JP2013133434A - Thermoplastic elastomer composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a thermoplastic elastomer composition which is excellent in the balance of various characteristics such as flexibility, insulating properties, heat conductivity, heat resistance, and heat fusibility with polar resins, e.g. polycarbonate resin, and is suitable for a material for sealing heat-releasing members, and the like.SOLUTION: The thermoplastic elastomer composition comprises a thermoplastic elastomer component (A) comprising at least one of the group consisting of the following components (A-1) to (A-3), a granular filler component (B) comprising at least one of the group consisting of the following components (B-1) to (B-3), and a fibrous filler component (C) comprising the following component (C-1). The component (A-1): a polyester-based thermoplastic elastomer; the component (A-2): a urethane-based thermoplastic elastomer; the component (A-3): an acrylic thermoplastic elastomer; the component (B-1): calcium carbonate; the component (B-2): magnesium hydroxide; the component (B-3): magnesium oxide; and the component (C-1): carbon fibers.

Description

The present invention relates to a thermoplastic elastomer composition, and more particularly, it has an excellent balance of various properties such as insulation, thermal conductivity, flexibility, heat resistance, and heat-fusibility with a polar resin such as a polycarbonate resin. The present invention relates to a thermoplastic elastomer composition suitable for a sealing material for an electronic substrate heat radiating member.
The present invention also provides a molded body formed by molding the thermoplastic elastomer composition, a composite molded body in which the molded body is heat-sealed with a polycarbonate resin, and a sealing material and an adhesive made of the thermoplastic elastomer composition. It relates to the agent.

  In recent years, in various electronic members, the amount of heat generation tends to increase due to the improvement in processing speed and mounting density of integrated circuits. For this reason, in various electronic members, a heat dissipation measure is required, and a heat dissipation measure is taken by using a material having a high thermal conductivity as a constituent material of the member.

  Conventionally, a thermally conductive resin composition containing a thermoplastic elastomer and a thermally conductive material as described in Patent Documents 1 to 3 has been proposed as a material having excellent insulation, thermal conductivity, and flexibility. ing. Patent Document 1 describes a resin composition containing a styrene elastomer and / or a hydrogenated product thereof, a hydrocarbon rubber softener and a heat conductive material, and Patent Document 2 discloses a styrene elastomer and / or Or a hydrogenated product thereof, a softening agent for hydrocarbon rubber, an ethylene polymer, and a resin composition containing a heat conductive material. Patent Document 3 discloses a styrene elastomer and / or water thereof. A resin composition containing an additive, a hydrocarbon rubber softener, a propylene polymer, and a thermally conductive material is described.

  In applications such as personal computer casings, polycarbonate resin is widely used as a material for heat dissipation members. For this reason, as a sealing material for a polycarbonate resin member, not only thermal conductivity, but also excellent flexibility to prevent a gap between the polycarbonate resin members and heat fusion with the polycarbonate resin were excellent. Things are needed.

However, as a result of the study of the present inventors, the thermoplastic elastomer compositions described in Patent Documents 1 to 3 have poor heat fusion properties with polar resins such as polycarbonate resins and polybutylene terephthalate resins. A problem has been found that it is difficult to use the material as a heat sealing material.
In addition, since the thermoplastic elastomer composition described in Patent Documents 1 to 3 and the conventional thermoplastic elastomer compositions are not sufficiently insulating, the electronic member used around the electronic substrate is a substrate. A problem has been found that can cause dielectric breakdown.

JP 2001-106865 A Japanese Patent Laying-Open No. 2005-075895 JP 2002-121354 A

  The present invention is well balanced in various properties such as insulation, thermal conductivity, flexibility, heat resistance, and heat fusion with a polar resin such as polycarbonate resin, and is a sealing material for heat dissipation members of electronic boards such as CPUs. It is an object of the present invention to provide a thermoplastic elastomer composition suitable for the above.

As a result of intensive studies to solve the above problems, the present inventor has blended a specific filler with a specific thermoplastic elastomer, so that it has heat insulation properties, thermal conductivity, heat resistance, and polar resin. It has been found that a thermoplastic elastomer composition excellent in balance and flexibility can be realized.
The present invention has been completed based on such findings, and the following [1] to [9] are summarized.

[1] From the thermoplastic elastomer component (A) containing at least one of the group consisting of the following components (A-1) to (A-3) and the following components (B-1) to (B-3): A thermoplastic elastomer composition comprising at least a particulate filler component (B) containing at least one of the group consisting of and a fibrous filler component (C) containing the following component (C-1).
Component (A-1): Polyester thermoplastic elastomer Component (A-2): Urethane thermoplastic elastomer Component (A-3): Acrylic thermoplastic elastomer Component (B-1): Calcium carbonate Component (B-2) ): Magnesium hydroxide Component (B-3): Magnesium oxide Component (C-1): Carbon fiber

[2] 15 to 50 parts by weight of the thermoplastic elastomer component (A), 84 to 20 parts by weight of the particulate filler component (B), and 1 to 30 parts by weight of the fibrous filler component (C) (however, The total amount of the component (A), the component (B), and the component (C) is 100 parts by weight.), The thermoplastic elastomer composition according to [1].

[3] The thermoplastic elastomer composition according to [1] or [2], wherein the component (A-1) includes a polybutylene terephthalate-polyalkylene ether block copolymer.

[4] The thermoplastic elastomer composition according to any one of [1] to [3], wherein the thermoplastic elastomer component (A) further includes the following component (A-4).
(A-4): Styrene elastomer and / or hydrogenated product of styrene elastomer

[5] The thermoplastic elastomer composition according to any one of [1] to [4], wherein the thermoplastic elastomer component (A) further contains the following component (A-5).
Component (A-5): Hydrocarbon softener

[6] A molded article obtained by molding the thermoplastic elastomer composition according to any one of [1] to [5].

[7] A composite molded product obtained by heat-sealing the molded product according to [6] with a polycarbonate resin.

[8] A sealing material comprising the thermoplastic elastomer composition according to any one of [1] to [5].

[9] An adhesive comprising the thermoplastic elastomer composition according to any one of [1] to [5].

  ADVANTAGE OF THE INVENTION According to this invention, the thermoplastic elastomer composition excellent in the softness | flexibility, insulation, thermal conductivity, heat resistance, the heat sealing property with polar resins like a polycarbonate resin, etc. is provided.

Hereinafter, embodiments of the present invention will be described in detail.
The present invention is not limited to the following description, and can be arbitrarily modified and implemented without departing from the gist of the present invention. In addition, in this specification, when expressing by putting a numerical value or a physical-property value before and behind using "-", it shall use as what includes the value before and behind.

The thermoplastic elastomer composition of the present invention includes a thermoplastic elastomer component (A) containing at least one member selected from the group consisting of the following components (A-1) to (A-3), and the following component (B-1). A granular filler component (B) including at least one of the group consisting of (B-3) and a fibrous filler component (C) including the following component (C-1) are included. .
Component (A-1): Polyester thermoplastic elastomer Component (A-2): Urethane thermoplastic elastomer Component (A-3): Acrylic thermoplastic elastomer Component (B-1): Calcium carbonate Component (B-2) ): Magnesium hydroxide Component (B-3): Magnesium oxide Component (C-1): Carbon fiber

  The thermoplastic elastomer composition of the present invention containing both the particulate filler component (B) and the fibrous filler component (C) as filler components is excellent in insulation and thermal conductivity, and in particular, the particulate filler component (B). Compared with the case where only one of the fibrous filler component (C) and the thermoplastic elastomer component (A) are used, the present invention has a feature that it is excellent in heat fusion with a polar resin such as a polycarbonate resin. The remarkable effect relating to the heat-fusibility with this polar resin is that the particulate filler component (B) inhibits the orientation of the fibrous filler component (C) in the matrix of the thermoplastic elastomer component (A), and the fibrous It is considered that the filler component (C) is entangled with the interface of the polycarbonate resin substrate.

[Thermoplastic elastomer component (A)]
In the thermoplastic elastomer composition of the present invention, the thermoplastic elastomer component (A) has at least one of the group consisting of the following components (A-1) to (A-3) as an essential component, and in some cases, Furthermore, the following component (A-4) and / or component (A-5) is included.
Component (A-1): Polyester thermoplastic elastomer Component (A-2): Urethane thermoplastic elastomer Component (A-3): Acrylic thermoplastic elastomer Component (A-4): Styrene elastomer and / or its Hydrogenated component (A-5): Hydrocarbon softener

  The thermoplastic elastomer component (A) contained in the thermoplastic elastomer composition of the present invention is an elastomer that exhibits plasticity when heated. In addition, the thermoplastic elastomer component (A) is a component having a durometer A (type A durometer hardness) measured in accordance with JIS-K6253 of usually 10 or more and 95 or less. The Duro A hardness of the thermoplastic elastomer component (A) is preferably 15 or more, and preferably 80 or less, more preferably 60 or less.

<Component (A-1)>
The polyester-based thermoplastic elastomer of component (A-1) used in the present invention is preferably a block copolymer having a hard segment having crystallinity and a soft segment having flexibility. More preferred is a hard material made of a cyclic polyester (in this specification, “cyclic polyester” means a dicarboxylic acid or alkyl ester thereof as a raw material containing a dicarboxylic acid having a cyclic structure or an alkyl ester thereof). A block copolymer (hereinafter referred to as “polyalkylene ether unit”) having a segment (hereinafter referred to as “cyclic polyester unit”) and a soft segment (hereinafter also referred to as “polyalkylene ether unit”). "Cyclic polyester-polyalkylene ether block copolymer"), hard segment composed of cyclic polyester, and chain aliphatic polyester (in this specification, "chain aliphatic polyester" is a raw material) Dicarboxylic acid or its alkyl A block copolymer having a soft segment (hereinafter sometimes referred to as “chain aliphatic polyester unit”) comprising an ester is an aliphatic dicarboxylic acid having only a chain structure or an alkyl ester thereof. Polymers (hereinafter sometimes referred to as “cyclic polyester-chain aliphatic polyester block copolymers”), and cyclic polyester-polyalkylene ether block copolymers are more preferable.

  As the cyclic polyester-polyalkylene ether block copolymer, a block copolymer (hereinafter, referred to as “aromatic polyester unit”) and a polyalkylene ether unit (hereinafter, referred to as “aromatic polyester unit”) and a hard segment comprising an aromatic polyester. "Aromatic polyester-polyalkylene ether block copolymer"), hard segment made of alicyclic polyester (hereinafter sometimes referred to as "alicyclic polyester unit") and polyalkylene ether. Examples thereof include block copolymers having units (hereinafter, sometimes referred to as “alicyclic polyester-polyalkylene ether block copolymers”), and among these, aromatic polyester-polyalkylene ether block copolymers. Is preferred.

  The aromatic polyester unit preferably contains polybutylene terephthalate as a hard segment. At this time, it is preferable to include polytetramethylene ether glycol as a soft segment (hereinafter sometimes referred to as “polytetramethylene ether unit”).

  In addition, as the alicyclic polyester-polyalkylene ether block copolymer, an alicyclic dicarboxylic acid (in the present specification, “alicyclic dicarboxylic acid” means that two carboxyl groups are directly bonded to a cyclic aliphatic hydrocarbon. And a compound obtained by using alicyclic diol and polyalkylene ether as raw materials. The alicyclic polyester unit preferably includes a hard segment obtained using cyclohexanedicarboxylic acid and cyclohexanedimethanol as raw materials. The polyalkylene ether unit of the alicyclic polyester-polyalkylene ether block copolymer preferably contains polytetramethylene ether glycol as a soft segment.

  As the cyclic polyester-chain aliphatic polyester block copolymer, a block copolymer having a hard segment composed of an aromatic polyester and a soft segment composed of a chain aliphatic polyester (hereinafter referred to as “aromatic polyester-chain aliphatic”). A block copolymer having a hard segment composed of an alicyclic polyester and a soft segment composed of a chain aliphatic polyester (hereinafter referred to as “alicyclic polyester-chain fatty acid”). In some cases, aromatic polyester-chain aliphatic polyester block copolymers are preferable. Among the aromatic polyester-chain aliphatic polyester block copolymers, a polybutylene terephthalate-chain aliphatic polyester block copolymer in which the aromatic polyester unit is made of polybutylene terephthalate is more preferable. The chain aliphatic polyester unit is preferably obtained from a chain aliphatic dicarboxylic acid having 4 to 10 carbon atoms typified by sebacic acid and adipic acid and a chain aliphatic diol.

  The component (A-1) polyester-based thermoplastic elastomer preferably has a melting point observed. In the polyester thermoplastic elastomer of component (A-1), when the melting point is observed, the melting point is usually due to a crystalline hard segment, and by using a high melting point raw material for the hard segment, The melting point of the component (A-1) can be increased. On the other hand, when the proportion of the soft segment in the polyester thermoplastic elastomer of component (A-1) is increased, the melting point of component (A-1) tends to decrease.

The melting point of the polyester thermoplastic elastomer of component (A-1) is mainly derived from the hard segment. Therefore, the hard segment is preferably crystalline and has a melting point. Although there is no restriction | limiting in particular in the minimum of melting | fusing point originating in this hard segment, Usually, it is 100 degreeC or more, Preferably it is 120 degreeC or more. There exists a tendency for the heat resistance of the polyester-type thermoplastic elastomer of the component (A-1) to fall that the melting point derived from this hard segment is less than the said lower limit. Moreover, although the upper limit of melting | fusing point originating in a hard segment is not limited, Usually, it is 300 degrees C or less, Preferably it is 260 degrees C or less.
The melting point of the raw material of the hard segment is the temperature of the melting peak when the temperature is raised at a rate of temperature rise of 10 ° C./min using a differential scanning calorimeter (DSC).

  As the flexible soft segment, polyalkylene ether glycol is preferable, and linear and branched fats such as polymethylene glycol, polyethylene glycol, polypropylene glycol, polytrimethylene glycol, polytetramethylene glycol, polyhexamethylene glycol and the like. In addition to the group ether, a single polymer or copolymer of an alicyclic ether such as a condensate of cyclohexanediol or a condensate of cyclohexanedimethanol can be used. Moreover, the random copolymer in these ether units may be sufficient. A block copolymer having a polyalkylene ether unit can also be used. Furthermore, among these, linear and branched aliphatic ether glycols such as polymethylene glycol, polyethylene glycol, polypropylene glycol, polytrimethylene glycol, polytetramethylene glycol, and polyhexamethylene glycol are more preferable. Are polymethylene glycol, polyethylene glycol, polypropylene glycol, polytrimethylene glycol and polytetramethylene glycol, and particularly preferred is polytetramethylene glycol. These may be used alone or in combination of two or more.

  The polyester-based thermoplastic elastomer of component (A-1) has flexibility based on the soft segment, and this flexibility is expressed as durometer A (type A durometer hardness) measured according to JIS-K6253. Can do. The duro A hardness of the component (A-1) is usually 10 or more and 95 or less. The Duro A hardness of the polyester-based thermoplastic elastomer (A-1) is preferably 15 or more, and is usually 95 or less, preferably 80 or less, more preferably 60 or less.

  The number average molecular weight of the polyalkylene ether unit contained in the cyclic polyester-polyalkylene ether block copolymer is preferably 600 to 4000, particularly 800 to 2500, and particularly 900 to 2100. Here, the number average molecular weight of the polyalkylene ether unit refers to a value in terms of polystyrene measured by gel permeation chromatography (GPC).

  These polyalkylene ether units may contain only one type in the cyclic polyester-polyalkylene ether block copolymer, or may contain two or more types having different number average molecular weights and constituent components. .

  There is no restriction | limiting in particular as a manufacturing method of the polyester-type thermoplastic elastomer of a component (A-1), For example, the aromatic polyester and polyalkylene ether glycol are used among cyclic polyester-polyalkylene ether block copolymers. If it is an aliphatic polyester-polyalkylene ether block copolymer, the raw material is a C2-C12 chain aliphatic and / or alicyclic diol, an aromatic dicarboxylic acid or an alkyl ester thereof, and a polyalkylene ether glycol. And an oligomer obtained by esterification reaction or transesterification reaction can be obtained by polycondensation.

  As said C2-C12 chain | strand-shaped aliphatic and / or alicyclic diol, what is normally used as a raw material of polyester can be used. For example, chain aliphatic diols include ethylene glycol, propylene glycol, trimethylene glycol, 1,3-butylene glycol, 1,4-butylene glycol, 1,6-hexene glycol and the like, among which 1,4 -Butylene glycol is preferred. Examples of the alicyclic diol include 1,4-cyclohexene glycol and 1,4-cyclohexanedimethanol, and 1,4-cyclohexanedimethanol is preferable. These C2-C12 chain aliphatic and / or alicyclic diols may be used alone or in a mixture of two or more.

  As the aromatic dicarboxylic acid or an alkyl ester thereof, those generally used as a raw material for polyester can be used. For example, terephthalic acid and its lower component (in this specification, “lower” means 4 or less carbon atoms). ) Alkyl esters, isophthalic acid, phthalic acid, 2,5-norbonane dicarboxylic acid, 1,4-naphthalic acid, 1,5-naphthalic acid, 4,4-oxybenzoic acid, 2,6-naphthalenedicarboxylic acid and the like And the lower alkyl esters. Among these, terephthalic acid and isophthalic acid are preferable, and terephthalic acid is particularly preferable. These aromatic dicarboxylic acids may be used alone or in combination of two or more.

  Moreover, when manufacturing an alicyclic polyester-polyalkylene ether block copolymer, the aromatic dicarboxylic acid used as a raw material in the case of manufacturing said aromatic polyester-polyalkylene ether block copolymer, or its alkyl ester Instead of alicyclic dicarboxylic acid or its alkyl ester, it may be used. That is, it is obtained by esterification reaction or transesterification reaction using a chain aliphatic and / or alicyclic diol having 2 to 12 carbon atoms, an alicyclic dicarboxylic acid or an alkyl ester thereof, and a polyalkylene ether glycol as raw materials. The obtained oligomer can be obtained by polycondensation.

  As the alicyclic dicarboxylic acid or alkyl ester thereof, those generally used as raw materials for polyesters can be used. For example, cyclohexane dicarboxylic acid and its lower alkyl ester, cyclopentane dicarboxylic acid and their lower alkyl ester, etc. Can be mentioned. Among these, cyclohexanedicarboxylic acid and lower alkyl esters thereof are preferable, and cyclohexanedicarboxylic acid is particularly preferable. One of these alicyclic dicarboxylic acids may be used alone, or two or more thereof may be used in combination.

The content of each of the hard segment and the soft segment in the polyester elastomer of the component (A-1) used in the present invention is not limited. However, from the balance between the crystallinity of the hard segment and the flexibility of the soft segment, usually the following It becomes a range.
That is, the content of the hard segment is usually 10% by weight or more, preferably 20% by weight or more. The content of the hard segment is usually 95% by weight or less, preferably 90% by weight or less, more preferably 80% by weight or less. The content of the soft segment is usually 5% by weight or more, preferably 10% by weight or more, more preferably 20% by weight or more. Further, the content of the soft segment is usually 90% by weight or less, preferably 80% by weight or less. In addition, the content of the hard segment and the soft segment in the component (A-1) can be calculated based on the chemical shift of the hydrogen atom and the content thereof using nuclear magnetic resonance spectroscopy (NMR). .

  As the aromatic polyester-polyalkylene ether block copolymer, a polybutylene terephthalate-polyalkylene ether block copolymer is preferable because the crystallization rate is particularly high and the moldability is excellent. 2-12 are preferable, as for carbon number of an alkylene group, 2-8 are more preferable, 2-5 are still more preferable, and 4 is especially preferable.

  The component (A-1) in the present invention may be copolymerized with a small amount of one or more of trifunctional or higher alcohols and / or tricarboxylic acids and / or esters thereof in addition to the above components. A chain aliphatic dicarboxylic acid such as an acid or a dialkyl ester thereof may also be introduced as a copolymerization component.

  The polyester thermoplastic elastomer of component (A-1) used in the present invention has a melt flow rate (hereinafter abbreviated as “MFR”) at a measurement temperature of 230 ° C. and a measurement load of 21.18 N of 0.1 g / 10. It is preferably at least 5 minutes, more preferably at least 5 g / 10 minutes, and even more preferably at least 10 g / minute. On the other hand, it is preferably 100 g / 10 min or less, more preferably 80 g / 10 min or less, and even more preferably 65 g / 10 min or less. When the MFR of the component (A-1) is not less than the above lower limit value, it is preferable in terms of moldability of the thermoplastic elastomer composition, and on the other hand, if it is not more than the above upper limit value, the particulate filler component for the thermoplastic elastomer component (A) ( B) and the dispersibility of the fibrous filler component (C) are preferred.

  As the component (A-1), “Polyester (registered trademark)” (manufactured by Nippon Synthetic Chemical Industry Co., Ltd.), “Primalloy (registered trademark)” (manufactured by Mitsubishi Chemical Corporation), “Perprene (registered trademark)” ( Commercial products such as “Toyobo Co., Ltd.” and “Hytrel (registered trademark)” (manufactured by DuPont) can be used.

  As the component (A-1), a polyester-based thermoplastic elastomer such as a cyclic polyester-polyalkylene ether block copolymer may be used alone or in combination of two or more.

<Component (A-2)>
The urethane-based thermoplastic elastomer of component (A-2) used in the present invention is preferably a diisocyanate compound and a molecular weight from the viewpoint of ensuring good adhesion to various base resins, molding processability, and rubbery feel. What has the hard segment which consists of about 50-500 glycol, and the soft segment which consists of a diisocyanate compound and long-chain glycol is mentioned. As the long-chain glycol, a polyether type such as a polyalkylene glycol having a molecular weight of about 500 to 10,000, or a polyester type such as polyalkylene adipate, polycaprolactone, polycarbonate or the like is used. Moreover, as a diisocyanate compound, well-known usual things, such as phenylene diisocyanate, trigen diisocyanate, xylene diisocyanate, 4, 4- diphenylmethane diisocyanate, hexamethylene diisocyanate, are used preferably. These diisocyanate compounds may be the same or different in each of the soft segment and the hard segment.

  This type of (A-2) urethane-based thermoplastic elastomer is represented by the following general formula (1).

(A in the above formula (1) represents a hard segment composed of a diisocyanate compound and glycol, B represents a soft segment composed of a diisocyanate compound and a long-chain glycol, and Y represents a residue of a urethane-bonded diisocyanate compound. )

  Commercially available polyurethane thermoplastic elastomers of component (A-2) include “Elastollan (registered trademark)” (manufactured by BASF), “Pandex (registered trademark)” (manufactured by DIC Bayer), “Rezamin (registered) Trademark) "(manufactured by Dainichi Seika Kogyo Co., Ltd.).

  As the component (A-2), the urethane-based thermoplastic elastomer may be used alone or in combination of two or more.

<Component (A-3)>
Examples of the acrylic thermoplastic elastomer of the component (A-2) used in the present invention include acrylic ABA triblock copolymers composed of acrylic acid esters and methacrylic acid esters.

  The acrylic ABA type triblock copolymer is an ABA type triblock copolymer in which the ABA type A block component or B block component is a methacrylic ester, and the B block component or A block component is an acrylate ester. Preferably, it is an ABA type triblock copolymer in which the A block component is a methacrylic acid ester and the B block component is an acrylate ester.

  Examples of the methacrylate ester of the A block component include, for example, methyl methacrylate, ethyl methacrylate, -n-propyl methacrylate, isopropyl methacrylate, -n-butyl methacrylate, isobutyl methacrylate, -tert-butyl methacrylate, Methacrylic acid-n-pentyl, methacrylic acid-n-hexyl, cyclohexyl methacrylate, methacrylic acid-n-heptyl, methacrylic acid-n-octyl, methacrylic acid-2-ethylhexyl, nonyl methacrylate, decyl methacrylate, dodecyl methacrylate , Phenyl methacrylate, toluyl methacrylate, benzyl methacrylate, isobornyl methacrylate, 2-methoxyethyl methacrylate, 3-methoxybutyl methacrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl tacrylate, stearyl methacrylate, glycidyl methacrylate, 2-aminoethyl methacrylate, γ- (methacryloyloxypropyl) trimethoxysilane, γ- (methacryloyloxypropyl) dimethoxymethylsilane, ethylene oxide of methacrylic acid Adduct, trifluoromethyl methyl methacrylate, 2-trifluoromethyl ethyl methacrylate, 2-perfluoroethyl ethyl methacrylate, 2-perfluoroethyl-2-perfluorobutyl ethyl methacrylate, 2-perfluoroethyl methacrylate Perfluoromethyl methacrylate, diperfluoromethyl methyl methacrylate, 2-perfluoromethyl-2-perfluoroethyl methyl methacrylate, 2-perfluorohexyl methacrylate Examples thereof include one or a combination of two or more of ethyl, 2-perfluorodecylethyl methacrylate, 2-perfluorohexadecylethyl methacrylate, etc. Among them, methyl methacrylate and dodecyl methacrylate are preferable, and in particular, methacryl Methyl acid is preferred.

  Examples of the acrylic ester of the B block component include methyl acrylate, ethyl acrylate, acrylic acid-n-propyl, isopropyl acrylate, acrylic acid-n-butyl, acrylic acid isobutyl, acrylic acid-tert-butyl, -N-pentyl acrylate, n-hexyl acrylate, cyclohexyl acrylate, n-heptyl acrylate, n-octyl acrylate, 2-ethylhexyl acrylate, nonyl acrylate, decyl acrylate, dodecyl acrylate , Phenyl acrylate, toluyl acrylate, benzyl acrylate, isobornyl acrylate, 2-methoxyethyl acrylate, 3-methoxybutyl acrylate, 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, acrylic Acid Allyl, glycidyl acrylate, 2-aminoethyl acrylate, γ- (acryloyloxypropyl) trimethoxysilane, γ- (acryloyloxypropyl) dimethoxymethylsilane, ethylene oxide adduct of acrylic acid, trifluoromethylmethyl acrylate, 2-trifluoromethylethyl acrylate, 2-perfluoroethylethyl acrylate, 2-perfluoroethyl-2-perfluorobutylethyl acrylate, 2-perfluoroethyl acrylate, perfluoromethyl acrylate, diacrylate Perfluoromethylmethyl, 2-perfluoromethyl-2-perfluoroethylmethyl acrylate, 2-perfluorohexylethyl acrylate, 2-perfluorodecylethyl acrylate, 2-perfluorohexyl acrylate Mention may be made of one or more combinations of such Deshiruechiru, among others, methyl acrylate, butyl -n- acrylate are preferred.

  Among them, an ABA type triblock copolymer composed of polymethyl methacrylate and poly-n-butyl acrylate is preferable. Among them, polymethacrylate having a glass transition temperature (Tg) of 100 to 120 ° C. And an ABA triblock copolymer of a combination of a polyacrylic acid ester having a glass transition temperature (Tg) of −40 to −50 ° C. is preferable.

  The weight average molecular weight (Mw) of the acrylic thermoplastic elastomer of the component (A-3) is 10,000 to 1,000,000, particularly 30,000 to 500,000, especially 50,000 to 150,000. Is preferred. The acrylic ABA type triblock copolymer preferably has a weight average molecular weight (Mw) to number average molecular weight (Mn) ratio (Mw / Mn) of 1.0 to 1.8. It is preferably 1 to 1.5. The weight average molecular weight and number average molecular weight can be measured by gel permeation chromatography (hereinafter sometimes abbreviated as GPC).

  “Clarity (registered trademark)” (manufactured by Kuraray Co., Ltd.) is an example of a commercially available acrylic ABA type triblock copolymer of an acrylic thermoplastic elastomer.

  The acrylic thermoplastic elastomer of component (A-3) may be used alone or in combination of two or more.

<Component (A-4)>
Examples of the styrene-based elastomer of the component (A-4) used in the present invention include styrene-butadiene copolymer rubber and styrene-isoprene copolymer rubber. Among these, from the viewpoint of heat resistance and flexibility, Styrenic block copolymers are preferred, styrenic block copolymers having a polymer block consisting of vinyl aromatic hydrocarbon units and a polymer block consisting of conjugated diene units are more preferred, and the following formula (2) and / Or a copolymer of a vinyl aromatic hydrocarbon represented by formula (3) and a conjugated diene block and a hydrogenated product thereof (hydrogenated derivative) (hereinafter sometimes referred to as a “hydrogenated block copolymer”). The hydrogenation of a copolymer of a vinyl aromatic hydrocarbon and a conjugated diene block represented by the following formula (2) and / or formula (3) In is most preferable.

S- (DS) m (2)
(SD) n (3)
(In the formula, S represents a polymer block composed of vinyl aromatic hydrocarbon units, D represents a polymer block composed of conjugated diene units, and m and n represent integers of 1 to 5).

  The block copolymer described above may be linear, branched and / or radial.

As the monomeric vinyl aromatic hydrocarbon constituting the polymer block of S, a styrene derivative such as styrene or α-methylstyrene is preferable.
The conjugated diene monomer constituting the polymer block of D is preferably butadiene and / or isoprene.

  When the block copolymer represented by the formula (2) and / or the formula (3) is a hydrogenated block copolymer, and the polymer block of D is composed only of butadiene, The 1,2-addition structure is preferably 20 to 70% by weight in order to maintain the properties as an elastomer after hydrogenation.

  m and n are preferably large in the sense of lowering the order-disorder transition temperature, but are preferably small in terms of ease of production and cost. As a block copolymer (including a hydrogenated block copolymer), since it is excellent in rubber elasticity, the block copolymer represented by the formula (3) (including the hydrogenated block copolymer) is more preferable than the formula ( The block copolymer represented by 2) (including a hydrogenated block copolymer) is preferred, and the block copolymer represented by the formula (2) wherein m is 3 or less (including a hydrogenated block copolymer). ) Is more preferable, and a block copolymer (including a hydrogenated block copolymer) represented by the formula (2) in which m is 2 or less is particularly preferable.

  The ratio of “polymer block of S” in the block copolymer (including hydrogenated block copolymer) represented by the formula (2) and / or the formula (3) depends on the mechanical strength of the thermoplastic elastomer and The larger one is preferable from the viewpoint of heat-sealing strength, and the smaller one is preferable from the viewpoint of flexibility, profile extrusion moldability, and difficulty of bleeding out. Specifically, the ratio of the “polymer block of S” in the block copolymer of the formula (2) (including the hydrogenated block copolymer) is preferably 10% by weight or more, and 15% by weight. More preferably, it is more preferably 20% by weight or more. On the other hand, it is preferably 50% by weight or less, more preferably 45% by weight or less, and 40% by weight or less. It is particularly preferred.

  The weight average molecular weight of the styrenic elastomer such as a block copolymer (including a hydrogenated block copolymer) represented by the formula (2) and / or the formula (3) is preferably larger in terms of mechanical strength. However, the smaller one is preferable in terms of molding appearance and fluidity. Specifically, the weight average molecular weight of the styrene elastomer is preferably 10,000 or more, more preferably 30,000 or more, and on the other hand, preferably 450,000 or less, and 400,000 or less. More preferably, it is more preferably 200,000 or less, and most preferably 180,000 or less. Here, the weight average molecular weight is a weight average molecular weight in terms of polystyrene measured by gel permeation chromatography (hereinafter sometimes abbreviated as GPC) under the following conditions.

(Measurement condition)
Equipment: “150C ALC / GPC” manufactured by Nihon Millipore
Column: Showa Denko "AD80M / S" 3 detectors: FOXBORO infrared spectrophotometer "MIRANIA" measurement Wavelength 3.42 [mu] m
Solvent: o-dichlorobenzene Temperature: 140 ° C
Flow rate: 1 cm ³ / min Injection volume: 200 microliters Concentration: 2 mg / cm ³
Addition of 0.2% by weight of 2,6-di-t-butyl-p-phenol as an antioxidant

  As a manufacturing method of the above-mentioned block copolymer, any method may be used as long as the above-described structure and physical properties are obtained, and a known manufacturing method can be used.

  Commercial products of such hydrogenated block copolymers include “Clayton (registered trademark) G” manufactured by Kraton Polymer Co., “Septon (registered trademark)” manufactured by Kuraray Co., Ltd., “Tuftec® (registered trademark)” manufactured by Asahi Kasei Corporation. Or the like.

  As the component (A-4), the styrene elastomer and / or hydrogenated product thereof may be used alone or in combination of two or more.

  The amount of the block copolymer represented by the formula (2) and / or formula (3) and / or the hydrogenated block copolymer thereof contained in the component (A-4) is 20% by weight or more. It is preferably 30% by weight or more, more preferably 40% by weight or more, and the upper limit is usually 100% by weight.

<Component (A-5)>
The component (A-5) hydrocarbon rubber softener used in the present invention is effective for improving the flexibility and fluidity of the thermoplastic elastomer composition of the present invention. In addition, although component (A-5) itself is not a thermoplastic elastomer, it is used together with at least one of components (A-1) to (A-3) essential in component (A) of the present invention. (A) The characteristic as a thermoplastic elastomer is expressed as a whole.

  The hydrocarbon rubber softener is preferably a mineral oil softener or a synthetic resin softener, and more preferably a mineral oil softener because of its high affinity for the component (A-5).

  Mineral oil softeners are generally a mixture of aromatic hydrocarbons, naphthenic hydrocarbons and paraffinic hydrocarbons, with paraffinic oils in which 50% or more of all carbon atoms are paraffinic hydrocarbons, Those in which about 30 to 45% of all carbon atoms are naphthenic hydrocarbons are called naphthenic oils, and those in which 35% or more of all carbon atoms are aromatic hydrocarbons are called carbon atom aromatic oils. ing. The hydrocarbon rubber softener used as the component (A-5) may be any one of the above-mentioned various softeners or a mixture of a plurality of kinds, but among these, since the hue is good, Paraffinic oil is preferred. Examples of the synthetic resin softener include polybutene and low molecular weight polybutadiene.

  The kinematic viscosity at 40 ° C. of the hydrocarbon rubber softener is preferably higher in terms of improving the fluidity of the thermoplastic elastomer component (A), but is preferably lower in terms of the difficulty of fogging and the like. Specifically, it is preferably 20 centistokes or more, more preferably 50 centistokes or more, and on the other hand, it is preferably 800 centistokes or less, and preferably 600 centistokes or less. In addition, the flash point (COC method) of the hydrocarbon rubber softener is preferably 200 ° C. or higher, and more preferably 250 ° C. or higher.

<Combination ratio>
The thermoplastic elastomer composition of the present invention comprises a thermoplastic elastomer component (A) that contains at least one of components (A-1) to (A-3), thereby heat melting to a polar resin typified by a polycarbonate resin. Even if it adds a granular filler component (B) and a fibrous filler component (C) with a component (A-4), it can be made excellent in a flexibility.

  The thermoplastic elastomer composition of the present invention includes components (A-1) to (A-3) (hereinafter referred to as “essential components (A-1) to (A-3)” as the thermoplastic elastomer component (A). 1) may be included, or two or more of these may be included. However, each of them may be used individually when used alone. Is preferable because it is more effectively exhibited. Components (A-1) to (A-3) are all common in that they are excellent in heat-fusibility to polar resins, but component (A-1) is effective in terms of imparting heat resistance. A-2) is effective in terms of imparting flexibility, and component (A-3) is effective in terms of imparting scratch resistance when formed into a molded body.

  Moreover, the thermoplastic elastomer component (A) according to the present invention may be composed only of the essential components (A-1) to (A-3), and the essential components (A-1) to (A-3). And the component (A-4) styrene elastomer and / or hydrogenated product thereof, and carbonization of the essential components (A-1) to (A-3) and the component (A-5) It may contain a hydrogen rubber softener, and the essential components (A-1) to (A-3) and the component (A-4) styrene elastomer and / or its hydrogenated product and component ( A-5) a hydrocarbon-based rubber softener may be included, but when component (A-4) is included, it is preferable that component (A-5) is also included.

  Moreover, the thermoplastic elastomer component (A) according to the present invention includes at least one component and the component (A-4) among the essential components (A-1) to (A-3), and the component (A- When 5) is not included, the content of the component (A-4) in the thermoplastic elastomer component (A) is 99% by weight or less, particularly 97% by weight or less, and 50% by weight or more, particularly 75% by weight or more. It is preferable. By including the component (A-4) in the thermoplastic elastomer component (A), an effect that flexibility can be improved is exhibited. However, if the content of the component (A-4) is too small, this effect is low. If the amount is too large, the heat fusion property to a polar resin typified by polycarbonate tends to be low.

  The thermoplastic elastomer component (A) according to the present invention includes at least one component and the component (A-5) among the essential components (A-1) to (A-3), and the component (A-4) Is not contained, the content of the component (A-5) in the thermoplastic elastomer component (A) is usually 10% by weight or less, particularly preferably 5% by weight or less. In the case where the thermoplastic elastomer component (A) according to the present invention contains the essential components (A-1) to (A-3) and the component (A-5) and does not contain the component (A-4), If the content of (A-5) is too large, an oil bleed phenomenon may occur.

When the thermoplastic elastomer component (A) according to the present invention includes at least one of the essential components (A-1) to (A-3), the component (A-4), and the component (A-5), The content of the component (A-4) in the thermoplastic elastomer component (A) according to the invention is 49.5% by weight or less, particularly 47.5% by weight or less, 25% by weight or more, especially 37.5% by weight or more. The content of component (A-5) is 49.5% by weight or less, particularly 47.5% by weight or less, 25% by weight or more, particularly 37.5% by weight or more, and component (A-4) and component The content ratio with (A-5) is component (A-4): component (A-5) = 1: 4 to 0.2 (weight ratio), particularly 1: 2 to 0.5 (weight ratio). A range is preferable.
When the thermoplastic elastomer component (A) includes the component (A-4), it is preferable that the component (A-5) further includes the effect of improving flexibility and fluidity, but the content ratio of each component is the above. When out of the range, the respective blending effects may not be sufficiently obtained.

  In any case, the total content of the essential components (A-1) to (A-3) in the thermoplastic elastomer component (A) is 1% by weight or more in order to sufficiently obtain the effects of the present invention. In particular, it is preferably 5% by weight or more.

  The thermoplastic elastomer component (A) according to the present invention contains other thermoplastic elastomers other than the components (A-1) to (A-5) as long as the object of the present invention is not impaired. Also good. In this case, other elastomers include, for example, ethylene / propylene copolymer rubber (EPM), ethylene / propylene / nonconjugated diene copolymer rubber (EPDM), ethylene / butene copolymer rubber (EBM), ethylene / propylene / butene. Olefin-based elastomers such as copolymer rubbers; Polyamide-based elastomers such as polyamide-polyol copolymers; Polyvinyl chloride-based elastomers and polybutadiene-based elastomers, their hydrogenated products, acid anhydrides, etc. to modify polar functional groups One or two or more of those introduced, and those obtained by grafting, random and / or block copolymerization of other monomers can be mentioned, but these other in the thermoplastic elastomer component (A) The content of the elastomer is usually 0 to 80% by weight or less, preferably 50% by weight. Lower, and more preferably not more than 25 wt%.

[Granular filler component (B)]
The thermoplastic elastomer composition of the present invention contains at least one particulate filler component (B) from the group consisting of the following components (B-1) to (B-3).
Component (B-1): Calcium carbonate Component (B-2): Magnesium hydroxide Component (B-3): Magnesium oxide

  These particulate filler components (B) can be used in combination with the thermoplastic elastomer component (A) because they are excellent in dispersibility in the matrix of the thermoplastic elastomer component (A). Insulation and thermal conductivity can be imparted to the plastic elastomer composition.

  Among the particulate filler components (B) used in the thermoplastic elastomer composition of the present invention, the calcium carbonate of the component (B-1) is preferable from the viewpoint of water resistance, and the component (B-2) from the viewpoint of improving flame retardancy. From the viewpoint of vibration damping properties, the component (B-3) magnesium oxide is preferable.

  These components (B-1) to (B-3) may be used alone or in combination of two or more.

  The particulate filler component (B) listed above may be subjected to a surface treatment with a surface treatment agent such as a coupling agent such as silane or titanate or a fatty acid ester, if necessary. Further, the shape may be a tetrapot type.

  The average particle diameter of the particulate filler component (B) (particle diameter of 50% cumulative distribution in the laser diffraction method) is preferably 0.1 μm or more, more preferably 0.5 μm or more, on the other hand, 300 μm or less is preferable, and 250 μm or less is preferable. More preferred is 150 μm or less. When the average particle size of the particulate filler component (B) is 0.1 μm or more, the dispersibility is good in the kneader and it becomes easy to obtain a molded article having good physical properties and appearance. On the other hand, when the average particle size of the particulate filler component (B) is 300 μm or less, the mechanical properties such as tensile elongation and impact properties of the obtained molded product tend to be good while maintaining dispersibility and appearance. .

  The average particle diameter of the particulate filler component (B) can be measured using a laser diffraction particle size distribution meter or the like. For example, the particulate filler component (B) is added to a measurement allowable concentration in water or alcohol. Thus, a suspension can be prepared and dispersed by an ultrasonic disperser for measurement.

[Fibrous filler component (C)]
The thermoplastic elastomer composition of the present invention contains a fibrous filler component (C) containing the following component (C-1).
Ingredient (C-1): Carbon fiber

  “Fibrous” in the fibrous filler component of component (C) usually refers to a fibrous filler having a fiber diameter of 5 to 20 μm.

  Examples of the carbon fiber shape of the component (C-1) include a chopped fiber having a fiber diameter of 5 to 20 μm and a fiber length of 2 to 8 mm, a milled fiber having a fiber diameter of 5 to 20 μm, and a fiber length of 20 to 400 μm. Any of these can be used in the method. The carbon fiber of component (C-1) preferably has a thermal conductivity of 100 W / (m · K) or higher, more preferably a thermal conductivity of 400 W / (m · K) or higher.

  The component (C-1) carbon fibers are roughly classified into polyacrylonitrile, pitch, rayon, polyvinyl alcohol, etc., and any of these as the component (C-1) carbon fibers used in the present invention. Pitch-based carbon fibers are preferably used.

  As such carbon fibers, commercially available products include Raheama (Rahima) (registered trademark) manufactured by Teijin Ltd., Torayca (registered trademark) manufactured by Toray Industries, Inc., Tenax (registered trademark) manufactured by Toho Tenax Co., Ltd., Examples include Pyrofil (registered trademark) manufactured by Mitsubishi Rayon Co., Ltd., DIALEAD (registered trademark) manufactured by Mitsubishi Plastics, Inc., and GRANOC (registered trademark) manufactured by Nippon Graphite Fiber Co., Ltd.

  In the present invention, as the carbon fiber of the component (C-1), one kind may be used alone, or two or more kinds having different shapes (fiber diameter and fiber length) or different origins may be used in combination.

[Blend ratio of thermoplastic elastomer component (A), granular filler component (B) and fibrous filler component (C)]
In the thermoplastic elastomer composition of the present invention, the blending ratio of the thermoplastic elastomer component (A) to the insulating inorganic filler (B) and the fibrous filler component (C) is preferably the thermoplastic elastomer component (A) 15 -50 parts by weight, particulate filler component (B) 84-20 parts by weight, and fibrous filler component (C) 1-30 parts by weight (however, component (A), component (B) and component (C) 100 parts by weight in total). In particular, the thermoplastic elastomer component (A) is preferably 15 to 40 parts by weight, the granular filler component (B) 84 to 55 parts by weight, and the fibrous filler component (C) 1 to 15 parts by weight.

When the thermoplastic elastomer component (A) is less than the above range and the particulate filler component (B) and the fibrous filler component (C) are large, the flexibility and heat-fusibility to polar resins tend to be inferior. On the other hand, when the thermoplastic elastomer component (A) component is larger than the above range and the granular filler component (B) and the fibrous filler component (C) are small, the thermal conductivity tends to be inferior.
Moreover, even if the blending ratio of the particulate filler component (B) and the fibrous filler component (C) is more or less than the above range, the heat-fusibility to the polar resin tends to be lowered.

  In particular, the blending ratio of the fibrous filler component (C) to the granular filler component (B) (weight of (B)) / (weight of (C)) is 1/99 to 50/50, more preferably 5/95 to 60. When it is / 40, the particulate filler component (B) tends to hinder the orientation of the fibrous filler component (C), and the effects such as fusion property, thermal conductivity, and insulation to the polar resin are particularly excellent. It will be.

  In addition, when using as a granular filler component (B) combining 2 or more types of the group which consists of component (B-1)-(B-3), there is no restriction | limiting in particular in the usage rate.

[Other ingredients]
The thermoplastic elastomer composition of the present invention includes other components (the present ones) other than the thermoplastic elastomer component (A), the particulate filler component (B), and the fibrous filler component (C) as long as the object of the present invention is not impaired. In the specification, it may be simply referred to as “other components”). Examples of the other components include resins other than the thermoplastic elastomer component (A) (sometimes simply referred to as “other resins” in the present specification) and various additives.

  Examples of other resins that can be contained in the thermoplastic elastomer composition of the present invention include polyolefin resins, polyester resins, polyamide resins, styrene resins, acrylic resins, polycarbonate resins, and polyvinyl chloride resins. Other resins mentioned above may contain only one type or two or more types.

  Examples of the polyolefin resin include homopolymers having 2 to 4 carbon atoms such as ethylene, propylene, and 1-butene, and copolymers having these as main components. Specifically, these polyolefin resins are not limited to homopolymers such as polyethylene, polypropylene, poly-1-butene, and the like, as long as the main component is an α-olefin having 2 to 4 carbon atoms. It also includes a copolymer with ~ 20 α-olefin or a vinyl compound such as vinyl acetate, vinyl chloride, acrylic acid, methacrylic acid or styrene. Further, it may be a graft copolymer graft-modified with an unsaturated carboxylic acid such as maleic anhydride, maleic acid, acrylic acid or a derivative thereof. Furthermore, these polyolefin resins may be a mixture.

  Polyester resins include terephthalic acid, isophthalic acid, diphenyl ether-4,4-dicarboxylic acid, aromatic dicarboxylic acids such as naphthalene-1,4- or 2,6-dicarboxylic acid, oxalic acid, succinic acid, adipic acid, sebacin Acid, aliphatic dicarboxylic acid such as undecadicarboxylic acid, acid component of dicarboxylic acid such as alicyclic dicarboxylic acid such as cyclohexanedicarboxylic acid, and ethylene glycol, propylene glycol, 1,4-butanediol, neopentyl glycol, etc. Polycondensates with aliphatic glycols, cycloaliphatic glycols such as cyclohexanedimethanol, and glycol components such as aromatic diols such as bisphenol A. Specifically, polyethylene terephthalate (PET), copolymerized PET, polybutylene Terephthalate, polyethylene naphth , Poly cyclohexylene terephthalate, and the like. In addition, polycarboxylic acid such as polylactic acid, polyglycolic acid, poly-β-hydroxybutyrate, poly-β-hydroxyvalerate, poly-γ-butyrolactone, poly-δ-valerolactone, poly-ε-caprolactone, etc. A condensate is also mentioned. Among these, PET and copolymerized PET are particularly preferable. However, the polyester resin mentioned here does not include those corresponding to the component (A-1).

  Polyamide resins include aliphatic diamines such as hexamethylene diamine and decamethylene diamine, diamines such as alicyclic diamine and aromatic diamine, aliphatic dicarboxylic acids such as adipic acid and sebacic acid, and fats such as cyclohexane dicarboxylic acid. Polyamides obtained by polycondensation with dicarboxylic acids such as aromatic dicarboxylic acids such as cyclic dicarboxylic acid, terephthalic acid and isophthalic acid; Polyamides obtained by condensation of aminocarboxylic acids such as ε-aminocaproic acid; ε-caprolactam and the like Examples thereof include polyamides obtained from lactams and copolymerized polyamides composed of these components. Specifically, nylon 6, nylon 66, nylon 610, nylon 9, nylon 11, nylon 12, nylon 6/66 copolymer, nylon 66/610 copolymer, nylon 6/11 copolymer and the like can be mentioned. Among these, nylon 6 and nylon 66, which are excellent in melting point, rigidity and the like, are preferable.

  The styrene resin is a resin mainly composed of styrene such as a homopolymer of styrene, a copolymer of styrene and acrylonitrile, methyl (meth) acrylate, or a modified rubber thereof, and more specifically, polystyrene, High impact polystyrene (rubber compounded polystyrene), styrene-acrylonitrile copolymer (SAN), styrene-methyl methacrylate copolymer, acrylonitrile-butadiene-styrene copolymer rubber (ABS), styrene-maleic anhydride copolymer ( SMA) and the like. However, the styrene resin mentioned here does not include those corresponding to the component (A-4).

  Acrylic resins include polymethyl acrylate, polyethyl acrylate, polybutyl acrylate, poly-2-ethylhexyl acrylate, polymethyl methacrylate, polyacrylonitrile, polymethacrylonitrile, methyl methacrylate-acrylonitrile copolymer, Examples thereof include methyl methacrylate-α-methylstyrene copolymer and acrylonitrile-methyl acrylate-butadiene copolymer. Of these, polyacrylonitrile is preferred. The acrylic resin mentioned here does not include those corresponding to the component (A-3).

  Examples of the polycarbonate resin include various polycarbonates obtained by reacting a dihydroxy compound with phosgene or diphenyl carbonate by a known method. Examples of the dihydroxy compound include hydroquinone, resorcinol, 4,4′-dihydroxydiphenylmethane, 4,4′-dihydroxydiphenylethane, 4,4′-dihydroxydiphenyl-n-butane, 4,4′-dihydroxydiphenyl-2,2- Propane (bisphenol A), 4,4′-dihydroxydichlorodiphenyl-2,2-propane, 4,4′-dihydroxydiphenyl-1,1-cyclohexane, 4,4′-dihydroxydiphenylethylphenylmethane, 2,2 ′ -Dihydroxydiphenyl, 2,6-dihydroxynaphthalene, 4,4'-dihydroxydiphenyl ether and the like are used. Of these, polycarbonate using 4,4'-dihydroxy-phenyl-2,2-propane (bisphenol A) is preferred because of its excellent mechanical performance and transparency.

  Examples of the polyvinyl chloride resin include a homopolymer or a copolymer of vinyl chloride. Further included are homopolymers or copolymers of vinylidene chloride. Although the monomer copolymerizable with a polyvinyl chloride resin is not limited, For example, ethylene, propylene, acrylonitrile, vinyl acetate, maleic acid or its ester, acrylic acid or its ester, methacrylic acid or its ester, etc. are mentioned. Further, a polymer blend of polyvinyl chloride resin, for example, a polymer blend composed of polyvinyl chloride resin and polyvinylidene chloride may be used.

  Additives that can be contained in the thermoplastic elastomer composition of the present invention include antioxidants, molding aids such as crystal nucleating agents and lubricants, UV stabilizers, light stabilizers such as hindered amine compounds, and hydrolysis resistance improvers. And coloring agents such as pigments and dyes, antistatic agents, conductive agents, flame retardants, reinforcing agents, fillers, plasticizers, mold release agents and the like.

  Among these, as the antioxidant, a dithiocarbamate-based antioxidant, a hindered phenol-based antioxidant, a sulfur-based antioxidant, a phosphorus-based antioxidant, or the like can be used.

  As the dithiocarbamate-based antioxidant, a metal salt of dialkyldithiocarbamate is preferable, among which nickel dialkyldithiocarbamate is preferable, and nickel dibutyldithiocarbamate is particularly preferable because it has a large effect of improving heat aging resistance.

Specific examples of hindered phenol antioxidants include 2,4-dimethyl-6-t-butylphenol, 2,6-di-t-butylphenol, 2,6-di-t-butyl-p-cresol, hydroxy Methyl-2,6-di-t-butylphenol, 2,6-di-t-α-dimethylamino-p-cresol, 2,5-di-t-butyl-4-ethylphenol, 4,4′-bis (2,6-di-t-butylphenol), 2,2'-methylene-bis-4-methyl-6-t-butylphenol, 2,2'-methylene-bis (4-ethyl-6-t-butylphenol) 4,4′-methylene-bis (6-tert-butyl-o-cresol)
4,4′-methylene-bis (2,6-di-t-butylphenol), 2,2′-methylene-bis (4-methyl-6-cyclohexylphenol), 4,4′-butylidene-bis (3 -Methyl-6-tert-butylphenol), 4,4′-thiobis (6-tert-butyl-3-methylphenol), bis (3-methyl-4-hydroxy-5-tert-butylbenzyl) sulfide, 4, 4'-thiobis (6-t-butyl-o-cresol), 2,2'-thiobis (4-methyl-6-t-butylphenol), 2,6-bis (2'-hydroxy-3'-t-) Butyl-5′-methylbenzyl) -4-methylphenol, 3,5-di-tert-butyl-4-hydroxybenzenesulfonic acid diethyl ester, 2,2′-dihydroxy-3,3′-di (α-methyl) (Cyclohexyl)- 5,5′-dimethyl-diphenylmethane, α-octadecyl-3 (3 ′, 5′-di-t-butyl-4′-hydroxyphenyl) propionate, 6- (hydroxy-3,5-di-t-butylanilino) -2,4-bis-octyl-thio-1,3,5-triazine, hexamethylene glycol-bis [β- (3,5-di-t-butyl-4-hydroxyphenol) propionate], N, N ' Hexamethylene-bis (3,5-di-t-butyl-4-hydroxyhydrocinnamic acid amide), 2,2-thio [diethyl-bis-3 (3,5-di-t-butyl-4-hydroxy Phenyl) propionate], 3,5-di-t-butyl-4-hydroxybenzenephosphonic acid dioctadecyl ester, tetrakis [methylene-3 (3,5-di-t-butyl-4-hydro) Cyphenyl) propionate] methane, 1,3,5-trimethyl-2,4,6-tris (3,5-di-t-butyl-4-hydroxybenzyl) benzene, 1,1,3-tris (2-methyl -4-hydroxy-5-di-t-butylphenyl) butane, tris (3,5-di-t-butyl-4-hydroxyphenyl) isocyanurate, tris [β- (3,5-di-t-butyl) -4 hydroxyphenyl) propionyl-oxyethyl] isocyanurate and the like.
Among these, the use of those having a molecular weight of 500 or more such as tetrakis [methylene-3 (3,5-di-t-butyl-4-hydroxyphenyl) propionate] methane is preferable.

  The sulfur-based antioxidant is a compound containing sulfur such as thioether, dithioate, mercaptobenzimidazole, thiocarbanilide, and thiodipropion ester. However, those corresponding to the above dithiocarbamate antioxidants are not included. Among these, thiodipropion ester compounds are particularly preferable.

  Examples of phosphorus antioxidants include phosphorus-containing compounds such as phosphoric acid, phosphorous acid, hypophosphorous acid derivatives, phenylphosphonic acid, polyphosphonate, dialkylpentaerythritol diphosphite, and dialkylbisphenol A diphosphite.

  These antioxidants may be used alone or in combination of two or more.

  In the thermoplastic elastomer composition of the present invention, the antioxidant content is preferably about 100 parts by weight in total of the thermoplastic elastomer component (A), the particulate filler component (B), and the fibrous filler component (C). 0.01 to 5 parts by weight. If the content is less than 0.01 parts by weight, the effect of improving the heat aging resistance tends to be insufficient. On the other hand, even if it is used in excess of 5 parts by weight, an effect commensurate with the increase in the addition amount is obtained. Not only is it not economical, but it may cause problems such as bleeding, and the mechanical strength of the composition may decrease.

  The total content of the additives in the thermoplastic elastomer composition of the present invention is about 100 parts by weight in total of the thermoplastic elastomer component (A), the particulate filler component (B), and the fibrous filler component (C). The amount is preferably 10 parts by weight or less, and more preferably 5 parts by weight or less.

[Physical properties]
The thermoplastic elastomer composition of the present invention has an excellent balance of insulation, thermal conductivity, flexibility, and thermal fusion with a polar resin.

  The thermal conductivity of the thermoplastic elastomer composition of the present invention can be evaluated as the thermal conductivity as shown in the examples below. A higher value of this thermal conductivity is evaluated as being superior in thermal conductivity, and in the thermoplastic elastomer of the present invention, preferably 0.5 W / (K · m) or more, more preferably 1 W / (K · m). Above, more preferably 3 W / (K · m) or more. The upper limit of the thermal conductivity is not particularly limited, but it is about 10 W / (K · m) that can be achieved by the thermoplastic elastomer composition of the present invention.

  The flexibility of the thermoplastic elastomer of the present invention can be evaluated as a duro A hardness as shown in the examples below. This duro A hardness is evaluated to be superior in flexibility as the value is lower, preferably 100 or less, and more preferably 80 or less.

  The thermoplastic elastomer composition of the present invention can be evaluated for its heat-fusibility with a polar resin such as polycarbonate as shown in the examples below. It is evaluated that the larger the value of the polycarbonate fusion strength, the better the fusion property with the polar resin, and this value is preferably 10 N / 25 mm or more, and more preferably 15 N / 25 mm or more.

The insulation property of the thermoplastic elastomer composition of the present invention can be evaluated as a volume resistivity as shown in the examples described later. A higher value of the volume resistivity is evaluated as being superior in insulation, and is preferably 10 ⁸ Ω · cm or more, and more preferably 10 ¹⁰ Ω · cm or more.

[Production method]
The method for producing the thermoplastic elastomer composition of the present invention is not particularly limited. According to a conventional method, the thermoplastic elastomer component (A), the particulate filler component (B), and the fibrous filler component (C) It can be produced by dry blending with other components added as necessary, followed by melt-kneading.
In addition, when using a component (A-4) and a component (A-5) as a thermoplastic elastomer component (A), after mixing a component (A-4) and a component (A-5) previously, other Mixing with the component is preferable in terms of workability in handling the component (A-5) which is a liquid component at normal temperature (23 ° C.).

[Molded body]
By molding the thermoplastic elastomer composition of the present invention, it can be used as various molded products. Specific examples of the molded body include an injection molded body, an extrusion molded body, and a press molded body. In the thermoplastic elastomer composition of the present invention, various injection methods such as a normal injection molding method, extrusion molding method, press molding method and the like can be used, and if necessary, a gas injection molding method, an injection compression molding method, By using various molding methods such as a short shot foam molding method, a molded body can be obtained.

In particular, the molding conditions for injection molding the thermoplastic elastomer composition of the present invention are as follows.
The molding temperature is generally 150 to 300 ° C, preferably 180 to 280 ° C. The injection pressure is usually 5 to 100 MPa, preferably 10 to 80 MPa. The mold temperature is usually from 0 to 80 ° C, preferably from 20 to 60 ° C.

  The molded body formed by molding the thermoplastic elastomer composition of the present invention can be used as a composite molded body by heat-sealing to a polar resin such as polycarbonate resin or polybutylene terephthalate resin.

[Usage]
The thermoplastic elastomer composition of the present invention has a good balance of insulation, thermal conductivity, flexibility, and thermal fusion with a polar resin such as a polycarbonate resin. In particular, it is useful as a sealing material and an adhesive used for a polycarbonate resin member in a part where insulation and heat dissipation are required in an electronic member such as a housing of a personal computer. By using the thermoplastic elastomer composition of the present invention, the polycarbonate resin member is heat-sealed, and good insulation, flexibility and thermal conductivity are exhibited at this portion. In addition, the use of the thermoplastic elastomer composition of the present invention is not limited to the sealing material and adhesive of the heat radiating member, but includes automobile parts, home appliance parts, electronic parts, electric wire coverings, medical parts, footwear, miscellaneous goods. It can also be used for applications that require rubber elasticity in a wide range of fields.

  Hereinafter, although the specific aspect of this invention is demonstrated in detail using an Example, this invention is not limited by a following example, unless the summary is exceeded. In addition, the values of various production conditions and evaluation results in the following examples have meanings as preferable values of the upper limit or the lower limit in the embodiment of the present invention, and the preferable range is the above-described upper limit or lower limit value. A range defined by a combination of values of the following examples or values of the examples may be used.

  In the following examples and comparative examples, the raw materials used for the preparation of the thermoplastic elastomer composition and the evaluation methods of the obtained thermoplastic elastomer composition are as follows.

[Raw materials]
Polyester thermoplastic elastomer (component (A-1)):
“Primalloy (registered trademark) A1703C” manufactured by Mitsubishi Chemical Corporation
Polybutylene terephthalate-polytetramethylene ether block copolymer
Number average molecular weight of polytetramethylene ether unit: 2000
Polytetramethylene ether unit content: 77% by weight
Content of polybutylene terephthalate unit: 23% by weight
Melting point (measured with DSC apparatus): 150 ° C
MFR (measurement temperature 230 ° C., measurement load 21.18 N): 25 g / 10 minutes
Duro A hardness: 75

Hydrogenated product of styrene elastomer (component (A-4)):
“Kraton (registered trademark) G1641” manufactured by Kraton Polymer Co., Ltd.
Hydrogenated product of styrene-butadiene-styrene block copolymer (represented by the formula (2))
Weight average molecular weight: 80,000
Styrene content (content of “polymer block of S” in formula (2)): 32% by weight

Hydrocarbon softener (component (A-5)):
"Diana Process Oil PW90" made by Idemitsu Kosan Co., Ltd.
Paraffinic oil

<Granular filler component (B)>
Calcium carbonate (component (B-1)):
"Softon (registered trademark) 1200" manufactured by Shiraishi Calcium
Average particle size: 1.8μm (catalog value)

Magnesium hydroxide (component (B-2)):
“Kisuma (registered trademark) 5A” manufactured by Kyowa Chemical Industry Co., Ltd.
Average particle size: 1.8μm (catalog value)

Magnesium oxide (component (B-3)):
"Starmag (registered trademark) P" manufactured by Kamishima Chemical Co., Ltd.
Average particle size: 3.5μm (catalog value)

<Fibrous filler component (C)>
Carbon fiber (component (C-1)):
“DIALEAD (registered trademark) K223HE” manufactured by Mitsubishi Plastics, Inc.
Pitch-based carbon fiber
Fiber diameter: 11 μm, fiber length: 6 mm
Tensile elastic modulus: 900 GPa, tensile strength: 3,800 MPa,
Elongation at break: 0.3%, density: 550 g / cm ³ ,
Thermal conductivity: 550 W / (m · K)

Antioxidant (other ingredients):
"Irganox (registered trademark) 1010" manufactured by BASF
Tetrakis [methylene-3 (3,5-di-tert-butyl-4-hydroxyphenyl) propionate] methane

[Evaluation method]
<Thermal conductivity>
The pellets of the thermoplastic elastomer composition obtained in each example were press-molded at 240 ° C., and the thermal conductivity was measured by a laser flash method. The thermal conductivity indicates that the larger the value is, the better the thermal conductivity is, and the heat conductive material is preferably 1 W / (K · m) or more, preferably 3 W / (K · m) or more. It is more preferable.

<Duro A hardness>
The pellets of the thermoplastic elastomer composition obtained in each example were molded into a sheet of 100 mm × 100 mm × 3 mm at an injection temperature of 240 ° C. and a mold temperature of 40 ° C. using an injection molding machine, and JIS-K6253 The Duro A hardness was measured according to the standard. The duro A hardness indicates that the smaller the value, the better the flexibility, and the flexibility material is preferably 100 or less.

<Polycarbonate fusion strength>
Using an injection molding machine, polycarbonate resin ("Novalex (registered trademark) H-3000" manufactured by Mitsubishi Engineering Plastics Co., Ltd.) was molded into a 100 mm x 100 mm x 2 mm sheet, and the resulting sheet was 100 mm x 100 mm The sheet was inserted into a 3 mm sheet mold. Next, the thermoplastic elastomer composition pellets obtained in each example were injected into the gap between the molded sheet and the mold using an injection molding machine at an injection temperature of 240 ° C. and a mold temperature of 40 ° C. Fusion molding was performed.

  The obtained two-layer molded sheet was cut into strip-shaped test pieces of 25 mm × 100 mm × 3 mm, and the skin material layer (thermoplastic elastomer composition) and the core material layer (polycarbonate resin) were pulled at 180 ° C. in a tensile rate of 200 mm / min. A peel test was conducted to measure the fusion strength of the skin material layer / core material layer. The larger this value is, the better the heat fusion property with the polycarbonate resin is, and the fusion strength is preferably 1 N / 25 mm or more, but the material breaks down (the test piece breaks without peeling between the layers). Most preferably.

<Volume specific resistivity>
The pellets of the thermoplastic elastomer composition obtained in each example were molded into a sheet of 100 mm × 100 mm × 3 mm at an injection temperature of 240 ° C. and a mold temperature of 40 ° C. using an injection molding machine, and JIS-K6271 The volume resistivity was measured in accordance with the standard. The volume resistivity indicates that the larger the value is, the better the insulation is. The insulating material is preferably 10 ⁸ Ω · cm or more, and more preferably 10 ¹⁰ Ω · cm or more.

[Examples 1-4, Comparative Examples 1-4]
The raw materials were mixed with the formulation shown in Table 1, and the resulting mixture was melt-kneaded (cylinder temperature 220 ° C. to 250 ° C.) with a biaxial kneader to produce pellets of a thermoplastic elastomer composition. The above-described evaluation was performed using the obtained pellets, and the results are shown in Table-1.

[Evaluation of results]
As is clear from Table 1, Comparative Examples 1 to 3 which contain the particulate filler component (B) but do not contain the fibrous filler component (C) are excellent in insulation and flexibility, but are thermally conductive and polar resins. It was inferior to the heat-fusibility with. On the other hand, Comparative Example 4 which contains the fibrous filler component (C) but does not contain the particulate filler component (B) is excellent in thermal conductivity and flexibility, but is inferior in thermal fusion with a polar resin and insulation. It was.
On the other hand, Examples 1-4 which correspond to the thermoplastic elastomer composition of this invention containing a granular filler component (B) and a fibrous filler component (C) are heat conductive and heat fusion with a polar resin. It can be seen that it has an excellent balance of adherence, flexibility, and insulation, and in particular, is excellent in heat fusion with a polycarbonate resin.
In particular, when the thermoplastic elastomer component (A), the particulate filler (B), and the fibrous filler (C) are used, the same polycarbonate elastomer fusion strength is used as the thermoplastic elastomer component (A). It was shown that the value was improved about twice as much as the case where only the granular filler (B) was used without using the fibrous filler (C).

  The thermoplastic elastomer composition of the present invention has a good balance of insulation, thermal conductivity, flexibility, and thermal fusion with a polar resin such as a polycarbonate resin. In particular, it is useful as a sealing material and an adhesive used for a polycarbonate resin member in a part where insulation and heat dissipation are required in an electronic member such as a housing of a personal computer. By using the thermoplastic elastomer composition of the present invention, the polycarbonate resin member is heat-sealed, and good insulation, flexibility and thermal conductivity are exhibited at this portion. Further, the thermoplastic elastomer composition of the present invention is widely used in various parts such as sealing materials, grips, gaskets, etc. in the fields of automobile parts, home appliance parts, electronic parts, electric wire coatings, medical parts, footwear, sundries, etc. can do.

Claims (9)

The thermoplastic elastomer component (A) containing at least one of the group consisting of the following components (A-1) to (A-3), and the group consisting of the following components (B-1) to (B-3) A thermoplastic elastomer composition comprising at least a particulate filler component (B) containing at least one of them and a fibrous filler component (C) containing the following component (C-1).
Component (A-1): Polyester thermoplastic elastomer Component (A-2): Urethane thermoplastic elastomer Component (A-3): Acrylic thermoplastic elastomer Component (B-1): Calcium carbonate Component (B-2) ): Magnesium hydroxide Component (B-3): Magnesium oxide Component (C-1): Carbon fiber   15 to 50 parts by weight of the thermoplastic elastomer component (A), 84 to 20 parts by weight of the particulate filler component (B), and 1 to 30 parts by weight of the fibrous filler component (C) (however, the component ( The total amount of A), component (B), and component (C) is 100 parts by weight.), The thermoplastic elastomer composition according to claim 1.   The thermoplastic elastomer composition according to claim 1 or 2, wherein the component (A-1) comprises a polybutylene terephthalate-polyalkylene ether block copolymer. The thermoplastic elastomer composition according to any one of claims 1 to 3, wherein the thermoplastic elastomer component (A) further comprises the following component (A-4).
(A-4): Styrene elastomer and / or hydrogenated product of styrene elastomer The thermoplastic elastomer composition according to any one of claims 1 to 4, wherein the thermoplastic elastomer component (A) further comprises the following component (A-5).
Component (A-5): Hydrocarbon softener   The molded object formed by shape | molding the thermoplastic elastomer composition of any one of Claims 1 thru | or 5.   A composite molded product obtained by heat-sealing the molded product according to claim 6 with a polycarbonate resin.   The sealing material which consists of a thermoplastic-elastomer composition of any one of Claims 1 thru | or 5.   An adhesive comprising the thermoplastic elastomer composition according to any one of claims 1 to 5.