WO2021206077A1 - Resin composition pellet - Google Patents

Resin composition pellet Download PDF

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Publication number
WO2021206077A1
WO2021206077A1 PCT/JP2021/014587 JP2021014587W WO2021206077A1 WO 2021206077 A1 WO2021206077 A1 WO 2021206077A1 JP 2021014587 W JP2021014587 W JP 2021014587W WO 2021206077 A1 WO2021206077 A1 WO 2021206077A1
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WO
WIPO (PCT)
Prior art keywords
component
resin composition
pellet
styrene
mass
Prior art date
Application number
PCT/JP2021/014587
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French (fr)
Japanese (ja)
Inventor
弘起 川上
良佑 近藤
Original Assignee
出光興産株式会社
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Priority to JP2022514078A priority Critical patent/JPWO2021206077A1/ja
Publication of WO2021206077A1 publication Critical patent/WO2021206077A1/en

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Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
    • B29B9/00—Making granules
    • B29B9/16—Auxiliary treatment of granules
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J3/00—Processes of treating or compounding macromolecular substances
    • C08J3/12—Powdering or granulating
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
    • C08J7/04—Coating
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/16—Nitrogen-containing compounds
    • C08K5/20—Carboxylic acid amides
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L25/00—Compositions of, homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring; Compositions of derivatives of such polymers
    • C08L25/02—Homopolymers or copolymers of hydrocarbons
    • C08L25/04—Homopolymers or copolymers of styrene
    • 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
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B3/00—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties
    • H01B3/18—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances
    • H01B3/30—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances plastics; resins; waxes
    • H01B3/44—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances plastics; resins; waxes vinyl resins; acrylic resins

Definitions

  • the present invention relates to resin composition pellets.
  • Patent Document 1 describes a resin composition for a water-stopping material, which comprises a styrene-based elastomer and a polystyrene-based polymer having a syndiotactic structure as a water-stopping thermoplastic elastomer resin composition.
  • Patent Document 2 states that as a thermoplastic elastomer resin composition, hydrogen is added to a polyester block copolymer for the purpose of improving various properties such as blocking between pellets, flexibility, heat resistance, and mechanical properties.
  • thermoplastic elastomer resin composition containing a hydrogenated thermoplastic block copolymer having a styrene-based elastomer and / or a crystalline polyolefin block and a fatty acid amide compound is disclosed.
  • Patent Document 1 The resin composition for the wire harness water blocking material described in Patent Document 1 can be molded by injection molding, but the resin composition pellet of Patent Document 1 having adhesion to the electric wire coating material is easy to block. A dispersion step or a crushing step is required before molding, and if the pellets are fixed, the pellets cannot be transported from the hopper to the molding machine, and there is a problem that molding is not possible.
  • Patent Document 2 shows an example in which a plurality of specific resins and fatty acid amide compounds are melt-kneaded in order to suppress blocking, but in recent years, a wire harness water blocking material having better adhesion has been required. Therefore, even this method is insufficient to suppress blocking.
  • An object to be solved by the present invention is to provide a resin composition pellet with less blocking, which is suitable for a water blocking material for a connector, particularly a water blocking material for a wire harness connector.
  • the present inventors have impregnated a fatty acid amide compound into a composition containing a styrene-based elastomer and a polystyrene-based polymer (SPS) having a mainly syndiotactic structure in a specific mass ratio. It has been found that the above-mentioned problems can be solved by the above-mentioned problems, and the present invention has been completed. That is, the present invention is as follows.
  • the mass ratio [(A) / (B)] of the component A) to the component (B) is 50/50 to 85/15, and the component (C) is formed into a pellet containing the components (A) and (B).
  • the component (A) is styrene isoprene styrene block copolymer (SIS), styrene butadiene styrene block copolymer (SBS), styrene ethylene propylene block copolymer (SEP), styrene ethylene butylene styrene block copolymer.
  • the resin composition according to the above [1] which is at least one selected from the group consisting of (SEBS), styrene ethylene propylene styrene block copolymer (SEPS), and styrene ethylene ethylene propylene styrene block copolymer (SEEPS). Material pellets.
  • the component (C) is at least one selected from the group consisting of stearic acid amide, oleic acid amide, erucic acid amide, methylene bisstearic acid amide, and ethylene bisstearic acid amide.
  • the mass ratio [(A) / (B)] of is 50/50 to 85/15, and the amount of the component (C) attached is 40 mass ppm or more with respect to the total of the components (A) and (B).
  • a method for producing resin composition pellets [9] The resin composition pellet according to the above [8], wherein the temperature of the pellet surface in the step of adhering the component (C) to the pellet containing the component (A) and the component (B) is 100 ° C. or lower. Production method.
  • a resin composition pellet with less blocking which is suitable for a water blocking material for a connector, particularly a water blocking material for a wire harness connector.
  • the resin composition pellet of the present invention is a resin composition containing (A) component: a styrene-based elastomer, (B) component: a polystyrene-based polymer having a mainly syndiotactic structure, and (C) component: a fatty acid amide compound.
  • the mass ratio [(A) / (B)] of the component (A) to the component (B) is 50/50 to 85/15
  • the component (C) is the component (A) and the component (B).
  • the content of the component (C) is 40% by mass or more with respect to the total of the components (A) and (B).
  • the resin used to stop water in the connector is required to have adhesion, heat resistance and flexibility to an electric wire coating material containing polyethylene as a main component. Since the styrene-based elastomer of the component (A) and the polystyrene-based polymer having a mainly syndiotactic structure of the component (B) are contained in a specific ratio, a water blocking material having excellent performance can be obtained. Among them, it has excellent adhesion to the wire coating material and has an excellent water-stopping effect.
  • the resin composition pellet of the present invention is composed of such a resin composition having excellent adhesion to the electric wire coating material, a specific amount of the fatty acid amide compound of the component (C) is adhered to the pellet surface. As a result, the pellets have less blocking, and blocking between pellets can be suppressed while maintaining the performance required for the connector after molding.
  • styrene-based elastomer examples include styrene-isoprene styrene block copolymer (SIS), styrene butadiene styrene block copolymer (SBS), and styrene ethylene propylene block copolymer.
  • SIS styrene-isoprene styrene block copolymer
  • SBS styrene butadiene styrene block copolymer
  • styrene ethylene propylene block copolymer examples include styrene-isoprene styrene block copolymer (SIS), styrene butadiene styrene block copolymer (SBS), and styrene ethylene propylene block copolymer.
  • SEP coalescing
  • SEBS styreneethylene butylene styrene block copolymer
  • SEPS styreneethylene propylene styrene block copolymer
  • SEEPS styreneethylene ethylenepropylene styrene block copolymer
  • styrene-based elastomers styrene ethylene butylene styrene block copolymer (SEBS) is preferable, and unmodified styrene ethylene butylene styrene block copolymer (SEBS) is more preferable.
  • SEBS styrene ethylene butylene styrene block copolymer
  • SEBS unmodified styrene ethylene butylene styrene block copolymer
  • the MFR of the styrene-based elastomer is preferably 0.0 (No Flow) to 10 g / 10 minutes under the measurement conditions of a temperature of 230 ° C. and a load of 2.16 kgf.
  • the syndiotactic structure in the polystyrene-based polymer (SPS) which is a component (B) and mainly has a syndiotactic structure refers to a syndiotactic structure whose three-dimensional chemical structure is a syndiotactic structure, that is, a main chain formed from a carbon-carbon bond. It has a three-dimensional structure in which phenyl groups, which are side chains, are alternately located in opposite directions, and its tacticity is quantified by a nuclear magnetic resonance method (13 C-NMR method) using isotope carbon.
  • the tacticity of the syndiotactic structure measured by the nuclear magnetic resonance method is the abundance ratio of a plurality of consecutive constituent units, for example, diad for two, triad for three, and so on. In the case of five, it can be indicated by pentad, but for polystyrene-based polymers having a predominantly syndiotactic structure, which is the component (B), usually 75% or more, preferably 85% or more of racemic diad, or A polystyrene-based polymer having a syndiotacticity of 30% or more, preferably 50% or more in lasemipentad is used.
  • polystyrene-based polymer in SPS as the component (B) examples include polystyrene, poly (alkyl styrene), poly (styrene halogenated), poly (alkyl styrene halide), poly (alkoxystyrene), and poly (vinyl benzoic acid ester). ), These hydrides and mixtures thereof, or copolymers containing these as main components.
  • poly (halogenated styrene) includes poly (chlorostyrene), poly (bromostyrene), poly (fluorostyrene) and the like.
  • examples of poly (alkyl styrene halogenated) include poly (chloromethyl styrene), and examples of poly (alkoxy styrene) include poly (methoxy styrene) and poly (ethoxy styrene).
  • polystyrene-based polymers particularly preferable are polystyrene, poly (p-methylstyrene), poly (m-methylstyrene), poly (p- or t-butylstyrene), and poly (p-chlorostyrene). ), Poly (m-chlorostyrene), poly (p-fluorostyrene), polystyrene hydride and copolymers containing these structural units.
  • Such SPS is produced, for example, in a styrene-based monomer (the above-mentioned polystyrene-based polymer) by using a titanium compound and a condensation product of water and trialkylaluminum as a catalyst in an inert hydrocarbon solvent or in the absence of a solvent. It can be produced by polymerizing (corresponding monomer) (see JP-A-62-187708).
  • the poly (alkyl styrene halide) can be obtained by the method described in JP-A No. 1-46912, and the hydrogenated polymer can be obtained by the method described in JP-A-1-178505.
  • the molecular weight of SPS which is the component (B), is not particularly limited, but the weight average molecular weight is 1 ⁇ 10 4 or more and 1 ⁇ 10 6 from the viewpoint of the fluidity of the resin during molding and the mechanical properties of the obtained molded product. It is preferably 50,000 or more and 500,000 or less, more preferably 50,000 or more and 300,000 or less. When the weight average molecular weight is 1 ⁇ 10 4 or more, a molded product having sufficient mechanical properties can be obtained. On the other hand, if the weight average molecular weight is 1 ⁇ 106 or less, there is no problem in the fluidity of the resin during molding.
  • the MFR of SPS (B) measured under the conditions of a temperature of 300 ° C.
  • a load of 1.2 kgf is preferably 2 g / 10 minutes or more, preferably 4 g / 10 minutes or more.
  • a load of 1.2 kgf is preferably 2 g / 10 minutes or more, preferably 4 g / 10 minutes or more.
  • it is 50 g / 10 minutes or less a molded product having sufficient mechanical properties can be obtained, preferably 30 g / 10 minutes or less.
  • phase separation can be suppressed due to the relationship with the MFR of the styrene-based elastomer, and a product having excellent appearance and flexibility can be obtained.
  • the mass ratio [(A) / (B)] of the component (A) to the component (B) is 50/50 to 85/15, preferably 60/40 to 85/15, and 70/30 to 70. It is more preferably 85/15, and even more preferably 73/27 to 85/15.
  • Sufficient heat resistance required when the component (B) (SPS) is less than 15 parts by mass with respect to a total of 100 parts by mass of the component (A) and the component (B), especially when used as a water blocking material. If the effect of improving the property is not obtained and the amount is more than 50 parts by mass, the necessary adhesion to the electric wire covering material may not be maintained, especially when used as a water blocking material. On the other hand, the mass ratio is excellent in adhesion and heat resistance.
  • the total content of the component (A) and the component (B) in the pellet containing the component (A) and the component (B) without the component (C) is preferably 90% by mass or more, more preferably 90% by mass or more. It is 95% by mass or more, more preferably 99% by mass or more, and even more preferably 99.5% by mass or more. There is no upper limit, but it is 100% by mass or less.
  • the resin composition pellet of the present invention further contains a fatty acid amide compound which is a component (C).
  • the component (C) is attached to a pellet containing the components (A) and (B), and the content of the component (C) is 40 mass ppm with respect to the total of the components (A) and (B). That is all.
  • the fatty acid amide compound as the component (C) is preferably at least one selected from the group consisting of fatty acid amides and alkylene fatty acid amides, and more preferably alkylene fatty acid amides.
  • Preferred fatty acid amides include stearic acid amides, oleic acid amides, erucic acid amides and the like.
  • Preferred alkylene fatty acid amides include methylene bisstearic amides, ethylene bisstearic amides and the like.
  • the fatty acid amide compound as the component (C) is at least one selected from the group consisting of stearic acid amides, oleic acid amides, erucic acid amides, methylene bisstearic acid amides, and ethylene bisstearic acid amides. It is preferably an ethylene bisstearic acid amide, more preferably.
  • the component (C) is attached to a pellet containing the component (A) and the component (B).
  • adherered means a state in which the composition of the component is bonded to the surface of the pellet while maintaining at least a part of the composition, excluding those mixed with the component of the pellet at the molecular level. Be taken.
  • the particles composed of the component (C) are physically bonded to the pellet surface.
  • the content of the component (C) is 40 mass ppm or more, more preferably 80 mass ppm or more, and 90 mass ppm with respect to the total of the component (A) and the component (B).
  • the above is more preferable, 110 mass ppm or more is more preferable, 120 mass ppm or more is more preferable, and 140 mass ppm or more is further preferable.
  • the upper limit of the content is not limited, but from the viewpoint of economy, 1000 mass ppm or less is preferable, less than 300 mass ppm is more preferable, and less than 200 mass ppm is further preferable. Within this range, blocking can be effectively suppressed.
  • the resin composition pellet of the present invention may contain any additive in addition to the components (A), (B) and (C).
  • Optional additives include antioxidants, polyphenylene ethers, nucleating agents and the like. From the viewpoint of adhesion to the electric wire coating material, it is preferable that the resin composition pellet of the present invention does not substantially contain a mold release agent as an additive.
  • the specific addition amount that is substantially not contained is more preferably less than 500 mass ppm, still more preferably less than 50 mass ppm, based on the resin composition pellets.
  • the antioxidant may be added in an amount of 5% by mass or less with respect to the resin composition pellets for the purpose of enhancing the thermal stability of the water blocking material as a product.
  • the antioxidant known ones can be used, but in the present invention, it is preferable that the phosphorus-based antioxidant is substantially not contained.
  • phosphorus-based antioxidant When a phosphorus-based antioxidant is used, phosphoric acid gas is generated during molding, and the phosphoric acid gas tends to enter between the wire coating material and the water blocking material to reduce the adhesiveness. Therefore, this is included as much as possible in the present invention. It is desirable not to.
  • Substantially free of phosphorus-based antioxidants means that the content of phosphorus-based antioxidants is less than 3000 mass ppm, more preferably less than 1000 mass ppm, still more preferably, relative to the resin composition pellets. It means that it is less than 500 mass ppm, more preferably less than 50 mass ppm.
  • the antioxidant it is preferable to use a phenolic antioxidant.
  • the phenolic antioxidant include triethylene glycol bis [3- (3-tert-butyl-5-methyl-4-hydroxyphenyl) propionate] and 1,6-hexanediol bis [3- (3).
  • antioxidants include pentaerythritol tetrakis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate] (BASF Corporation, "IRGANOX1010”), 1,3,5-.
  • Tris- (3', 5'-di-tert-butyl-4'-hydroxybenzyl) isocyanuric acid manufactured by ADEKA Corporation, "ADEKA STAB AO-20" and the like can be used.
  • Polyphenylene ether Adhesion can be improved by adding polyphenylene ether.
  • unmodified SEBS When unmodified SEBS is used as a water blocking material from the viewpoint of water absorption, it is preferable to use unmodified polyphenylene ether.
  • the polyphenylene ether is preferably contained in the resin composition pellet in an amount of 0.1 to 10% by mass, more preferably 0.5 to 9% by mass, and even more preferably 2 to 8% by mass.
  • the effect of improving the adhesiveness of the polyphenylene ether can be obtained, and by setting it to 10% by mass or less, the elongation of the elastomer is not hindered and the required flexibility is obtained. Be done.
  • polyphenylene ether examples include poly (2,3-dimethyl-6-ethyl-1,4-phenylene ether), poly (2-methyl-6-chloromethyl-1,4-phenylene ether), and poly.
  • poly (2,6-dimethyl-1,4-phenylene ether) is particularly preferable.
  • the polyphenylene ether may be used alone or in combination of two or more. These polyphenylene ethers are known compounds, and are described in US Pat. Nos. 3,306,874, 3,306,875, 3,257,357 and 3,257,358. Can be referenced. Polyphenylene ethers are usually prepared by an oxidation coupling reaction to produce homopolymers or copolymers in the presence of copper amine complexes and one or more phenolic compounds substituted at two or three sites.
  • copper amine complex copper amine complexes derived from the first, second and third amines can be used.
  • nuclear agent Since the resin mixture constituting the resin composition pellet contains a nucleating agent (crystallization nucleating agent), the crystallization rate at the time of molding the resin composition pellet can be appropriately maintained, the mass productivity of the pellet can be ensured, and heat resistance can be ensured. It will also be excellent in sex.
  • nucleating agents can be used, for example, metal salts of carboxylic acids such as aluminum di (p-tert-butylbenzoate), sodium-2,2'-methylenebis (4,6-di-tert).
  • Examples thereof include metal salts of phosphoric acid such as -butylphenyl) phosphate and sodium methylenebis (2,4-di-tert-butylphenol) acid phosphate, talc, phthalocyanine derivatives, and phosphoric acid ester compounds.
  • Specific product names include "ADEKASTAB NA-10”, “ADEKASTAB NA-11”, “ADEKASTAB NA-21”, “ADEKASTAB NA-30”, “ADEKASTAB NA-30”, and DIC Corporation manufactured by ADEKA CORPORATION. Examples include PTBBA-AL manufactured by the company.
  • the content of the nucleating agent in the resin composition pellets is preferably 0.2% by mass or more, more preferably 0.5% by mass or more, and preferably 2.0% by mass. Hereinafter, it is more preferably 1.5% by mass or less. If it is 0.2% by mass or more, the mass productivity and heat resistance of the resin molding material pellets constituting the resin member are excellent, and if it is 2.0% by mass or less, the generation of gas derived from the nucleating agent can be suppressed and the adhesion is good. Does not reduce.
  • the nucleating agent may be used alone or in combination of two or more.
  • the resin composition pellet of the present invention is preferably used as a water blocking material for connectors. That is, the resin composition pellet of the present invention is preferably used as a water blocking material for a connector.
  • the component (A): a styrene-based elastomer, the component (B): a polystyrene-based polymer having a syndiotactic structure, and the component (C): a fatty acid amide compound are contained, and the component (A) and ( The mass ratio [(A) / (B)] of the component B) is 50/50 to 85/15, and the component (C) is attached to the pellet containing the components (A) and (B).
  • the resin composition pellet in which the content of the component (C) is 40% by mass or more with respect to the total of the components (A) and (B) is preferably used as a water blocking material for a connector.
  • the resin composition pellet By melting the resin composition pellet and molding it into a desired shape, it can be used as a water blocking material for a connector. Further, the resin composition pellet can be used as a water blocking material for a connector, more specifically, as a water blocking material for a wire harness connector by injection molding or the like.
  • the molding method of the water blocking material is not particularly limited, and molding can be performed by a known method such as injection molding or extrusion molding.
  • the molding temperature at the time of injection molding is preferably equal to or higher than the melting point of the SPS used and lower than 350 ° C. By setting the molding temperature to be equal to or higher than the melting point of SPS, there is no possibility that the fluidity will decrease.
  • the mold temperature is preferably 30 to 80 ° C, more preferably 30 to 60 ° C.
  • the mold temperature is preferably 30 to 80 ° C, more preferably 30 to 60 ° C.
  • the resin composition pellet of the present invention adheres the component (C) only to the surface of the pellet to suppress blocking, a high blocking suppressing effect can be exhibited with a relatively small amount of the component (C).
  • the amount of the component (C) can be adjusted to a small amount within the range described above.
  • the resin composition pellet of the present invention can be extremely suitably used for a water blocking material for a connector, an electronic device, an in-vehicle / transmission component, a transformer / coil power module and its device, a relay, a sensor, and the like.
  • a water blocking material for a connector, an electronic device, an in-vehicle / transmission component, a transformer / coil power module and its device, a relay, a sensor, and the like.
  • the resin composition pellet of the present invention may be produced by any method, but it is preferably produced by the following method. That is, the method for producing a resin composition pellet of the present invention comprises (A) component: a styrene-based elastomer, (B) component: a polystyrene-based polymer having a mainly syndiotactic structure, and (C) component: a fatty acid amide compound.
  • the mass ratio [(A) / (B)] of the component (A) to the component (B) is 50/50 to 85/15, and the amount of the component (C) attached is between the component (A) and (B). ) 40 mass ppm or more with respect to the total of the components.
  • pellets containing the component (A) and the component (B) are prepared.
  • the pellets of the component (A) and the component (B) may be mixed at room temperature and then blended by various methods such as melt-kneading, and the method is not particularly limited.
  • melt kneading using a twin-screw extruder is preferably used.
  • kneading at a temperature equal to or higher than the melting point of SPS, which is the component (B), and lower than 350 ° C. is preferable.
  • the kneading temperature By setting the kneading temperature to be equal to or higher than the melting point of SPS, the viscosity of SPS does not become too high, so that the productivity does not decrease. Further, by setting the kneading temperature to less than 350 ° C., there is no possibility that the SPS is thermally decomposed. It is preferable to add any of the above-mentioned additives, such as an antioxidant, when the component (A) and the component (B) are melt-kneaded. By kneading the component (A) and the component (B) at the same time, the effect of the additive can be exerted on the entire resin composition pellet, and the performance of the additive can be imparted to the water blocking material which is a product.
  • an antioxidant such as an antioxidant
  • the molten resin composition obtained by melt-kneading is pelletized to obtain pellets.
  • the method for pelletizing is not limited, but a method of cooling the molten resin and cutting it to obtain pellets is preferable, and an underwater cut method is more preferable. That is, the present production method includes a step of pelletizing the molten resin composition containing the components (A) and (B) by an underwater cut method to obtain pellets containing the components (A) and (B). Is preferable. By pelletizing by the underwater cut method, the shape of the pellets can be made uniform even though the composition has high flexibility.
  • the strands of this composition When the strands of this composition are pulled and cooled using a water tank, the strands are soft, the force of the cutter applied to the strands is dispersed, and the shape tends to be non-uniform.
  • the pellets are cut in a molten state and then cooled in water, so that even a highly flexible composition can be made into uniform pellets.
  • the component (C) is attached to a pellet containing the components (A) and (B). Adhesion is achieved by mixing the pellet containing the components (A) and (B) with the component (C).
  • the temperature of the pellet surface in the step of adhering the component (C) to the pellet containing the component (A) and the component (B) is preferably 100 ° C. or lower, more preferably 80 ° C. or lower, and 60 ° C. or lower. Is more preferable.
  • the lower limit is not limited, but is preferably 0 ° C. or higher.
  • the component (C): fatty acid amide compound attached to the resin composition pellets obtained in Examples and Comparative Examples was quantified as follows. 50 g of the resin composition pellets obtained in Examples and Comparative Examples was placed in a container, 200 mL of methanol was added, and the mixture was stirred for 10 minutes. After separating the methanol solution and the pellet, the methanol solution was concentrated with an evaporator and dried. The mass of the solid content (fatty acid amide compound) was measured, and the mass ratio (mass ppm) in the pellet of the resin composition used for the measurement was determined.
  • ⁇ Blocking test (2) Accelerated test> The resin composition pellets obtained in Examples and Comparative Examples were placed in a metal container so as to have an apparent depth of 2.5 cm, and the surface was flattened. An aluminum plate and a stainless steel weight were placed on the pellets so that a pressure of 0.075 kg / cm 2 was applied to the pellets. In that state, after leaving it in an environment of 60 ° C. for 140 hours, the stainless steel weight and the aluminum plate were removed, the metal container was turned over so as not to give vibration, and some pellets were discharged. The percentage (mass%) of the residual pellets remaining in the metal container was measured. The smaller the proportion of residual pellets, the more the blocking is suppressed and the better. The results of this test are shown in Table 2.
  • ⁇ Blocking test (3) Sensory test> The metal container after the blocking tests (1) and (2) was subjected to vibration, its loosening was observed, and the remaining pellets were further stirred with a finger, and the loosening was observed and evaluated according to the following criteria. .. A: Although it is agglomerated, it can be easily loosened (unraveled by vibration). B: Aggregates but loosens (can be loosened by stirring with fingers) C: Cannot be loosened (partially agglomerated lumps remain)
  • the temperature of the surface of the pellet immediately after blending was 35 ° C. Since the amount of the component (C) attached (content of the component (C)) varies depending on the total amount charged due to the influence of loss due to adhesion to the piping during feeding, etc., the finally obtained resin composition.
  • the pellet was quantified by the method described in ⁇ Component (C): Quantification of fatty acid amide compound> to determine the amount of component (C) attached (content of component (C)) of each example. The evaluation results are shown in Tables 1 and 2.
  • the resin composition pellet of the present invention has less blocking and is excellent as a pellet for a water blocking material for a connector.

Abstract

This resin composition pellet contains: a styrene-based elastomer as an (A) component; a polystyrene-based polymer, mainly having a syndiotactic structure, as a (B) component; and a fatty acid amide compound as a (C) component, wherein the mass ratio [(A)/(B)] of the (A) component to the (B) component is 50/50 to 85/15, the (C) component is attached to a pellet containing the (A) component and the (B) component, and the content of the (C) component is at least 40 ppm by mass with respect to the total amount of the (A) component and the (B) component.

Description

樹脂組成物ペレットResin composition pellets
　本発明は、樹脂組成物ペレットに関する。 The present invention relates to resin composition pellets.
　自動車や二輪車などに搭載される電子制御ユニットは、水のかからない非被水領域に搭載される場合においても、接続するコネクタ、特にワイヤーハーネスコネクタは雨水等が浸入しやすい被水領域を通って配線される場合が多いため、コネクタ側から電子制御ユニット内への水の浸入を防止することが重要である。
　従来、コネクタの止水には耐熱性を必要とされるケースが多く、シリコーン樹脂をはじめとして硬化性の樹脂をポッティングする方法が用いられている。これらの樹脂は硬化のために長時間の工程が必要であり、また、硬化するまで単体で形状保持が出来ないため、箱型の中に流し入れる必要がある。 Even when the electronic control unit mounted on an automobile or a two-wheeled vehicle is mounted in a non-water-covered area where it is not exposed to water, the connector to be connected, especially the wire harness connector, is wired through the water-covered area where rainwater or the like easily enters. Therefore, it is important to prevent water from entering the electronic control unit from the connector side.
Conventionally, heat resistance is often required to stop water in a connector, and a method of potting a curable resin such as a silicone resin is used. Since these resins require a long process for curing and cannot maintain their shape by themselves until they are cured, they need to be poured into a box mold.
　このような状況において、ポッティング法を用いずに、射出成形によって成形できる材料が求められている。そこで、特許文献１には、止水可能な熱可塑性エラストマー樹脂組成物として、スチレン系エラストマーと、主としてシンジオタクチック構造を有するポリスチレン系重合体を含有することを特徴とする止水材用樹脂組成物が開示されている。
　一方で、特許文献２には、熱可塑性エラストマー樹脂組成物として、ペレット間のブロッキング、柔軟性、耐熱性、機械的物性等の諸特性の向上を目的として、ポリエステルブロック共重合体に、水素添加されたスチレン系エラストマーおよび／または結晶性ポリオレフィンブロックを有する水素添加された熱可塑性ブロック共重合体と、脂肪酸アミド化合物を配合した熱可塑性エラストマー樹脂組成物が開示されている。 In such a situation, there is a demand for a material that can be molded by injection molding without using the potting method. Therefore, Patent Document 1 describes a resin composition for a water-stopping material, which comprises a styrene-based elastomer and a polystyrene-based polymer having a syndiotactic structure as a water-stopping thermoplastic elastomer resin composition. The thing is disclosed.
On the other hand, Patent Document 2 states that as a thermoplastic elastomer resin composition, hydrogen is added to a polyester block copolymer for the purpose of improving various properties such as blocking between pellets, flexibility, heat resistance, and mechanical properties. A thermoplastic elastomer resin composition containing a hydrogenated thermoplastic block copolymer having a styrene-based elastomer and / or a crystalline polyolefin block and a fatty acid amide compound is disclosed.
特開２０１２－１６７１３３号公報Japanese Unexamined Patent Publication No. 2012-167133 特開２００４－１４３３５１号公報Japanese Unexamined Patent Publication No. 2004-143351
　特許文献１に記載のワイヤーハーネス止水材用の樹脂組成物は、射出成形によって成形することができるが、電線被覆材との密着性を有する特許文献１の樹脂組成物ペレットはブロッキングしやすく、成形前に分散工程や粉砕工程が必要となり、固着した場合には、ホッパーから成形機へペレットを搬送できず、成形できないという問題がある。
　特許文献２には、ブロッキングを抑制するために複数の特定の樹脂と脂肪酸アミド化合物を溶融混練した例が示されているが、近年ではより密着性に優れたワイヤーハーネス止水材が求められており、この方法によってもブロッキングの抑制には不十分である。
　そのため、コネクタ用止水材、特にワイヤーハーネスコネクタ用止水材に好適な、ブロッキングの少ない樹脂組成物ペレットが求められていた。
　本発明が解決しようとする課題は、コネクタ用止水材、特にワイヤーハーネスコネクタ用止水材に好適な、ブロッキングの少ない樹脂組成物ペレットを提供することである。 The resin composition for the wire harness water blocking material described in Patent Document 1 can be molded by injection molding, but the resin composition pellet of Patent Document 1 having adhesion to the electric wire coating material is easy to block. A dispersion step or a crushing step is required before molding, and if the pellets are fixed, the pellets cannot be transported from the hopper to the molding machine, and there is a problem that molding is not possible.
Patent Document 2 shows an example in which a plurality of specific resins and fatty acid amide compounds are melt-kneaded in order to suppress blocking, but in recent years, a wire harness water blocking material having better adhesion has been required. Therefore, even this method is insufficient to suppress blocking.
Therefore, there has been a demand for resin composition pellets with less blocking, which are suitable for water-stopping materials for connectors, particularly water-stopping materials for wire harness connectors.
An object to be solved by the present invention is to provide a resin composition pellet with less blocking, which is suitable for a water blocking material for a connector, particularly a water blocking material for a wire harness connector.
　本発明者等は、上記課題について鋭意検討を行った結果、スチレン系エラストマーと、主としてシンジオタクチック構造を有するポリスチレン系重合体(ＳＰＳ)を特定の質量比で含む組成物に脂肪酸アミド化合物を添着させることで前記課題を解決できることを見出し、本発明を完成するに至った。
　すなわち、本発明は以下の通りである。 As a result of diligent studies on the above-mentioned problems, the present inventors have impregnated a fatty acid amide compound into a composition containing a styrene-based elastomer and a polystyrene-based polymer (SPS) having a mainly syndiotactic structure in a specific mass ratio. It has been found that the above-mentioned problems can be solved by the above-mentioned problems, and the present invention has been completed.
That is, the present invention is as follows.
［１］（Ａ）成分：スチレン系エラストマー、（Ｂ）成分：主としてシンジオタクチック構造を有するポリスチレン系重合体、及び（Ｃ）成分：脂肪酸アミド化合物を含有する樹脂組成物ペレットであって、（Ａ）成分と（Ｂ）成分の質量比［（Ａ）／（Ｂ）］が５０／５０～８５／１５であり、（Ｃ）成分が、（Ａ）成分と（Ｂ）成分を含むペレットに添着しており、（Ｃ）成分の含有量が、（Ａ）成分と（Ｂ）成分の合計に対し、４０質量ｐｐｍ以上である、樹脂組成物ペレット。
［２］（Ａ）成分が、スチレンイソプレンスチレンブロック共重合体（ＳＩＳ）、スチレンブタジエンスチレンブロック共重合体（ＳＢＳ）、スチレンエチレンプロピレンブロック共重合体（ＳＥＰ）、スチレンエチレンブチレンスチレンブロック共重合体（ＳＥＢＳ）、スチレンエチレンプロピレンスチレンブロック共重合体（ＳＥＰＳ）、及びスチレンエチレンエチレンプロピレンスチレンブロック共重合体（ＳＥＥＰＳ）からなる群より選ばれる少なくとも１つである、前記［１］に記載の樹脂組成物ペレット。
［３］（Ｃ）成分が、脂肪酸アミド及びアルキレン脂肪酸アミドからなる群より選ばれる少なくとも１つである、前記［１］又は［２］に記載の樹脂組成物ペレット。
［４］（Ｃ）成分が、ステアリン酸アミド、オレイン酸アミド、エルカ酸アミド、メチレンビスステアリン酸アミド、及びエチレンビスステアリン酸アミドからなる群より選ばれる少なくとも１つである、前記［１］～［３］のいずれか１つに記載の樹脂組成物ペレット。
［５］（Ａ）成分と（Ｂ）成分を含むペレット中の（Ａ）成分と（Ｂ）成分の合計含有量が、９０質量％以上である、前記［１］～［４］のいずれか１つに記載の樹脂組成物ペレット。
［６］（Ａ）成分と（Ｂ）成分の質量比［（Ａ）／（Ｂ）］が、７３／２７～８５／１５である、前記［１］～［５］のいずれか１つに記載の樹脂組成物ペレット。
［７］コネクタ用止水材に用いる、前記［１］～［６］のいずれか１つに記載の樹脂組成物ペレット。
［８］（Ａ）成分：スチレン系エラストマー、（Ｂ）成分：主としてシンジオタクチック構造を有するポリスチレン系重合体、及び（Ｃ）成分：脂肪酸アミド化合物を含有する樹脂組成物ペレットの製造方法であって、（Ｃ）成分を（Ａ）成分と（Ｂ）成分を含むペレットに添着する工程を有し、（Ａ）成分と（Ｂ）成分を含むペレット中の（Ａ）成分と（Ｂ）成分の質量比［（Ａ）／（Ｂ）］が５０／５０～８５／１５であり、（Ｃ）成分の添着量が、（Ａ）成分と（Ｂ）成分の合計に対し、４０質量ｐｐｍ以上である、樹脂組成物ペレットの製造方法。
［９］前記（Ｃ）成分を（Ａ）成分と（Ｂ）成分を含むペレットに添着する工程におけるペレット表面の温度が、１００℃以下である、前記［８］に記載の樹脂組成物ペレットの製造方法。
［１０］（Ａ）成分と（Ｂ）成分を含む溶融樹脂組成物をアンダーウォーターカット法でペレット化して（Ａ）成分と（Ｂ）成分を含むペレットを得る工程を含む、前記［８］又は［９］に記載の樹脂組成物ペレットの製造方法。 [1] A resin composition pellet containing a component (A): a styrene-based elastomer, a component (B): a polystyrene-based polymer mainly having a syndiotactic structure, and a component (C): a fatty acid amide compound. The mass ratio [(A) / (B)] of the component A) to the component (B) is 50/50 to 85/15, and the component (C) is formed into a pellet containing the components (A) and (B). A resin composition pellet that is attached and has a content of the component (C) of 40% by mass or more with respect to the total of the components (A) and (B).
[2] The component (A) is styrene isoprene styrene block copolymer (SIS), styrene butadiene styrene block copolymer (SBS), styrene ethylene propylene block copolymer (SEP), styrene ethylene butylene styrene block copolymer. The resin composition according to the above [1], which is at least one selected from the group consisting of (SEBS), styrene ethylene propylene styrene block copolymer (SEPS), and styrene ethylene ethylene propylene styrene block copolymer (SEEPS). Material pellets.
[3] The resin composition pellet according to the above [1] or [2], wherein the component (C) is at least one selected from the group consisting of fatty acid amides and alkylene fatty acid amides.
[4] The component (C) is at least one selected from the group consisting of stearic acid amide, oleic acid amide, erucic acid amide, methylene bisstearic acid amide, and ethylene bisstearic acid amide. The resin composition pellet according to any one of [3].
[5] Any of the above [1] to [4], wherein the total content of the component (A) and the component (B) in the pellet containing the component (A) and the component (B) is 90% by mass or more. The resin composition pellet according to one.
[6] One of the above [1] to [5], wherein the mass ratio [(A) / (B)] of the component (A) to the component (B) is 73/27 to 85/15. The resin composition pellets described.
[7] The resin composition pellet according to any one of the above [1] to [6], which is used as a water blocking material for a connector.
[8] A method for producing a resin composition pellet containing a component (A): a styrene-based elastomer, a component (B): a polystyrene-based polymer having a syndiotactic structure, and a component (C): a fatty acid amide compound. It has a step of adhering the component (C) to the pellet containing the component (A) and the component (B), and the component (A) and the component (B) in the pellet containing the component (A) and the component (B). The mass ratio [(A) / (B)] of is 50/50 to 85/15, and the amount of the component (C) attached is 40 mass ppm or more with respect to the total of the components (A) and (B). A method for producing resin composition pellets.
[9] The resin composition pellet according to the above [8], wherein the temperature of the pellet surface in the step of adhering the component (C) to the pellet containing the component (A) and the component (B) is 100 ° C. or lower. Production method.
[10] The above-mentioned [8] or the above-mentioned [8], which comprises a step of pelletizing a molten resin composition containing the component (A) and the component (B) by an underwater cut method to obtain pellets containing the component (A) and the component (B). The method for producing a resin composition pellet according to [9].
　本発明によれば、コネクタ用止水材、特にワイヤーハーネスコネクタ用止水材に好適な、ブロッキングの少ない樹脂組成物ペレットを提供することができる。 According to the present invention, it is possible to provide a resin composition pellet with less blocking, which is suitable for a water blocking material for a connector, particularly a water blocking material for a wire harness connector.
　以下、本発明の一実施形態について説明する。本発明の内容は以下に説明する実施形態に限定されるものではない。
　なお、本明細書において、数値の記載に関する「Ａ～Ｂ」という用語は、「Ａ以上Ｂ以下」（Ａ＜Ｂの場合）又は「Ａ以下Ｂ以上」（Ａ＞Ｂの場合）を意味する。また、本発明において、好ましい態様の組み合わせは、より好ましい態様である。 Hereinafter, an embodiment of the present invention will be described. The content of the present invention is not limited to the embodiments described below.
In addition, in this specification, the term "AB" regarding the description of a numerical value means "A or more and B or less" (in the case of A <B) or "A or less and B or more" (in the case of A> B). .. Further, in the present invention, the combination of preferred embodiments is a more preferred embodiment.
［樹脂組成物ペレット］
　本発明の樹脂組成物ペレットは、（Ａ）成分：スチレン系エラストマー、（Ｂ）成分：主としてシンジオタクチック構造を有するポリスチレン系重合体、及び（Ｃ）成分：脂肪酸アミド化合物を含有する樹脂組成物ペレットであって、（Ａ）成分と（Ｂ）成分の質量比［（Ａ）／（Ｂ）］が５０／５０～８５／１５であり、（Ｃ）成分が、（Ａ）成分と（Ｂ）成分を含むペレットに添着しており、（Ｃ）成分の含有量が、（Ａ）成分と（Ｂ）成分の合計に対し、４０質量ｐｐｍ以上である。 [Resin composition pellets]
The resin composition pellet of the present invention is a resin composition containing (A) component: a styrene-based elastomer, (B) component: a polystyrene-based polymer having a mainly syndiotactic structure, and (C) component: a fatty acid amide compound. In the pellet, the mass ratio [(A) / (B)] of the component (A) to the component (B) is 50/50 to 85/15, and the component (C) is the component (A) and the component (B). ) Is adhered to the pellet containing the component, and the content of the component (C) is 40% by mass or more with respect to the total of the components (A) and (B).
　コネクタの止水に用いられる樹脂には、ポリエチレンを主成分とする電線被覆材との密着性、耐熱性及び柔軟性が求められるが、本発明の樹脂組成物ペレットを構成する樹脂組成物は、特定の比率で（Ａ）成分のスチレン系エラストマーと（Ｂ）成分の主としてシンジオタクチック構造を有するポリスチレン系重合体を含むため、これらの性能にも優れる止水材を得ることができる。なかでも電線被覆材との密着性に優れ、止水効果に優れている。本発明の樹脂組成物ペレットは、このような電線被覆材との密着性に優れる樹脂組成物で構成されているにもかかわらず、（Ｃ）成分の脂肪酸アミド化合物が特定量、ペレット表面に添着していることで、ブロッキングの少ないペレットとなっており、成形後のコネクタに必要とされる性能を維持しつつ、ペレット同士のブロッキングを抑制することができる。 The resin used to stop water in the connector is required to have adhesion, heat resistance and flexibility to an electric wire coating material containing polyethylene as a main component. Since the styrene-based elastomer of the component (A) and the polystyrene-based polymer having a mainly syndiotactic structure of the component (B) are contained in a specific ratio, a water blocking material having excellent performance can be obtained. Among them, it has excellent adhesion to the wire coating material and has an excellent water-stopping effect. Although the resin composition pellet of the present invention is composed of such a resin composition having excellent adhesion to the electric wire coating material, a specific amount of the fatty acid amide compound of the component (C) is adhered to the pellet surface. As a result, the pellets have less blocking, and blocking between pellets can be suppressed while maintaining the performance required for the connector after molding.
＜（Ａ）成分：スチレン系エラストマー＞
　本発明の樹脂組成物ペレットに用いられる（Ａ）成分であるスチレン系エラストマーとしては、スチレンイソプレンスチレンブロック共重合体（ＳＩＳ）、スチレンブタジエンスチレンブロック共重合体（ＳＢＳ）、スチレンエチレンプロピレンブロック共重合体（ＳＥＰ）、スチレンエチレンブチレンスチレンブロック共重合体（ＳＥＢＳ）、スチレンエチレンプロピレンスチレンブロック共重合体（ＳＥＰＳ）、及びスチレンエチレンエチレンプロピレンスチレンブロック共重合体（ＳＥＥＰＳ）からなる群より選ばれる１つ以上が好ましく、これらのスチレン系エラストマーは一種のみを単独で又は二種以上を組み合わせて用いることができる。また、これらスチレン系エラストマーの中では、スチレンエチレンブチレンスチレンブロック共重合体（ＳＥＢＳ）が好ましく、未変性のスチレンエチレンブチレンスチレンブロック共重合体（ＳＥＢＳ）がより好ましい。未変性ＳＥＢＳを用いることで、吸水しにくくなり、コネクタの止水材用途として好ましい。
　スチレン系エラストマーのＭＦＲは温度２３０℃、荷重２．１６ｋｇｆの測定条件下において、０．０（Ｎｏ　Ｆｌｏｗ）～１０ｇ／１０分であることが好ましい。 <Component (A): Styrene-based elastomer>
Examples of the styrene-based elastomer as the component (A) used in the resin composition pellet of the present invention include styrene-isoprene styrene block copolymer (SIS), styrene butadiene styrene block copolymer (SBS), and styrene ethylene propylene block copolymer. One selected from the group consisting of coalescing (SEP), styreneethylene butylene styrene block copolymer (SEBS), styreneethylene propylene styrene block copolymer (SEPS), and styreneethylene ethylenepropylene styrene block copolymer (SEEPS). The above is preferable, and these styrene-based polymers can be used alone or in combination of two or more. Among these styrene-based elastomers, styrene ethylene butylene styrene block copolymer (SEBS) is preferable, and unmodified styrene ethylene butylene styrene block copolymer (SEBS) is more preferable. By using unmodified SEBS, it becomes difficult to absorb water, which is preferable as a water blocking material for connectors.
The MFR of the styrene-based elastomer is preferably 0.0 (No Flow) to 10 g / 10 minutes under the measurement conditions of a temperature of 230 ° C. and a load of 2.16 kgf.
＜（Ｂ）成分：主としてシンジオタクチック構造を有するポリスチレン系重合体＞
　（Ｂ）成分である主としてシンジオタクチック構造を有するポリスチレン系重合体（ＳＰＳ）におけるシンジオタクチック構造とは、立体化学構造がシンジオタクチック構造、即ち炭素－炭素結合から形成される主鎖に対して側鎖であるフェニル基が交互に反対方向に位置する立体構造を有するものであり、そのタクティシティーは同位体炭素による核磁気共鳴法（13Ｃ－ＮＭＲ法）により定量される。
　核磁気共鳴法（13Ｃ－ＮＭＲ法）により測定されるシンジオタクチック構造のタクティシティーは、連続する複数個の構成単位の存在割合、例えば２個の場合はダイアッド、３個の場合はトリアッド、５個の場合はペンタッドによって示すことができるが、（Ｂ）成分である主としてシンジオタクチック構造を有するポリスチレン系重合体には、通常はラセミダイアッドで７５％以上、好ましくは８５％以上、若しくはラセミペンタッドで３０％以上、好ましくは５０％以上のシンジオタクティシティーを有するポリスチレン系重合体が用いられる。 <Component (B): Polystyrene polymer mainly having a syndiotactic structure>
The syndiotactic structure in the polystyrene-based polymer (SPS) which is a component (B) and mainly has a syndiotactic structure refers to a syndiotactic structure whose three-dimensional chemical structure is a syndiotactic structure, that is, a main chain formed from a carbon-carbon bond. It has a three-dimensional structure in which phenyl groups, which are side chains, are alternately located in opposite directions, and its tacticity is quantified by a nuclear magnetic resonance method (13 C-NMR method) using isotope carbon.
The tacticity of the syndiotactic structure measured by the nuclear magnetic resonance method ( 13 C-NMR method) is the abundance ratio of a plurality of consecutive constituent units, for example, diad for two, triad for three, and so on. In the case of five, it can be indicated by pentad, but for polystyrene-based polymers having a predominantly syndiotactic structure, which is the component (B), usually 75% or more, preferably 85% or more of racemic diad, or A polystyrene-based polymer having a syndiotacticity of 30% or more, preferably 50% or more in lasemipentad is used.
　（Ｂ）成分であるＳＰＳにおけるポリスチレン系重合体としては、ポリスチレン、ポリ（アルキルスチレン）、ポリ（ハロゲン化スチレン）、ポリ（ハロゲン化アルキルスチレン）、ポリ（アルコキシスチレン）、ポリ（ビニル安息香酸エステル）、これらの水素化重合体及びこれらの混合物、あるいはこれらを主成分とする共重合体が挙げられる。
　ここでポリ（アルキルスチレン）としては、ポリ（メチルスチレン）、ポリ（エチルスチレン）、ポリ（イソプロピルスチレン)、ポリ（ｔ－ブチルスチレン）、ポリ（フェニルスチレン）、ポリ（ビニルナフタレン）、ポリ(ビニルスチレン）などがあり、ポリ（ハロゲン化スチレン）としては、ポリ（クロロスチレン）、ポリ（ブロモスチレン）、ポリ（フルオロスチレン）などがある。また、ポリ（ハロゲン化アルキルスチレン）としては、ポリ（クロロメチルスチレン）など、またポリ（アルコキシスチレン）としては、ポリ（メトキシスチレン）、ポリ（エトキシスチレン）などがある。 Examples of the polystyrene-based polymer in SPS as the component (B) include polystyrene, poly (alkyl styrene), poly (styrene halogenated), poly (alkyl styrene halide), poly (alkoxystyrene), and poly (vinyl benzoic acid ester). ), These hydrides and mixtures thereof, or copolymers containing these as main components.
Here, as poly (alkyl styrene), poly (methyl styrene), poly (ethyl styrene), poly (isopropyl styrene), poly (t-butyl styrene), poly (phenyl styrene), poly (vinyl naphthalene), poly (poly (vinyl naphthalene)) Vinyl styrene) and the like, and poly (halogenated styrene) includes poly (chlorostyrene), poly (bromostyrene), poly (fluorostyrene) and the like. Further, examples of poly (alkyl styrene halogenated) include poly (chloromethyl styrene), and examples of poly (alkoxy styrene) include poly (methoxy styrene) and poly (ethoxy styrene).
　なお、これらの中で特に好ましいポリスチレン系重合体としては、ポリスチレン、ポリ（ｐ－メチルスチレン）、ポリ（ｍ－メチルスチレン）、ポリ（ｐ－又はｔ－ブチルスチレン）、ポリ（ｐ－クロロスチレン）、ポリ（ｍ－クロロスチレン）、ポリ（ｐ－フルオロスチレン）、水素化ポリスチレン及びこれらの構造単位を含む共重合体が挙げられる。
　このようなＳＰＳは、例えば、不活性炭化水素溶媒中又は溶媒の不存在下に、チタン化合物及び水とトリアルキルアルミニウムの縮合生成物を触媒として、スチレン系単量体（上記ポリスチレン系重合体に対応する単量体）を重合することにより製造することができる（特開昭６２－１８７７０８号公報参照）。また、ポリ（ハロゲン化アルキルスチレン）については特開平１－４６９１２号公報に記載の方法、水素化重合体は特開平１－１７８５０５号公報に記載の方法などにより得ることができる。これらのＳＰＳは一種のみを単独で又は二種以上を組み合わせて用いることができる。 Among these, polystyrene-based polymers particularly preferable are polystyrene, poly (p-methylstyrene), poly (m-methylstyrene), poly (p- or t-butylstyrene), and poly (p-chlorostyrene). ), Poly (m-chlorostyrene), poly (p-fluorostyrene), polystyrene hydride and copolymers containing these structural units.
Such SPS is produced, for example, in a styrene-based monomer (the above-mentioned polystyrene-based polymer) by using a titanium compound and a condensation product of water and trialkylaluminum as a catalyst in an inert hydrocarbon solvent or in the absence of a solvent. It can be produced by polymerizing (corresponding monomer) (see JP-A-62-187708). The poly (alkyl styrene halide) can be obtained by the method described in JP-A No. 1-46912, and the hydrogenated polymer can be obtained by the method described in JP-A-1-178505. These SPSs can be used alone or in combination of two or more.
　（Ｂ）成分であるＳＰＳの分子量については特に制限はないが、成形時の樹脂の流動性及び得られる成形体の機械的性質の観点から、重量平均分子量が１×１０4以上１×１０6以下であることが好ましく、５０，０００以上５００，０００以下であることがより好ましく、５０，０００以上３００，０００以下であることが更に好ましい。重量平均分子量が１×１０4以上であれば、十分な機械的性質を有する成形体を得ることができる。一方、重量平均分子量が１×１０6以下であれば成形時の樹脂の流動性にも問題がない。
　温度３００℃、荷重１．２ｋｇｆの条件下で測定されたＳＰＳ（Ｂ）のＭＦＲは、２ｇ／１０分以上、好ましくは４ｇ／１０分以上であることが好ましい。この範囲であれば、成形時の樹脂の流動性にも問題がない。また、５０ｇ／１０分以下であれば十分な機械的性質を有する成形体を得ることができ、好ましくは３０ｇ／１０分以下である。また、この範囲であれば、スチレン系エラストマーのＭＦＲとの関係から、相分離を抑制でき、外観や柔軟性に優れたものを得ることができる。 The molecular weight of SPS, which is the component (B), is not particularly limited, but the weight average molecular weight is 1 × 10 4 or more and 1 × 10 6 from the viewpoint of the fluidity of the resin during molding and the mechanical properties of the obtained molded product. It is preferably 50,000 or more and 500,000 or less, more preferably 50,000 or more and 300,000 or less. When the weight average molecular weight is 1 × 10 4 or more, a molded product having sufficient mechanical properties can be obtained. On the other hand, if the weight average molecular weight is 1 × 106 or less, there is no problem in the fluidity of the resin during molding.
The MFR of SPS (B) measured under the conditions of a temperature of 300 ° C. and a load of 1.2 kgf is preferably 2 g / 10 minutes or more, preferably 4 g / 10 minutes or more. Within this range, there is no problem with the fluidity of the resin during molding. Further, if it is 50 g / 10 minutes or less, a molded product having sufficient mechanical properties can be obtained, preferably 30 g / 10 minutes or less. Further, within this range, phase separation can be suppressed due to the relationship with the MFR of the styrene-based elastomer, and a product having excellent appearance and flexibility can be obtained.
　（Ａ）成分と（Ｂ）成分の質量比［（Ａ）／（Ｂ）］は、５０／５０～８５／１５であり、６０／４０～８５／１５であることが好ましく、７０／３０～８５／１５であることがより好ましく、７３／２７～８５／１５であることが更に好ましい。（Ａ）成分と（Ｂ）成分の合計１００質量部に対して（Ｂ）成分（ＳＰＳ）が１５質量部未満の場合には、特に、止水材として用いた場合に要求される十分な耐熱性向上効果が得られず、５０質量部よりも多い場合には、特に止水材として用いた場合、必要な電線被覆材との密着性が維持できなくなるおそれがある。一方、前記質量比であると、密着性にも優れ、耐熱性にも優れるものとなる。
　（Ｃ）成分が添着していない（Ａ）成分と（Ｂ）成分を含むペレット中の（Ａ）成分と（Ｂ）成分の合計含有量は、好ましくは９０質量％以上であり、より好ましくは９５質量％以上であり、更に好ましくは９９質量％以上であり、より更に好ましくは９９．５質量％以上である。上限には制限はないが、１００質量％以下である。 The mass ratio [(A) / (B)] of the component (A) to the component (B) is 50/50 to 85/15, preferably 60/40 to 85/15, and 70/30 to 70. It is more preferably 85/15, and even more preferably 73/27 to 85/15. Sufficient heat resistance required when the component (B) (SPS) is less than 15 parts by mass with respect to a total of 100 parts by mass of the component (A) and the component (B), especially when used as a water blocking material. If the effect of improving the property is not obtained and the amount is more than 50 parts by mass, the necessary adhesion to the electric wire covering material may not be maintained, especially when used as a water blocking material. On the other hand, the mass ratio is excellent in adhesion and heat resistance.
The total content of the component (A) and the component (B) in the pellet containing the component (A) and the component (B) without the component (C) is preferably 90% by mass or more, more preferably 90% by mass or more. It is 95% by mass or more, more preferably 99% by mass or more, and even more preferably 99.5% by mass or more. There is no upper limit, but it is 100% by mass or less.
＜（Ｃ）成分：脂肪酸アミド化合物＞
　本発明の樹脂組成物ペレットは、更に（Ｃ）成分である脂肪酸アミド化合物を含有する。
　（Ｃ）成分は、（Ａ）成分と（Ｂ）成分を含むペレットに添着しており、（Ｃ）成分の含有量は、（Ａ）成分と（Ｂ）成分の合計に対し、４０質量ｐｐｍ以上である。 <Component (C): fatty acid amide compound>
The resin composition pellet of the present invention further contains a fatty acid amide compound which is a component (C).
The component (C) is attached to a pellet containing the components (A) and (B), and the content of the component (C) is 40 mass ppm with respect to the total of the components (A) and (B). That is all.
　（Ｃ）成分である脂肪酸アミド化合物は、脂肪酸アミド及びアルキレン脂肪酸アミドからなる群より選ばれる少なくとも１つであることが好ましく、アルキレン脂肪酸アミドであることがより好ましい。
　好ましい脂肪酸アミドとしては、ステアリン酸アミド、オレイン酸アミド、エルカ酸アミド等が挙げられる。
　好ましいアルキレン脂肪酸アミドとしては、メチレンビスステアリン酸アミド、エチレンビスステアリン酸アミド等が挙げられる。
　したがって、（Ｃ）成分である脂肪酸アミド化合物は、ステアリン酸アミド、オレイン酸アミド、エルカ酸アミド、メチレンビスステアリン酸アミド、及びエチレンビスステアリン酸アミドからなる群より選ばれる少なくとも１つであることが好ましく、エチレンビスステアリン酸アミドであることがより好ましい。 The fatty acid amide compound as the component (C) is preferably at least one selected from the group consisting of fatty acid amides and alkylene fatty acid amides, and more preferably alkylene fatty acid amides.
Preferred fatty acid amides include stearic acid amides, oleic acid amides, erucic acid amides and the like.
Preferred alkylene fatty acid amides include methylene bisstearic amides, ethylene bisstearic amides and the like.
Therefore, the fatty acid amide compound as the component (C) is at least one selected from the group consisting of stearic acid amides, oleic acid amides, erucic acid amides, methylene bisstearic acid amides, and ethylene bisstearic acid amides. It is preferably an ethylene bisstearic acid amide, more preferably.
　（Ｃ）成分は、（Ａ）成分と（Ｂ）成分を含むペレットに添着している。ここで、「添着している」とは、ペレット表面にその成分の組成を、少なくとも一部は維持したまま結合している状態をいい、ペレットの成分と分子レベルで混合しているものは除かれる。
　本発明においては、（Ｃ）成分から構成される粒子がペレット表面に物理的に結合していることがより好ましい。
　（Ｃ）成分が（Ａ）成分と（Ｂ）成分を含むペレットに添着していることで、表面に局在する（Ｃ）成分が、単なる化学的な滑剤としてのみならず、物理的にペレット間に空間を形成することで、効率的にブロッキングを抑制できるものと考えられる。 The component (C) is attached to a pellet containing the component (A) and the component (B). Here, "adhered" means a state in which the composition of the component is bonded to the surface of the pellet while maintaining at least a part of the composition, excluding those mixed with the component of the pellet at the molecular level. Be taken.
In the present invention, it is more preferable that the particles composed of the component (C) are physically bonded to the pellet surface.
By adhering the component (C) to the pellet containing the components (A) and (B), the component (C) localized on the surface is not only a chemical lubricant but also a physical pellet. By forming a space between them, it is considered that blocking can be suppressed efficiently.
　本発明の樹脂組成物ペレットにおいて、（Ｃ）成分の含有量は、（Ａ）成分と（Ｂ）成分の合計に対し、４０質量ｐｐｍ以上であり、８０質量ｐｐｍ以上がより好ましく、９０質量ｐｐｍ以上がより好ましく、１１０質量ｐｐｍ以上がより好ましく、１２０質量ｐｐｍ以上がより好ましく、１４０質量ｐｐｍ以上が更に好ましい。また、含有量の上限には制限はないが、経済性の観点から、１０００質量ｐｐｍ以下が好ましく、３００質量ｐｐｍ未満がより好ましく、２００質量ｐｐｍ未満が更に好ましい。この範囲であれば、効果的にブロッキングを抑制することができる。 In the resin composition pellet of the present invention, the content of the component (C) is 40 mass ppm or more, more preferably 80 mass ppm or more, and 90 mass ppm with respect to the total of the component (A) and the component (B). The above is more preferable, 110 mass ppm or more is more preferable, 120 mass ppm or more is more preferable, and 140 mass ppm or more is further preferable. The upper limit of the content is not limited, but from the viewpoint of economy, 1000 mass ppm or less is preferable, less than 300 mass ppm is more preferable, and less than 200 mass ppm is further preferable. Within this range, blocking can be effectively suppressed.
＜任意の添加剤＞
　本発明の樹脂組成物ペレットには、前記（Ａ）成分、（Ｂ）成分及び（Ｃ）成分以外に任意の添加剤が含まれていてもよい。
　任意の添加剤としては、酸化防止剤、ポリフェニレンエーテル、核剤等が挙げられる。なお、電線被覆材との密着性の点から、本発明の樹脂組成物ペレットには、添加剤として離型剤は実質的に含まないことが好ましい。実質的に含まないとする具体的な添加量は、樹脂組成物ペレットに対して、より好ましくは５００質量ｐｐｍ未満、更に好ましくは５０質量ｐｐｍ未満である。 <Any additive>
The resin composition pellet of the present invention may contain any additive in addition to the components (A), (B) and (C).
Optional additives include antioxidants, polyphenylene ethers, nucleating agents and the like. From the viewpoint of adhesion to the electric wire coating material, it is preferable that the resin composition pellet of the present invention does not substantially contain a mold release agent as an additive. The specific addition amount that is substantially not contained is more preferably less than 500 mass ppm, still more preferably less than 50 mass ppm, based on the resin composition pellets.
（酸化防止剤）
　酸化防止剤は、製品としての止水材の熱安定性を高める目的で、樹脂組成物ペレットに対して、５質量％以内で添加してもよい。
　酸化防止剤としては公知のものを使用することができるが、本発明においては、リン系酸化防止剤を実質的に含まない方が好ましい。リン系酸化防止剤を用いると、成形時にリン酸ガスを生じ、リン酸ガスが電線被覆材と止水材の間に入ることで密着性が低下する傾向があるため、本発明においては極力含まないことが望ましい。「リン系酸化防止剤を実質的に含まない」とは、リン系酸化防止剤の含有量が、樹脂組成物ペレットに対して、３０００質量ｐｐｍ未満、より好ましくは１０００質量ｐｐｍ未満、更に好ましくは５００質量ｐｐｍ未満、より更に好ましくは５０質量ｐｐｍ未満であることをいう。 (Antioxidant)
The antioxidant may be added in an amount of 5% by mass or less with respect to the resin composition pellets for the purpose of enhancing the thermal stability of the water blocking material as a product.
As the antioxidant, known ones can be used, but in the present invention, it is preferable that the phosphorus-based antioxidant is substantially not contained. When a phosphorus-based antioxidant is used, phosphoric acid gas is generated during molding, and the phosphoric acid gas tends to enter between the wire coating material and the water blocking material to reduce the adhesiveness. Therefore, this is included as much as possible in the present invention. It is desirable not to. "Substantially free of phosphorus-based antioxidants" means that the content of phosphorus-based antioxidants is less than 3000 mass ppm, more preferably less than 1000 mass ppm, still more preferably, relative to the resin composition pellets. It means that it is less than 500 mass ppm, more preferably less than 50 mass ppm.
　酸化防止剤としては、フェノール系酸化防止剤を用いることが好ましい。フェノール系酸化防止剤としては、例えば、トリエチレングリコール・ビス［３－（３－ｔｅｒｔ－ブチル－５－メチル－４－ヒドロキシフェニル）プロピオネート］、１，６－ヘキサンジオール・ビス［３－（３，５－ジ－ｔｅｒｔ－ブチル－４－ヒドロキシフェニル）プロピオネート］、ペンタエリスリトールテトラキス［３－（３，５－ジ－ｔｅｒｔ－ブチル－４－ヒドロキシフェニル）プロピオネート］、オクタデシル－３－（３，５－ジ－ｔｅｒｔ－ブチル－４－ヒドロキシフェニル）プロピオネート、３，５－ジ－ｔｅｒｔ－ブチル－４－ヒドロキシベンジルフォスフォネート－ジエチルエステル、Ｎ，Ｎ’－ヘキサメチレンビス（３，５－ジ－ｔｅｒｔ－ブチル－４－ヒドロキシ－ヒドロシンナムアミド）、１，３，５－トリメチル－２，４，６－トリス（３，５－ジ－ｔｅｒｔ－ブチル－４－ヒドロキシベンジル）ベンゼン、３，９－ビス［２－｛３－（３－ｔｅｒｔ－ブチル－４－ヒドロキシ－５－メチルフェニル）プロピオニルオキシ｝－１，１－ジメチルエチル］－２，４，８，１０－テトラオキサスピロ［５．５］ウンデカン等を挙げることができる。
　酸化防止剤の市販品としては、ペンタエリスリトールテトラキス［３－（３，５－ジ－ｔ－ブチル－４－ヒドロキシフェニル）プロピオネート］（ＢＡＳＦ株式会社製、「ＩＲＧＡＮＯＸ１０１０」）、１，３，５－トリス－（３’，５’－ジ‐ｔｅｒｔ－ブチル－４’－ヒドロキシベンジル）イソシアヌル酸（株式会社ＡＤＥＫＡ製、「アデカスタブ　ＡＯ－２０」）等を用いることができる。 As the antioxidant, it is preferable to use a phenolic antioxidant. Examples of the phenolic antioxidant include triethylene glycol bis [3- (3-tert-butyl-5-methyl-4-hydroxyphenyl) propionate] and 1,6-hexanediol bis [3- (3). , 5-Di-tert-butyl-4-hydroxyphenyl) propionate], pentaerythritol tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate], octadecyl-3- (3,5) -Di-tert-butyl-4-hydroxyphenyl) propionate, 3,5-di-tert-butyl-4-hydroxybenzylphosphonate-diethyl ester, N, N'-hexamethylenebis (3,5-di-) tert-butyl-4-hydroxy-hydrocinnamamide), 1,3,5-trimethyl-2,4,6-tris (3,5-di-tert-butyl-4-hydroxybenzyl) benzene, 3,9 -Bis [2- {3- (3-tert-butyl-4-hydroxy-5-methylphenyl) propionyloxy} -1,1-dimethylethyl] -2,4,8,10-tetraoxaspiro [5. 5] Benzyl and the like can be mentioned.
Commercially available antioxidants include pentaerythritol tetrakis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate] (BASF Corporation, "IRGANOX1010"), 1,3,5-. Tris- (3', 5'-di-tert-butyl-4'-hydroxybenzyl) isocyanuric acid (manufactured by ADEKA Corporation, "ADEKA STAB AO-20") and the like can be used.
（ポリフェニレンエーテル）
　ポリフェニレンエーテルを添加することで密着性を向上させることができる。止水材用として吸水性の観点から未変性ＳＥＢＳを用いる場合には、未変性ポリフェニレンエーテルを用いることが好ましい。
　ポリフェニレンエーテルは、樹脂組成物ペレット中、０．１～１０質量％含有することが好ましく、０．５～９質量％含有することがより好ましく、２～８質量％含有することが更に好ましい。ポリフェニレンエーテルを０．１質量％以上含有させることによりポリフェニレンエーテルによる接着性の向上効果が得られ、１０質量％以下とすることにより、エラストマーの伸びが阻害されず、必要とされる柔軟性が得られる。 (Polyphenylene ether)
Adhesion can be improved by adding polyphenylene ether. When unmodified SEBS is used as a water blocking material from the viewpoint of water absorption, it is preferable to use unmodified polyphenylene ether.
The polyphenylene ether is preferably contained in the resin composition pellet in an amount of 0.1 to 10% by mass, more preferably 0.5 to 9% by mass, and even more preferably 2 to 8% by mass. By containing 0.1% by mass or more of the polyphenylene ether, the effect of improving the adhesiveness of the polyphenylene ether can be obtained, and by setting it to 10% by mass or less, the elongation of the elastomer is not hindered and the required flexibility is obtained. Be done.
　ポリフェニレンエーテル（ＰＰＥ）の例としては、ポリ（２，３－ジメチル－６－エチル－１，４－フェニレンエーテル）、ポリ（２－メチル－６－クロロメチル－１，４－フェニレンエーテル）、ポリ（２－メチル－６－ヒドロキシエチル－１，４－フェニレンエーテル）、ポリ（２－メチル－６－ｎ－ブチル－１，４－フェニレンエーテル）、ポリ（２－エチル－６－イソプロピル－１，４－フェニレンエーテル）、ポリ（２－エチル－６－ｎ－プロピル－１，４－フェニレンエーテル）、ポリ（２，３，６－トリメチル－１，４－フェニレンエーテル）、ポリ〔２－（４’－メチルフェニル）－１，４－フェニレンエーテル〕、ポリ（２－ブロモ－６－フェニル－１，４－フェニレンエーテル）、ポリ（２－メチル－６－フェニル－１，４－フェニレンエーテル）、ポリ（２－フェニル－１，４－フェニレンエーテル）、ポリ（２－クロロ－１，４－フェニレンエーテル）、ポリ（２－メチル－１，４－フェニレンエーテル）、ポリ（２－クロロ－６－エチル－１，４－フェニレンエーテル）、ポリ（２－クロロ－６－ブロモ－１，４－フェニレンエーテル）、ポリ（２，６－ジ－ｎ－プロピル－１，４－フェニレンエーテル）、ポリ（２－メチル－６－イソプロピル－１，４－フェニレンエーテル）、ポリ（２－クロロ－６－メチル－１，４－フェニレンエーテル）、ポリ（２－メチル－６－エチル－１，４－フェニレンエーテル）、ポリ（２，６－ジブロモ－１，４－フェニレンエーテル）、ポリ（２，６－ジクロロ－１，４－フェニレンエーテル）、ポリ（２，６－ジエチル－１，４－フェニレンエーテル）及びポリ（２，６－ジメチル－１，４－フェニレンエーテル）等が挙げられる。この中で、特にポリ（２，６－ジメチル－１，４－フェニレンエーテル）が好ましい。なお、上記ポリフェニレンエーテルは、一種のみを単独で、又は二種以上を組み合わせて用いることができる。
　これらのポリフェニレンエーテルは、公知の化合物であり、米国特許第３，３０６，８７４号，同３，３０６，８７５号，同３，２５７，３５７号及び同３，２５７，３５８号の各明細書を参照することができる。ポリフェニレンエーテルは、通常、銅アミン錯体、および二箇所もしくは三箇所を置換した一種以上のフェノール化合物の存在下で、ホモポリマー又はコポリマーを生成する酸化カップリング反応によって調製される。ここで、銅アミン錯体は、第一，第二及び第三アミンから誘導される銅アミン錯体を使用できる。 Examples of polyphenylene ether (PPE) include poly (2,3-dimethyl-6-ethyl-1,4-phenylene ether), poly (2-methyl-6-chloromethyl-1,4-phenylene ether), and poly. (2-Methyl-6-hydroxyethyl-1,4-phenylene ether), poly (2-methyl-6-n-butyl-1,4-phenylene ether), poly (2-ethyl-6-isopropyl-1, 4-phenylene ether), poly (2-ethyl-6-n-propyl-1,4-phenylene ether), poly (2,3,6-trimethyl-1,4-phenylene ether), poly [2- (4) '-Methylphenyl) -1,4-phenylene ether], poly (2-bromo-6-phenyl-1,4-phenylene ether), poly (2-methyl-6-phenyl-1,4-phenylene ether), Poly (2-phenyl-1,4-phenylene ether), poly (2-chloro-1,4-phenylene ether), poly (2-methyl-1,4-phenylene ether), poly (2-chloro-6- Ethyl-1,4-phenylene ether), poly (2-chloro-6-bromo-1,4-phenylene ether), poly (2,6-di-n-propyl-1,4-phenylene ether), poly (2,6-di-n-propyl-1,4-phenylene ether), poly ( 2-Methyl-6-isopropyl-1,4-phenylene ether), poly (2-chloro-6-methyl-1,4-phenylene ether), poly (2-methyl-6-ethyl-1,4-phenylene ether) ), Poly (2,6-dibromo-1,4-phenylene ether), Poly (2,6-dichloro-1,4-phenylene ether), Poly (2,6-diethyl-1,4-phenylene ether) and Examples thereof include poly (2,6-dimethyl-1,4-phenylene ether). Of these, poly (2,6-dimethyl-1,4-phenylene ether) is particularly preferable. The polyphenylene ether may be used alone or in combination of two or more.
These polyphenylene ethers are known compounds, and are described in US Pat. Nos. 3,306,874, 3,306,875, 3,257,357 and 3,257,358. Can be referenced. Polyphenylene ethers are usually prepared by an oxidation coupling reaction to produce homopolymers or copolymers in the presence of copper amine complexes and one or more phenolic compounds substituted at two or three sites. Here, as the copper amine complex, copper amine complexes derived from the first, second and third amines can be used.
（核剤）
　樹脂組成物ペレットを構成する樹脂混合物が核剤（結晶化核剤）を含むことにより、樹脂組成物ペレット成形時の結晶化速度を適切に保ち、ペレットの量産性を担保することができ、耐熱性にも優れたものとなる。核剤としては公知のものを使用することができ、例えば、アルミニウムジ（ｐ－ｔｅｒｔ－ブチルベンゾエート）等のカルボン酸の金属塩、ナトリウム－２，２’－メチレンビス（４，６－ジ－ｔｅｒｔ－ブチルフェニル）ホスフェート、メチレンビス（２，４－ジ－ｔｅｒｔ－ブチルフェノール）アシッドホスフェートナトリウム等のリン酸の金属塩、タルク、フタロシアニン誘導体、リン酸エステル系化合物などを挙げることができる。具体的な商品名としては、株式会社ＡＤＥＫＡ製の「Ａｄｅｋａｓｔａｂ　ＮＡ－１０」、「Ａｄｅｋａｓｔａｂ　ＮＡ－１１」、「Ａｄｅｋａｓｔａｂ　ＮＡ－２１」、「Ａｄｅｋａｓｔａｂ　ＮＡ－３０」、「Ａｄｅｋａｓｔａｂ　ＮＡ－３５」、ＤＩＣ株式会社製のＰＴＢＢＡ－ＡＬ等が挙げられる。
　樹脂混合物が核剤を含む場合の核剤の含有量は、樹脂組成物ペレット中、好ましくは０．２質量％以上、より好ましくは０．５質量％以上であり、好ましくは２．０質量％以下、より好ましくは１．５質量％以下である。０．２質量％以上であると樹脂部材を構成する樹脂成形材料ペレットの量産性や耐熱性に優れ、２．０質量％以下であれば核剤に由来するガスの発生を抑制でき、密着性を低下させることはない。核剤は、一種を単独で、又は二種以上を組み合わせて用いることができる。 (Nuclear agent)
Since the resin mixture constituting the resin composition pellet contains a nucleating agent (crystallization nucleating agent), the crystallization rate at the time of molding the resin composition pellet can be appropriately maintained, the mass productivity of the pellet can be ensured, and heat resistance can be ensured. It will also be excellent in sex. Known nucleating agents can be used, for example, metal salts of carboxylic acids such as aluminum di (p-tert-butylbenzoate), sodium-2,2'-methylenebis (4,6-di-tert). Examples thereof include metal salts of phosphoric acid such as -butylphenyl) phosphate and sodium methylenebis (2,4-di-tert-butylphenol) acid phosphate, talc, phthalocyanine derivatives, and phosphoric acid ester compounds. Specific product names include "ADEKASTAB NA-10", "ADEKASTAB NA-11", "ADEKASTAB NA-21", "ADEKASTAB NA-30", "ADEKASTAB NA-30", and DIC Corporation manufactured by ADEKA CORPORATION. Examples include PTBBA-AL manufactured by the company.
When the resin mixture contains a nucleating agent, the content of the nucleating agent in the resin composition pellets is preferably 0.2% by mass or more, more preferably 0.5% by mass or more, and preferably 2.0% by mass. Hereinafter, it is more preferably 1.5% by mass or less. If it is 0.2% by mass or more, the mass productivity and heat resistance of the resin molding material pellets constituting the resin member are excellent, and if it is 2.0% by mass or less, the generation of gas derived from the nucleating agent can be suppressed and the adhesion is good. Does not reduce. The nucleating agent may be used alone or in combination of two or more.
＜コネクタ用止水材への使用＞
　本発明の樹脂組成物ペレットは、コネクタの止水材用途として使用することが好ましい。すなわち、本発明の樹脂組成物ペレットは、コネクタ用止水材に用いることが好ましい。
　具体的には、（Ａ）成分：スチレン系エラストマー、（Ｂ）成分：主としてシンジオタクチック構造を有するポリスチレン系重合体、及び（Ｃ）成分：脂肪酸アミド化合物を含有し、（Ａ）成分と（Ｂ）成分の質量比［（Ａ）／（Ｂ）］が５０／５０～８５／１５であり、（Ｃ）成分が、（Ａ）成分と（Ｂ）成分を含むペレットに添着しており、（Ｃ）成分の含有量が、（Ａ）成分と（Ｂ）成分の合計に対し、４０質量ｐｐｍ以上である、樹脂組成物ペレットは、コネクタ用止水材に用いることが好ましい。 <Use as a waterproof material for connectors>
The resin composition pellet of the present invention is preferably used as a water blocking material for connectors. That is, the resin composition pellet of the present invention is preferably used as a water blocking material for a connector.
Specifically, the component (A): a styrene-based elastomer, the component (B): a polystyrene-based polymer having a syndiotactic structure, and the component (C): a fatty acid amide compound are contained, and the component (A) and ( The mass ratio [(A) / (B)] of the component B) is 50/50 to 85/15, and the component (C) is attached to the pellet containing the components (A) and (B). The resin composition pellet in which the content of the component (C) is 40% by mass or more with respect to the total of the components (A) and (B) is preferably used as a water blocking material for a connector.
　前記樹脂組成物ペレットを融解し、目的の形状に合わせて成形することで、コネクタ用止水材として使用することができる。また、前記樹脂組成物ペレットを射出成形などにより、コネクタ用止水材、更に具体的には、ワイヤーハーネスコネクタ用止水材として使用することができる。
　止水材の成形方法については特に制限はなく、射出成形、押出成形等公知の方法により成形することができる。射出成形のときの成形温度は、用いるＳＰＳの融点以上、３５０℃未満が好ましい。成形温度をＳＰＳの融点以上とすることにより、流動性が低下するおそれがない。また、成形温度を３５０℃未満とすることにより、ＳＰＳが熱分解するおそれがない。また金型温度としては、３０～８０℃が好ましく、３０～６０℃が更に好ましい。金型温度を３０℃以上とすることにより、ＳＰＳが十分結晶化し、ＳＰＳの特徴が十分発揮される。また、金型温度を８０℃以下とすることにより、容易に離型することができる。 By melting the resin composition pellet and molding it into a desired shape, it can be used as a water blocking material for a connector. Further, the resin composition pellet can be used as a water blocking material for a connector, more specifically, as a water blocking material for a wire harness connector by injection molding or the like.
The molding method of the water blocking material is not particularly limited, and molding can be performed by a known method such as injection molding or extrusion molding. The molding temperature at the time of injection molding is preferably equal to or higher than the melting point of the SPS used and lower than 350 ° C. By setting the molding temperature to be equal to or higher than the melting point of SPS, there is no possibility that the fluidity will decrease. Further, by setting the molding temperature to less than 350 ° C., there is no possibility that the SPS is thermally decomposed. The mold temperature is preferably 30 to 80 ° C, more preferably 30 to 60 ° C. By setting the mold temperature to 30 ° C. or higher, the SPS is sufficiently crystallized and the characteristics of the SPS are fully exhibited. Further, by setting the mold temperature to 80 ° C. or lower, the mold can be easily released.
　本発明の樹脂組成物ペレットは、（Ｃ）成分をペレット表面のみに添着してブロッキングを抑制するものであるため、比較的少量の（Ｃ）成分で高いブロッキング抑制効果を発現することができる。（Ｃ）成分がコネクタ用止水材の物性に影響を与える場合には、（Ｃ）成分の量を前述に記載の範囲内で、少量に調整することも可能である。 Since the resin composition pellet of the present invention adheres the component (C) only to the surface of the pellet to suppress blocking, a high blocking suppressing effect can be exhibited with a relatively small amount of the component (C). When the component (C) affects the physical properties of the water blocking material for the connector, the amount of the component (C) can be adjusted to a small amount within the range described above.
　本発明の樹脂組成物ペレットはコネクタの止水材用として、電子機器、車載・電送部品、トランス・コイルパワーモジュール及びそのデバイス、リレー、センサー等に極めて好適に使用することができる。本発明の樹脂組成物ペレットを成形し、止水材に用いることで、特に雨やウォッシャー液などがかかりやすい場所に使用しても、電子制御ユニットへの水の侵入を効果的に防止することができる。 The resin composition pellet of the present invention can be extremely suitably used for a water blocking material for a connector, an electronic device, an in-vehicle / transmission component, a transformer / coil power module and its device, a relay, a sensor, and the like. By molding the resin composition pellet of the present invention and using it as a water blocking material, it is possible to effectively prevent water from entering the electronic control unit even when it is used in a place where it is easily exposed to rain or washer fluid. Can be done.
［樹脂組成物ペレットの製造方法］
　本発明の樹脂組成物ペレットは、いかなる方法で製造してもよいが、以下の方法で製造することが好ましい。
　すなわち、本発明の樹脂組成物ペレットの製造方法は、（Ａ）成分：スチレン系エラストマー、（Ｂ）成分：主としてシンジオタクチック構造を有するポリスチレン系重合体、及び（Ｃ）成分：脂肪酸アミド化合物を含有する樹脂組成物ペレットの製造方法であって、（Ｃ）成分を（Ａ）成分と（Ｂ）成分を含むペレットに添着する工程を有し、（Ａ）成分と（Ｂ）成分を含むペレット中の（Ａ）成分と（Ｂ）成分の質量比［（Ａ）／（Ｂ）］が５０／５０～８５／１５であり、（Ｃ）成分の添着量が、（Ａ）成分と（Ｂ）成分の合計に対し、４０質量ｐｐｍ以上である。 [Manufacturing method of resin composition pellets]
The resin composition pellet of the present invention may be produced by any method, but it is preferably produced by the following method.
That is, the method for producing a resin composition pellet of the present invention comprises (A) component: a styrene-based elastomer, (B) component: a polystyrene-based polymer having a mainly syndiotactic structure, and (C) component: a fatty acid amide compound. A method for producing a resin composition pellet containing a component (C), which comprises a step of adhering a component (C) to a pellet containing the components (A) and (B), and a pellet containing the components (A) and (B). The mass ratio [(A) / (B)] of the component (A) to the component (B) is 50/50 to 85/15, and the amount of the component (C) attached is between the component (A) and (B). ) 40 mass ppm or more with respect to the total of the components.
　本製造方法において、まず（Ａ）成分と（Ｂ）成分を含むペレットを作製する。
　具体的には、（Ａ）成分と（Ｂ）成分のそれぞれのペレットを室温で混合した後、溶融混練など様々な方法でブレンドすればよく、その方法は特に制限はされない。混合・混練方法として、二軸押出機を用いた溶融混練が好ましく用いられる。
　二軸押出機を用いた溶融混練においては、（Ｂ）成分であるＳＰＳの融点以上、３５０℃未満での混練が好ましい。混練温度をＳＰＳの融点以上とすることにより、ＳＰＳの粘度が高くなりすぎることがないため、生産性が低下することがない。また、混練温度を３５０℃未満とすることにより、ＳＰＳが熱分解するおそれがない。
　前述の任意の添加剤、たとえば、酸化防止剤等は（Ａ）成分と（Ｂ）成分を溶融混練する際に、添加することが好ましい。（Ａ）成分と（Ｂ）成分と同時に混練することによって、添加剤の効果を樹脂組成物ペレット全体に発揮させることができ、製品である止水材に添加剤の性能を付与することができる。
　溶融混練して得られた溶融樹脂組成物をペレット化して、ペレットを得る。
　ペレット化の方法としては、制限はないが、溶融樹脂を冷却し、切断してペレットを得る方法が好ましく、アンダーウォーターカット法がより好ましい。すなわち、本製造方法においては、（Ａ）成分と（Ｂ）成分を含む溶融樹脂組成物をアンダーウォーターカット法でペレット化して（Ａ）成分と（Ｂ）成分を含むペレットを得る工程を含むことが好ましい。
　アンダーウォーターカット法でペレット化することで、柔軟性の高い組成物であるにもかかわらず、ペレットの形状を均一にすることができる。この組成物のストランドを引き、水槽を用いて冷却した場合には、ストランドが柔らかく、ストランドにかかるカッターの力が分散して、形状が不均一になりやすい。一方、アンダーウォーターカット法であれば、溶融状態でカットし、その後水中で冷却されるために、柔軟性が高い組成物でも均一なペレットにすることができる。 In this production method, first, pellets containing the component (A) and the component (B) are prepared.
Specifically, the pellets of the component (A) and the component (B) may be mixed at room temperature and then blended by various methods such as melt-kneading, and the method is not particularly limited. As a mixing / kneading method, melt kneading using a twin-screw extruder is preferably used.
In melt-kneading using a twin-screw extruder, kneading at a temperature equal to or higher than the melting point of SPS, which is the component (B), and lower than 350 ° C. is preferable. By setting the kneading temperature to be equal to or higher than the melting point of SPS, the viscosity of SPS does not become too high, so that the productivity does not decrease. Further, by setting the kneading temperature to less than 350 ° C., there is no possibility that the SPS is thermally decomposed.
It is preferable to add any of the above-mentioned additives, such as an antioxidant, when the component (A) and the component (B) are melt-kneaded. By kneading the component (A) and the component (B) at the same time, the effect of the additive can be exerted on the entire resin composition pellet, and the performance of the additive can be imparted to the water blocking material which is a product. ..
The molten resin composition obtained by melt-kneading is pelletized to obtain pellets.
The method for pelletizing is not limited, but a method of cooling the molten resin and cutting it to obtain pellets is preferable, and an underwater cut method is more preferable. That is, the present production method includes a step of pelletizing the molten resin composition containing the components (A) and (B) by an underwater cut method to obtain pellets containing the components (A) and (B). Is preferable.
By pelletizing by the underwater cut method, the shape of the pellets can be made uniform even though the composition has high flexibility. When the strands of this composition are pulled and cooled using a water tank, the strands are soft, the force of the cutter applied to the strands is dispersed, and the shape tends to be non-uniform. On the other hand, in the underwater cut method, the pellets are cut in a molten state and then cooled in water, so that even a highly flexible composition can be made into uniform pellets.
　次に（Ｃ）成分を（Ａ）成分と（Ｂ）成分を含むペレットに添着する。
　添着は（Ａ）成分と（Ｂ）成分を含むペレットと、（Ｃ）成分を混合することで達成される。
　（Ｃ）成分を（Ａ）成分と（Ｂ）成分を含むペレットに添着する工程におけるペレット表面の温度は、１００℃以下であることが好ましく、８０℃以下であることがより好ましく、６０℃以下であることが更に好ましい。下限には制限はないが、０℃以上であることが好ましい。前記温度範囲で処理することで、ペレット表面に均一かつ効率的に添着することが可能となる。 Next, the component (C) is attached to a pellet containing the components (A) and (B).
Adhesion is achieved by mixing the pellet containing the components (A) and (B) with the component (C).
The temperature of the pellet surface in the step of adhering the component (C) to the pellet containing the component (A) and the component (B) is preferably 100 ° C. or lower, more preferably 80 ° C. or lower, and 60 ° C. or lower. Is more preferable. The lower limit is not limited, but is preferably 0 ° C. or higher. By treating in the above temperature range, it becomes possible to uniformly and efficiently adhere to the pellet surface.
　以下の実施例により、本発明を更に具体的に説明するが、本発明はこれらの実施例に限定されるものではない。 The present invention will be described in more detail with reference to the following examples, but the present invention is not limited to these examples.
［測定・評価］
＜（Ｃ）成分：脂肪酸アミド化合物の定量＞
　実施例及び比較例で得られた樹脂組成物ペレットに添着している（Ｃ）成分：脂肪酸アミド化合物は、次のようにして定量した。
　実施例及び比較例で得られた樹脂組成物ペレット５０ｇを容器に入れ、メタノールを２００ｍＬ入れて１０分撹拌し、メタノール溶液とペレットを分離後、メタノール溶液をエバポレーターで濃縮し、乾燥して得られた固体分（脂肪酸アミド化合物）の質量を測定し、測定に用いた樹脂組成物ペレット中の質量割合（質量ｐｐｍ）を求めた。 [Measurement / Evaluation]
<Component (C): Quantification of fatty acid amide compound>
The component (C): fatty acid amide compound attached to the resin composition pellets obtained in Examples and Comparative Examples was quantified as follows.
50 g of the resin composition pellets obtained in Examples and Comparative Examples was placed in a container, 200 mL of methanol was added, and the mixture was stirred for 10 minutes. After separating the methanol solution and the pellet, the methanol solution was concentrated with an evaporator and dried. The mass of the solid content (fatty acid amide compound) was measured, and the mass ratio (mass ppm) in the pellet of the resin composition used for the measurement was determined.
＜ブロッキング試験（１）：実用試験＞
　実施例及び比較例で得られた樹脂組成物ペレットを、見た目深さが２．５ｃｍとなるように金属製容器に入れ、表面を平らにならした。
　ペレットの上にアルミ板、更にステンレス製の錘を載せ、ペレットに０．０７５ｋｇ／ｃｍ2の圧力がかかるようにした。その状態で、４０℃の環境下、２ヵ月放置した後、ステンレス製の錘とアルミ板を除き、振動を与えないように金属製容器を裏返し、一部のペレットを排出した。金属製容器に残存した残存ペレットの割合（質量％）を測定した。残存ペレットの割合が少ないほど、ブロッキングが抑制されており、良好である。本試験の結果を表１に示す。 <Blocking test (1): Practical test>
The resin composition pellets obtained in Examples and Comparative Examples were placed in a metal container so as to have an apparent depth of 2.5 cm, and the surface was flattened.
An aluminum plate and a stainless steel weight were placed on the pellets so that a pressure of 0.075 kg / cm 2 was applied to the pellets. In that state, after leaving it in an environment of 40 ° C. for 2 months, the stainless steel weight and the aluminum plate were removed, the metal container was turned over so as not to give vibration, and some pellets were discharged. The percentage (mass%) of the residual pellets remaining in the metal container was measured. The smaller the proportion of residual pellets, the more the blocking is suppressed and the better. The results of this test are shown in Table 1.
＜ブロッキング試験（２）：加速試験＞
　実施例及び比較例で得られた樹脂組成物ペレットを、見た目深さが２．５ｃｍとなるように金属製容器に入れ、表面を平らにならした。
　ペレットの上にアルミ板、更にステンレス製の錘を載せ、ペレットに０．０７５ｋｇ／ｃｍ2の圧力がかかるようにした。その状態で、６０℃の環境下、１４０時間放置した後、ステンレス製の錘とアルミ板を除き、振動を与えないように金属製容器を裏返し、一部のペレットを排出した。金属製容器に残存した残存ペレットの割合（質量％）を測定した。残存ペレットの割合が少ないほど、ブロッキングが抑制されており、良好である。本試験の結果を表２に示す。 <Blocking test (2): Accelerated test>
The resin composition pellets obtained in Examples and Comparative Examples were placed in a metal container so as to have an apparent depth of 2.5 cm, and the surface was flattened.
An aluminum plate and a stainless steel weight were placed on the pellets so that a pressure of 0.075 kg / cm 2 was applied to the pellets. In that state, after leaving it in an environment of 60 ° C. for 140 hours, the stainless steel weight and the aluminum plate were removed, the metal container was turned over so as not to give vibration, and some pellets were discharged. The percentage (mass%) of the residual pellets remaining in the metal container was measured. The smaller the proportion of residual pellets, the more the blocking is suppressed and the better. The results of this test are shown in Table 2.
＜ブロッキング試験（３）：官能試験＞
　前記ブロッキング試験（１）及び（２）試験後の金属製容器に振動を与え、そのほぐれ方を観察し、更に残存ペレットを指で撹拌し、そのほぐれ方を観察し、以下の基準で評価した。
　　Ａ：凝集しているが簡単にほぐせる（振動でほぐれる）
　　Ｂ：凝集しているがほぐせる（指で撹拌することでほぐせる）
　　Ｃ：ほぐせない（一部凝集した塊状物が残る） <Blocking test (3): Sensory test>
The metal container after the blocking tests (1) and (2) was subjected to vibration, its loosening was observed, and the remaining pellets were further stirred with a finger, and the loosening was observed and evaluated according to the following criteria. ..
A: Although it is agglomerated, it can be easily loosened (unraveled by vibration).
B: Aggregates but loosens (can be loosened by stirring with fingers)
C: Cannot be loosened (partially agglomerated lumps remain)
［樹脂組成物ペレットの製造］
実施例１～４（リボンブレンダーによる添着）
　（Ａ）成分であるスチレンエチレンブチレンスチレンブロック共重合体（旭化成株式会社製、「タフテック　Ｈ１０４１」、スチレン／エチレンブチレン質量比：３０／７０、ＭＦＲ（温度２３０℃、荷重２．１６ｋｇｆ）：５ｇ／１０分）７５．７質量部、（Ｂ）成分であるホモシンジオタクチックポリスチレン（ラセミペンタッドタクティシティー：９８％、ＭＦＲ（温度３００℃、荷重１．２ｋｇｆ）：１３ｇ／１０分）２４．３質量部、酸化防止剤（ＢＡＳＦ社製、「ＩＲＧＡＮＯＸ１０１０」）０．２質量部をドライブレンドした後、二軸押出機を用い、シリンダー温度２９０℃で溶融混練を行い、ダイスから押し出された溶融樹脂をアンダーウォーターカット装置（ＧＡＬＡ社製、「ＧＡＬＡ　ＵＮＤＥＲＷＡＴＥＲ　ＰＥＬＬＥＴＩＺＩＮＧ　ＳＹＳＴＥＭ　Ｍｏｄｅｌ６」）により切断し、（Ａ）成分と（Ｂ）成分を含むペレットを調製した。ペレットは脱水器を用いて水との分離を行った。分離にはエアーを用いた。
　得られたペレットをリボンブレンダーに入れ、容量式フィーダーに（Ｃ）成分であるエチレンビスステアリン酸アミド（花王株式会社製、「カオーワックスＥＢ－ＦＦ」）を入れ、各実施例で（Ｃ）成分の添加量を変えて添加し、リボンブレンダーでペレットと（Ｃ）成分をブレンドすることで、（Ｃ）成分がペレット表面に添着した樹脂組成物ペレットを得た。ブレンド直後のペレットの表面の温度は３５℃であった。（Ｃ）成分の添着量（（Ｃ）成分の含有量）はフィード時の配管への付着によるロス等の影響により、全体の仕込み量等によって変動するため、最終的に得られた樹脂組成物ペレットを前記の＜（Ｃ）成分：脂肪酸アミド化合物の定量＞に記載した方法で定量することで各実施例の（Ｃ）成分の添着量（（Ｃ）成分の含有量）を求めた。表１及び表２に評価結果を示す。 [Manufacturing of resin composition pellets]
Examples 1 to 4 (attachment by ribbon blender)
Styrene ethylene butylene styrene block copolymer (A) component (manufactured by Asahi Kasei Co., Ltd., "Tough Tech H1041", styrene / ethylene butylene mass ratio: 30/70, MFR (temperature 230 ° C., load 2.16 kgf): 5 g / 10 minutes) 75.7 parts by mass, homosyntheotactic polystyrene (B semipentad tacticity: 98%, MFR (temperature 300 ° C., load 1.2 kgf): 13 g / 10 minutes) 24.3 After dry blending 0.2 parts by mass and 0.2 parts by mass of antioxidant (BASF, "IRGANOX1010"), melt kneading was performed at a cylinder temperature of 290 ° C using a twin-screw extruder, and the molten resin extruded from the die. Was cut by an underwater cutting device (“GALA UNDERWATER PELLETIZING SYSTEM MODEL 6” manufactured by GALA) to prepare pellets containing the components (A) and (B). The pellet was separated from water using a dehydrator. Air was used for separation.
The obtained pellets are placed in a ribbon blender, ethylene bisstearic acid amide (manufactured by Kao Corporation, "Kaohwax EB-FF"), which is a component (C), is placed in a capacitive feeder, and the component (C) is used in each example. Was added in different amounts, and the pellet and the component (C) were blended with a ribbon blender to obtain a resin composition pellet in which the component (C) was adhered to the surface of the pellet. The temperature of the surface of the pellet immediately after blending was 35 ° C. Since the amount of the component (C) attached (content of the component (C)) varies depending on the total amount charged due to the influence of loss due to adhesion to the piping during feeding, etc., the finally obtained resin composition. The pellet was quantified by the method described in <Component (C): Quantification of fatty acid amide compound> to determine the amount of component (C) attached (content of component (C)) of each example. The evaluation results are shown in Tables 1 and 2.
　実施例５～７及び比較例１～４（手撹拌による添着）
　（Ａ）成分であるスチレンエチレンブチレンスチレンブロック共重合体（旭化成株式会社製、「タフテック　Ｈ１０４１」、スチレン／エチレンブチレン質量比：３０／７０、ＭＦＲ（温度２３０℃、荷重２．１６ｋｇｆ）：５ｇ／１０分）、（Ｂ）成分であるホモシンジオタクチックポリスチレン（ラセミペンタッドタクティシティー：９８％、ＭＦＲ（温度３００℃、荷重１．２ｋｇｆ）：１３ｇ／１０分）、酸化防止剤（ＢＡＳＦ社製、「ＩＲＧＡＮＯＸ１０１０」）を表１及び表２に示す組成となるように配合し、ドライブレンドした後、二軸押出機を用い、シリンダー温度２９０℃で溶融混練を行い、ダイスから押し出された溶融樹脂をアンダーウォーターカット装置（ＧＡＬＡ社製、「ＧＡＬＡ　ＵＮＤＥＲＷＡＴＥＲ　ＰＥＬＬＥＴＩＺＩＮＧ　ＳＹＳＴＥＭ　Ｍｏｄｅｌ６」）により切断し、（Ａ）成分と（Ｂ）成分を含むペレットを調製した。ペレットは脱水器を用いて水との分離を行った。分離にはエアーを用いた。
　得られたペレットを前記ブロッキング試験（１）及び（２）で用いた金属製容器に入れ、表１及び表２に示した添着量となるように（Ｃ）成分であるエチレンビスステアリン酸アミド（花王株式会社製、「カオーワックスＥＢ－ＦＦ」）を入れ、（Ｃ）成分がペレット表面に均一に添着するまで、２３℃で撹拌することで、（Ｃ）成分がペレット表面に添着した樹脂組成物ペレットを得た。この時のペレットの表面の温度は２３℃であった。
　なお、比較例１は（Ｂ）成分を用いず、（Ａ）成分のみを用いてペレットを調製し、前記の方法で（Ｃ）成分を添着した。比較例３は（Ｃ）成分を添着していない（Ａ）成分と（Ｂ）成分を含むペレットを評価に用いた。表１及び表２に評価結果を示す。 Examples 5 to 7 and Comparative Examples 1 to 4 (attachment by hand stirring)
(A) Component styrene ethylene butylene styrene block copolymer (manufactured by Asahi Kasei Co., Ltd., "Tough Tech H1041", styrene / ethylene butylene mass ratio: 30/70, MFR (temperature 230 ° C., load 2.16 kgf): 5 g / 10 minutes), (B) component homosyntheotactic polystyrene (lasemipentad tacticity: 98%, MFR (temperature 300 ° C., load 1.2 kgf): 13 g / 10 minutes), antioxidant (manufactured by BASF) , "IRGANOX1010") was blended so as to have the compositions shown in Tables 1 and 2, and then dry-blended, melt-kneaded at a cylinder temperature of 290 ° C. using a twin-screw extruder, and the molten resin extruded from the die. Was cut by an underwater cutting device (“GALA UNDERWATER PELLETIZING SYSTEM MODEL 6” manufactured by GALA) to prepare pellets containing the components (A) and (B). The pellet was separated from water using a dehydrator. Air was used for separation.
The obtained pellets were placed in the metal containers used in the blocking tests (1) and (2), and ethylene bisstearic acid amide (C) was used as a component (C) so as to have the amount of adhesion shown in Tables 1 and 2. Kao Corporation, "Kaohwax EB-FF") is added, and the mixture is stirred at 23 ° C. until the component (C) is uniformly adhered to the surface of the pellet. A product pellet was obtained. The temperature of the surface of the pellet at this time was 23 ° C.
In Comparative Example 1, pellets were prepared using only the component (A) without using the component (B), and the component (C) was attached by the above method. In Comparative Example 3, pellets containing the components (A) and (B) without the component (C) were used for evaluation. The evaluation results are shown in Tables 1 and 2.
Figure JPOXMLDOC01-appb-T000001
Figure JPOXMLDOC01-appb-T000001
Figure JPOXMLDOC01-appb-T000002
Figure JPOXMLDOC01-appb-T000002
　表に示した通り、実施例の結果から、本発明の樹脂組成物ペレットは、ブロッキングが少なく、コネクタの止水材用のペレットとして、優れることがわかる。 As shown in the table, from the results of the examples, it can be seen that the resin composition pellet of the present invention has less blocking and is excellent as a pellet for a water blocking material for a connector.

Claims (10)

  1. 　（Ａ）成分：スチレン系エラストマー、（Ｂ）成分：主としてシンジオタクチック構造を有するポリスチレン系重合体、及び（Ｃ）成分：脂肪酸アミド化合物を含有する樹脂組成物ペレットであって、
    　（Ａ）成分と（Ｂ）成分の質量比［（Ａ）／（Ｂ）］が５０／５０～８５／１５であり、
    　（Ｃ）成分が、（Ａ）成分と（Ｂ）成分を含むペレットに添着しており、
    　（Ｃ）成分の含有量が、（Ａ）成分と（Ｂ）成分の合計に対し、４０質量ｐｐｍ以上である、樹脂組成物ペレット。     A resin composition pellet containing a component (A): a styrene-based elastomer, a component (B): a polystyrene-based polymer mainly having a syndiotactic structure, and a component (C): a fatty acid amide compound.
    The mass ratio [(A) / (B)] of the component (A) to the component (B) is 50/50 to 85/15.
    The component (C) is attached to the pellet containing the components (A) and (B).
    A resin composition pellet in which the content of the component (C) is 40 mass ppm or more with respect to the total of the components (A) and (B).
  2. 　（Ａ）成分が、スチレンイソプレンスチレンブロック共重合体（ＳＩＳ）、スチレンブタジエンスチレンブロック共重合体（ＳＢＳ）、スチレンエチレンプロピレンブロック共重合体（ＳＥＰ）、スチレンエチレンブチレンスチレンブロック共重合体（ＳＥＢＳ）、スチレンエチレンプロピレンスチレンブロック共重合体（ＳＥＰＳ）、及びスチレンエチレンエチレンプロピレンスチレンブロック共重合体（ＳＥＥＰＳ）からなる群より選ばれる少なくとも１つである、請求項１に記載の樹脂組成物ペレット。 The component (A) is styreneisoprene styrene block copolymer (SIS), styrene butadiene styrene block copolymer (SBS), styrene ethylene propylene block copolymer (SEP), styrene ethylene butylene styrene block copolymer (SEBS). The resin composition pellet according to claim 1, which is at least one selected from the group consisting of styrene ethylene propylene styrene block copolymer (SEPS) and styrene ethylene ethylene propylene styrene block copolymer (SEEPS).
  3. 　（Ｃ）成分が、脂肪酸アミド及びアルキレン脂肪酸アミドからなる群より選ばれる少なくとも１つである、請求項１又は２に記載の樹脂組成物ペレット。 The resin composition pellet according to claim 1 or 2, wherein the component (C) is at least one selected from the group consisting of fatty acid amides and alkylene fatty acid amides.
  4. 　（Ｃ）成分が、ステアリン酸アミド、オレイン酸アミド、エルカ酸アミド、メチレンビスステアリン酸アミド、及びエチレンビスステアリン酸アミドからなる群より選ばれる少なくとも１つである、請求項１～３のいずれか１つに記載の樹脂組成物ペレット。 Any one of claims 1 to 3, wherein the component (C) is at least one selected from the group consisting of stearic acid amides, oleic acid amides, erucic acid amides, methylene bisstearic acid amides, and ethylene bisstearic acid amides. The resin composition pellet according to one.
  5. 　（Ａ）成分と（Ｂ）成分を含むペレット中の（Ａ）成分と（Ｂ）成分の合計含有量が、９０質量％以上である、請求項１～４のいずれか１つに記載の樹脂組成物ペレット。 The resin according to any one of claims 1 to 4, wherein the total content of the component (A) and the component (B) in the pellet containing the component (A) and the component (B) is 90% by mass or more. Composition pellets.
  6. 　（Ａ）成分と（Ｂ）成分の質量比［（Ａ）／（Ｂ）］が、７３／２７～８５／１５である、請求項１～５のいずれか１つに記載の樹脂組成物ペレット。 The resin composition pellet according to any one of claims 1 to 5, wherein the mass ratio [(A) / (B)] of the component (A) to the component (B) is 73/27 to 85/15. ..
  7. 　コネクタ用止水材に用いる、請求項１～６のいずれか１つに記載の樹脂組成物ペレット。 The resin composition pellet according to any one of claims 1 to 6, which is used as a water blocking material for a connector.
  8. 　（Ａ）成分：スチレン系エラストマー、（Ｂ）成分：主としてシンジオタクチック構造を有するポリスチレン系重合体、及び（Ｃ）成分：脂肪酸アミド化合物を含有する樹脂組成物ペレットの製造方法であって、
    　（Ｃ）成分を（Ａ）成分と（Ｂ）成分を含むペレットに添着する工程を有し、
    　（Ａ）成分と（Ｂ）成分を含むペレット中の（Ａ）成分と（Ｂ）成分の質量比［（Ａ）／（Ｂ）］が５０／５０～８５／１５であり、
    　（Ｃ）成分の添着量が、（Ａ）成分と（Ｂ）成分の合計に対し、４０質量ｐｐｍ以上である、樹脂組成物ペレットの製造方法。     A method for producing a resin composition pellet containing a component (A): a styrene-based elastomer, a component (B): a polystyrene-based polymer mainly having a syndiotactic structure, and a component (C): a fatty acid amide compound.
    It has a step of adhering the component (C) to a pellet containing the component (A) and the component (B).
    The mass ratio [(A) / (B)] of the component (A) and the component (B) in the pellet containing the component (A) and the component (B) is 50/50 to 85/15.
    A method for producing a resin composition pellet, wherein the amount of the component (C) attached is 40 mass ppm or more with respect to the total of the component (A) and the component (B).
  9. 　前記（Ｃ）成分を（Ａ）成分と（Ｂ）成分を含むペレットに添着する工程におけるペレット表面の温度が、１００℃以下である、請求項８に記載の樹脂組成物ペレットの製造方法。 The method for producing a resin composition pellet according to claim 8, wherein the temperature of the pellet surface in the step of adhering the component (C) to the pellet containing the component (A) and the component (B) is 100 ° C. or lower.
  10. 　（Ａ）成分と（Ｂ）成分を含む溶融樹脂組成物をアンダーウォーターカット法でペレット化して（Ａ）成分と（Ｂ）成分を含むペレットを得る工程を含む、請求項８又は９に記載の樹脂組成物ペレットの製造方法。 The method according to claim 8 or 9, wherein the molten resin composition containing the component (A) and the component (B) is pelletized by an underwater cut method to obtain pellets containing the component (A) and the component (B). A method for producing resin composition pellets.
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