred. Only 1 kind of these α -olefins may be used, or 2 or more kinds may be used in combination.
Further, as the other monomer, a non-conjugated diene may be used. Examples of the non-conjugated diene include 1,4-pentadiene, 1,4-hexadiene, 1,5-hexadiene, 1,7-octadiene, 1,9-decadiene, 3,6-dimethyl-1,7-octadiene, 4,5-dimethyl-1,7-octadiene, 5-methyl-1,8-nonadiene, dicyclopentadiene, 5-ethylidene-2-norbornene, 5-vinyl-2-norbornene and 2,5-norbornadiene. Among them, dicyclopentadiene and 5-ethylene-2-norbornene are particularly preferable. Only 1 kind of the non-conjugated diene may be used, or 2 or more kinds may be used in combination.
As the copolymer rubber, ethylene- α -olefin binary copolymer rubber, ethylene- α -olefin-non-conjugated diene ternary copolymer rubber, and the like are preferable. As the ethylene- α -olefin binary copolymer rubber, ethylene-propylene copolymer rubber and ethylene-1-butene copolymer rubber are often used. The ethylene content in these copolymer rubbers is preferably 50 to 95 mol%, particularly preferably 60 to 90 mol%, based on 100 mol% of the total copolymer rubber.
Further, as the ethylene- α -olefin-nonconjugated diene terpolymer rubber, ethylene-propylene-dicyclopentadiene terpolymer rubber, ethylene-propylene-5-vinyl-2-norbornene terpolymer rubber, ethylene-1-butene-dicyclopentadiene terpolymer rubber, and ethylene-1-butene-5-vinyl-2-norbornene terpolymer rubber are used in many cases. The ethylene content in these copolymer rubbers is preferably 50 to 95 mol%, particularly preferably 60 to 90 mol%, based on 100 mol% of the total of the ethylene unit and the propylene unit or the 1-butene unit. Further, the content of dicyclopentadiene or 5-vinyl-2-norbornene is preferably 3 to 10 mol%, particularly preferably 3 to 8 mol% based on 100 mol% of the total of the ethylene unit and the propylene unit or the 1-butene unit.
If the ethylene content in the copolymer rubber is less than 50 mol%, the crosslinking efficiency tends to be lowered (particularly when an organic peroxide is used as a crosslinking agent), and the copolymer rubber may not have ideal physical properties. On the other hand, if the ethylene content exceeds 95 mol%, the copolymer rubber is undesirably reduced in flexibility.
Further, the intrinsic viscosity [. Eta. ] of the ethylene-alpha-olefin-based copolymer rubber measured at 135 ℃ using decalin is 1.0dl/g or more, preferably 2.0 to 6.8dl/g, more preferably 3.5 to 6.8dl/g, and most preferably 4.5 to 6.0dl/g. If the intrinsic viscosity is less than 2.0dl/g, the rebound resilience may be lowered. On the other hand, if it exceeds 6.8dl/g, the processability at the time of molding tends to be lowered, which is not preferable.
As the copolymer rubber, in addition to the above-mentioned binary copolymer rubber and ternary copolymer rubber, halogenated copolymer rubbers in which hydrogen atoms contained in these copolymer rubbers are partially substituted with halogen atoms such as chlorine atoms and bromine atoms can be used. Further, a graft copolymer rubber obtained by graft-copolymerizing monomers such as vinyl chloride, vinyl acetate, (meth) acrylic acid methyl ester, (meth) acrylic acid glycidyl ester, (meth) acrylamide, and other (meth) acrylic acid derivatives, maleic acid derivatives such as maleic acid, maleic anhydride imide, and maleic acid dimethyl ester, and conjugated dienes such as butadiene, isoprene, and chloroprene, with a monomer such as a binary copolymer rubber, a ternary copolymer rubber, and a halogenated copolymer rubber, may be used. Only 1 type of the halogenated copolymer rubber and the graft copolymer rubber may be used, or 2 or more types may be used in combination, or the halogenated copolymer rubber and the graft copolymer rubber may be used.
The copolymer rubber can be produced by a medium-low pressure polymerization method such as a method of polymerizing ethylene, α -olefin and a non-conjugated diene in the case of using a catalyst comprising a ziegler-natta catalyst, a soluble vanadium compound and an organoaluminum compound mixed in a solvent, and supplying hydrogen as a molecular weight modifier as necessary. The polymerization can be carried out by a gas phase method such as a fluidized bed and a stirred bed, or a liquid phase method such as a slurry method and a solution method.
As soluble vanadium compounds, preference is given to using VOCl 3 And/or VCl 4 And an alcohol. Examples of the alcohol include methanol, ethanol, n-propanol, isopropanol, n-butanol, sec-butanol, tert-butanol, n-hexanol, n-octanol, 2-ethylhexanol, n-decanol, and n-dodecanol. Among them, alcohols having 3 to 8 carbon atoms are preferable.
Further, as the organoaluminum compound, for example, methylaluminoxane which is a reaction product of triethylaluminum, triisobutylaluminum, tri-n-hexylaluminum, diethylaluminum chloride, diisobutylaluminum chloride, ethylaluminum sesquichloride, butylaluminum sesquichloride, ethylaluminum dichloride, butylaluminum dichloride, trimethylaluminum and water can be used. Among them, ethylaluminum sesquichloride, butylaluminum sesquichloride, a mixture of ethylaluminum sesquichloride and butylaluminum sesquichloride, and a mixture of triisobutylaluminum and butylaluminum sesquichloride are particularly preferable.
The solvent is preferably a hydrocarbon solvent, and particularly preferably n-pentane, n-hexane, n-heptane, n-octane, isooctane, or cyclohexane. Only 1 kind of these substances may be used, or 2 or more kinds may be used in combination.
The content of the rubber contained in the polymer composition is preferably 20 to 95 parts by mass, more preferably 40 to 94 parts by mass, most preferably 60 to 93 parts by mass, per 100 parts by mass of the total of the rubber and the olefin-based resin. When the rubber content is less than 20 parts by mass, the flexibility and elasticity of the rubber particle-containing composition [ A ] having a specific particle diameter tend to be lowered. On the other hand, if the content exceeds 95 parts by mass, the flowability of the rubber particle-containing composition [ A ] having a specific particle diameter is lowered, and the moldability is remarkably deteriorated, which is not preferable.
(3) Gel fraction of rubber
The gel fraction of the rubber contained in the specific-particle-diameter rubber particle-containing composition [ a ] is 80% or more, preferably 90% or more, particularly preferably 95% or more, further preferably 96% or more, and further preferably 97% or more. In view of the fact that the rubber particle-containing composition [ A ] having a specific particle diameter is excellent in mechanical strength, the gel fraction is preferably 95% or more, and if it is less than 95%, the mechanical strength is lowered and the rubber elasticity is not satisfactory. The method of measuring the gel fraction is as follows.
About 200mg of the composition [ A ] containing rubber particles having a specific particle diameter was weighed and cut into fine pieces. Thereafter, the pellet was immersed in 100ml of cyclohexane at 23 ℃ for 48 hours using a closed vessel. Then, the chips were taken out onto a filter paper and dried under reduced pressure at 105 ℃ for 1 hour by a vacuum dryer. From the mass of the dried residue, (1) the mass of a cyclohexane-insoluble component (filler, pigment, etc.) other than the rubber and the olefin-based resin, and (2) the mass of the olefin-based resin contained in the sample before cyclohexane immersion were subtracted, and the obtained value was defined as "corrected final mass (p)".
On the other hand, (3) the mass of cyclohexane-soluble components (e.g., softener) other than rubber and olefin-based resin, (1) the mass of cyclohexane-insoluble components (filler, pigment, etc.) other than rubber and olefin-based resin, and (4) the mass of olefin-based resin were subtracted from the mass of the sample, and the obtained value was defined as "corrected initial mass (q)".
The gel fraction (cyclohexane-insoluble matter) was determined by the following equation.
Gel fraction (% by mass) = [ { corrected final mass (p) } ÷ { corrected initial mass (q) } × 100
(4) Content of rubber
The rubber content is preferably 20 to 95 parts by mass, more preferably 40 to 94 parts by mass, and most preferably 60 to 93 parts by mass, per 100 parts by mass of the total of the rubber and the olefin resin. If the content of the rubber is less than 20 parts by mass, the flexibility and elasticity of the thermoplastic elastomer tend to be reduced. On the other hand, if the content exceeds 95 parts by mass, the thermoplastic elastomer composition is not preferable because the fluidity is lowered and the moldability is not satisfactory.
(5) Crosslinked rubber particles
The crosslinked rubber particles in the rubber particle-containing composition [ A ] having a specific particle diameter can be observed with a transmission electron microscope (hereinafter referred to as "TEM"). By subjecting a TEM photograph obtained by photographing the crosslinked rubber particles to image analysis, the number average particle diameter dn of the rubber particles in the specific-particle-diameter rubber particle-containing composition [ A ] is 3 μm or less, preferably 2 μm or less, more preferably 1.4 μm or less, most preferably 1.0 μm or less, and the ratio dv/dn of the volume average particle diameter dv determined from the number average particle diameter dn to the number average particle diameter dn is 1.5 or less, preferably 1.4 or less, more preferably 1.3 or less, as calculated using the area of the crosslinked rubber particles obtained by the image analysis. Within this range, the rubber particle-containing composition [ A ] having a specific particle diameter can be obtained, which has the desired favorable rubber elasticity, mechanical properties and moldability. Even if the dv/dn ratio is 1.5 or less, the moldability tends to be lowered if the number-average particle diameter dn exceeds 2 μm, particularly 3 μm. Even if the number average particle diameter dn is 3 μm or less, particularly 2 μm or less, if the dv/dn ratio exceeds 1.5, the mechanical properties tend to be lowered. When the dv/dn ratio is 1, the particle diameters are all uniform, and when the ratio is larger than 1, the particle diameters are all non-uniform.
When the composition [ a ] having a specific particle diameter is observed by TEM, first, the composition [ a ] having a specific particle diameter is flaked by a freezing and slicing machine, and dyed with a coloring agent such as ruthenium tetraoxide, osmium tetraoxide, chlorosulfonic acid, uranium acetate, phosphotungstic acid, iodide ion, trifluoroacetic acid, or the like. In selecting a coloring agent, it is necessary to select an optimum coloring agent according to the kind of the functional group of the molecule of the specific-particle-diameter rubber particle-containing composition [ a ] to be observed. Ruthenium tetroxide and osmium tetroxide are most suitable as the coloring agent.
Then, the dyed sheet containing the composition [ A ] and having the rubber particles of the specific particle diameter was magnified 2000 times by TEM and photographed.
The number average particle diameter and the volume average particle diameter are obtained by Image analysis using TEM photographs, and for example, image-Pro Plus Ver.4.0for Windows (sold by MediaCybernetics, USA プラネトロン) and the like can be used as Image analysis software.
The area of the crosslinked particles is obtained by image analysis, and the number average particle diameter dn and the volume average particle diameter dv can be calculated by the following formula. Specifically, the calculation method described in j.macro mol.sci. -phys., B38 (5&6), 527 (1999) can be used.
1) The area of the crosslinked rubber particles obtained by image analysis of the TEM photograph was converted into a diameter (dn) at true circle j ) Calculation formula
Figure C20051007795600171
A: area of crosslinked rubber particles obtained by image analysis of TEM photograph
2) Calculation formula of number average crosslinked rubber particle diameter (dn)
Figure C20051007795600172
3) Calculation formula of volume-average crosslinked rubber particle diameter (dv)
(2) Olefin resin
The olefinic resin used in the rubber particle-containing composition [ a ] having a specific particle diameter of the present invention may be a crystalline olefinic resin and/or a non-crystalline olefinic resin.
(1) Crystalline olefin resin
The crystalline olefin resin is not particularly limited, and is preferably a crystalline olefin resin having α -olefin as a main constituent unit. That is, when the total amount of the olefin-based resin is 100 mol%, the content of the α -olefin unit is preferably 80 mol% or more, and particularly preferably 90 mol% or more.
The crystalline olefin resin may be a homopolymer of α -olefin or a copolymer of 2 or more types of α -olefin. Further, the copolymer may be a copolymer of an α -olefin and a monomer other than the α -olefin. In addition, a mixture of 2 or more different crystalline olefin resins and/or copolymer resins may be used.
The α -olefin used for producing the crystalline olefin resin is preferably an α -olefin having 3 or more carbon atoms, and more preferably an α -olefin having 3 to 12 carbon atoms described in the copolymer rubber. In addition, when the crystalline olefin-based resin is a copolymer with ethylene, the ethylene content is preferably 40 mol% or less, and particularly preferably 20 mol% or less, when the total amount of the copolymer is 100 mol%.
When the crystalline olefin-based resin is a copolymer, the copolymer may be either a random copolymer or a block copolymer. However, in order to obtain a random copolymer having the crystallinity described below, the total content of the constituent units other than the α -olefin is preferably 15 mol% or less, and particularly preferably 10 mol% or less, when the total content of the random copolymer is defined as 100 mol%. In the case of a block copolymer, when the total amount of the block copolymer is 100 mol%, the total content of the constituent units other than the α -olefin is preferably 40 mol% or less, and particularly preferably 20 mol% or less.
The random copolymer can be produced, for example, by the same method as that for the above-mentioned copolymer rubber. Further, the block copolymer can be produced by living polymerization using a ziegler-natta catalyst or the like.
The crystallinity of the crystalline olefin-based resin is preferably 50% or more, more preferably 53% or more, and most preferably 55% or more, as represented by the crystallinity measured by the X-ray diffraction method. In addition, the crystallinity is closely related to the density. For example, in the case of polypropylene, the density of the alpha-form crystals (monoclinic form) is 0.936g/cm 3 About, the density of the disc-shaped microcrystal (quasi-hexagonal crystal form) is 0.886g/cm 3 About, the density of the amorphous (random) component was 0.850g/cm 3 Left and right. Further, in the case of poly-1-butene, the density of isotactic crystals was 0.91g/cm 3 About, the density of the amorphous (random) component was 0.87g/cm 3 Left and right. Therefore, when it is 50% in crystallinityIn the case of the above crystalline polymer, the density is preferably 0.89g/cm 3 Above, particularly preferably 0.90 to 0.94g/cm 3 . If the crystallinity is less than 50% or the density is less than 0.89g/cm 3 In the presence of the rubber particle-containing composition [ A ] having a specific particle diameter]The heat resistance, strength and the like of the steel sheet tend to be lowered.
Further, the melting point (hereinafter, simply referred to as "T") which is the maximum peak temperature of the crystalline olefin-based resin measured by a differential scanning calorimeter m ") varies depending on the monomers used, but is preferably 100 ℃ or higher, particularly preferably 120 ℃ or higher. If the T is m When the temperature is less than 100 ℃, sufficient heat resistance and strength tend not to be obtained.
The melt flow rate (hereinafter abbreviated as "MFR") of the crystalline olefin resin measured at a temperature of 230 ℃ and a load of 2.16kg is preferably 0.1 to 100g/10 min, particularly preferably 0.5 to 80g/10 min. When the MFR is less than 0.1g/10 min, the processability in kneading, the processability in extrusion, etc. tend to be unsatisfactory. On the other hand, if the MFR exceeds 100g/10, the strength tends to decrease.
Therefore, it is particularly preferable to use a crystalline olefin resin having a crystallinity of 50% or more and a density of 0.89g/cm 3 Above, a content of ethylene units of 20 mol% or less, T m Polypropylene and/or a copolymer of propylene and ethylene having a melting point of 140 to 170 ℃ and an MFR of 0.1 to 100g/10 min at 100 ℃ or higher.
(2) Amorphous olefin resin
The amorphous olefin resin is not particularly limited, and is preferably an amorphous olefin resin containing an α -olefin unit as a main component. That is, the α -olefin is preferably contained in an amount of 50 mol% or more, particularly preferably 60 mol% or more, based on 100 mol% of the whole amorphous olefin resin.
The amorphous olefin resin may be a homopolymer of α -olefin or a copolymer of 2 or more kinds of α -olefin. Further, a copolymer of an α -olefin and a monomer other than the α -olefin may be used. Further, a mixture of 2 or more different polymers and/or copolymers may be used.
The α -olefin used for producing the amorphous olefin resin is preferably an α -olefin having 3 or more carbon atoms, and more preferably an α -olefin having 3 to 12 carbon atoms, which is the same as in the case of the copolymer rubber.
Examples of the noncrystalline olefin resin include homopolymers such as random polypropylene and random poly-1-butene, copolymers of propylene and another α -olefin such as ethylene, 1-butene, 1-pentene, 1-hexene, 4-methyl-1-pentene, 1-octene and 1-decene (preferably containing 50 mol% or more of propylene units), copolymers of 1-butene and another α -olefin such as ethylene, propylene, 1-pentene, 1-hexene, 4-methyl-1-pentene, 1-octene and 1-decene (preferably containing 50 mol% or more of 1-butene units), and the like.
When the amorphous olefin-based resin is composed of a copolymer, the copolymer may be either a random copolymer or a block copolymer. However, in the case of a block copolymer, α -olefin units mainly composed of propylene units, 1-butene units, and the like must be combined in a random structure. In addition, in the noncrystalline olefin-based resin composed of a copolymer of an α -olefin having 3 or more carbon atoms and ethylene, the α -olefin content is preferably 50 mol% or more, and particularly preferably 60 to 100 mol% when the total amount of the copolymer is 100 mol%.
As the noncrystalline olefin resin, atactic polypropylene (containing propylene in an amount of 50 mol% or more), a copolymer of propylene (containing propylene in an amount of 50 mol% or more) and ethylene, a copolymer of propylene (containing propylene in an amount of 50 mol% or more) and 1-butene, and the like are particularly preferable.
Further, the random polypropylene can be obtained as a by-product of crystalline polypropylene. Further, random polypropylene and random poly-1-butene can be obtained by polymerization using a catalyst in which a compound and methylaluminoxane are combined. The random copolymer can be produced by the same method as that for the above-mentioned copolymer rubber, and the block copolymer can be produced by living polymerization using a Ziegler-Natta catalyst or the like.
The melt viscosity of the amorphous olefin-based resin at 190 ℃ is preferably 50 pas or less, more preferably 0.1 to 30 pas or less, and most preferably 0.2 to 20 pas. When the melt viscosity exceeds 50 pas, the adhesion strength between the vulcanized rubber and the adherend tends to decrease when the vulcanized rubber and the thermoplastic elastomer are injection-melted.
The crystallinity of the amorphous olefin-based resin measured by an X-ray diffraction method is preferably less than 50%, more preferably 30% or less, and most preferably 20% or less. The crystallinity is closely related to the density, as in the case of the crystalline olefin resin, and the density is preferably 0.85 to 0.89g/cm 3 More preferably 0.85 to 0.88g/cm 3 . Has a crystallinity of more than 50% and a density of more than 0.89g/cm 3 At least one of the above-mentioned (3) and (3) tends to decrease the strength of the contact with the adherend when the vulcanized rubber and the thermoplastic elastomer are injection-melted.
Further, the number average molecular weight (M) of the amorphous olefin resin n ) Preferably 1000 to 20000, more preferably 1500 to 15000.
The olefin-based resin may be used in combination with a crystalline olefin-based resin or an amorphous olefin-based resin, or may be used alone.
(3) Content of olefin resin
The content of the olefinic resin is preferably 5 to 80 parts by mass, more preferably 6 to 60 parts by mass, and most preferably 7 to 40 parts by mass, per 100 parts by mass of the total of the rubber and the olefinic resin. If the content of the olefin resin is less than 5 parts by mass, the rubber particle-containing composition [ A ] having a specific particle diameter may not have a good sea-island structure (the olefin resin is a sea (matrix) and the crosslinked rubber is an island (domain structure)) which is a characteristic feature of a dynamically crosslinked elastomer, and the moldability and mechanical properties may be deteriorated. On the other hand, if the content exceeds 80 parts by mass, the rubber particles having a specific particle diameter containing the composition [ A ] are not preferable because flexibility and rubber elasticity are lowered.
(3) Softening agent
The rubber particle-containing composition [ a ] having a specific particle diameter usually contains a softening agent. The softening agent is not particularly limited, and examples thereof include (1) carboxylic acid-based softening agents: stearic acid, lauric acid, and the like, (2) vegetable oil softeners: coconut oil, cottonseed oil, linseed oil, rapeseed oil, etc., (3) pine tar oil, (4) ointment: white ointment, black ointment, translucent ointment, etc., (5) mineral oil softening agent: paraffin mineral oil, naphthalene mineral oil, aromatic mineral oil, and the like, (6) ester softener: dibutyl phthalate, dioctyl adipate, di (butyl glycol) adipate, di (butyl glycol monobutyl ether) adipate, dioctyl sebacate, dibutyl sebacate, tricresyl phosphate, cresylphenyl phosphate, tributyl phosphate, trioctyl phosphate, tributoxyethyl phosphate, polyether plasticizers, adipic acid-based polyesters, and the like, (7) hydrocarbon-based softening agents: polybutene-based, polybutadiene-based, and the like. Among them, mineral oil-based softeners are preferable, and mineral oil-based softeners having a weight average molecular weight of 300 to 2000, particularly 500 to 1500, are more preferable. The softening agent for rubber composed of mineral oil hydrocarbon is generally a mixture of an aromatic ring, a naphthalene ring, and a paraffin chain, and is classified into paraffin oil in which the number of carbons in the paraffin chain is 50% or more of the total number of carbons, naphthalene oil in which the number of carbons in the naphthalene ring is 30 to 45% of the total number of carbons, and aromatic oil in which the number of carbons in the aromatic ring is 30% or more of the total number of carbons. In the present invention, paraffin-based oils are preferred, and hydrogenated paraffin-based oils are particularly preferred. Further, a mineral oil-based hydrocarbon having a kinematic viscosity at 40 ℃ of 20 to 800cSt, particularly 50 to 600cSt, and a pour point of-40 to 0 ℃, particularly-30 to 0 ℃ is preferable. Only 1 kind of these substances may be used, or 2 or more kinds may be used in combination.
The content of the softener may be 200 parts by mass or less, preferably 180 parts by mass or less, more preferably 150 parts by mass or less, and most preferably 100 parts by mass or less per 100 parts by mass of the rubber. When the content of the softening agent exceeds 150 parts by mass, particularly 200 parts by mass, the softening agent precipitates from the rubber particle-containing composition [ A ] having a specific particle diameter, and the mechanical properties and rubber elasticity tend to be lowered. When the oil-extended rubber is used as the softener, the softener may be contained in the oil-extended rubber alone or may be added later and mixed.
The rubber particle-containing composition [ A ] having a specific particle diameter can be easily processed by injection molding, extrusion molding, blow molding, compression molding, vacuum molding, lamination molding, calender molding, etc., and can be a thermoplastic elastomer molded article having excellent rubber elasticity and mechanical properties.
[2] Thermoplastic elastomer composition containing acrylate resin
Another thermoplastic elastomer composition according to the present invention (hereinafter referred to as "acrylate-containing composition [ B ]") is characterized in that: the rubber composition is formed by dynamically heat-treating a polymer composition containing a rubber, an olefin resin, a (meth) acrylate resin, and a hydrogenated diene copolymer in the presence of a crosslinking agent.
In the acrylate resin-containing composition [ B ], the rubber and the olefin resin may be used as described above. As the rubber, an ethylene- α -olefin random copolymer rubber is particularly preferable. As the olefin-based resin, a crystalline olefin-based resin and/or an amorphous olefin-based resin can be used. As the crystalline olefin-based resin, polypropylene and a propylene-ethylene copolymer are particularly preferable. Further, as the noncrystalline olefin-based resin, random polypropylene (containing propylene in an amount of 50 mol% or more), a copolymer of propylene (containing propylene in an amount of 50 mol% or more) and ethylene, and a copolymer of propylene (containing propylene in an amount of 50 mol% or more) and 1-butene are particularly preferable.
In the acrylate resin-containing composition [ B ], the rubber is preferably 20 to 95% by mass, more preferably 30 to 90% by mass, based on 100% by mass of the total of the rubber, the olefin resin, the (meth) acrylate resin, and the hydrogenated diene polymer. The olefin resin is preferably 3 to 70% by mass, more preferably 5 to 60% by mass. If the content of the rubber is less than 20% by mass, the flexibility and rubber elasticity of the acrylate resin-containing composition [ B ] are reduced. On the other hand, if it exceeds 95 mass%, the flowability of the acrylate-based resin-containing composition [ B ] tends to be lowered, and the moldability tends to be remarkably deteriorated. If the content of the olefin-based resin is less than 3% by mass, the phase structure (morphology) of the acrylate-based resin-containing composition [ B ] may not have a good sea island structure (the olefin-based resin is a sea (matrix) and the crosslinked rubber is an island (domain structure)) which is a characteristic feature of the dynamically crosslinked elastomer, and the moldability and mechanical properties may be deteriorated. On the other hand, if it exceeds 70% by mass, the flexibility and rubber elasticity of the acrylic resin containing [ B ] are lowered, so that it is not preferable.
The acrylate resin-containing composition [ B ] usually contains the above-mentioned softening agent. The content of the softener may be 200 parts by mass or less, preferably 180 parts by mass or less, more preferably 150 parts by mass or less, and most preferably 100 parts by mass or less per 100 parts by mass of the rubber. If the content of the softener exceeds 150 parts by mass, particularly exceeds 200 parts by mass, the softener precipitates from the acrylate-based resin composition [ B ], and mechanical properties and rubber elasticity tend to be lowered. When the softener is oil-extended rubber, it may be only the softener contained in the oil-extended rubber, or it may be added later and mixed.
(1) (meth) acrylate resin
As the (meth) acrylate-based resin, a polymer of a vinyl monomer containing a monomer having an acrylic group or a methacrylic group as a main component can be used. The monomer having an acrylic group or a methacrylic group means a monomer having 1 or more acrylic groups or methacrylic groups, and examples thereof include: alkyl acrylates such as methyl acrylate, ethyl acrylate, n-propyl acrylate, isopropyl acrylate, n-butyl acrylate, t-butyl acrylate, sec-butyl acrylate, 2-methylbutyl acrylate, 3-methylbutyl acrylate, n-hexyl acrylate, n-heptyl acrylate, n-octyl acrylate, 2-ethylhexyl acrylate, etc., diacrylates such as ethylene glycol diacrylate, 1,2-propanediol diacrylate, 1,3-propanediol diacrylate, 1,2-butanediol diacrylate, 1,3-butanediol diacrylate, 1,4-butanediol diacrylate, etc., alkyl methacrylates such as methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, isopropyl methacrylate, n-butyl methacrylate, t-butyl methacrylate, sec-butyl methacrylate, 2-methylbutyl methacrylate, 3-methylbutyl methacrylate, n-hexyl methacrylate, n-heptyl methacrylate, n-octyl methacrylate, 2-ethylhexyl methacrylate, etc., alkyl methacrylates such as 5364 zxft-butyl methacrylate, 3579-dimethyl butanediol 86565, 3579-dimethyl butanediol 86579, 3579, etc.
Among the (meth) acrylate-based resins, a homopolymer of methyl methacrylate or a copolymer containing methyl methacrylate as a main component and a small amount of another monomer is preferable. Examples of the other monomers include: acrylic acid, metal acrylates, acrylates such as methyl acrylate, ethyl acrylate, N-butyl acrylate, sec-butyl acrylate, tert-butyl acrylate and 2-ethylhexyl acrylate, methacrylates such as metal methacrylates, ethyl methacrylate, N-butyl methacrylate, sec-butyl methacrylate, tert-butyl methacrylate, 2-hydroxyethyl methacrylate, glycidyl methacrylate and cyclohexyl methacrylate, acetates such as vinyl acetate, aromatic vinyl compounds such as styrene and alpha-methylstyrene, and maleimides such as maleic anhydride, monoalkyl maleates, dialkyl maleates and N-phenylmaleimide.
The type of the copolymer is not particularly limited, and may be any of a random copolymer, a block copolymer such as a diblock, triblock, multiblock, and tapered block, a multistage graft copolymer, and the like. The structure of the (meth) acrylate resin is not particularly limited, and may be any of a linear type, a branched type, and a multilayer type.
The MFR of the (meth) acrylate-based resin measured at 230 ℃ under a load of 3.8kg is not particularly limited, but is preferably 0.1 to 100g/10 min, more preferably 0.5 to 80g/10 min.
The content of the (meth) acrylate resin in the acrylate resin-containing composition [ B ] is preferably 1 to 20% by mass, more preferably 5 to 15% by mass. If the content is less than 1% by mass, the scratch resistance of the acrylate resin composition [ B ] is lowered. On the other hand, if it exceeds 20 mass%, the flexibility and rubber elasticity of the composition [ B ] containing an acrylic ester resin are lowered, so that it is not preferable.
(2) Hydrogenated diene polymer
Examples of the hydrogenated diene polymer include hydrogenated diene polymers such as homopolymers of a conjugated diene monomer, random copolymers of a conjugated diene monomer and a vinyl aromatic monomer, block copolymers composed of a polymer block of a vinyl aromatic monomer and a polymer block of a conjugated diene monomer, block copolymers composed of a polymer block of a vinyl aromatic monomer and an random copolymer block of a conjugated diene monomer and a vinyl aromatic monomer, block copolymers composed of a polymer block of a conjugated diene monomer and a tapered block composed of a vinyl aromatic monomer and a conjugated diene monomer and in which a vinyl aromatic monomer is gradually increased, block copolymers composed of a random copolymer block of a conjugated diene monomer and a vinyl aromatic monomer and a tapered block composed of a vinyl aromatic monomer and in which a vinyl aromatic monomer is gradually increased, and block copolymers composed of a polybutadiene block having a vinyl bond of 30 mass% or less and a polymer block composed of a conjugated diene monomer having a vinyl bond of more than 30 mass% (hereinafter, these hydrogenated diene polymers may also be referred to as "polymers before hydrogenation").
Among these hydrogenated diene polymers, hydrogenated products of conjugated diene polymers having a polymer block (a) mainly composed of a vinyl aromatic monomer and a polymer block (B) mainly composed of a conjugated diene monomer are preferable.
The polymer block (a) is a homopolymer of a vinyl aromatic monomer or a block copolymer having a copolymerized structure of a vinyl aromatic monomer unit containing more than 50% by mass, preferably 70% by mass of a vinyl aromatic monomer unit and another copolymerizable monomer, preferably a conjugated diene, and the polymer block (B) is a homopolymer of a conjugated diene monomer or a block copolymer having a structure of copolymerizing 5% by mass or less of another monomer such as a vinyl aromatic monomer and having a block structure of (a-B) n-a type (n is an integer of 1 to 10) or (a-B) m type (m is an integer of 2 to 10). In addition, the end A blocks may have shorter B blocks. Further, the block copolymer may have a structure of [ (A-B) n ] M-M type (M represents a coupling agent residue such as Si or Sn, M represents a valence of the coupling agent residue and is an integer of 2 to 4, and n represents an integer of 1 to 10, preferably 1 or 2).
The block copolymer may have a plurality of polymer blocks (A) and/or polymer blocks (B), and may be, for example, A 1 -B-A 2 Form A or A 1 -B 1 -A 2 -B 2 And (4) molding. Here, the block A is formed 1 And A 2 The monomer units (A) may be the same or different. In addition, the block B 1 And B 2 The weight average molecular weights of the respective polymers may be the same or different.
Examples of the vinyl aromatic monomer used for producing the polymer before hydrogenation include styrene, α -methylstyrene, p-methylstyrene, t-butylstyrene, divinylbenzene, N-dimethyl-p-aminoethylstyrene, 2,4-dimethylstyrene, N-diethyl-p-aminoethylstyrene, 2,4-dimethylstyrene, vinylnaphthalene, vinylanthracene, etc., and styrene and α -methylstyrene are preferable. Only 1 kind of these substances may be used, or 2 or more kinds may be used in combination.
Further, as the conjugated diene monomer used for producing the polymer before hydrogenation, 1,3-butadiene, isoprene, 2,3-dimethyl-1,3-butadiene, 1,3-pentadiene, 2-methyl-1,3-pentadiene, 1,3-hexadiene, 4,5-dimethyl-1,3-octadiene, chloroprene and the like can be mentioned, and 1,3-butadiene and isoprene are preferable. Only 1 kind of these substances may be used, or 2 or more kinds may be used in combination.
In the polymer block A, the other monomers copolymerizable with the vinyl aromatic monomer are mainly the above-mentioned conjugated diene monomers, and 1,3-butadiene and isoprene are particularly preferred.
The ratio of the conjugated diene monomer and the vinyl aromatic monomer (conjugated diene monomer/vinyl aromatic monomer) used for producing the polymer before hydrogenation is preferably 95/5 to 40/60, more preferably 93/7 to 45/55, by mass.
The vinyl bond content of the conjugated diene unit in the polymer before hydrogenation (the proportion of 1,2-and 3,4-vinyl bonds in the conjugated diene unit in the polymer before hydrogenation) is not particularly limited, but is preferably 50 to 85%, more preferably 60 to 85%.
In the hydrogenated diene copolymer, it is preferable that 80% or more, particularly preferably 90% or more, of the double bonds derived from the conjugated diene contained in the conjugated diene unit of the polymer before hydrogenation is saturated. If the saturation ratio is less than 80%, the weather resistance and the like are lowered. The hydrogenated diene polymer has a weight average molecular weight of 5000 to 1000000, preferably 10000 to 500000.
The content of the hydrogenated diene polymer in the acrylate resin composition [ B ] is preferably 1 to 10% by mass, more preferably 2 to 9% by mass. If the content is less than 1 mass%, the compatibility of the rubber, particularly the ethylene- α -olefin copolymer rubber, the olefin resin and the (meth) acrylate resin is deteriorated, and the mechanical properties tend to be deteriorated. On the other hand, if it exceeds 20 mass%, the flexibility and rubber elasticity of the acrylate resin-containing composition [ B ] are lowered, which is not preferable.
The acrylic resin-containing composition [ B ] has flexibility and excellent scratch resistance and moldability, and can be widely used as interior and exterior skin materials such as bumpers, exterior trim laces, weather strips for window sealing, weather strips for door sealing, weather strips for body sealing, side rafters at the top, emblems, interior panels, and floor boxes of automobiles in which olefin-based thermoplastic elastomers have been conventionally used, as well as for sealing materials for airplanes and ships, or interior and exterior skin materials, sealing materials for civil engineering and construction, interior and exterior skin materials, waterproof sealing materials, and the like, sealing materials for general machines and devices, gaskets or housings for weak electric parts, miscellaneous goods, sporting goods, and the like.
[3] Thermoplastic elastomer composition containing maleimide
Further, another thermoplastic elastomer composition of the present invention (hereinafter, referred to as "maleimide compound-containing composition [ C ]") is characterized in that: the polymer composition is obtained by dynamically heat-treating a polymer composition containing a rubber, an olefin resin, a softener and a maleimide compound in the presence of a crosslinking agent, wherein the olefin resin is 5 to 36% by mass when the total of the rubber, the olefin resin and the softener is 100% by mass, and the maleimide compound is 0.3 to 10 parts by mass when the total of the rubber, the olefin resin and the softener is 100 parts by mass.
In the maleimide compound-containing composition [ C ], the above-mentioned materials can be used for the rubber and the olefin resin, respectively. As the rubber, an ethylene- α -olefin random copolymer rubber is particularly preferable. As the olefin-based resin, a crystalline olefin-based resin and/or a non-crystalline olefin-based resin can be used. As the crystalline olefin-based resin, polypropylene and a propylene-ethylene copolymer are particularly preferable. Further, as the noncrystalline olefin resin, atactic polypropylene (containing 50 mol% or more of propylene), a copolymer of propylene (containing 50 mol% or more) and ethylene, and a copolymer of propylene (containing 50 mol% or more) and 1-butene are particularly preferable.
In the maleimide compound-containing composition [ C ], the rubber is preferably 20 to 85 mass%, more preferably 30 to 80 mass%, based on 100 mass% in total of the rubber, the olefin-based resin, and the softener. The olefin resin is preferably 5 to 36% by mass, more preferably 10 to 36% by mass. If the content of the rubber is less than 20% by mass, the flexibility and rubber elasticity of the maleimide compound-containing composition [ C ] are lowered. On the other hand, if it exceeds 85 mass%, the flowability of the maleimide compound-containing composition [ C ] tends to be lowered, and the moldability tends to be remarkably deteriorated. Further, if the content of the olefin-based resin is less than 5% by mass, the phase structure (morphology) of the maleimide compound-containing composition [ C ] may not have a good sea-island structure (the olefin-based resin is a sea (matrix) and the crosslinked rubber is an island (domain structure)) which is a characteristic feature of the dynamically crosslinked elastomer, and the moldability and mechanical properties may be deteriorated. On the other hand, if the content of the olefin-based resin is excessive, the maleimide compound-containing composition [ C ] is not preferable because flexibility and rubber elasticity are reduced.
The maleimide compound-containing composition [ C ] usually contains the above-mentioned softening agent. The content of the softener is 10 to 75% by mass, preferably 20 to 60% by mass, when the total of the rubber, the olefin resin, and the softener is 100% by mass. If the content of the softener is less than 10% by mass, the moldability of the maleimide compound-containing composition [ C ] is not satisfactory. On the other hand, if it exceeds 75% by mass, the rubber elasticity and mechanical properties are deteriorated. When the oil-extended rubber is used as the softening agent, the softening agent may be contained in the oil-extended rubber alone or may be added to the oil-extended rubber later.
In the maleimide compound-containing composition [ C ], the polymer composition may further contain a (meth) acrylate resin. As the (meth) acrylate resin, the (meth) acrylate resin described above can be used. The (meth) acrylate resin is preferably 1 to 30 parts by mass, and more preferably 5 to 15 parts by mass, based on 100% by mass of the total of the rubber, the olefin resin, and the softener. When the content of the (meth) acrylate-based resin is less than 1 part by mass, the scratch resistance of the maleimide compound-containing composition [ C ] is not preferable. On the other hand, if it exceeds 30 parts by mass, the flexibility and rubber elasticity of the maleimide compound-containing composition [ C ] are lowered, which is not preferable.
In addition, in the maleimide compound-containing composition [ C ], the polymer composition may contain a hydrogenated diene polymer in addition to the (meth) acrylate resin. As the hydrogenated diene polymer, the hydrogenated diene polymer described above can be used. The content of the hydrogenated diene polymer is preferably 0.1 to 1, more preferably 0.3 to 0.7, in terms of the mass ratio to the (meth) acrylate resin. If the mass ratio is less than 0.1, the compatibility of the rubber, particularly the ethylene- α -olefin random copolymer rubber, with the olefin resin and the (meth) acrylate resin tends to be poor, and the mechanical properties tend to be low. On the other hand, if it exceeds 1, the flexibility and rubber elasticity of the composition [ C ] containing a maleimide compound are lowered, so that it is not preferable.
(1) Maleimide compound
The maleimide compound functions as a crosslinking aid when crosslinking is performed using a crosslinking agent, particularly an organic peroxide. The maleimide compound may, for example, be N, N '-m-phenylene bismaleimide, and N, N' -tolylmaleimide (CAS number: 3006-93-7) is preferred.
The content of the maleimide compound is 0.3 to 10 parts by mass, preferably 0.4 to 8 parts by mass, and more preferably 0.5 to 5 parts by mass, per 100 parts by mass of the total amount of the rubber, the olefin resin and the softener. If the content of the maleimide compound is less than 0.3 part by mass, the maleimide compound-containing composition [ C ] may not have excellent injection fusibility and rebound resilience of the injection-fused portion. On the other hand, if it exceeds 10 parts by mass, the degree of crosslinking becomes excessively high, and the moldability may deteriorate, whereby the injection fusibility may be adversely impaired.
The maleimide compound-containing composition [ C ] has excellent injection weldability, and therefore can be a thermoplastic elastomer molded article obtained by injection welding and compounding it with an olefin-based vulcanized rubber such as ethylene-propylene rubber, ethylene-propylene-diene rubber, ethylene-butylene rubber, or ethylene-butylene-diene rubber, a vulcanized rubber such as ethylene-acrylate rubber, chlorinated polyethylene, chlorosulfonated polyethylene, styrene-butadiene rubber, nitrile rubber, chloroprene rubber, acrylic rubber, or urethane rubber, or a thermoplastic elastomer such as an olefin-based thermoplastic elastomer, a polyester-based thermoplastic elastomer, a polyurethane-based thermoplastic elastomer, or a polyamide-based thermoplastic elastomer. Particularly preferred adherends are olefin-based vulcanized rubbers and olefin-based thermoplastic elastomers.
[4] Thermoplastic elastomer composition containing polysiloxane
Further, another thermoplastic elastomer composition of the present invention (hereinafter, referred to as "silicone-containing composition [ D ]") is characterized in that: the polymer composition is formed by dynamically heat treating a polymer composition containing rubber, a softener, an olefin resin, a low-viscosity unmodified organopolysiloxane having a viscosity of less than 10000cSt measured at 25 ℃ according to JIS K2283, a high-viscosity unmodified organopolysiloxane having a viscosity of 10000cSt or more measured at 25 ℃ according to JIS K2283, and a modified organopolysiloxane in the presence of a crosslinking agent.
In the polysiloxane-containing composition [ D ], the rubber and the olefin resin may be used as described above. As the rubber, ethylene- α -olefin copolymer rubber is particularly preferable. As the olefin-based resin, a crystalline olefin-based resin and/or a non-crystalline olefin-based resin can be used. As the crystalline olefin-based resin, polypropylene and propylene-ethylene copolymer are particularly preferable. Further, as the amorphous olefin-based resin, atactic polypropylene (having a propylene content of 50 mol% or more), a copolymer of propylene (having a propylene content of 50 mol% or more) and ethylene, and a copolymer of propylene (having a propylene content of 50 mol% or more) and 1-butene are particularly preferable.
In the polysiloxane-containing composition [ D ], the rubber is preferably 20 to 69 parts by mass, more preferably 23 to 65 parts by mass, and most preferably 25 to 60 parts by mass, based on 100 parts by mass of the total of the rubber, the olefin-based resin, and the softener. The olefin-based resin is preferably 1 to 50 parts by mass, more preferably 2 to 45 parts by mass, and most preferably 5 to 40 parts by mass. If the rubber content is less than 20 parts by mass, the flexibility and rubber elasticity of the polysiloxane-containing composition [ D ] are reduced. On the other hand, if it exceeds 69 parts by mass, the fluidity of the silicone-containing composition [ D ] tends to be lowered, and the moldability tends to be remarkably deteriorated. If the content of the olefin resin is less than 1 part by mass, the phase structure (morphology) of the polysiloxane-containing composition [ D ] is not a good sea-island structure (the olefin resin is a sea (matrix) and the crosslinked rubber is an island (domain structure)) which is a characteristic feature of the dynamically crosslinked thermoplastic elastomer, and the moldability and mechanical properties may be deteriorated. On the other hand, if it exceeds 50 parts by mass, the flexibility and rubber elasticity of the composition [ D ] containing a polysiloxane are lowered, so that it is not preferable.
The silicone-containing composition [ D ] usually contains the aforementioned softening agent. The content of the softener is preferably 20 to 79 parts by mass, more preferably 25 to 75 parts by mass, and most preferably 25 to 70 parts by mass, per 100 parts by mass of the total of the rubber, the olefin-based resin, and the softener. If the content of the softener is less than 20 parts by mass, the fluidity of the composition [ D ] containing a polysiloxane is insufficient. On the other hand, if the amount exceeds 79 parts by mass, the dispersion of the rubber and the olefin resin may be poor during kneading, and the rubber elasticity may also tend to be reduced. When the oil-extended rubber is used, the softener may be a softener contained in the oil-extended rubber alone, or may be added later and compounded.
The polysiloxane-containing composition [ D ] can also be obtained by dynamically heat treating a polymer composition containing an oil-extended rubber, an olefin resin, an unmodified organopolysiloxane having a viscosity of less than 10000cSt measured at 25 ℃ in accordance with JIS K2283, an unmodified organopolysiloxane having a viscosity of 10000cSt or more measured at 25 ℃ in accordance with JIS K2283, and a modified organopolysiloxane in the presence of a crosslinking agent, wherein the oil-extended rubber contains 30 to 70% by mass of the rubber and 30 to 70% by mass of the softening agent when the total of the rubber and the softening agent is 100% by mass.
In the polysiloxane-containing composition [ D ] using the oil-extended rubber, the rubber and the olefin resin may be used separately from each other. As the rubber, ethylene- α -olefin copolymer rubber is particularly preferable. As the olefin-based resin, a crystalline olefin-based resin and/or an amorphous olefin-based resin can be used. As the crystalline olefin-based resin, polypropylene and a propylene-ethylene copolymer are particularly preferable. Further, as the noncrystalline olefin-based resin, particularly preferred are atactic polypropylene (having a propylene content of 50 mol% or more), a copolymer of propylene (having a propylene content of 50 mol% or more) and ethylene, and a copolymer of propylene (having a propylene content of 50 mol% or more) and 1-butene.
The content of each of the rubber and the softener constituting the oil-extended rubber is preferably 30 to 70% by mass, more preferably 35 to 65% by mass, and most preferably 40 to 60% by mass, when the total is 100% by mass. When the rubber content is less than 30% by mass or the softening agent content exceeds 70% by mass, the softening agent precipitates from the silicone-containing composition [ D ], and the mechanical properties and rubber elasticity tend to be lowered. On the other hand, if the rubber content exceeds 70% by mass or the softening agent content is less than 30% by mass, the moldability of the silicone-containing composition [ D ] tends to be lowered. The softening agent is not particularly limited, and the above-described various substances can be used.
In addition, the silicone-containing composition [ D ] may further contain a softening agent by post-addition as necessary. The softener to be added later is preferably 50 parts by mass or less, more preferably 45 parts by mass or less, and most preferably 40 parts by mass or less, when the total of the oil-extended rubber, the olefin-based resin, and the softener to be added later is 100 parts by mass. If the content exceeds 50 parts by mass, the dispersion of the rubber and the olefin resin may be poor during kneading, and the rubber elasticity may tend to be lowered. The softener to be added later is not particularly limited, and the above-described various materials can be used.
In the polysiloxane-containing composition [ D ], the oil-extended rubber is preferably 30 to 99 parts by mass, more preferably 35 to 97 parts by mass, and most preferably 40 to 95 parts by mass, per 100 parts by mass of the total of the oil-extended rubber, the olefin-based resin, and the softener to be added later. The amount of the olefin resin is preferably 1 to 50 parts by mass, more preferably 2 to 45 parts by mass, and most preferably 5 to 40 parts by mass. If the content of the rubber is less than 30 parts by mass, the flexibility of the composition [ D ] containing a polysiloxane may be reduced. On the other hand, if it exceeds 99 parts by mass, the fluidity of the polysiloxane-containing composition [ D ] tends to be lowered, and the moldability tends to be remarkably deteriorated. Further, if the content of the olefin-based resin is less than 1 part by mass, the phase structure (morphology) of the polysiloxane-containing composition [ D ] may not have a good sea-island structure (the olefin-based resin is a sea (matrix) and the crosslinked rubber is an island (domain structure)) which is a characteristic feature of the dynamic crosslinked thermoplastic elastomer, and the moldability and mechanical properties may be deteriorated. On the other hand, if it exceeds 50 parts by mass, the flexibility and rubber elasticity of the silicone-containing composition [ D ] are lowered, so that it is not preferable.
(1) Low-viscosity or high-viscosity unmodified organopolysiloxanes
The low-viscosity or high-viscosity unmodified organopolysiloxane is not particularly limited. Examples of the unmodified organopolysiloxane include dimethylpolysiloxane, methylphenylpolysiloxane, fluoropolysiloxane, tetramethyltetraphenylpolysiloxane, methylhydrodienylpolysiloxane, and the like, and among them, dimethylpolysiloxane is preferable. The low-viscosity unmodified organopolysiloxane and the high-viscosity unmodified organopolysiloxane may be the same compound or different compounds.
(4) Low viscosity unmodified organopolysiloxanes
A low-viscosity unmodified organopolysiloxane having a viscosity at 25 ℃ specified in JIS K2283 of less than 10000cSt, preferably less than 7000cSt, more preferably less than 5000cSt.
The content of the low-viscosity unmodified organopolysiloxane is preferably 1 to 10 parts by mass, more preferably 1 to 8 parts by mass, and most preferably 1 to 5 parts by mass, per 100 parts by mass of the total of the oil-extended rubber, the olefin-based resin, and the softening agent added later. Further, if a low viscosity unmodified organopolysiloxane having a viscosity of less than 10000cSt at 25 ℃ specified in JIS K2283 is used alone, there is a tendency that the low viscosity unmodified organopolysiloxane precipitates from the polysiloxane-containing composition [ D ].
(2) High viscosity unmodified organopolysiloxanes
A high-viscosity unmodified organopolysiloxane having a viscosity at 25 ℃ specified in JIS K2283 of 10000cSt or more, preferably 10000 to 1000000cSt, more preferably 10000 to 100000cSt.
The content of the low-viscosity unmodified organopolysiloxane is preferably 1 to 10 parts by mass, more preferably 1 to 8 parts by mass, and most preferably 1 to 5 parts by mass, when the total of the oil-extended rubber, the olefin-based resin, and the softener to be added later is 100 parts by mass. Further, if a high-viscosity unmodified organopolysiloxane having a viscosity at 25 ℃ of 10000cSt or more, which is prescribed in JIS K2283, is used alone, the slipperiness is sometimes insufficient, and therefore, it is not preferable.
When a low-viscosity unmodified organopolysiloxane having a viscosity at 25 ℃ of less than 10000cSt as defined in JIS K2283 and a high-viscosity unmodified organopolysiloxane having a viscosity at 25 ℃ of 10000cSt or more as defined in JIS K2283 are used in combination, the sliding property is remarkably improved. The content of each of them is preferably 1 to 10 parts by mass of the low-viscosity unmodified organopolysiloxane and 1 to 10 parts by mass of the high-viscosity unmodified organopolysiloxane, more preferably 1 to 5 parts by mass of the low-viscosity unmodified organopolysiloxane and 1 to 5 parts by mass of the high-viscosity unmodified organopolysiloxane.
(2) Modified organopolysiloxane
The modified organopolysiloxane is not particularly limited as long as it is chemically modified with a functional group, and examples thereof include acrylic modification, epoxy modification, alkyl modification, amino modification, carboxyl modification, alcohol modification, fluorine modification, alkylallyl polyether modification, and epoxy polyether modification. Among them, acrylic-modified organopolysiloxanes are preferable, and a mixture of monomers copolymerizable with acrylic acid esters or acrylic acid is preferably graft-copolymerized with the organopolysiloxanes.
Examples of the acrylate ester which can be graft-polymerized to the organopolysiloxane include alkyl acrylates such as methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, hexyl acrylate, pentyl acrylate, octyl acrylate, 2-ethylhexyl acrylate, lauryl acrylate, and stearyl acrylate, alkoxyalkyl acrylates such as methoxyethyl acrylate and butoxyethyl acrylate, cyclohexyl acrylate, phenyl acrylate, and benzyl acrylate, and only 1 kind of these may be used, or 2 or more kinds may be used in combination.
Examples of the monomer copolymerizable with the acrylic acid ester include hydroxyl group-containing unsaturated monomers such as 2-hydroxyethyl (meth) acrylate and 2-hydroxypropyl (meth) acrylate. Only 1 kind of them may be used, or 2 or more kinds may be used in combination.
In the graft polymerization, the ratio of the organopolysiloxane to the acrylate or the monomer copolymerizable with the acrylate, preferably the mass ratio of [ organopolysiloxane/acrylate or monomer copolymerizable with acrylate ] is 9/1 to 1/9, more preferably 8/2 to 2/8. Examples of the acrylic-modified organopolysiloxane include "X-22-8171" manufactured by Shin-Etsu Chemical Co., ltd and "Chaline R-2" manufactured by Nissin Chemical Industry Co., ltd.
The content of the modified organopolysiloxane is preferably 0.2 to 20 parts by mass, more preferably 0.5 to 15 parts by mass, and most preferably 1 to 10 parts by mass, per 100 parts by mass of the total of the oil-extended rubber, the olefin-based resin, and the softener to be added later. The modified organopolysiloxane functions as a compatibilizer for the polymer composition and the unmodified organopolysiloxane in the silicone-containing composition [ D ] due to the effect of imparting slidability. Therefore, if the content of the modified organopolysiloxane is less than 0.2 parts by mass, the compatibilization is not satisfactory, poor dispersion of the unmodified organopolysiloxane with the polymer composition occurs in a kneader, and molding processability such as extrusion molding and injection molding tends to deteriorate. On the other hand, if it exceeds 20 parts by mass, flexibility and mechanical properties tend to be reduced.
Since the polysiloxane-containing composition [ D ] has excellent rubber elasticity and thermoplasticity, it can be easily processed by a common molding method for thermoplastic resins, for example, injection molding, extrusion molding, slush molding, compression molding, vacuum molding, lamination molding, calender molding, and the like. Further, secondary processing such as foaming, stretching, adhesion, printing, painting, and plating can be easily performed as necessary. Therefore, the polysiloxane-containing composition [ D ] can be widely used for general processed products in addition to various composite processed products having an injection-welded part. For example, the present invention can be used for bumpers, exterior trims, weather strips for window sealing, weather strips for door sealing, weather strips for body sealing, side rafters for roofs, emblems, and interior and exterior skin materials of automobiles, sealing materials for airplanes and ships, interior and exterior skin materials, and the like, sealing materials for civil engineering and construction, interior and exterior skin materials, waterproof sealing materials, and the like, sealing materials for general machines and devices, gaskets and housings for weak electric parts, miscellaneous goods, sporting goods, and the like.
[5] Crosslinking agent
The crosslinking agent used for crosslinking may be the same as that used in any of the rubber particle-containing composition [ a ], the acrylate resin-containing composition [ B ], the maleimide compound-containing composition [ C ] and the silicone-containing composition [ D ] having a specific particle diameter. Examples of the crosslinking agent include an organic peroxide, a phenol resin crosslinking agent, sulfur, a sulfur compound, p-benzoquinone, a p-benzoquinone dioxime derivative, a bismaleimide compound, an epoxy compound, a silane compound, an amino resin, a polyol crosslinking agent, polyamine, a triazine compound, and a metal soap, and particularly, an organic peroxide and a phenol resin crosslinking agent are preferable.
The organic peroxide is preferably used in such a manner that the melting point of the polyolefin resin used is denoted as T m 1 minute half-life temperature T of organic peroxide h At T m ≤T h ≤T m +50 (. Degree. C.) range.If T is h Less than T m If the melt kneading of the rubber and the olefin resin is not sufficiently performed, the crosslinking reaction starts, and the rubber elasticity and mechanical strength of the thermoplastic elastomer composition may be reduced. On the other hand, if T h Exceeds T m +50 (. Degree. C.), the crosslinking temperature is too low to cause insufficient crosslinking, and the rubber elasticity and mechanical strength of the thermoplastic elastomer composition tend to decrease.
Examples of the organic peroxide include 1,3-di (t-butylperoxyisopropyl) benzene, 2,5-dimethyl-2,5-di (t-butylperoxy) hexyne-3, 25-dimethyl-25-di (t-butylperoxy) hexene-3, 2,5-dimethyl-2,5-di (t-butylperoxy) hexane, 2,2-di (t-butylperoxy) -p-isopropylbenzene, dicumyl peroxide, di-t-butyl peroxide, p-menthane oxide, 1,1-di (t-butylperoxy) -3265 zxft-trimethylcyclohexane, dilauroyl peroxide, diacetyl peroxide, t-butyl peroxybenzoate, 3579 zxft-benzoyl peroxide, p-chlorobenzoyl peroxide, benzoyl peroxide, di (t-butylperoxy) peroxybenzoate, 3265 zxft-butyl peroxyisopropyl 3525-di (t-butylperoxy) valerate, and the like. Among them, those having a high decomposition temperature such as 1,3-bis (t-butylperoxyisopropyl) benzene, 2,5-dimethyl-2,5-bis (t-butylperoxy) hexyne-3, 2,5-dimethyl-2,5-bis (t-butylperoxy) hexane are preferable. Only 1 kind of them may be used, or 2 or more kinds may be used in combination.
Further, when an organic peroxide is used as the crosslinking agent, the crosslinking reaction can be stabilized by using a crosslinking assistant in combination, and particularly, a uniform crosslinked structure can be formed. Examples of the crosslinking assistant include sulfur compounds such as sulfur or powdered sulfur, colloidal sulfur, precipitated sulfur, insoluble sulfur, surface-treated sulfur and dipentamethylenethiuram tetrasulfide, oxime compounds such as hydroquinone oxime and p, p ' -dibenzoylquinone oxime, ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, diallyl phthalate, tetraallyloxyethane, triallyl cyanurate, N ' -m-xylylenebismaleimide, N ' -tolylbismaleimide, maleic anhydride, divinylbenzene and zinc di (meth) acrylate. Among them, p '-dibenzoylquinone oxime, N' -m-phenylenedimaleimide and divinylbenzene are preferable. Only 1 kind of them may be used, or 2 or more kinds may be used in combination. Among these crosslinking aids, N' -m-phenylenedimaleimide acts as a crosslinking agent and can be used as a crosslinking agent.
When an organic peroxide is used as the crosslinking agent, the amount thereof is preferably 0.05 to 10 parts by mass, more preferably 0.1 to 5 parts by mass, per 100 parts by mass of the polymer composition. If the content of the organic peroxide is less than 0.05 part by mass, the degree of crosslinking is insufficient, and the rubber elasticity and mechanical strength of the thermoplastic elastomer composition may be lowered. On the other hand, if it exceeds 10 parts by mass, the degree of crosslinking is excessively increased, and the moldability tends to be deteriorated or the mechanical properties tend to be lowered.
The amount of the crosslinking assistant used when an organic peroxide is used as the crosslinking agent is preferably 10 parts by mass or less, more preferably 0.2 to 5 parts by mass, per 100 parts by mass of the polymer composition. If the content of the crosslinking assistant exceeds 10 parts by weight, the degree of crosslinking becomes too high, and the moldability tends to deteriorate or the mechanical properties tend to deteriorate.
Further, examples of the phenol-based crosslinking agent include a para-substituted phenol-based compound represented by the following general formula (I), an ortho-substituted phenol-aldehyde condensate, a meta-substituted phenol-aldehyde condensate, a bromoalkylphenol-aldehyde condensate, and the like, and the para-substituted phenol-based compound is particularly preferable.
Wherein n is an integer of 0 to 10, X is a hydroxyl group, a haloalkyl group or a halogen atom, and R is a saturated hydrocarbon group having 1 to 15 carbon atoms.
The para-substituted phenol compound is obtained by a condensation reaction of a para-substituted phenol and an aldehyde (preferably, formaldehyde) in the presence of a basic catalyst.
When a phenol-based crosslinking agent is used as the crosslinking agent, the amount is preferably 0.2 to 10 parts by mass, more preferably 0.5 to 5 parts by mass, per 100 parts by mass of the polymer composition. If the amount of the phenol-based crosslinking agent is less than 0.2 parts by mass, the degree of crosslinking is insufficient, and the rubber elasticity and mechanical strength of the thermoplastic elastomer composition may be deteriorated. On the other hand, if it exceeds 10 parts by mass, the moldability of the thermoplastic elastomer tends to deteriorate.
These phenol crosslinking agents may be used alone, but a crosslinking accelerator may be used in combination for adjusting the crosslinking rate. Examples of the crosslinking accelerator include metal halides such as tin dichloride and iron trichloride, and organic halides such as chlorinated polypropylene, brominated butyl rubber and chloroprene rubber.
In addition to the crosslinking accelerator, it is more preferable to use a metal oxide such as zinc oxide or a dispersant such as stearic acid.
[6] Other various additives
The rubber particle composition [ a ] having a specific particle diameter, the acrylate resin-containing composition [ B ], the maleimide compound-containing composition [ C ] and the polysiloxane-containing composition [ D ] may contain, as required, various other additives, for example, a lubricant, an antioxidant, a heat stabilizer, a weather resistant agent, a metal inactivator, an ultraviolet absorber, a light stabilizer, a stabilizer such as a copper harm inhibitor, a processing aid, a mold release agent, a flame retardant, an antistatic agent, an antibacterial/antifungal agent, a dispersant, a plasticizer, a crystal nucleating agent, a thickener, a foaming aid, titanium oxide, a colorant such as carbon black, metal powder such as ferrite, inorganic fiber such as glass fiber and metal fiber, organic fiber such as carbon fiber and aramid fiber, composite fiber, inorganic whisker such as calcium titanate whisker, glass bead, glass flake, asbestos, mica, calcium carbonate, magnesium carbonate, clay, kaolin, talc, wet silica, dry silica, calcium silicate, hydrotalcite, diatomaceous earth, graphite, light stone, cork powder, cotton linter, cork powder, barium sulfate filler, silicic acid filler, polymer beads, natural synthetic beads, a mixture of these, wax, a mixture of these, a low molecular weight polyolefin powder, a low molecular weight rubber powder, a silicone oil, and the like.
[7] Method for producing thermoplastic elastomer composition
The rubber particle-containing composition [ a ], the acrylate resin-containing composition [ B ], the maleimide compound-containing composition [ C ] and the polysiloxane-containing composition [ D ] (hereinafter, these compositions [ a ] to [ D ] are collectively referred to as "thermoplastic elastomer compositions") having a specific particle diameter can be produced by the same method.
(1) Method for manufacturing using batch type internal mixer and continuous extruder
The thermoplastic elastomer composition can be produced by the following method: a polymer composition containing a rubber and a polyolefin resin, at least a part of a crosslinking agent, and other components added as needed are mixed and dispersed using a batch type internal mixer to prepare a kneaded product, and then the kneaded product is dynamically crosslinked using a continuous extruder such as a twin-screw extruder. Further, the present invention can be produced by the following method: a polymer composition containing a rubber and a polyolefin resin, and other components not containing a crosslinking agent added as needed are mixed and dispersed using a batch type internal mixer to prepare a kneaded product, and then the kneaded product, the crosslinking agent, and other components added as needed are dynamically crosslinked by a continuous extruder such as a twin-screw extruder. The term "dynamic crosslinking" means that crosslinking is performed under both the application of a shearing force and the application of heat. Further, the mixing step for mixing and dispersing and the crosslinking step for dynamic crosslinking may be continuously performed.
(1) Batch type closed mixing mill
Examples of the internal mixer include a pressure kneader, a banbury kneader, and a brabender kneader.
When the polymer composition is mixed and dispersed using an internal mixer, the method for supplying the softening agent is not particularly limited, and the softening agent may be previously blended in the polymer composition or may be supplied to the internal mixer separately from the polymer composition. Further, the softener may be supplied after mixing and dispersing the polymer composition, or oil-extended rubber may be used.
In particular, in the production of the polysiloxane-containing composition [ D ], when the polymer composition is melt-kneaded by using an internal mixer except for the crosslinking agent, the unmodified and modified polyorgano-cinnamyl oxide and the softening agent may be previously mixed with the polymer composition, or may be supplied to the internal mixer without being previously mixed, and the order is not particularly limited. The polymer composition may be melt-kneaded and then charged with the unmodified polyorganomyroxane, the modified polyorganomyroxane, and the softener, or may be initially charged into a closed kneader together with the polymer composition and melt-kneaded, and the order is not particularly limited.
In addition, in order to charge the kneaded material prepared by the internal mixer into the continuous extruder, it is preferable to previously cut the kneaded material into small pieces. The method for producing the chips is not particularly limited, and the chips may be processed into a pellet form, or the chips may be processed into a pellet form by a plate granulator, and the kneaded product may be chopped.
(2) Continuous extruder
The continuous extruder is not particularly limited, and a single screw extruder, a twin rotor type extruder, or the like can be used, but a twin screw extruder is preferable, and a twin screw extruder having an L/D (ratio of the screw effective length L to the outer diameter D) of preferably 30 or more, more preferably 36 to 60 is particularly preferable. As the twin-screw extruder, for example, any twin-screw extruder having 2 screws engaged or not engaged can be used. More preferably, the twin-screw extruder has 2 screws rotating in the same direction and meshing with each other. Examples of such a twin-screw extruder include GT manufactured by Kuibei corporation, KTX manufactured by Kobe Steel works, TEX manufactured by Nippon Steel works, TEM manufactured by Toshiba mechanical Co., ltd., and ZSK (both trademarks) manufactured by Warner Inc.
In the case of producing a thermoplastic elastomer composition by dynamic crosslinking using a continuous extruder, the method of supplying the crosslinking agent may be, for example, a method of mixing the crosslinking agent with a kneaded product subjected to the crosslinking reaction in advance using a blender and supplying the crosslinking agent to the continuous extruder, or a method of supplying the crosslinking agent from an opening of a cylinder provided between a hopper and a die, and the like, and is not particularly limited.
The method of supplying the filler and the like is also not particularly limited, and may be added to an internal mixer, may be added to a continuous extruder, or may be supplied to both of them.
The conditions for dynamic crosslinking vary depending on the melting point of the olefin resin used, the type of crosslinking agent, and the like, but the treatment temperature is preferably the melting point (T) of the olefin resin m ) Above and below 250 ℃. If the melting temperature of the olefin-based resin is lower than the melting temperature of the olefin-based resin, the rubber and the olefin-based resin cannot be sufficiently melt-kneaded, resulting in insufficient kneading and the thermoplastic elastomer may sometimes be usedThe mechanical properties of the composition are reduced. On the other hand, if the temperature exceeds 250 ℃, deterioration of the rubber occurs, and the mechanical properties of the thermoplastic elastomer composition tend to be lowered.
(2) Method for producing a continuous counter-rotating twin-screw kneader and co-rotating twin-screw extruder
The thermoplastic elastomer composition can be produced by the following method: a polymer composition containing a rubber and an olefinic resin is supplied from a raw material introducing part of a continuous counter-rotating twin-screw kneader provided upstream and an extruding apparatus provided downstream in series with a counter-rotating twin-screw extruder, and the raw material composition is mixed and dispersed by the continuous counter-rotating twin-screw kneader, and dynamic crosslinking is performed by the counter-rotating twin-screw extruder while maintaining the temperature of the kneaded material at the outlet of the continuous counter-rotating twin-screw kneader at 250 ℃ or lower.
In this production method, melt kneading of the polymer composition and mixing and dispersion of the crosslinking agent are carried out in a continuous counter-rotating twin-screw kneader, and the kneaded product controlled to a certain temperature or lower is fed to a co-rotating twin-screw extruder to complete the dynamic crosslinking reaction. The temperature of the kneaded product at the outlet of the continuous counter-rotating twin-screw kneader differs depending on the olefin-based resin and the crosslinking agent used, but it is necessary to control the temperature to a temperature at which the melt kneading of the polymer composition can be performed in a state in which the crosslinking reaction in the continuous counter-rotating twin-screw kneader is suppressed, and the temperature is kept at 250 ℃ or lower in order to prevent the deterioration of the rubber and the olefin-based resin contained in the polymer composition.
Further, the thermoplastic elastomer composition can be produced by the following method: the raw material is introduced from a continuous counter-rotating twin-screw kneader disposed upstream and an extrusion apparatus in which a downstream co-rotating twin-screw extruder is disposed in seriesA polymer composition containing rubber, olefin resin and organic peroxide is supplied to the inlet, the raw material composition is mixed and dispersed by a continuous counter-rotating twin-screw kneader, and the temperature t of the kneaded material at the outlet of the continuous counter-rotating twin-screw kneader is controlled a Is controlled at T h -30≤t a ≤T h +30, dynamic crosslinking with a co-rotating twin-screw extruder, wherein the melting point of the olefin resin is denoted as T m The 1 minute half-life temperature of the organic peroxide is T h When the organic peroxide satisfies T m ≤T h ≤T m +50(℃)。
In this production method, melt kneading of the polymer composition and mixing and dispersion of the crosslinking agent are carried out in a continuous counter-rotating twin-screw kneader, and the kneaded product controlled to a certain temperature or lower is fed to a co-rotating twin-screw extruder to complete the dynamic crosslinking reaction. Temperature t of kneaded material at outlet of continuous counter-rotating twin-screw kneader a The melt kneading of the polymer composition is carried out at a temperature which is controlled so that the crosslinking reaction in the continuous counter-rotating twin-screw kneader is suppressed, although the melt kneading varies depending on the olefin resin and the crosslinking agent used. Therefore, the temperature must be not higher than the temperature at which the crosslinking reaction can be suppressed. When at least an organic peroxide is used as the crosslinking agent, the half-life temperature in 1 minute is denoted as T h It must be at T h -30≤t a ≤T h +30 (. Degree. C.) (preferably T) h -20 ≤t a ≤T h +25 (. Degree. C.), more preferably T h -10≤t a ≤T h +20 (. Degree. C.)). If the temperature t of the kneaded mixture at the outlet of the continuous counter-rotating twin-screw kneader is set a Exceeds T h +30 ℃ since the crosslinking reaction proceeded vigorously in the continuous counter-rotating twin-screw kneaderIn the state of (3) or in the state of the completion of the crosslinking reaction, the kneaded product is fed to a co-rotating twin-screw extruder, so that the thermoplastic elastomer composition has mechanical propertiesAnd the moldability is deteriorated. On the other hand, if the temperature t is a Deficiency of T h When the temperature is 30 ℃ below zero, melt kneading is insufficient, and the mechanical strength of the thermoplastic elastomer composition tends to be lowered.
Examples of the continuous counter-direction twin-screw kneader include CIM manufactured by Nippon Steel works, and Mixtron FCM/NCM/LCM/ACM manufactured by Shen Steel works (both trade names).
The co-rotating twin-screw extruder is not limited, and in particular, a twin-screw extruder having an L/D (ratio of the effective screw length L to the outer diameter D) of 30 or more, more preferably 36 to 60 is preferably used.
The method for supplying the crosslinking agent is not particularly limited, and it may be supplied by mixing in the polymer composition or by supplying in the mixing and dispersing step, and specifically includes: (1) a method of mixing the polymer composition to be subjected to the crosslinking reaction with a blender and supplying the mixture to a continuous counter-rotating twin-screw kneader, and (2) a method of supplying the mixture from a hopper of the continuous counter-rotating twin-screw kneader. Further, (3) the kneading apparatus can be supplied from a barrel opening part provided between a hopper of the continuous counter-rotating twin-screw kneader and an outlet of the kneader.
When the thermoplastic elastomer composition is produced in a coupled apparatus, the method of supplying the softener, filler and the like is not particularly limited, and examples thereof include (1) a method of mixing the rubber and the olefinic resin to be supplied for crosslinking reaction in advance using a blending mixer and supplying the mixture to a continuous counter-rotating twin-screw kneader, (2) a method of supplying the mixture from a hopper of the continuous counter-rotating twin-screw kneader, a co-rotating twin-screw extruder or both, (3) a method of supplying the mixture from a barrel opening provided between the hopper and a die of the continuous counter-rotating twin-screw kneader, the co-rotating twin-screw extruder or both, and (4) a method of supplying the mixture to the co-rotating twin-screw extruder using a side feeder.
In particular, in the production of the polysiloxane-containing composition [ D ], when the thermoplastic elastomer composition is produced by a continuous extruder, as a method for supplying the unmodified and modified organopolysiloxane, in the case of a powder, a method in which the polymer composition to be subjected to the crosslinking reaction is mixed in advance with a mixer and supplied to a continuous extruder; when it is a liquid, it may be a method of previously mixing with the polymer composition to be supplied for the crosslinking reaction using a mixer, supplying to a continuous extruder, or a method of supplying from a barrel opening part provided between a hopper and a die.
As a method for granulating the thermoplastic elastomer composition produced by these methods, a known granulating apparatus such as strand cut (strand cut), underwater cut, spray cut, and thermal cut can be used, and is not particularly limited.
Best mode for carrying out the invention
The present invention will be specifically described below with reference to examples. The present invention is not limited to the following examples as long as the gist thereof is not exceeded.
1. Examples of the composition [ A ] containing rubber particles having a specific particle diameter
The rubber, crystalline olefin resin, amorphous olefin resin, softener, crosslinking agent, and the like used as raw materials are as follows.
[1] Raw materials
(1) Rubber composition
(1) EPDM (a 11): an ethylene/propylene/5-ethylidene-2-norbornene terpolymer rubber having an ethylene content of 66 mass%, a 5-ethylidene-2-norbornene content of 4.5 mass%, an intrinsic viscosity measured at 135 ℃ in a decalin solvent of 4.7dl/g, and a mineral Oil softener (trade name: diana Process Oil PW-380, idemitsu Kosan Co., ltd., manufactured by Ltd.) in an amount of 50 mass%;
(2) EPDM (a 12): an ethylene/propylene/5-ethylidene-2-norbornene terpolymer rubber having an ethylene content of 66 mass%, a 5-ethylidene-2-norbornene content of 4.5 mass%, an intrinsic viscosity measured at 135 ℃ in a decalin solvent of 3.8dl/g, and a mineral Oil softener (trade name: diana Process Oil PW-380, idemitsu Kosan Co., ltd.) in an amount of 40 mass%;
(3) EPDM (a 13): an ethylene/propylene/5-ethylidene-2-norbornene terpolymer rubber having an ethylene content of 66 mass%, a 5-ethylidene-2-norbornene content of 4.5 mass%, an intrinsic viscosity measured at 135 ℃ in a decalin solvent of 2.8dl/g, and a mineral Oil softener (trade name: diana Process Oil PW-380, idemitsu Kosan Co., ltd.) in an amount of 20 mass%.
(2) Olefin resin
(1) Crystalline olefin resin (b 11): propylene polymer having a density of 0.90g/cm 3 An MFR (temperature 230 ℃ C., load weight 2.16 kg) of 5g/10 min (trade name: novateceppma 4, manufactured by Nippon Polychemco.);
(2) crystalline olefin resin (b 12): propylene/ethylene random copolymer having a density of 0.90g/cm 3 An MFR (temperature 230 ℃ C., load weight 2.16 kg) of 3g/10 min (trade name: novateecPPBC 5CW, manufactured by Nippon PolychemCo., ltd.);
(3) crystalline olefin resin (b 13): propylene/ethylene random copolymer having a density of 0.90g/cm 3 An MFR (temperature 230 ℃ C., load weight 2.16 kg) of 23g/10 min (trade name: novatecpfl 25R, manufactured by Nippon PolychemCo., ltd.);
(4) non-crystalline olefin resin (b 2): a propylene/1-butene amorphous copolymer having a propylene content of 71 mol%, a melt viscosity of 8Pas and a density of 0.87g/cm 3 And Mn of 6500 (trade name: APAOUT2780, manufactured by Ube industries Ltd.).
(4) Crosslinking agent
(1) Crosslinking agent (h 1): 2,5-dimethyl-2,5-di (t-butylperoxy) hexane-3,1 minute half life temperature is 194.3 ℃ (trade name: perhexa 25B-40, manufactured by NOF Corp.);
(2) crosslinking agent (h 2): 2,5-dimethyl-2,5-di (t-butylperoxy) hexyne-3, a1 minute half-life temperature of 179.8 ℃ (trade name: perhexa 25B-40, manufactured by NOF Corp.);
(3) crosslinking agent (h 3): divinylbenzene (purity 55%) (manufactured by Sankyo Kasei co.).
(5) Anti-aging agent (j 1): under the trade name Irganox 1010 (manufactured by Ciba specialty Chemicals Co.).
(6) Lubricant (silicone oil (k 1)): polydimethylsiloxane (trade name: SH-200 (100 cSt), manufactured by Toray Dow Corning Silicone Ltd.).
[2] Production of composition [ A ] containing rubber particles having specific particle diameter
(1) Production method Using closed Mixer and continuous extruder (production method 1)
Examples 1,3 and 5
According to the formulation shown in Table 1, a raw material composition containing no crosslinking agent was charged into a pressure kneader (manufactured by Moriyama Company Ltd.) heated to 150 ℃ and kneaded at 40rpm for 15 minutes until the components were uniformly dispersed. Thereafter, the composition in a molten state was granulated using a feeder-ruder (manufactured by Moriyama Company Ltd.) set at 180 ℃ and 40rpm. To the obtained pellets were added the crosslinking agents (h 1) to (h 3) in the compounding ratios shown in Table 1, and the mixture was mixed for 30 seconds using a Henshel mixer. Then, the mixture was fed to a twin-screw extruder (corotating non-intermeshing screw, L/D (outer diameter 45mm, ratio of effective screw length L to outer diameter D) =38.5, product name "PCM-45", manufactured by Ikegai Ltd.) by a gravimetric feeder (product name: KF-C88, manufactured by Kubota Co., ltd.) at a discharge rate of 40kg/hr, and extruded while being subjected to dynamic heat treatment at a set temperature of 200 ℃ and at a screw rotation rate of 300rp m, to obtain a composition [ A ] containing rubber particles having a specific particle diameter.
(2) Manufacturing method using two connecting devices of continuous counter-rotating twin-screw kneader and co-rotating twin-screw extruder (manufacturing method 2)
Examples 2,4 and 6 and comparative example 4
The raw material compositions in the compounding ratios shown in table 1 were mixed for 30 seconds using a henschel mixer. Then, the mixed raw material composition was fed from a raw material inlet of a continuous counter-rotating twin-screw mixer using 2 gravimetric feeders (manufactured by Kubota co., trademark) at a discharge rate of 40kg/hr to an apparatus in which a counter-rotating twin-screw extruder (a counter-rotating intermeshing type 2 rotor, L/D =10, a trademark "Mixtron LCM", manufactured by Kobe Steel ltd., trademark "TEX 44SS", manufactured by Japan Steel Work co., trademark) was connected to the rear of the continuous counter-rotating twin-screw mixer, and melt-kneading was performed with a barrel temperature of 80 ℃, a rotor revolution of 350 to 800rpm, a gate opening of 1 to 40%, and a hole opening of 100%. Then, the molten composition was fed to a co-rotating twin-screw extruder directly connected to a continuous counter-rotating twin-screw kneader, and a crosslinking reaction by dynamic heat treatment was carried out at a barrel temperature of 200 ℃ and a screw revolution of 400rpm to produce a composition [ A ] containing rubber particles having a specific particle diameter. Further, a mineral oil-based softener was pressed from the 1 st barrel of the mixing rotor of the continuous counter-rotating twin-screw kneader.
(3) Manufacturing method using continuous extruder (manufacturing method 3)
Comparative examples 1 to 3
After mixing the raw material compositions in the compounding ratios shown in table 1 for 30 seconds using a Henshel mixer, rubber and olefin resins mixed with various additives were fed into a twin-screw extruder (a non-intermeshing screw in the same direction, L/D =38.5, trade name "P CM-45", manufactured by ikegai ltd.) at a discharge rate of 40kg/hr using 2 gravimetric feeders (manufactured by KF-C88, kubota co., trade name), and extruded while performing dynamic heat treatment at a barrel temperature of 200 ℃ and a screw revolution of 300rpm, to obtain a composition [ a ] containing rubber particles having a specific particle diameter.
In addition, in the production by these three methods, the temperature of the kneaded material at the outlet of the continuous counter-rotating twin-screw mixer and the temperature of the kneaded material at the outlet of the Co-rotating twin-screw extruder were measured by using a non-contact thermometer (trade name: PT-3LF, manufactured by Optex Co.).
[3] Evaluation of composition [ A ] containing rubber particles having specific particle diameter
In order to evaluate the composition [ a ] containing rubber particles having a specific particle diameter obtained as described above, the following measurements were carried out.
(1) Melt flow index (MFR): measured at 230 ℃ under a load of 10 kg.
(2) Hardness: according to JIS K6253.
(3) Tensile break strength and tensile break elongation: according to JIS K6251.
(4) Compression set: according to JIS K6262.
(5) Extrusion processability: the plate extrusion was carried out using a Labplastmill extruder (outer diameter =20mm, L/D =25, manufactured by Toyo Seiki co.) under the following conditions (die width 25mm, thickness 1.5 mm), and the appearance thereof was visually evaluated. The surfaces were smooth and edged and were marked with "O" and were all marked with "X".
(setting of Labplastmill extruder)
Barrel C1:180 deg.C
Barrel C2:190 deg.C
Barrel C3:210 deg.C
Die opening: 205 deg.C
Screw revolution: 40rpm
(6) Granules
As an index of melt-kneading property, "pellets" of the composition [ A ] containing rubber particles having a specific particle diameter were measured. The term "pellet" means a visually large gel, an unmelted olefin resin, or fish eyes, which is generated when the rubber and olefin resin are not sufficiently melt-kneaded during the production of the composition [ a ] containing rubber particles having a specific particle diameter and the dynamic treatment is carried out in the presence of a crosslinking agent. The evaluation of "pellets" was carried out by using an electric heating type 6 inch Roll (manufactured by Kansai Roll Co., ltd.), forming the composition [ A ] containing rubber particles having a specific particle diameter into a sheet at a temperature of 180 ℃ and a Roll pitch of 0.5mm, and visually counting the "pellets" existing on the sheet having a size of 20X 20 cm. The judgment criteria are as follows.
0 to less than 30: the number is very small; 30-less than 100: less; more than 100: multiple component
(7) Gel fraction: measured according to the method described previously.
(8) Taking a TEM photograph
A TEM photograph of the composition [ A ] containing rubber particles having a specific particle diameter was obtained by slicing the composition [ A ] containing rubber particles having a specific particle diameter with a cryo-microtome, dyeing the slices with ruthenium tetroxide, and photographing the slices at an magnification of 2000 times with a transmission electron microscope (trade name: H-7500, manufactured by Hitachi Ltd.).
In Image analysis of TEM photographs, the area of the crosslinked rubber particles was determined using Image-Pro Plus Ver.4.0for Windows (manufactured by MediaCybernetics) as Image analysis software.
The number average particle diameter dn and the volume average particle diameter dv are determined from the area of the cross-linked rubber particles obtained by the above formula, and dv/dn is calculated.
TABLE 1
Oil extended rubber Intrinsic viscosity (dl/g) Content of mineral oil softener (% by mass) Examples Comparative example
1 2 3 4 5 6 1 2 3 4
Oil-filled EPDM (a 11) 4.7 50 - - - - 75(375) 75(375) - - 75(375) -
Oil-free EPDM (a 12) 3.8 40 80(48) 80(48) - - - - 80(48) - - 80(48)
Oil-filled EPDM (a 13) 2.8 20 - - 75(60) 75(60) - - - 75(60) - -
Crystalline olefin resin (b 11) - - 25 25 - - - 25 - -
Crystalline olefin resin (b 12) 20 20 - - - - 20 - - 20
Crystalline olefin resin (b 13) - - - - 7 7 - - 7 -
Amorphous olefin resin (b 2) - - - - 7 7 - - 7 -
After addition of mineral oil softener (g 1) - - - - 11 11 - - 11 -
Content of softener (parts by mass) when rubber is 100 parts by mass 66.7 66.7 25 25 129 129 66.7 25 129 66.7
The total mass of the rubber and the olefin resin is 100 Content in parts by weight (parts by mass) EPDM 70.6 70.6 70.6 70.6 72.8 72.8 70.6 70.6 70.6 70.6
Total of olefin resins 29.4 29.4 29.4 29.4 27.2 27.2 29.4 29.4 27.2 29.4
Crosslinking agent (h 1) 1 1 - - - - - - - 1
Crosslinking agent (h 2) - - 0.7 0.7 1 1 - 0.7 1 -
Crosslinking agent (h 3) 1.2 1.2 0.7 0.7 1.2 1.2 1.2 0.7 1.2 1.2
The total weight (parts by mass) of the crosslinking agent per 100 parts by mass of the total of the rubber and the olefin-based resin 3.2 3.2 1.6 1.6 4.3 4.3 1.8 1.6 4.3 3.2
Anti-aging agent (j 1) 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1
Silicone oil (k 1) 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2
Manufacturing method 1 2 1 2 1 2 3 3 3 2
Gate opening (%) - 40 - 15 - 1 - - - 10
Opening of hole (%)% of continuously counter-rotating twin-shaft kneading machine - 100 - 100 - 100 - - - 30
Number of revolutions of rotor (rpm) of continuous counter-rotating twin-shaft kneading machine - 750 - 350 - 800 - - - 500
Temperature (. Degree. C.) of the kneaded product at the outlet of the continuous counter-rotating twin-screw kneader - 194 - 196 - 169 - - - 261
Temperature (. Degree. C.) of kneaded product at outlet of co-rotating twin-screw extruder 225 222 266 275 251 247 246 273 244 251
<Physical Properties>MFR (g/10min) 25 10 17 10 75 120 46 25 143 5
Hardness (Shore A hardness) 73 75 86 87 49 50 73 87 49 75
Tensile breaking Strength (MPa) 8.1 9.9 9.8 9.9 3.9 43 7 9.2 3.2 5.4
Tensile elongation at break (% 600 640 650 670 620 650 590 630 600 530
Compression set (%) 38 34 45 49 38 33 45 56 40 39
Extrusion processability ○ ○ ○ ○ ○ ○ × × × ×
Granules Chinese character shao (a Chinese character of 'shao') Is rarely used A little bit Is rarely used Chinese character shao (a Chinese character of 'shao') A little bit Multiple purpose Multiple purpose Multiple purpose Multiple purpose
Gel fraction (%) 97.4 98.7 97.8 98.9 99.4 99.3 97.9 98.5 99.1 98.1
Image analysis result of TEM photograph Number average particle diameter dn (. Mu.m) 0.773 0.567 0.672 0.598 0.729 0.644 1.304 1.228 1.173 2.134
Volume average particle diameter dv (. Mu.m) 1.016 0.722 0.885 0.718 0.938 0.759 2.127 1.998 1.862 3.677
dv/dn 1314 1.273 1317 1.201 1.287 1.179 1.631 1.627 1.587 1.723
The EPDM content (parts by mass) is shown in parentheses in the column of the oil-extended EPDM.
[4] Effects of the embodiments
As can be seen from Table 1, the rubber particles having a specific particle diameter obtained by production method 1Compound [ A ]]The physical properties and extrusion processability of examples 1,3 and 5 were excellent, and the pellets in the molded article were small. Further, the composition [ A ] containing rubber particles having a specific particle diameter obtained by production method 2]In comparative example 4, the kneaded material temperature t at the outlet of the continuous counter-rotating twin-screw kneader was a Higher than 250 ℃ and inferior in extrusion processability. Further, a large number of particles were observed in the molded article, and the average particle diameter of the crosslinked rubber particles was large, and the dv/dn ratio was also high. On the other hand, in examples 2,4 and 6, the kneaded material temperature t at the outlet of the continuous counter-rotating twin-screw kneader was set to a Are all lower than 250 ℃ and, in addition, have a half-life temperature T of 1 min with the crosslinking agent h Relation T of h -30≤t a ≤T h +30 is true. Further, the extrusion processability was excellent, and the pellets on the molded article were small, and particularly in examples 2 and 4, the pellets were very small. Further, the number average particle diameter dn is preferably from 0.55 to 0.65. Mu.m, and the dy/dn ratio is preferably from 1.18 to 1.27.
Further, the composition [ A ] containing rubber particles having a specific particle diameter obtained by the production method 3 (comparative examples 1 to 3) was poor in extrusion processability, had many particles, had a large average particle diameter of the crosslinked rubber particles, and had a high dv/dn ratio.
2. Example of composition [ B ] containing acrylate resin
The rubber, crystalline olefin resin, amorphous olefin resin, softener, crosslinking agent, and the like used as raw materials are as follows.
[1] Starting materials
(1) Ethylene- α -olefin random copolymer rubber (a 11): an ethylene/propylene/5-ethylidene-2-norbornene terpolymer rubber having an ethylene content of 66 mass%, a 5-ethylidene-2-norbornene content of 4.5 mass%, an intrinsic viscosity [ eta ] =4.7dl/g measured in a decalin solvent at 135 ℃, and a mineral Oil softener (trade name: diana Process Oil PW-380, idemitsu Kosan Co., ltd.) content of 50 mass%.
(2) Olefin resin
(1) Crystalline olefin resin (b 1)3): propylene/ethylene random copolymer having a density of 0.90g/cm 3 An MFR (temperature 230 ℃ C., load weight 2.16 kg) of 23g/10 min (trade name: novatecepPFL 25R, manufactured by Nippon PolychemCo., ltd.);
(2) non-crystalline olefin resin (b 2): a propylene/1-butene amorphous copolymer having a propylene content of 71 mol%, a melt viscosity of 8Pas and a density of 0.87g/cm 3 And Mn of 6500 (trade name: APAOUT2780, manufactured by Ube industries Ltd.).
(3) (meth) acrylate resin (c 1): methyl methacrylate/methyl acrylate copolymer having a density of 1.19g/cm 3 The MFR (temperature 230 ℃ C., load weight 3.8 kg) was 8g/10min (trade name: parapetG, manufactured by Kuraray Ltd.).
(4) Hydrogenated diene Polymer (d 1)
The hydrogenated diene polymer was synthesized in the following manner. Further, various measurements were carried out by the following methods.
(1) Vinyl aromatic compound content: at 679cm -1 The absorption of phenyl group (2) is measured by infrared analysis.
(2) Vinyl bond content of conjugated diene: calculated by the Morello method using infrared analysis.
(3) Hydrogenation rate: using carbon tetrachloride as solvent, and reacting at 90MHz, 1 H-NMR spectrum was calculated.
(4) Weight average molecular weight: the molecular weight distribution was determined in terms of polystyrene using tetrahydrofuran as a solvent and gel permeation gas chromatography (GPC) at 38 ℃.
Method for synthesizing hydrogenated diene polymer
2.5kg of cyclohexane, 15g of tetrahydrofuran, 110g of styrene (component A), and 0.55g of n-butyllithium were charged in a 5-liter autoclave, and polymerization was carried out at 50 ℃ until the polymerization conversion rate became 98% or more. Thereafter, 220g of 1,3-butadiene (block B component) was added to the solution to polymerize the solution until the polymerization conversion rate reached 98% or more, and 110g of styrene (block A component) was added to the solution to polymerize the solution until the polymerization conversion rate reached 100%.
After completion of the polymerization, 0.33g of n-butyllithium, 0.61g of t-hydroxy-4-methyl-2-pentanone, 0.21g of bis (cyclopentadienyl) titanium dichloride and 0.76g of diethylaluminum chloride were added while maintaining the reaction solution at 70 ℃ under a hydrogen pressure of 10kg/cm 2 Then, the reaction was carried out for 1 hour to carry out hydrogenation. The reaction solution was put into a large amount of methanol and mixed, and the precipitated solid matter was recovered and dried to obtain a block copolymer. The hydrogenated diene polymer (d 1) was an A-B-A type, the hydrogenation rate was 95%, the butadiene unit content in the block B was 1,2-vinyl bond content was 80%, the mass ratio of the block A/the block B was 50/50, and the weight-average molecular weight was 100000.
(5) Crosslinking agent and crosslinking aid
(1) Crosslinking agent (h 1): 2,5-dimethyl-2,5-di (t-butylperoxy) hexane (trade name: perhexa 25B-40, manufactured by NOF Corp.);
(2) crosslinking aid (i 1): divinylbenzene (purity 55%), manufactured by Sankyo Kasei co;
(3) crosslinking assistant (i 2): under the trade name Vulnoc PM, manufactured by Ouchishinsko Chemical Industries Co., ltd.
(6) Other additives
(1) Antioxidant (j 1): under the trade name Irganox 1010, ciba Specialty Chemicals Co;
(2) silicone oil (k 1): a polydimethylsiloxane, available under the trade name SH-200 (100 cSt) manufactured by Toray Dow-Corning Silicone Co.
Example 7
[2] Production of composition [ B ] containing acrylate-based resin
80 parts by mass of an ethylene- α -olefin random copolymer rubber (a 11), 10 parts by mass of a crystalline olefin resin (b 13), 5 parts by mass of an amorphous olefin resin (b 2), 5 parts by mass of a (meth) acrylate resin (c 1), 2 parts by mass of a hydrogenated diene polymer (d 1), 0.1 part by mass of an antioxidant (j 1) and 0.2 part by mass of a silicone oil (k 1) were charged into a 10-liter twin-wrist pressure kneader (manufactured by Moriyama Company ltd) heated to 150 ℃ and kneaded at 40rp m for 20 minutes. Thereafter, the composition in a molten state was granulated by a feeder-ruder (manufactured by Moriyama Company Ltd.) set at 180 ℃ and 40rpm. Then, 0.5 part by mass of the crosslinking agent (h 2) and 0.5 part by mass of the crosslinking assistant (i 2) were added to the obtained pellets, and the mixture was mixed in a Henshel mixer for 30 seconds. Then, the mixture was extruded by a twin-screw extruder (trade name: PCM-45, manufactured by Ikegai Ltd., which is a homodromous full-intermeshing screw having a ratio L/D of the length L of the screw flight portion to the diameter D of the screw of 33.5) under conditions of 230 ℃ and 300rpm and a residence time of 2 minutes to produce an acrylate resin-containing composition [ B ] which is a granular dynamically crosslinkable thermoplastic elastomer composition.
[3] Preparation of test piece
The obtained thermoplastic elastomer pellets were injection-molded using an injection molding machine (trade name: N-100, manufactured by Japan Steel Work Co.) to prepare sheets having a thickness of 2mm, a length of 120mm and a width of 120mm, which were used for various evaluations.
[4] Evaluation of composition [ B ] containing acrylate-based resin
(1) Fluidity: the melt flow index was measured at a temperature of 230 ℃ under a load of 10kg and used as an index of fluidity.
(2) Hardness: the flexibility was measured according to JIS K6253.
(3) Tensile break strength and tensile break elongation: measured according to JIS K6251.
(4) Compression set: the rubber elasticity was measured at 70 ℃ for 22 hours in accordance with JIS K6262.
(5) Scratch resistance test (1): a metal claw (made of tungsten carbide) having a certain load weight (a load increased from 10g at the initial stage to 10g at a time) was scanned on the surface of the molded article using a Taber scratch tester (Taber scratch tester) manufactured by Toyo Seiki mfg. The greater the load weight value, the more excellent the scratch resistance.
(6) Scratch resistance test (2): the surface of the molded piece was scratched with the fingernail of a thumb, and the degree of scratching was visually judged.
The evaluation criteria are: a circle indicates no scratch, a triangle indicates a slight scratch, and a x indicates a deep scratch.
The measurement results are shown in table 2.
Examples 8 to 10 and comparative examples 5 to 10
In the same manner as in example 7, compositions [ B ] containing an acrylic resin in a granular form and test pieces were prepared in the compounding ratios shown in Table 2. The evaluation results of the obtained composition [ B ] containing an acrylate resin are shown in table 2.
TABLE 2
Examples Comparative example
7 8 9 10 5 6 7 8 9 10
Oil-extended EPDM (a 11) (mineral oil softener content 50 mass%) 80(40) 65(32.5) 70(35) 60(30) 70(35) 85(42.5) 80(40) 65(32.5) 70(35) 60(30)
Crystalline olefin resin (b13) 10 20 10 22 25 13 20 22 22 22
Amorphous olefin resin (b2) 5 - 5 3 5 2 - 3 3 3
(meth) acrylate resin (c1) 5 10 10 10 - - - 10 - 10
Hydrogenated diene polymer (d1) 2 5 5 5 - - - - 5 5
Rubber, olefin resin, (methyl) Acrylate resin and hydrogenated diene resin When the total amount of the polymers is 100 mass% Content (mass%) EPDM 64.5 48.1 53.8 42.9 53.8 73.9 66.7 48.1 53.8 42.9
Total of olefin resins 24.2 29.6 23.1 35.7 46.2 26.1 33.3 37 38.5 35.7
(meth) acrylate resin 8.1 14.8 15.4 14.3 - - - 14.9 - 14.3
Hydrogenated diene polymer 3.2 7.5 7.7 7.1 - - - - 7.7 7.1
Crosslinking agent (h1) 0.5 1 1 1 1 1 1 1 1 -
Crosslinking aid (i1) - 1.25 1.25 - 0 1.25 1.25 - - -
(i2) 0.5 - - 0.5 0.5 - - 0.5 0.5 -
Anti-aging agent (i1) 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1
Silicone oil (k1) 0.2 0.2 0.2 0.2 1.2 0.2 0.2 0.2 0.2 0.2
Fluidity of the resin MFR(190℃×21.1N)(g/10min) 3 10 4 32 35 2 6 30 39 14
Mechanical characteristics Hardness (Shore A hardness) 60 80 68 88 86 60 74 86 82 86
Tensile breaking Strength (MPa) 6.2 7 5.4 8.5 10.3 7 8.2 5.1 9.8 4.1
Tensile elongation at Break (%) 740 650 720 650 760 600 650 660 680 720
Compression set CS(701℃×22hr)(％) 45 51 50 61 51 58 40 65 61 90
Scratch resistance test ① 40 50 40 50 Less than 10 Less than 10 Less than 10 40 Less than 10 Less than 10
② ○ ○ ○ ○ × × × ○ × ×
The EPDM content (parts by mass) is shown in parentheses in the column of the oil-extended EPDM.
(6) Effects of the embodiments
As can be seen from table 2, examples 7 to 10 have excellent scratch resistance, mechanical properties, and rubber elasticity. In addition, comparative examples 5 to 7 did not contain a (meth) acrylate resin and a hydrogenated diene polymer, and therefore had poor scratch resistance. In addition, comparative example 8 does not contain a hydrogenated diene polymer, and therefore has poor mechanical properties. Further, comparative example 9 has poor scratch resistance because it does not contain a (meth) acrylate resin, and comparative example 10 has poor mechanical properties, rubber elasticity and scratch resistance because it is not crosslinked.
3. Composition containing maleimide compound [ C ]
The rubber, crystalline olefin resin, amorphous olefin resin, softener, crosslinking agent, and the like used as raw materials are as follows.
[1] Raw materials
(1) Ethylene-alpha-olefin random copolymer rubber
An Oil-extended ethylene- α -olefin random copolymer comprising an ethylene/propylene/5-ethylidene-2-norbornene terpolymer rubber (a 11) (containing 66 mass% of ethylene and 4.5 mass% of 5-ethylidene-2-norbornene in a decalin solvent, and having an intrinsic viscosity [ η ] =4.7dl/g measured at 135 ℃) and a mineral Oil softener (trade name: diana Process Oil PW-380, idemitsu Kosan Co., ltd., manufactured by Ltd.) in a weight ratio of 50/50.
(2) Olefin resin
(1) Crystalline olefin resin (b 13): propylene/ethylene random copolymer having a density of 0.90g/cm 3 An MFR (temperature 230 ℃ C., load weight 2.16 kg) of 23g/10 min (trade name: novatecpfl 25R, manufactured by Nippon PolychemCo., ltd.);
(2) non-crystalline olefin resin (b 2): a propylene/1-butene amorphous copolymer having a propylene content of 71 mol%, a melt viscosity of 8Pas and a density of 0.87g/cm 3 And Mn is 6500 (trade name: APAOUT2780", manufactured by Ube industries Ltd.).
(3) (meth) acrylate-based resin
Methyl methacrylate-methyl acrylate copolymer (c 1): the density was 1.19g/cm 3 The MFR (temperature 230 ℃ C., load weight 3.8 kg) was 8g/10min (trade name: parapetG, manufactured by Kuraray Ltd.).
(4) Hydrogenated diene Polymer (d 1)
The hydrogenated diene polymer was synthesized in the following manner. Further, various measurements were carried out by the following methods.
(1) Vinyl aromatic Compound content: at 679cm -1 The absorption of phenyl group (2) is measured by infrared analysis.
(2) Vinyl bond content of conjugated diene: calculated by the Morello method using infrared analysis.
(3) Hydrogenation rate: using carbon tetrachloride as solvent, and reacting at 90MHz, 1 H-NMR spectrum was calculated.
(4) Weight average molecular weight: the molecular weight distribution was determined in terms of polystyrene using tetrahydrofuran as a solvent and gel permeation gas chromatography (GPC) at 38 ℃.
Method for synthesizing hydrogenated diene polymer
2.5kg of cyclohexane, 15g of tetrahydrofuran, 110g of styrene (component A), and 0.55g of n-butyllithium were charged in a 5-liter autoclave, and polymerization was carried out at 50 ℃ until the polymerization conversion rate became 98% or more. Thereafter, 220g of 1,3-butadiene (block B component) was added to the solution to polymerize the solution until the polymerization conversion rate reached 98% or more, and 110g of styrene (block A component) was added to the solution to polymerize the solution until the polymerization conversion rate reached 100%.
After completion of the polymerization, 0.33g of n-butyllithium, 0.61g of t-hydroxy-4-methyl-2-pentanone, 0.21g of bis (cyclopentadienyl) titanium dichloride and 0.76g of diethylaluminum chloride were added while maintaining the reaction solution at 70 ℃ under a hydrogen pressure of 10kg/cm 2 Then, the reaction was carried out for 1 hour to carry out hydrogenation. The reaction solution was put into a large amount of methanol and mixed, and the precipitated solid matter was recovered and dried to obtain a block copolymer. The hydrogenated diene polymer (d 1) was of the A-B-A type, the hydrogenation rate was 95%, the content of 1,2-vinyl bonds in butadiene units of the block B was 80%, the mass ratio of the block A/block B was 50/50, and the weight-average molecular weight was 100000.
(5) Crosslinking agent
(1) Organic peroxide (h 1): 2,5-dimethyl-2,5-di (t-butylperoxy) hexane (trade name: perhexa 25B-40, manufactured by NOF Corp.);
(2) crosslinking aid (i 1): divinylbenzene (purity 55%), manufactured by Sankyo Kasei co.
(6) Maleimide compound (e 1): n, N' -m-phenylene bismaleimide (trade name: vulnoc PM, ouchishinsiko Chemical Industries Co., ltd., manufactured by Ltd.).
(7) Other additives
(1) Anti-aging agent (j 1): under the trade name Irganox 1010, ciba Specialty Chemicals Co;
(2) silicone oil: polydimethylsiloxane, trade name SH-200 (viscosity =100 cSt), manufactured by Toray Dow-Corning Silicone Co.
Example 11
[2] Production of Maleimide Compound-containing composition [ C ]
80 parts by mass of an ethylene- α -olefin random copolymer rubber (a 11), 15 parts by mass of a crystalline olefin resin (b 13), 5 parts by mass of an amorphous olefin resin (b 2), 0.5 part by mass of a maleimide compound (e 1) and 0.1 part by mass of an antioxidant (j 1) were put into a 10-liter twin-wrist pressure kneader (manufactured by Moriyama Company Ltd.) heated to 150 ℃ and kneaded at 40rpm for 20 minutes. Thereafter, the composition in a molten state was granulated by a feeder-ruder (manufactured by Moriyama Company Ltd.) set at 180 ℃ and 40rpm. Then, 1 part by mass of an organic peroxide (h 2) and 0.2 part by mass of a silicone oil (k 1) were mixed with the obtained pellets, and the mixture was mixed for 30 seconds by a Henshel mixer, and then extruded by a twin-screw extruder (trade name: PCM-45, manufactured by Ikegai Ltd., which is a homodromous fully-intermeshing screw, and the ratio L/D of the length L of the screw flight portion and the screw diameter D was 33.5) under dynamic heat treatment at 230 ℃ and 300rpm for 2 minutes of residence to obtain a maleimide compound-containing composition [ C ] which is a granular dynamic crosslinking thermoplastic elastomer composition.
[3] Preparation of test piece of Maleimide Compound-containing composition [ C ]
The obtained pellets of the maleimide compound-containing composition [ C ] were injection-molded using an injection molding machine (trade name: N-100, manufactured by Japan Steel Work Co., ltd.) to prepare sheets having a thickness of 2mm, a length of 120mm and a width of 120mm, which were used for various evaluations.
[4] Evaluation of Maleimide Compound-containing composition [ C ]
(1) Fluidity: the melt flow index was measured at a temperature of 230 ℃ under a load of 10kg, and used as an index of fluidity.
(2) Hardness: the flexibility was measured according to JIS K6253.
(3) Tensile break strength and tensile break elongation: measured according to JIS K6251.
(4) Compression set: the rubber elasticity was measured at 70 ℃ for 22 hours in accordance with JIS K6262.
(5) Injection weldability: using a test piece obtained by injection-welding a composition [ C ] containing a maleimide compound onto an olefin-based vulcanized rubber test piece, the test piece was bent at an angle of 180 ℃ from the joint between the composition [ C ] containing a maleimide compound and an adherend, and the peeling state of the adhesion interface after 10 repeated bending cycles was visually observed.
Evaluation criteria: the circle indicates no peeling, the triangle indicates that some peeling was found, and the x indicates that the peeling caused a break.
(1) Production of adherend
The following olefin-based vulcanized rubber sheets were produced as adherends and used for the tests.
100 parts by weight of an ethylene/propylene/5-ethylidene-2-norbornene terpolymer rubber (having an ethylene content of 72 mol%, a propylene content of 28 mol%, a Mooney viscosity of 92, an iodine value of 15, and a trade name of "EP 103A", manufactured by JSR Corp.), 145 parts by weight of Carbon black (trade name: seast 116, manufactured by Tokai Carbon Co., ltd.), 5 parts by weight of mineral Oil softener (g 1) (trade name: diana Process Oil PW380, manufactured by Idemitsu Kosan Co., manufactured by Ltd.), 5 parts by weight of active zinc white (manufactured by Sakai Chemical Industry Co., ltd.), 1 part by weight of stearic acid (manufactured by Asahi Denka Corp.), 1 part by weight of a processing aid (trade name: hitanol 1501, manufactured by Hitachi Chemical Co., ltd.), 1 part by weight of a release agent (trade name: structol 212, manufactured by Syland Zilaher Co., ltd.) and a plasticizer (polyethylene glycol) were kneaded for a mixing time of 50.5 rpm with a kneader (Steber) (Steber 1 part by weight, 3 rpm). Then, 10 parts by mass of a dehydrating agent (trade name: vesta PP, manufactured by Inoue Sekkai Kogyo Co., ltd.), a vulcanization accelerator (trade name: 1 part by mass, trade name PX:1 part by mass, trade name TT:0.5 part by mass, trade name D:1 part by mass, both manufactured by Ouchishinsko Chemical Industries Co., ltd.) and 2.2 parts by mass of sulfur were added, and the mixture was kneaded at 50 ℃ using a 6-inch open Roll (manufactured by Kansai Roll Co., ltd.). Then, the sheet was vulcanized at 170 ℃ for 10 minutes to obtain a 120mm square olefin-based vulcanized rubber sheet having a thickness of 2 mm. The sheet was punched out to a length of 60mm and a width of 50mm with a dumbbell cutter to prepare an adherend.
(2) Production of test piece having thermoplastic elastomer injection-welded to olefinic vulcanized rubber the above adherend (60 × 50 × 2 mm) was previously attached in a split mold (test piece shape of 120 × 120 × 2 mm) of an injection molding machine (N-100 model, manufactured by Jap an Steel Work co.), and each of the thermoplastic elastomer compositions obtained was injection-molded onto the adherend to produce a square plate (120 × 120 × 2 mm) having the thermoplastic elastomer composition and the olefinic vulcanized rubber (adherend) welded thereto.
(6) Scratch resistance tests (1) and (2): evaluation was carried out by the same method as described above. The same criteria apply.
The above results are shown in tables 3 and 4.
Examples 12 to 18 and comparative examples 11 to 15
In the same manner as in example 11, a granular maleimide compound-containing composition [ C ] was prepared in the blending ratios shown in tables 3 and 4, and test pieces were prepared. In addition, similarly to the containing maleimide compound composition [ C ] evaluation. The results are shown in tables 3 and 4.
TABLE 3
Examples Comparative example
11 12 13 14 15 11 12 13
Fitting for mixing Combination of Chinese herbs Oil-extended EPDM (a 11) (mineral oil softener content 50 mass%) 80(40) 80(40) 70(35) 75(375) 65(25) 80(40) 80(40) 80(40)
Crystalline olefin resin (b13) 15 15 25 20 10 15 15 15
Amorphous olefin resin (b2) 5 5 5 5 10 5 5 5
Maleimide compound (e1) 0.5 0.5 0.5 1 0.5 - 0.25 -
The content of maleimide compound per 100 parts by mass of the total of rubber, olefin resin and softener Volume (quality pan) 0.5 0.5 0.5 1 0.5 - 0.25 -
Post-addition of mineral oil-based softener (g1) - - - 15 - - -
Rubber, olefin resin and softener Content (by mass) of 100% by mass Volume%) EPDM 40 40 35 37.5 32.5 40 40 40
Total of olefinic resins 20 20 30 25 20 20 20 20
Mineral oil softener 40 40 35 375 475 40 40 40
Crosslinking agent (h1) 1 1 1 1 1 1 1 1
Crosslinking aid (h3) - - - - - - - 1.25
Anti-aging agent (1) 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1
Silicone oil (k1) 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2
Article (A) Property of (2) Fluidity of the resin MFR(230℃×5kg)(g/10min) 101 106 120 110 102 52 80 42
Mechanical characteristics Hardness (Shore A hardness) 67 65 8.6 78 49 67 68 57
Tensile breaking Strength (MPa) 6.5 6.2 9.7 8 35 5 6 8.8
Tensile elongation at Break (%) 740 570 680 640 660 810 780 720
Compression set CS(701℃×22hr)(％) 50 47 59 49 61 65 57 45
Injection weldability Flexural peeling Property 180 degree (visual) ○ ○ ○ ○ ○ × × ×
The EPDM content (parts by mass) is shown in parentheses in the column of the oil-extended EPDM.
TABLE 4
Examples Comparative example
16 17 18 14 15
Fitting for mixing Combination of Chinese herbs Oil-extended EPDM (a 11) (mineral oil softener content 50 mass%) 70(35) 80(40) 64(32) 70(35) 70(35)
Crystalline olefin resin (b13) 26 14 32 26 26
Amorphous olefin resin (b2) 4 6 4 4 4
Rubber, olefin resin and softener Content of 100 mass% (mass%) EPDM 35 40 32 35 35
Total of olefin resins 30 20 36 30 30
Mineral oil softener 35 40 32 35 35
Maleimide compound (e1) 0.6 1.2 0.6 - -
Maleimide compound in 100 parts by mass in total of rubber, olefin resin and softener Content of Compound (parts by mass) 0.6 1.2 0.6 - -
(meth) acrylate resin (c1) 12 12 12 12 12
(meth) propylene at a total of 100 parts by mass of the rubber, the olefin resin and the softener Content (parts by mass) of acid ester resin 12 12 12 12 12
Hydrogenated diene polymer (d1) 6(0.5) 6(0.5) 6(0.5) 6(0.5) 6(0.5)
Crosslinking agent (h1) 1.2 1.2 1.2 - 1.2
Crosslinking aid (h3) - - - - 1.5
Anti-aging agent (j1) 0.12 0.12 0.12 0.12 0.12
Silicone oil (k1) 0.24 0.24 0.24 0.24 0.24
Article (A) Property of (2) Fluidity of the resin MFR(230℃×5kg)(g/10min) 35 5 45 3 16
Mechanical characteristics Hardness (Shore A hardness) 88 70 92 89 88
Breaking Strength (MPa) 7.4 5.8 8 7.2 8
Elongation at Break (%) 850 730 600 1120 720
Compression set CS(701℃×22hr)(％) 59 55 66 88 56
Injection weldability Bending peelability, 180. (visual inspection) ○ ○ ○ × ×
Scratch resistance (1) 50 40 50 Less than 10 50
Scratch resistance (2) ○ ○ ○ × ○
The EPDM content (parts by mass) is shown in parentheses in the column of the oil-extended EPDM. In the column of the hydrogenated diene polymer, the mass ratio of the hydrogenated diene polymer to the (meth) acrylate resin is shown in parentheses.
(6) Effects of the embodiments
As can be seen from Table 3, examples 11 to 15 have excellent mechanical properties, rubber elasticity, and injection weldability. The maleimide compounds of comparative examples 11 and 12 were not added in the range of the present application, and therefore, the processability, mechanical properties, rubber elasticity and injection weldability were poor. In comparative example 13, since a crosslinking assistant other than the maleimide compound was used, the injection weldability was poor. In addition, as can be seen from table 4, examples 16 to 18 have excellent scratch resistance, mechanical properties, rubber elasticity, and injection weldability. In addition, comparative example 14 was poor in mechanical properties, rubber elasticity, scratch resistance, and injection weldability because it was not crosslinked. In addition, in comparative example 15, since a crosslinking assistant other than the maleimide compound was used, the injection weldability was poor.
4. Examples relating to polysiloxane-containing compositions [ D ]
The rubber, crystalline olefin resin, amorphous olefin resin, softener, crosslinking agent, and the like used as raw materials are as follows.
[1] Raw materials
(1) Oil extended rubber
(1) Oil-extended rubber (a 11): an ethylene/propylene/5-ethylidene-2-norbornene terpolymer rubber having an ethylene content of 66 mass%, a 5-ethylidene-2-norbornene content of 4.5 mass%, an intrinsic viscosity measured at 135 ℃ in a decalin solvent of 4.7dl/g, and a mineral Oil softener (trade name: diana Process Oil PW-380, idemitsu Kosan Co., ltd., manufactured by Ltd.) content of 50 mass%;
(2) oil-extended rubber (a 12): an ethylene/propylene/5-ethylidene-2-norbornene terpolymer rubber having an ethylene content of 66 mass%, a 5-ethylidene-2-norbornene content of 4.5 mass%, an intrinsic viscosity measured at 135 ℃ in a decalin solvent of 3.8dl/g, and a mineral Oil softener (trade name: diana Process Oil PW-380, idemitsu Kosan Co., ltd., manufactured by Ltd.) in an amount of 40 mass%.
(2) Olefin resin
(1) Propylene/ethylene random copolymer (b 13): the density is 0.90g/cm 3 MFR (temperature 230 ℃ C., load weight 2.16 kg) of 23g/10 min (trade name: novatecpFL 25R,manufactured by nippon polychem.);
(2) propylene/1-butene amorphous copolymer (b 2): a propylene content of 71 mol%, a melt viscosity of 8Pas and a density of 0.879g/cm 3 And Mn of 6500 (trade name: APAOUT2780, manufactured by Ube industries Ltd.).
(3) Unmodified organopolysiloxanes
(1) Polydimethylsiloxane (f 11): viscosity 100cSt (trade name: silicone oil SH-200, manufactured by Toray Dow-Corning Silicone Co.);
(2) polydimethylsiloxane (f 12): viscosity 1000cSt (trade name: silicone oil SH-200, manufactured by Toray Dow-Corning Silicone Co.);
(3) polydimethylsiloxane (f 13): viscosity 5000cSt (trade name: silicone oil SH-200, manufactured by Toray Dow-Corning Silicone Co.);
(4) polydimethylsiloxane (f 14): viscosity 12500cSt (trade name: silicone oil SH-200, manufactured by Toray Dow-Corning Silicone Co.);
(5) ultra-high molecular weight silicone rubber (f 15): viscosity is 1000000cSt or more (trade name: BY 16-140, manufactured BY Toray Dow-Corning Silicone Co., ltd.).
(4) Modified organopolysiloxane
Acrylic-modified silicone resin (f 2): under the trade name x-22-8171, manufactured by shin-Etsu Chemical Co., ltd.
(5) Mineral oil softener (g 1): under the trade name Diana Process Oil PW-380, idemitsu Kosan Co., ltd.
(6) Crosslinking agent and crosslinking assistant
(1) 2,5-dimethyl-2,5-di (t-butylperoxy) hexane (h 1) available under the tradename Perhexa 25B-40, manufactured by NOF Corp;
(2) n, N' -m-phenylene bismaleimide (h 2) under the trade name Vulnoc PM, ouchishishishinsko Chemical Industries Co., ltd.;
(3) crosslinking aid (h 3): divinylbenzene (manufactured by Sankyo Kasei co.).
(6) Aging additive (j 1): under the trade name Irganox 1010, ciba Specialty Chemicals Co.
[2] Production of polysiloxane-containing composition [ D ]
Examples 19 to 25 and comparative examples 16 to 20 (manufactured by internal mixer + continuous mixer)
According to the formulation shown in tables 5 and 6, the raw material composition containing no crosslinking agent was charged into a pressure kneader (manufactured by Moriyama Company Ltd.) heated to 150 ℃ and kneaded at 40rpm for 15 minutes until the components were uniformly dispersed. Thereafter, the composition in a molten state was granulated using a feeder-ruder (manufactured by Moriyama Company ltd.). Then, the crosslinking agent and the crosslinking aid were added to the pellets in the compounding ratios shown in tables 5 and 6, and mixed for 30 seconds using a Henshel mixer. Then, the mixture was fed to a twin-screw extruder (a corotating non-intermeshing screw, L/D =38.5, trade name "PCM-45", manufactured by Ikegai Ltd.) with a discharge rate of 40kg/hr using a gravimetric feeder, and extruded while being subjected to dynamic heat treatment at 200 ℃ and a screw revolution of 300rp m for a residence time of 2 minutes, to produce a polysiloxane-containing composition [ D ] which was a dynamic cross-linking type thermoplastic elastomer composition.
[3] Evaluation of polysiloxane-containing composition [ D ]
For evaluation of the polysiloxane-containing composition [ D ] obtained as described above, the following measurements were carried out.
(1) Melt flow index (MFR): the measurement was carried out at a temperature of 230 ℃ under a load of 10 kg.
(2) Hardness, tensile break strength and tensile break elongation: measured according to JIS K6301.
(3) Compression set: the measurement was carried out according to JIS K6301 under the conditions of 70 ℃ for 22 hours and 25% compression.
(4) Initial sliding property and durable sliding property
Using a reciprocating sliding tester (manufactured by TosokuSeimitsu Co., ltd.), the weight of the test piece was 233g/3cm 2 (surface pressure 78 g/cm) 2 ) The measurement was carried out at a glass ring test piece sliding speed of 100mm/min (1 stroke 50 mm) using a composition containing polysiloxane [ D ]]The static friction coefficient and the dynamic friction coefficient of the test piece (length 110mm, width 61mm, thickness 2 mm) were higher than those of a cylindrical glass ring test piece having an outer diameter of 25.7mm, an inner diameter of 20mm, a height of 16.5mm and a weight of 9.6 g. The initial sliding property was measured at room temperature using a test piece after 1 day of injection molding. In addition, the durable sliding property was obtained by leaving the test piece to stand on the teeth after injection moldingTest pieces after 500 hours in a wheel oven (georoven) were measured at room temperature.
(5) Precipitation test: the test piece composed of the polysiloxane-containing composition [ D ] was left to stand in a gear oven (manufactured by Toyo Seiki Co.) at a temperature of 100 ℃ for 120 hours, and the surface state of the test piece was visually observed.
(6) Extrusion processability: the plate extrusion was carried out using a Labplastmill extruder (outer diameter =20mm, L/D =25, manufactured by Toyo Seiki co.) under the following conditions (die width 25mm, thickness 1.5 mm), and the appearance thereof was visually evaluated. The surfaces were smooth and edged and were marked with "O" and were all marked with "X".
Barrel C1=180 ℃, barrel C2=190 ℃, barrel C3=210 ℃, die =205 ℃, screw revolutions: 40rpm.
(7) Injection weldability: using the test piece to which the silicone-containing composition [ D ] was injection-welded, the peeled state when bent at an angle of 180 ° was visually observed with the joint between the silicone-containing composition [ D ] and the adherend as a starting point.
Evaluation criteria: the circle indicates no peeling, the triangle indicates that some peeling was found, and the x indicates that the peeling caused a break.
In addition, with respect to the above (2) to (5), the silicone-containing composition [ D ] was prepared into an injection-molded test piece having a size of 120X 2mm by using an injection-molding machine (trade name N-100, manufactured by Japan Steel Work Co.).
[4] Production of adherend
With respect to (7) above, an adherend composed of an olefin-based vulcanized rubber was produced as follows and used for the test.
100 parts by weight of an ethylene/propylene/5-ethylidene-2-norbornene terpolymer rubber (72 mol% in ethylene content, 28 mol% in propylene content, 92 in Mooney viscosity, 15 in iodine value, trade name "EP 103A", manufactured by JSR Corp.) were compounded with 145 parts by weight of Carbon black (trade name: seast 116, manufactured by Tokai Carbon Co., ltd.), 5 parts by weight of mineral Oil softener (g 1) (trade name: diana Process Oil PW380, idemitsu Kosan Co., manufactured by Ltd.), 1 part by weight of active zinc white (manufactured by Sakai Chemical Industry Co., ltd.), 1 part by weight of stearic acid (manufactured by Asahi Denka Corp.), 1 part by weight of processing aid (trade name: hitanol 1501, manufactured by Hitachi Chemical Co., ltd.), 2 parts by weight of release agent (trade name: structol WB212, manufactured by Syl and Zilaher Co., ltd.) and 1 part by weight of plasticizer (polyethylene glycol).
Then, the mixture was kneaded in a Banbury mixer at 50 ℃ and 70rpm for 2.5 minutes. Then, 10 parts by mass of a dehydrating agent (trade name: vesta PP, manufactured by Inoue Sekkai Kogyo Co., ltd.), a vulcanization accelerator (trade name: 1 part by mass, trade name: PX:1 part by mass, trade name: 0.5 part by mass, trade name: D:1 part by mass, each manufactured by Ouchishinsko Chemical Industries Co., ltd.) and 2.2 parts by mass of sulfur were added, and kneading was performed at 50 ℃ using open rolls. Then, the cured product was vulcanized at 170 ℃ for 10 minutes to obtain a 120mm square vulcanized rubber sheet having a thickness of 2 mm. The sheet was punched out with a dumbbell cutter to have a length of 60mm and a width of 50mm to prepare an adherend.
[5] Production of test piece having thermoplastic elastomer injection-welded to olefinic vulcanized rubber
The above-mentioned adherend (60X 50X 2 mm) was attached in advance in a split mold (test piece shape of 120X 2 mm) of an injection molding machine (model N-100, manufactured by Japan Steel Work Co., ltd.), and each of the obtained thermoplastic elastomer compositions was injection-molded onto the adherend to prepare a square plate (120X 2 mm) in which the thermoplastic elastomer composition and the olefin-based vulcanized rubber (adherend) were fusion-bonded.
The results are shown in tables 5 to 6.
TABLE 5
Examples
Oil extended rubber Intrinsic viscosity (dl/g) Content of mineral oil-based softener (mass%) 19 20 21 22 23 24 25
Oil-filled EPDM(a11) 4.7 50 30 325 40 70 70 70 70
Oil-filled EPDM(a12) 3.8 40 30 325 40 - - - -
EPM contained in the oil-extended rubber and softening The total content of the agents is 100 wt% Measurement of (mass%) EPDM 45 45 55 50 50 50 50
Mineral oil softener 55 55 45 50 30 50 50
Crystalline olefin resin (b 13) 5 5 75 25 25 30 30
Amorphous olefin resin (b 2) 5 5 75 5 5 - -
After-addition of mineral oil softener (g 1) 25 15 5 - - - -
Oil-extended rubber, olefin resin and the total of the post-added softeners is 100 Content in parts by mass (mass) Share) Oil-extended EPDM 63.2 72.2 80 70 70 70 70
Total of olefin resins 10.5 11.1 15 30 30 30 30
Post-addition of softeners 26.3 16.7 5 - - - -
Low viscosity is not changed Organic polysilica Siloxane Viscosity 100cSt (f 11) - - - - 0.5 - 0.5
Viscosity 1000cSt (f 12) - 3 3 15 - 15 -
Viscosity 5000cSt (f 13) 15 - - - - - -
High viscosity is not changed Organic silicone Siloxane Viscosity 12500cSt (f 14) 15 3 3 15 - 15 -
Viscosity 1000000cSt (f 15) - - - - 25 - 25
Acrylic acid-modified organopolysiloxane (f 2) 1 1 1 1 0.5 1 0.5
Oil-extended rubber, olefin resin and the total of the post-added softeners is 100 Content in parts by mass (mass) In weight portion) Low viscosity unmodified organopolysiloxanes 1.6 3.7 3 15 0.5 15 0.5
High viscosity unmodified organopolysiloxanes 1.6 3.7 3 15 25 15 25
Acrylic acid modified organopolysiloxane 1.1 1.1 1 1 0.5 1 0.5
Crosslinking criminal (111) 1 1 1 0.5 0.5 0.5 0.5
Crosslinking agent (h 2) - - - 1 1 1 1
Crosslinking assistant (h 3) 1.3 13 13 - - - -
Anti-aging agent (j 1) 0.1 0.1 0.1 0.1 0.1 0.1 0.1
MFR (g/10min) 330 520 280 300 285 285 270
Hardness (JIS-A hardness) 42 41 51 85 87 87 87
Tensile breaking Strength (MPa) 3.9 3.7 4.6 10 9.8 9.8 10.1
Tensile elongation at Break (%) 800 770 760 740 710 710 720
Compression set (%) 42 43 46 59 60 60 60
Initial slidability Coefficient of static friction 0.61 0.45 0.32 0.29 0.3 0.45 0.31
Coefficient of dynamic friction 0.63 0.38 0.29 0.25 0.26 0.34 0.28
Durable sliding property Coefficient of static friction 0.57 0.52 0.62 0.3 0.35 0.52 0.36
Coefficient of dynamic friction 0.57 0.35 0.25 0.28 0.3 0.43 0.32
Precipitation test (O = no × = with) ○ ○ ○ ○ ○ ○ ○
Extrusion processability ○ ○ ○ ○ ○ ○ ○
Injection weldability ○ ○ ○ ○ ○ ○ ○
TABLE 6
Comparative example
Oil extended rubber Intrinsic viscosity (dl/g) Content of mineral oil-based softener (mass%) 16 17 18 19 20
Oil-extended EPDM (a 11) 4.7 50 32.5 32.5 32.5 32.5 32.5
Oil-filled EPDM (a 12) 3.8 40 32.5 32.5 32.5 32.5 32.5
EPDM and softener contained in the oil extended rubber Content at 100 mass% (mass%) EPDM 45 45 45 45 45
Mineral oil series softAgent for chemical treatment 55 55 55 55 55
Crystalline olefin resin (b 13) 5 5 5 5 5
Amorphous olefin resin (b 2) 5 5 5 5 5
After addition of mineral oil softener (g 1) 15 15 15 15 15
Oil extended rubber, olefin resin and post-addition When the total amount of the softening agent is 100 parts by massComprises Measured (parts by mass) Oil-extended EPDM 72.2 72.2 72.2 72.2 72.2
Total of olefin resins 11.1 11.1 11.1 11.1 11.1
Post-addition of softeners 16.7 16.7 16.7 16.7 16.7
Low viscosity unmodified organic polymers Siloxanes Viscosity 100cSt (f 11) 3 - - - -
Viscosity 1000cSt (f 12) - 3 - - 3
Viscosity 5000cSt (f 13) - - 3 - -
High viscosity unmodified organic polymers Siloxanes Viscosity 12500cSt (f 14) - - - 3 3
Viscosity 1000000cSt (f 15) - - - - -
Acrylic acid-modified organopolysiloxane (t 2) - - - - -
Oil extended rubber, olefin resin and post-addition The total content of the softening agent is 100 parts by mass Measured (parts by mass) Low viscosity unmodified organopolysiloxanes 3.3 3.3 3.3 - 3.3
High viscosity unmodified organopolysiloxanes - - - 3.3 3.3
Acrylic acid modified organopolysiloxane - - - - -
Crosslinking agent (h 1) 1 1 1 1 1
Crosslinking agent (h 2) - - - - -
Crosslinking assistant (h 3) 1.3 1.3 1.3 1.3 1.3
Anti-aging agent (j 1) 0.1 0.1 0.1 0.1 0.1
MFR (g/10min) 200 130 290 250 280
Hardness (JIS-A hardness) 43 43 42 42 42
Tensile breaking Strength (MPa) 4 3.9 4.2 4.1 3.7
Tensile elongation at Break (%) 760 760 780 770 680
Compression set (%) 39 40 43 45 43
Initial slidability Coefficient of static friction 0.55 0.81 0.93 0.97 0.6
Coefficient of dynamic friction 0.53 0.67 0.72 0.7 0.59
Durable sliding property Coefficient of static friction 1.5 1.48 1.16 0.88 1.25
Coefficient of dynamic friction 1.1 1 0.73 0.69 1.1
Precipitation test (O = no × = with) × × × ○ ×
Extrusion processability ○ ○ ○ ○ ×
Injection weldability ○ ○ ○ ○ ×
(6) Effects of the embodiments
As can be seen from tables 5 to 6, comparative examples 16 to 18 used only low viscosity unmodified organopolysiloxane, and did not use acrylic modified organopolysiloxane. Therefore, although extrusion processability and injection weldability are excellent, initial and durable sliding properties are poor, and precipitation occurs. In addition, comparative example 19 used only a high-viscosity unmodified organopolysiloxane, and did not use an acrylic-modified organopolysiloxane. Therefore, although extrusion processability and injection weldability are excellent, initial and durable sliding properties are poor. In addition, comparative example 20 contains unmodified organopolysiloxane of low viscosity and high viscosity, but does not contain acrylic modified organopolysiloxane. Therefore, initial and durable sliding properties, extrusion processability, and injection weldability are poor, and precipitation occurs. On the other hand, the silicone-containing compositions [ D ] of examples 19 to 25 were excellent in initial and durable sliding properties and extrusion processability, and no deposition of organopolysiloxane. Further, no peeling, breakage, etc. are generated, and excellent injection weldability is obtained.

Claims (8)

1. A thermoplastic elastomer composition characterized by: the polymer composition is obtained by dynamically heat treating a polymer composition containing an oil-extended rubber, an olefin resin, an optional post-addition softener, an unmodified organopolysiloxane having a viscosity of less than 10000cSt measured at 25 ℃ in accordance with JIS K2283, an unmodified organopolysiloxane having a viscosity of 10000cSt or more measured at 25 ℃ in accordance with JIS K2283, and a modified organopolysiloxane in the presence of a crosslinking agent, wherein the oil-extended rubber contains 30 to 70% by mass of the rubber and 30 to 70% by mass of the softener when the total of the rubber and the softener is 100% by mass.
2. The thermoplastic elastomer composition according to claim 1, wherein the oil-extended rubber is 30 to 99 parts by mass, the olefin-based resin is 1 to 50 parts by mass, and the post-addition softener is 0 to 50 parts by mass, based on 100 parts by mass of the total of the oil-extended rubber, the olefin-based resin, and the post-addition softener.
3. The thermoplastic elastomer composition according to claim 1, wherein the low-viscosity unmodified organopolysiloxane is 1 to 10 parts by mass, the high-viscosity unmodified organopolysiloxane is 1 to 10 parts by mass, and the modified organopolysiloxane is 0.2 to 20 parts by mass, based on 100 parts by mass of the total of the oil-extended rubber, the olefin-based resin, and the post-addition softener.
4. The thermoplastic elastomer composition according to claim 1, wherein said rubber is an ethylene- α -olefin copolymer rubber having an intrinsic viscosity η of 2.0 to 6.8dl/g as measured at 135 ℃ using decalin as a solvent.
5. A method for producing a thermoplastic elastomer composition, which is the method for producing the thermoplastic elastomer according to any one of claims 1 to 4, characterized in that: a polymer composition containing a rubber and an olefin resin and other additives not containing a crosslinking agent, or a polymer composition containing a rubber and an olefin resin, at least a part of a crosslinking agent and other additives not containing a crosslinking agent are melt-kneaded by an internal kneader to form a melt-kneaded product, and then the melt-kneaded product or the melt-kneaded product and additives containing at least a crosslinking agent are supplied to a continuous extruder and subjected to dynamic heat treatment.
6. A method for producing a thermoplastic elastomer composition, which is the method for producing the thermoplastic elastomer according to any one of claims 1 to 4, characterized in that: a crosslinking agent is mixed with a polymer composition containing rubber and an olefin resin, and then the mixture is supplied to a plurality of continuous kneaders connected to each other and dynamically heat-treated.
7. A method for producing a thermoplastic elastomer composition, which is the method for producing the thermoplastic elastomer according to any one of claims 1 to 4, characterized in that: a polymer composition containing a rubber and an olefin resin is fed from a raw material introducing part of a continuous counter-rotating twin-screw kneader of an extrusion apparatus in which an upstream continuous counter-rotating twin-screw kneader and a downstream co-rotating twin-screw extruder are arranged in series, the polymer composition is kneaded by the continuous counter-rotating twin-screw kneader, and the kneaded product is fed to the co-rotating twin-screw extruder while maintaining the temperature of the kneaded product at the outlet of the continuous counter-rotating twin-screw kneader at 250 ℃ or lower, thereby dynamically crosslinking the polymer composition.
8. A method for producing a thermoplastic elastomer composition, which is the method for producing the thermoplastic elastomer according to any one of claims 1 to 4, characterized in that: supplying a polymer composition containing a rubber, an olefin resin and an organic peroxide from a raw material inlet of a continuous counter-rotating twin-screw kneader of an extrusion apparatus in which an upstream continuous counter-rotating twin-screw kneader and a downstream co-rotating twin-screw extruder are arranged in series, kneading the polymer composition by the continuous counter-rotating twin-screw kneader, and while kneading the polymer composition, kneading the mixture at an outlet of the continuous counter-rotating twin-screw kneader at a temperature t a Control at T h -30≤t a ≤T h Supplying the kneaded mixture to the co-rotating twin-screw extruder at a temperature of +30 ℃ to dynamically crosslink the kneaded mixture, wherein the melting point of the olefin resin is T m 1 minute half-life of organic peroxideTemperature T h At T m ≤T h ≤T m A range of +50 ℃.
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