JP2005133021A - Thermoplastic elastomer composition - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a thermoplastic elastomer composition having excellent complexing and/or heat-welding property with ionomer resins, etc., excellent complexing and/or adhesiveness with a polyurethane sealant, excellent heat-resistance, moderate hardness and good moldability in extrusion molding, injection molding, etc., and provide a molded article produced by using the elastomer composition. <P>SOLUTION: The thermoplastic elastomer composition contains (a) 100 pts. wt. of an ethylenic resin polymerized with a metallocene catalyst and having a density of 0.85-0.91 g/cm<SP>3</SP>and (b) 5-180 pts. wt. of a partially hydrogenated product of a block copolymer of an aromatic vinyl compound and a conjugated diene compound wherein the hydrogenation ratio of the partially hydrogenated block copolymer is 3-90%. <P>COPYRIGHT: (C)2005,JPO&NCIPI

Description

  The present invention relates to a thermoplastic elastomer composition and a molded body using the same, and in particular, it has excellent heat-fusability and / or composite properties with an ionomer resin and the like, excellent heat resistance, and adhesion to a urethane sealant. The present invention also relates to a thermoplastic elastomer composition that is excellent in composite properties, has an appropriate hardness, and is excellent in molding processability such as extrusion molding and injection molding, and a molded body using the same.

  In recent years, polyolefin-based thermoplastic elastomers, styrene-based thermoplastic elastomers, etc., which are soft materials having rubber elasticity and do not require a vulcanization process and can be molded and recyclable in the same way as thermoplastic resins, are automobile parts. It is widely used in the fields of home appliance parts, electric wire coverings, medical parts, footwear, sundries, etc.

These thermoplastic elastomers are often used together with molded articles of various resins, and in that case, it is desirable that they are excellent in heat-fusibility with various resins. Conventionally, the thermoplastic elastomer has been widely used as a material for automobile parts as a lightweight and recyclable material, but has the disadvantages of being easily scratched, having insufficient surface gloss and poor adhesion.
On the other hand, in the automotive parts materials such as automobile molding materials from polyvinyl chloride resins that have been used in the past, there has been a demand for materials that do not contain halogens from the market due to recent environmental problems. An ionomer resin having scratch resistance, excellent surface gloss, and excellent affinity with metals has been attracting attention. However, since the ionomer resin alone is expensive in price, it is generally used only for the skin of the molded product, the base material is inexpensive, and a design using a more flexible thermoplastic elastomer has been generally performed.
However, the thermoplastic elastomer has a problem of poor adhesion to an ionomer resin or the like, and has been an obstacle to expanding its use.

As a means for solving these problems, for example, ethylene / (meth) acrylic acid / (meth) having a (meth) acrylic acid content of 5 to 15% by weight and a (meth) acrylic acid ester content of 5 to 25% by weight. ) Laminated lid material using a composition comprising an acrylic ester copolymer, low density polyethylene, and tackifying resin for the heat seal layer (see, for example, Patent Document 1), ethylene-vinyl acetate copolymer, polypropylene, and ethylene A composition for improving adhesion with a primer containing a polar monomer graft-modified styrene elastomer by blending an olefin thermoplastic elastomer formed from a copolymer rubber (see, for example, Patent Document 2); A composition comprising an ethylene / unsaturated ester copolymer, polypropylene, and a styrene elastomer (for example, special Reference 3), an ionomer resin composition comprising an ionomer, polypropylene, olefinic elastomer and the like obtained by neutralizing at least a part of carboxyl groups of an ethylene / unsaturated carboxylic acid copolymer with a metal ion (for example, patent document) 4)) and the like.
Further, a composition comprising an olefinic thermoplastic elastomer obtained by a reactor method and a non-halogen polar polymer as a composition having improved adhesion to an olefinic resin sheet (see, for example, Patent Document 5), a fiber fabric. As a composition layer having excellent adhesiveness formed on a base fabric, a soft material composed of a polypropylene resin, a styrene block copolymer, an ethylene-vinyl acetate copolymer, or an ethylene- (meth) acrylic acid (ester) copolymer A polyolefin-based composition (for example, see Patent Document 6) is disclosed.
However, none of the above prior art documents suggest or disclose heat fusion / adhesion with an ionomer resin or the like, and none of the compositions improve adhesiveness with an ionomer resin or the like. In addition, it is necessary to add a polar group-containing polymer or the like which is a similar component to an ionomer resin or the like, and even if a small amount of such a polar group-containing polymer is added, the effect is not sufficient. In addition to problems such as increased costs, excessive hardness, and poor compatibility, it is difficult to freely adjust the balance of moldability and flexural modulus of the thermoplastic elastomer composition. ing.

Furthermore, a composition comprising a polyolefin resin and a resin having a polar group as described above is disclosed as a composition in which various properties of the polyolefin resin are improved. For example, it is suitable for an insulating layer of an electric power cable made of an ethylene / (meth) acrylic acid ester / carbon monoxide copolymer, a styrene polymer, a copolymer of propylene and an α-olefin having 4 or more carbon atoms. A semiconductive composition having peelability (see, for example, Patent Document 7), a power cable comprising an ethylenically unsaturated ester copolymer having an unsaturated ester content of 10 to 50% by weight and a styrene triblock copolymer Composition excellent in releasability from insulating layer (see, for example, Patent Document 8), polypropylene having improved foaming properties such as a foamed sheet of polypropylene, a polypropylene system comprising an ethylene / unsaturated carboxylic acid copolymer or ionomer, and polyethylene Resin composition (for example, see Patent Document 9), sheet of polyethylene obtained by polymerization with a metallocene catalyst As a resin composition for a surface layer having a high anchoring property with respect to a styrene-based hot melt pressure-sensitive adhesive in a polyolefin pressure-sensitive adhesive sheet, a composition containing an ethylene-based ionomer in order to improve tearability (see, for example, Patent Document 10) A composition comprising a polyolefin such as a random type polypropylene, and a styrene-1,4-butadiene-butylene-styrene block copolymer (SBBS) (see, for example, Patent Document 11), comprising two or more plastic film layers. A composition comprising a polyolefin and a styrene-1,4-butadiene-butylene-styrene block copolymer (SBBS) as a polyolefin base layer composition having a high anchoring property to a styrene hot melt adhesive in a heat sealable sheet substrate ( For example, (See Patent Document 12.) Improved film blocking and low-temperature heat sealability from linear low-density polyethylene obtained by copolymerization of ethylene obtained from metallocene catalyst and α-olefin having 3 to 20 carbon atoms Therefore, a composition comprising an ethylene copolymer having a density of ethylene and a vinyl monomer having a polar group of 0.880 to 0.915 g / cm ³ (see, for example, Patent Document 13), ethylene · (meth) methacryl Ethylene / α-olefin random copolymer, ethylene vinyl acetate copolymer, ethylene / (meth) acrylic acid ester or styrene / conjugated diene / styrene block copolymer, etc. polymerized with acid copolymer with single site catalyst The environmental impact of using this composition is low, and it has excellent printability, low-temperature heat sealability, and hot tack properties. Toburo nonwoven (e.g., see Patent Document 14. ), A crosslinkable rubber such as an olefin elastomer polymerized with a metallocene catalyst, and an olefin resin such as polypropylene, which are treated in the presence of an inert gas such as carbon dioxide gas in order to suppress heat generation during the dynamic crosslinking process. A polyolefin-based thermoplastic elastomer (for example, see Patent Document 15) comprising the above composition is disclosed. However, none of the above-mentioned prior literatures suggests or discloses heat fusion / adhesion with an ionomer resin or the like, and none of these compositions has adhesiveness or heat fusion with an ionomer resin of a thermoplastic elastomer. It is not a resin composition intended to improve wearability.

In addition, the applicant of the present invention provides a polypropylene-based resin, a polyethylene-based resin polymerized with a single-site catalyst, an ethylene-based ionomer resin, and / or a polyolefin-based elastomer composition having improved heat-fusibility with a polymer having a polar group. Alternatively, a thermoplastic resin composition comprising a copolymer of ethylene and a polar group-containing monomer (see, for example, Patent Document 16), low linear expansion coefficient, adhesion to polyolefin resin, adhesion to ionomer resin, molding process A thermoplastic elastomer composition comprising an olefin copolymer rubber, a polypropylene resin, an ethylene / acrylic acid copolymer and / or an ethylene / methacrylic acid copolymer, and an inorganic filler as a polyolefin-based thermoplastic elastomer composition having excellent properties (for example, , See Patent Document 17). In molding materials (by extrusion molding), especially in window moldings (for example, front window moldings, etc.), even if they are fused with the ionomer of the skin, the sealing material between the glass and the base material is a urethane sealant. Since the fusibility (composite) and / or adhesiveness was insufficient, it was necessary to fuse and / or bond via an ionomer, and the product shape and extrusion process were complicated.
Japanese Patent No. 3130665 JP 2000-119455 A JP 2001-2855 A JP 2003-82184 A JP 2000-334901 A Japanese Patent Laid-Open No. 2002-274341 Japanese Patent No. 3231414 JP 2002-179854 A JP 2001-192515 A JP 2001-348468 A Japanese Patent Laid-Open No. 2002-113819 JP 2002-127316 A JP 2002-241514 A JP 2002-249972 A JP 2001-342262 A JP 2002-128970 A JP 2003-82171 A

  In view of the above problems, the object of the present invention is excellent in composite properties with ionomer resins and / or heat fusion, excellent in composite properties and / or adhesive properties with urethane sealants, excellent in heat resistance, moderate Another object of the present invention is to provide a thermoplastic elastomer composition having excellent hardness and excellent molding processability such as extrusion molding and injection molding (particularly extrusion molding), and a molded body using the same.

  As a result of intensive studies to achieve the above object, the present inventor melt-kneaded a partial hydrogenated product of a block copolymer of an aromatic vinyl compound and a conjugated diene compound in a specific ethylene polymer. Finds that a thermoplastic elastomer composition having excellent heat fusion with an ionomer resin, etc., excellent heat resistance, moderate hardness, and excellent processability such as extrusion molding and injection molding can be obtained. The present invention has been completed.

That is, according to the first invention of the present invention, (a) 100 parts by weight of an ethylene resin polymerized by a metallocene catalyst and having a density of 0.85 to 0.91 g / cm ³ , and (b) hydrogenation A thermoplastic elastomer composition comprising 5 to 180 parts by weight of a partially hydrogenated block copolymer of an aromatic vinyl compound and a conjugated diene compound having a rate of 3 to 90% is provided.

  According to the second invention of the present invention, there is further provided a thermoplastic elastomer composition characterized in that, in the first invention, (c) 1 to 200 parts by weight of a polar ethylene copolymer is further contained. Is done.

  According to a third invention of the present invention, in the second invention, (c) the polar ethylene-containing copolymer has a polar group-containing comonomer content of 5 to 55% by weight. Elastomeric compositions are provided.

  According to a fourth invention of the present invention, in the second or third invention, the thermoplastic elastomer composition is characterized in that (c) the polar ethylene copolymer is an ethylene-vinyl acetate copolymer. Is provided.

  According to a fifth aspect of the present invention, in any one of the first to fourth aspects, the thermoplastic elastomer composition further comprises (d) 1 to 400 parts by weight of a polypropylene resin. Is provided.

  According to a sixth invention of the present invention, in any one of the first to fifth inventions, (e) a block compound of an aromatic vinyl compound having a hydrogenation rate exceeding 95% and a conjugated diene compound is used. A thermoplastic elastomer composition comprising 1 to 400 parts by weight of a polymer is provided.

  In addition, according to the seventh invention of the present invention, in any one of the first to sixth inventions, (f) a non-aromatic hydrocarbon rubber softening agent is further contained in an amount of 1 to 250 parts by weight. A thermoplastic elastomer composition is provided.

  According to the eighth invention of the present invention, there is provided a thermoplastic elastomer composition for extrusion molding comprising the thermoplastic elastomer composition of any one of the first to seventh inventions.

  According to the ninth aspect of the present invention, there is provided a thermoplastic elastomer composition for composite molding with a urethane sealant comprising the thermoplastic elastomer composition according to any one of the first to eighth aspects.

  According to a tenth aspect of the present invention, there is provided a thermoplastic elastomer composition for composite molding with an ionomer resin comprising the thermoplastic elastomer composition according to any one of the first to ninth aspects.

  According to the eleventh aspect of the present invention, there is provided a molded article comprising the thermoplastic elastomer composition according to any one of the first to tenth aspects.

  According to the twelfth aspect of the present invention, there is provided a laminated molded article including a layer comprising the thermoplastic elastomer composition according to any one of the first to eleventh aspects.

  The thermoplastic elastomer composition of the present invention is excellent in heat-fusability and / or compositeness with an ionomer resin or the like, excellent in heat resistance, has an appropriate hardness, and / or adhesiveness with a urethane sealant and / or It is a thermoplastic elastomer composition having excellent composite properties and excellent molding processability such as extrusion molding and injection molding, and can be suitably used for a molded body with a layer using the same.

Hereinafter, each component of the resin composition of this invention is demonstrated.
1. Component of thermoplastic elastomer composition (a) Ethylene-based resin polymerized by metallocene-based catalyst and having a density of 0.85 to 0.91 g / cm ³ (a) Metallocene-based used in the thermoplastic elastomer composition of the present invention An ethylene-based resin that is polymerized by a catalyst and has a density of 0.85 to 0.91 g / cm ³ is a component that fulfills the function of ensuring moldability and improves the adhesion with an ionomer resin or the like.
Component (a) is polyethylene or a copolymer of ethylene and α-olefin mainly composed of ethylene, and is a crystalline polyethylene such as high-density polyethylene, low-density polyethylene, linear low-density polyethylene, or ultra-low-density polyethylene. , Ethylene-propylene copolymer rubber, ethylene-propylene-nonconjugated diene multicomponent copolymer rubber, ethylene-propylene-1-butene copolymer rubber, ethylene-1-butene copolymer rubber, ethylene-1-butene-nonconjugated diene multicomponent An amorphous or low crystallinity elastomer such as copolymer rubber can be used. One or two or more selected from these can be preferably used. In particular, an ethylene copolymer resin polymerized with a single-site catalyst, such as an ethylene-octene-1 copolymer, An ethylene / hexene-1 copolymer is preferred.

The density of the component (a) is preferably from 0.85~0.91g / cm ^3, more preferably 0.89~0.91g / cm ^3. When the density exceeds the upper limit, it becomes too hard and the adhesiveness deteriorates, and when it is less than the lower limit, the heat resistance deteriorates. Moreover, 60-110 degreeC is preferable and, as for melting | fusing point Tm of a component (a), More preferably, it is 60-100 degreeC. Here, Tm is a value obtained by measuring a range of −50 ° C. to 200 ° C. at a heating rate of 10 ° C./min using DSC.

Further, the MFR of the component (a) is preferably 0.5 dg / min or more, and if it exceeds 50 dg / min, the moldability is further improved, which is preferable. If it is less than the lower limit, there is a problem of decrease in manufacturability and molding processability, which is not preferable.
Here, MFR is a value measured according to JIS K 7210 (190 ° C., 21.18 N load).

  The component (a) polymerized with the metallocene catalyst used in the present invention is, for example, in accordance with the method described in JP-A 61-296008, Group 4b, Group 5b and Group 6b of the periodic table. A polymer polymerized by a polymer catalyst comprising a reaction product of a metallocene containing at least one of the above metals and an alumoxane, the reaction product being formed in the presence of a support Is mentioned. In addition, as described in JP-A-3-163008, group 3 (other than scandium) of the periodic table of elements, group 4 to 10 or a lanthanide series metal, and delocalized π substituted with a constraint-inducing portion A metal coordination complex comprising a binding moiety, the complex having a constrained geometry around the metal atom, between the center of the localized substituted π-bonded moiety and the center of at least one remaining substituent Such complexes in comparative complexes that differ only in that the constraint-induced substitutions are replaced by hydrogen, and further include one or more delocalized substituted π-bond moieties For each of the complexes, there may be mentioned polymers polymerized from metal coordination complexes characterized in that only one of each metal atom is a cyclic delocalized substituted π bond moiety.

(B) Aromatic vinyl compound having a hydrogenation rate of 3 to 90%-Partial hydrogenated product of block copolymer with conjugated diene compound (b) Aromatic vinyl compound used in the thermoplastic elastomer composition of the present invention- The partial hydrogenated product of the block copolymer with the conjugated diene compound is a component that performs the function of improving the adhesiveness with the ionomer resin or the like.
Component (b) is a conjugated diene block of a block copolymer comprising at least two polymer blocks A mainly composed of an aromatic vinyl compound and at least one polymer block B mainly composed of a conjugated diene compound. This is a partially hydride obtained by hydrogenating an aliphatic double bond portion derived from conjugated diene of 3 to 90%. For example, the hydrogen content of the conjugated diene block of the block copolymer of aromatic vinyl compound-conjugated diene compound having a structure such as ABA, BABA, ABBABA, etc. A hydrogenated block copolymer obtained by hydrogenation at 3 to 90% can be mentioned. Here, the polymer block A is preferably 40% by weight or less.

  The polymer block A mainly composed of an aromatic vinyl compound may be a polymer composed only of an aromatic vinyl compound or a copolymer of an aromatic vinyl compound and less than 50% by weight of a conjugated diene compound. The polymer block B mainly composed of a conjugated diene compound may be a polymer composed solely of a conjugated diene compound or a copolymer of a conjugated diene compound and less than 50% by weight of an aromatic vinyl compound.

  As the aromatic vinyl compound constituting the component (b), for example, one or two or more types can be selected from styrene, α-methylstyrene, vinyltoluene, p-tert-butylstyrene, etc. Among them, styrene is preferable. . Further, as the conjugated diene compound, for example, one or more kinds are selected from butadiene, isoprene, 1,3-pentadiene, 2,3-dimethyl-1,3-butadiene, etc., among which butadiene, isoprene, and these The combination of is preferable.

  The microstructure in the polymer block B mainly composed of a conjugated diene compound can be selected arbitrarily. In the butadiene block, the 1,2-microstructure has a lower limit of 1% or more, preferably 5% or more, more preferably 10% or more, and an upper limit of 95% or less, preferably 80% or less, more preferably 75% or less. is there.

  The hydrogenation rate of the aliphatic double bond based on the conjugated diene of the conjugated diene block in the hydrogenated copolymer of the component (b) is 3 to 90%, preferably 5 to 80%, more preferably 7 -75%, particularly preferably 9-60%. Further, the 1,2-vinyl bond after hydrogenation is preferably 0.5 to 12%, more preferably less than 10%, still more preferably 5% or less, and still more preferably 3% or less. When the hydrogenation rate exceeds the upper limit, the adhesive strength is lowered, which is not preferable. On the other hand, if the value is below the lower limit, the heat aging resistance deteriorates, which is not preferable.

  The number average molecular weight in terms of polystyrene of the hydrogenated block copolymer (b) having the above structure is 10,000 to 500,000, preferably 10,000 to 200,000, more preferably 10,000 to 150,000. 000 range. The molecular weight distribution (ratio (Mw / Mn) of weight average molecular weight (Mw) to number average molecular weight (Mn)) is preferably 10 or less, more preferably 5 or less, and more preferably 2 or less. The molecular structure of the hydrogenated block copolymer may be linear, branched, radial, or any combination thereof.

  When the number average molecular weight (Mn) is less than the lower limit, the mechanical properties, heat resistance, scratch resistance, and oil resistance of the molded product are lowered. On the other hand, when the upper limit is exceeded, fluidity is deteriorated, and appearance defects such as short shots and flow marks occur in the molded product in injection molding. In extrusion molding, the occurrence of rough skin, eye grease, etc. becomes prominent. In addition, the molecular weight in this invention is the value calculated | required on the basis of the polystyrene whose molecular weight is known by GPC. Therefore, the value is a relative value, not an absolute value, and may vary by about ± 30% depending on GPC conditions such as a reference sample, apparatus, and data processing method.

  Specific examples of the hydrogenated block polymer component (b) having a hydrogenation rate of 3 to 90% include partially hydrogenated styrene-butadiene-styrene copolymer having 1,2-bonds selectively hydrogenated in the butadiene block. Examples include coalescence (SBBS). Moreover, a partially hydrogenated styrene-isoprene-styrene copolymer, a partially hydrogenated styrene-isoprene / butadiene-styrene copolymer, and the like can be given. In the present invention, the hydrogenated product of the aromatic vinyl compound-conjugated diene compound block copolymer may be used alone or in combination of two or more.

  The compounding quantity of a component (b) is 5-180 weight part with respect to 100 weight part of component (a), Preferably it is 25-150 weight part. When the compounding amount of the component (b) exceeds the upper limit, the heat resistance, mechanical properties, and moldability of the resulting thermoplastic elastomer composition are lowered. On the other hand, if it is less than the lower limit, the heat-fusibility between the obtained thermoplastic elastomer composition and the ionomer resin is lowered.

(C) Polar ethylene copolymer In the thermoplastic elastomer composition of this invention, (c) polar ethylene copolymer can be used as needed. Component (c) is a component that improves adhesion.
Examples of the component (c) include an ethylene ionomer resin and a copolymer of ethylene and a polar group-containing comonomer represented by the formula (I) or (II).
^{_{CH 2 = C (R 1)}} -COOR 2 ... (I)
^{_{CH 2 = C (R 1)}} -OCOR 2 ... (II)
(Wherein R ¹ represents hydrogen or a methyl group, and R ² represents hydrogen or an alkyl group having 1 to 10 carbon atoms)

  The ethylene-based ionomer resin is one of carboxyl groups of an ethylene / α, β-unsaturated carboxylic acid copolymer or an ethylene / α, β-unsaturated carboxylic acid / α, β-unsaturated carboxylic acid ester copolymer. It is a resin whose part is neutralized and cross-linked by metal ions.

The proportion of the ethylene units in the ethylene copolymer before neutralization is preferably 75 to 99.5 mol%, more preferably 88 to 98 mol%, and the α, β-unsaturated carboxylic acid units occupy. The proportion is preferably 0.5 to 15 mol%, more preferably 1 to 6 mol%, and the proportion of the α, β-unsaturated carboxylic acid ester unit is preferably 0 to 10 mol%, more preferably Is 0 to 6 mol%.
Heat resistance, mechanical properties of the thermoplastic elastomer composition obtained when the content of the proportion of α, β-unsaturated carboxylic acid units and the content of the proportion of α, β-unsaturated carboxylic acid ester units exceeds the upper limit, Molding processability decreases. On the other hand, if it is less than the lower limit, the effect of improving the heat-fusibility with the ionomer resin is lowered.

  The α, β-unsaturated carboxylic acid constituting the copolymer is preferably one having 3 to 8 carbon atoms, more preferably acrylic acid, methacrylic acid, maleic acid, fumaric acid, maleic anhydride. Etc. are used. The α, β-unsaturated carboxylic acid ester is preferably one having 4 to 8 carbon atoms, more preferably methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, isobutyl acrylate. Butyl methacrylate, dimethyl phthalate and the like are used. As the α, β-unsaturated carboxylic acid, acrylic acid or methacrylic acid is particularly preferably used, and as the α, β-unsaturated carboxylic acid ester, isobutyl acrylate is particularly preferably used.

  Of the carboxyl groups in the ethylene copolymer, the proportion (neutralization degree) neutralized by metal ions is preferably 0 to 80%, more preferably 0 to 75%. If the neutralization degree of the carboxyl group by metal ions is 80% or more, the extrusion moldability of the resulting thermoplastic elastomer composition is deteriorated.

The metal ion is a metal ion having a valence of 1 to 3, particularly a metal ion having a valence of 1 to 3 of groups I, II, III, IV and VII in the periodic table. For example, Na ⁺ , K ⁺ , Li ⁺ , Cs ⁺ , Ag ⁺ , Hg ⁺ , Cu ⁺ , Be ⁺⁺ , Mg ⁺⁺ , Ca ⁺⁺ , Sr ⁺⁺ , Ba ⁺⁺ , Cu ⁺⁺ , Cd ⁺⁺ , Hg ⁺⁺ , Sn ^{+ pb ++, Fe ++, Co ++} , Ni ++, Zn ++, Al +++, Sc +++, Fe +++, Y +++ and the like. These metal ions may be a mixed component of two or more kinds, or may be a mixed component with ammonium ions. Of these metal ions, Zn ⁺⁺ and Na ⁺⁺ are particularly preferable.

  Examples of the monomer represented by the formula (I) or (II) in the copolymer of ethylene and the polar group-containing comonomer represented by the formula (I) or (II) include (meth) acrylic acid, vinyl acetate, Examples include methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, isobutyl acrylate, and butyl methacrylate.

  The content of the monomer represented by the formula (I) or (II) in the component (c) is preferably 5 to 55% by weight, more preferably 8 to 55% by weight. When the content of the monomer represented by the formula (I) or (II) exceeds the upper limit value, heat resistance, mechanical properties, and molding processability are deteriorated. On the other hand, if it is less than the lower limit, the effect of improving the heat-fusibility with the ionomer resin is lowered.

  Specific examples of component (c) are preferably ethylene / vinyl acetate copolymer (EVA), ethylene / methyl methacrylate copolymer (EMMA), ethylene / ethyl acrylate copolymer (EEA), ethylene / methyl acrylate copolymer. Examples thereof include a polymer (EMA), an ethylene / acrylic acid copolymer (EAA), and an ethylene / methacrylic acid copolymer (EMAA). Of these, ethylene / vinyl acetate copolymer (EVA) and ethylene / methacrylic acid copolymer (EMAA) are particularly preferable. When an ethylene / methacrylic acid copolymer (EMAA) is used, the adhesiveness is particularly excellent, and when an ethylene / vinyl acetate copolymer (EVA) is used, extrusion moldability such as variable extrusion and profile extrusion is particularly excellent.

Moreover, 0.5-50 dg / min is preferable and, as for MFR (190 degreeC, 21.18N load) of a component (c), More preferably, it is 1-30 dg / min. When MFR exceeds the upper limit, heat resistance is deteriorated. On the other hand, if it is less than the lower limit, the workability deteriorates.
Here, MFR is a value measured according to JIS K-6924 (JIS K-6730 has been abolished and shifted) (190 ° C., 21.18 N).

  Examples of products in the case of using an ethylene / vinyl acetate copolymer (EVA) as the component (c) used in the present invention include EVAFLEX EV-170 (MFR: 1 dg / min, vinyl acetate content: 33% by weight, tensile Strength: 17.7 MPa), EV-270 (MFR: 1 dg / min, vinyl acetate content: 28 wt%, tensile strength: 22.5 MPa), P-3307 (EV150) (MFR: 30 dg / min, containing vinyl acetate) Amount: 33 wt%, tensile strength: 9 MPa), P-2807 (EV250) (MFR: 15 dg / min, vinyl acetate content: 28 wt%, tensile strength: 14 MPa), P-2805 (EV260) (MFR: 6 dg) / Min, vinyl acetate content: 28 wt%, tensile strength: 22 MPa), P-2505 (EV360) (MFR: 2 dg / min, vinyl acetate included : 25 wt%, tensile strength: 27MPa), P-1907 (EV450) (MFR: 15dg / min, vinyl acetate content: 19 wt%, tensile strength: 13 MPa), and the like. Among these, EVAFLEX EV-270 is preferable.

  As an example of a product in the case of using an ethylene / methacrylic acid copolymer (EMAA) as the component (c) used in the present invention, NUCREL 0903HC (MFR: 3 dg / min, methacrylic acid content: 9% by weight, tensile strength: 27.5 MPa), 0908 C (MFR: 8 dg / min, methacrylic acid content: 9 wt%, tensile strength: 26 MPa), 0910 C (MFR: 10 dg / min, methacrylic acid content: 9 wt%, tensile strength: 23 MPa) 1027C (MFR: 27 dg / min, methacrylic acid content: 10% by weight, tensile strength: 19.5 MPa), 1108C (MFR: 8 dg / min, methacrylic acid content: 11% by weight, tensile strength: 27.5 MPa) 1207C (MFR: 7 dg / min, methacrylic acid content: 12% by weight, tensile strength: 29 MPa), 1214 (M R: 14dg / min, methacrylic acid content: 12 wt%, tensile strength: 27.5 MPa), and the like. Among these, NUCREL 0903HC is preferable.

  When used, the amount of component (c) is 1 to 200 parts by weight, preferably 20 to 150 parts by weight, based on 100 parts by weight of component (a). When the amount of component (c) exceeds the upper limit, the adhesiveness of the resulting thermoplastic elastomer composition is lowered.

(D) Polypropylene resin In the thermoplastic elastomer composition of the present invention, (d) a polypropylene resin can be used as necessary. The component (d) is a component that functions to improve moldability.
Component (d) is a propylene homopolymer or propylene based on propylene and other α-olefins such as ethylene, 1-butene, 1-hexene, 4-methyl-1-pentene, 1-octene and the like. And a copolymer thereof. Such a copolymer may be a random copolymer or a block copolymer, and is a composition in which a small amount of hydrocarbon rubber, for example, ethylene / propylene copolymer rubber is blended with such a polymer. Also good. Among these, a propylene-based block copolymer that is a copolymer of propylene and an α-olefin is preferable in terms of improving adhesive strength as compared with a propylene homopolymer.

  The propylene block copolymer that can be preferably used in the thermoplastic elastomer composition of the present invention is a block copolymer composed of a crystalline propylene polymer portion and an amorphous propylene / α-olefin copolymer portion. It is a coalescence. Examples of the crystalline propylene polymer portion include a propylene homopolymer or a random copolymer of propylene and a small amount of other α-olefin. On the other hand, examples of the amorphous propylene / α-olefin copolymer include non-crystalline random copolymers of propylene and other α-olefins.

  The other α-olefins are preferably those having 2 or 4 to 12 carbon atoms, and specific examples include ethylene, 1-butene, 3-methyl-1-butene, 3-methyl-1-pentene, Examples include 4-methyl-1-pentene, 4,4-dimethyl-1-pentene, vinylcyclopentane, vinylcyclohexane and the like. These α-olefins may be used alone or in combination of two or more.

  In addition to this α-olefin, 1,4-hexadiene, 5-methyl-1,5-hexadiene, 1,4-octadiene, cyclohexadiene, cyclooctadiene, dicyclopentadiene, 5-methylene-2-norbornene, A ternary or quaternary copolymer obtained by copolymerizing a non-conjugated diene such as 5-ethylidene-2-norbornene, 5-butylidene-2-norbornene, and 5-isopropenyl-2-norbornene can also be used.

The proportion of the amorphous propylene / α-olefin copolymer part in the propylene-based block copolymer is 30 to 90% by weight, preferably 40 to 80% by weight. When the proportion of the amorphous propylene / α-olefin copolymer part is less than 30% by weight, the flexibility of the product is inferior and the heat-sealing strength is also deteriorated. On the other hand, if it exceeds 90% by weight, the moldability deteriorates.
Here, the proportion of the non-crystalline propylene / α-olefin copolymer part is as follows. 1 g of propylene block copolymer is placed in 300 ml of xylene in an oil bath and dissolved under stirring at 140 ° C. which is the boiling point of xylene. Then, after 1 hour, the temperature was lowered to 100 ° C. within 1 hour while continuing the stirring, transferred to a quenching oil bath, rapidly cooled to 23 ± 2 ° C. with stirring, and the polymer was precipitated, and allowed to stand for 20 minutes or more. The resulting precipitate is naturally filtered with a filter paper, and the filtrate is evaporated to dryness using an evaporator, further dried under reduced pressure at 120 ° C. for 2 hours, and then allowed to cool to room temperature and measured for its weight. .

Furthermore, the propylene content of the amorphous propylene / α-olefin copolymer part is preferably 5 to 90% by weight, more preferably 10 to 85% by weight.
Here, the propylene content of the non-crystalline propylene / α-olefin copolymer part is a xylene-soluble polymer obtained when the proportion of the non-crystalline propylene / α-olefin copolymer part is measured. Is a value obtained by infrared spectroscopy.

  Moreover, the bending elastic modulus prescribed | regulated by JISK6758 (bending speed: 2.7 mm, 1/4 inch bending test piece) of a propylene-type block copolymer has preferable 1500 Mpa or less, More preferably, it is 50-1000 Mpa. When the flexural modulus exceeds 1500 MPa, the adhesiveness decreases.

Further, the peak top melting point on the highest temperature side of the melting curve measured using a DSC (differential scanning calorimeter) of the propylene-based block copolymer is preferably 125 ° C. or more, more preferably 125 to 166 ° C. . If the peak top melting point on the highest temperature side of the DSC melting curve is less than 135 ° C., the resulting thermoplastic elastomer composition tends to be sticky and the heat resistance tends to be inferior. On the other hand, when it exceeds 166 ° C., the heat-fusibility of the thermoplastic elastomer composition deteriorates.
Here, the peak top melting point of DSC is 5 minutes after cooling the sample to 250 ° C. using a differential scanning calorimeter (DSC) and then cooling it to −30 ° C. at a cooling rate of 20 ° C./min. This is a value obtained as a temperature indicating the main endothermic peak of the endothermic peak curve obtained when the temperature is raised to 250 ° C. at a rate of temperature rise of 20 ° C./min.

  Furthermore, the melt flow rate measured in accordance with JIS K7210 (230 ° C., 21.18 N load) of the propylene-based block copolymer is preferably 0.01 to 100 dg / min, more preferably 0.1 to 60 dg. / Min. If the melt flow rate is less than the above range, the molding processability of the thermoplastic elastomer composition tends to be inferior. On the other hand, if it exceeds the above range, it tends to be difficult to obtain sufficient mechanical strength.

The production method of the propylene-based block copolymer preferably used in the present invention is not particularly limited. For example, an organoaluminum compound such as triethylaluminum, a titanium atom, a magnesium atom, a halogen atom, and t-butyl-methyl-di- Using a catalyst composed of a solid component essentially containing an electron-donating compound such as an organic silicon compound such as ethoxysilane, propylene or other α-substantially about 2 to 12 carbon atoms in the first stage polymerization. In the presence of the catalyst, an olefin is supplied to produce a propylene homopolymer or a crystalline propylene polymer block composed of a propylene / α-olefin copolymer. And other α-olefin having about 2 to 12 carbon atoms, and in the presence of the catalyst, propylene · α- Made by preparing a non-crystalline propylene · alpha-olefin copolymer block consisting of olefin copolymer.
As described above, the propylene block copolymer used in the present invention is a copolymer in which a crystalline propylene polymer block and an amorphous propylene / α-olefin copolymer block are produced in a multi-stage process. It is a resin in which a crystalline propylene / α-olefin copolymer portion, for example, an ethylene / propylene copolymer rubber portion and an ethylene / butene-1 copolymer rubber portion are finely dispersed in the copolymer.

  The polymerization may be carried out by any of batch, continuous, and semi-batch methods. The first stage polymerization is carried out in the gas phase or in the solution, preferably in the gas phase, and the second stage and subsequent polymerizations. Is preferably carried out in the gas phase.

  In addition, the propylene block copolymer of the present invention is Catalloy (manufactured by Montel), P.I. E. It can be obtained as a commercial product under the trademarks of R (manufactured by Tokuyama) and Newcon (manufactured by Chisso).

  When blended, the amount of component (d) is 1 to 400 parts by weight, preferably 1 to 300 parts by weight, per 100 parts by weight of component (a). If the blending amount of component (d) exceeds the above upper limit value, the heat-fusability between the thermoplastic elastomer composition and the ionomer resin is slightly lowered and the hardness is increased, so that it is suitable only for applications that do not particularly require flexibility. is there.

(E) Hydrogenated product of block copolymer of aromatic vinyl compound and conjugated diene compound having a hydrogenation rate of 95% or more In the thermoplastic elastomer composition of the present invention, if necessary, (e) hydrogenation rate A hydrogenated product of a block copolymer of 95% or more of an aromatic vinyl compound and a conjugated diene compound can be used. The component (e) is a component that functions to improve moldability.
Component (e) is a conjugated diene block of a block copolymer comprising at least one polymer block A mainly composed of an aromatic vinyl compound and at least one polymer block B mainly composed of a conjugated diene compound. The hydrogenated high hydrogenation product is obtained by hydrogenating 90% or more of the aliphatic double bond portion derived from the conjugated diene. For example, a conjugated diene block of an aromatic vinyl compound-conjugated diene compound block copolymer having a structure such as A-B, A-B-A, B-A-B-A, or A-B-A-B-A. And a hydrogenated block copolymer obtained by hydrogenating to a hydrogenation rate of 90% or more. Among them, those having a structure of a triblock structure or more are preferable.

  The polymer block A mainly composed of an aromatic vinyl compound is preferably composed of an aromatic vinyl compound alone, or a conjugated diene hydrogenated with 50% by weight or more, preferably 70% by weight or more of the aromatic vinyl compound. It is a copolymer block with a compound.

  The polymer block B mainly composed of a hydrogenated conjugated diene compound is preferably composed of only a hydrogenated conjugated diene compound or 50% by weight or more, preferably 70%, of a hydrogenated conjugated diene compound. It is a copolymer block of at least% by weight and an aromatic vinyl compound.

  The block copolymer contains 5 to 60% by weight, preferably 20 to 50% by weight of an aromatic vinyl compound.

  As the aromatic vinyl compound constituting the block copolymer, for example, one or more kinds can be selected from styrene, α-methylstyrene, vinyltoluene, p-tert-butylstyrene, etc. preferable. In addition, as the conjugated diene compound, for example, one or two or more kinds are selected from butadiene, isoprene, 1,3-pentadiene, 2,3-dimethyl-1,3-butadiene, etc., among which butadiene, isoprene and These combinations are preferred.

  Further, in the polymer block A mainly composed of these aromatic vinyl compounds and the polymer block B mainly composed of conjugated diene compounds, the distribution of units derived from the conjugated diene compound or aromatic vinyl compound in the molecular chain is random, It may be tapered (in which the monomer component increases or decreases along the molecular chain), partially in a block form, or any combination thereof. When there are two or more polymer blocks A mainly composed of aromatic vinyl compounds or polymer blocks B mainly composed of conjugated diene compounds, each polymer block has a different structure even if each has the same structure. There may be.

  These block copolymers can be obtained by block polymerization in an inert medium using a lithium catalyst or a Ziegler type catalyst by a known method, for example, the method described in JP-B-40-23798. The hydrogenated block copolymer can be obtained by hydrogenating the above block copolymer by a known method. Hydrogenation mainly hydrogenates an aliphatic double bond derived from a conjugated diene in a block of a conjugated diene compound, and its hydrogenation rate needs to be 90% or more. When the hydrogenation rate is less than 90%, the flexibility tends to deteriorate.

  In the polymer (B) that is a hydrogenated component (e) and mainly comprises a conjugated diene compound, the microstructure is arbitrary. For example, in a polybutadiene block, a 1,2-microstructure is preferred. It is 20 to 50% by weight, particularly preferably 25 to 45% by weight. In the polyisoprene block, it is preferable that 70 to 100% by weight of isoprene has a 1,4-microstructure.

The number average molecular weight (Mn) in terms of polystyrene of the hydrogenated block copolymer (e) is 30,000 to 500,000, preferably 100,000 to 400,000, more preferably 150,000 to 350,000, More preferably, it is in the range of 200,000-350,000, and the molecular weight distribution (ratio (Mw / Mn) of weight average molecular weight (Mw) to number average molecular weight (Mn)) is preferably 5 or less, more preferably 2 It is as follows. The molecular structure of the block copolymer may be linear, branched, radial, or any combination thereof.
When the number average molecular weight (Mn) is less than the lower limit, the heat resistance, scratch resistance and oil resistance are lowered. On the other hand, when the upper limit is exceeded, fluidity is deteriorated, and appearance defects such as short shots and flow marks occur in the molded product in injection molding. In extrusion molding, the occurrence of rough skin, eye grease, etc. becomes prominent. In addition, the molecular weight in this invention is the value calculated | required on the basis of the polystyrene whose molecular weight is known by GPC. Therefore, the value is a relative value, not an absolute value, and may vary by about ± 30% depending on GPC conditions such as a reference sample, apparatus, and data processing method.

  Specific examples of the hydrogenated block copolymer of component (e) include styrene-ethylene / butene / styrene copolymer (SEBS), styrene / ethylene / propylene / styrene copolymer (SEPS), and styrene / ethylene / ethylene. -A propylene styrene copolymer (SEEPS) etc. can be mentioned.

  The amount of component (e) is 1 to 400 parts by weight, preferably 5 to 300 parts by weight, based on 100 parts by weight of component (a) when blended. If the blending amount of component (e) exceeds the above upper limit, the meltability is slightly lowered and the moldability is lowered, so that it is suitable only for applications that do not require particularly high moldability.

(F) Softener for non-aromatic hydrocarbon rubber In the thermoplastic elastomer composition of the present invention, (f) a softener for non-aromatic hydrocarbon rubber can be used as necessary. Component (f) is a component that functions to adjust the hardness of the resulting composition and to improve moldability.
The non-aromatic hydrocarbon rubber softeners used as component (f) are paraffinic and naphthenic ones. As the component (f), paraffin-based compounds are preferable, and paraffin-based compounds having less aromatic ring components are particularly suitable.

  These non-aromatic hydrocarbon rubber softeners have a dynamic viscosity at 37.8 ° C of 20 to 50,000 cSt, preferably 20 to 1,000 cSt, and a dynamic viscosity at 100 ° C of 5 to 1, It is preferably 500 cSt, preferably 5 to 100 cSt, the pour point is −10 to −25 ° C., and the flash point (COC) is 170 to 350 ° C. Furthermore, a thing with a weight average molecular weight of 100-2,000 is preferable.

  When blended, the amount of component (f) is preferably 1 to 250 parts by weight, more preferably 3 to 200 parts by weight, per 100 parts by weight of component (a). When the compounding amount of the component (f) exceeds the upper limit, the adhesiveness is lowered.

(G) Inorganic filler In the thermoplastic elastomer composition of this invention, (g) inorganic filler can be used as needed. The component (g) is a component that functions to improve the profile extrudability.
Component (g) includes talc, calcium carbonate, silica, diatomaceous earth, barium sulfate, magnesium carbonate, magnesium hydroxide, mica, clay, titanium oxide, carbon black, glass fiber, hollow glass balloon, carbon fiber, calcium titanate fiber Natural silicic acid, synthetic silicic acid (white carbon), chlorite and the like. Of these, talc and calcium carbonate are particularly preferred.

  When used, the amount of component (g) is preferably 1 to 300 parts by weight, more preferably 3 to 200 parts by weight, per 100 parts by weight of component (a). When the blending amount of the component (g) exceeds the above upper limit value, the fusion power is slightly lowered, the moldability is lowered, and the surface tends to become sticky by moving to the fusion target member, so that the surface property is not particularly required. Suitable for use only.

(H) Others In the thermoplastic elastomer composition of the present invention, a heat stabilizer, an antioxidant, a light stabilizer, an ultraviolet absorber, a crystal nucleating agent, and an antiblocking agent are further added as long as the object of the present invention is not impaired. , Sealants, mold release agents such as stearic acid and silicone oil, lubricants such as polyethylene wax, colorants, pigments, foaming agents (organic and inorganic), flame retardants (hydrated metal compounds, red phosphorus, poly (Ammonium phosphate, antimony, silicone) and the like can be blended.
Examples of the antioxidant include 2,6-di-tert-p-butyl-p-cresol, 2,6-di-tert-butylphenol, 2,4-dimethyl-6-tert-butylphenol, 4,4- Examples thereof include phenolic antioxidants such as dihydroxydiphenyl and tris (2-methyl-4-hydroxy-5-tert-butylphenyl) butane, phosphite antioxidants, thioether antioxidants, and the like. Of these, phenolic antioxidants and phosphite antioxidants are particularly preferred.
As the foaming agent, EXPANSEL (manufactured by EXPANSEL) and Matsumoto Microsphere (manufactured by Matsumoto Yushi Seiyaku Co., Ltd.) are preferable.

2. Production of Thermoplastic Elastomer Composition The thermoplastic elastomer composition of the present invention is prepared by adding the above components (a) to (b) or other components as necessary, and adding each component simultaneously or in any order. Can be manufactured.

  The method of melt kneading is not particularly limited, and generally known methods can be used. For example, a single screw extruder, a twin screw extruder, a roll, a Banbury mixer, or various kneaders can be used. For example, the above operation can be continuously performed by using a suitable L / D (47 or more) twin screw extruder, Banbury mixer, pressure kneader, or the like. Here, the temperature of melt kneading is preferably 160 to 220 ° C.

3. Applications The thermoplastic elastomer composition of the present invention is excellent in heat-fusability / adhesiveness and compositeness between urethane-based sealant and ionomer resin, etc., excellent in heat resistance, moderate hardness, extrusion molding, injection Excellent processability such as molding.
The resin that can be heat-sealed with the thermoplastic elastomer composition of the present invention is preferably an ionomer resin, an ethylene / acrylic acid copolymer, an ethylene / methacrylic acid copolymer, an ethylene / acrylic acid ester copolymer, an ethylene / acrylic acid ester copolymer, Examples thereof include polar resins composed of a methacrylic acid ester copolymer, an ethylene / vinyl acetate copolymer, a saponified ethylene / vinyl acetate copolymer, and the like. Among them, it is particularly excellent in heat fusion property with an ionomer resin.

The composite molded product of the thermoplastic elastomer composition and polar resin of the present invention can be used for various applications such as automobile members, building members, and weak electrical products. In particular, it is useful for various moldings such as automotive moldings, for example, window moldings, roof moldings, protector moldings, weather moldings, strip moldings, and the like that are mounted on automobiles.
In automotive window molding, it can be used as a member having adhesion and / or adhesion to both glass and urethane sealants, and the surface exposed on the outer surface of the molding is strong and scratch resistant. The thermoplastic elastomer composition of the present invention, which is an excellent ionomer resin, is formed by bonding and / or combining with a urethane-based sealant that adheres to the body of an automobile, thereby forming a glass edge portion that is said to be a conventional encapsulation. Since it is not necessary to cover the entire molding with the ionomer resin skin, there is an advantage of simplifying the product shape and the extrusion process. Lamination can be performed using, for example, coextrusion, insert molding, transfer molding.

  Here, an example of the urethane sealant is Penguin Seal # 560 manufactured by Sunstar Giken Co., Ltd., and a primer is Chemlok 459X manufactured by Road Far East Co., Ltd.

  EXAMPLES Hereinafter, although this invention is demonstrated in detail using an Example and a comparative example, this invention is not limited only to an Example. The evaluation methods and raw materials used in the examples are as follows.

1. Evaluation Method (1) Specific gravity: Based on JIS K 7112, the test piece was measured using a 2 mm thick press sheet.
(2) Hardness: In accordance with JIS K 7215, the test piece was measured with durometer hardness / type A using a 6.3 mm thick press sheet.
(3) Tensile strength, 100% elongation stress, elongation: In accordance with JIS K 6301, a 2 mm-thick press sheet was punched into a No. 3 dumbbell mold and used. The tensile speed was 500 mm / min.
(4) Ionomer fusion property: 180 degree peeling test (tensile speed 200 mm / min) using a composite molded body (width 25 mm × length 100 mm × thickness 5 mm strip test piece) having an adherend as a core. The peel strength (N / m) at the fusion interface of the core material / skin material was measured.
(5) Adhesiveness with urethane-based sealant: Two press sheets having a width of 30 mm, a length of 60 mm and a thickness of 2 mm are prepared, and a primer is applied to one side thereof. Next, the press sheet coated with the primer is left in an oven at 80 ° C. for 10 minutes. Next, a urethane-based sealant is applied to the surface of one press sheet to which the primer is applied, and another press sheet is placed on the surface so that the surface to which the primer is applied comes into contact with the urethane-based sealant, followed by pressure bonding. At this time, a urethane sealant having a thickness of 7 mm, a width of 30 mm, and a length of 60 mm is filled between the two press sheets without any gap. The test piece made as described above is allowed to stand at 23 ° C. for one week, and then a cut having a width of 30 mm and a depth of 10 mm is made on the width side end surface of the urethane sealant sandwiched between the two press sheets of the test piece. Then, holding the press sheet by hand and tearing it in the longitudinal direction, it was evaluated according to the following criteria.
○: Material destruction of urethane sealant ×: Interfacial delamination between urethane sealant and press sheet Note that urethane sealant is Penguin Seal # 560 manufactured by Sunstar Giken Co., Ltd., Primer is Chemlok 459X manufactured by Road Far East Co., Ltd. used.
(6) Heat aging resistance: In accordance with JIS K 6251, using the above-mentioned 2 mm-thick press sheet, punched into a No. 3 dumbbell-shaped test piece, and measured the tensile strength residual ratio (TS) after 100 ° C. and 168 hrs. . The tensile speed was 500 mm / min.
(7) Extrudability: A 50 mm × 1 mm sheet was extruded, the drawdown property, surface appearance and shape were observed, and evaluated according to the following criteria.
◎: Molded condition width is large and a very good molded product is obtained. ○: Molded condition width is large and a good molded product is obtained. Δ: Good product is obtained by condition adjustment. ×: Good even after condition adjustment. (8) Injection moldability: A sheet of 130 mm × 130 mm × 2 mm was injection molded, the appearance was visually observed, and the presence or absence of flow marks and sink marks was evaluated according to the following criteria.
○: Good (a wide range of molding conditions gives a good product)
Δ: Slightly bad (the molding condition width is narrow, but a good product may be obtained depending on the application and shape of the molded product)
×: Bad (good product cannot be obtained)

2. Raw materials used (a) Ethylene polymer polymerized by metallocene catalyst (s-PE): Engage EG8402 (manufactured by Dupont Dow Elastomer) Density: 0.902 g / cm ³ , Melting point: 100 ° C., MFR (190 ° C., 21.18 N load): 30 dg / min, hardness: 94 (Shore A), Mooney viscosity ML _{1 + 4} (121 ° C.): 5 or less, weight average molecular weight: 100,000
(B) Partially hydrogenated block copolymer (SBBS): Tuftec P JT-90C (manufactured by Asahi Kasei Corporation, styrene-butadiene-butylene-styrene copolymer; SBBS, styrene content 30% by weight, weight average molecular weight (Mw): 110,000, number average molecular weight (Mn): 99,000, molecular weight distribution: 1.11, hydrogenation rate of butadiene block: 75.1%, (hydrogenation rate of 1,2-butadiene 92.7%, 1 , 4-Butadiene hydrogenation rate 61.0%)
In the comparative examples, the following comparative components (1) to (5) were used in place of the component (a) or (b).
Comparative component (1) Very low density polyethylene (VLDPE): Excellen VL EUL430 (manufactured by Sumitomo Chemical Co., Ltd.) Density: 0.890 g / cm ³ , MFR (190 ° C., 21.18 N load): 4.0 dg / min, hard S: 82 (Shore A)
Comparative component (2) Block copolymer of non-hydrogenated aromatic vinyl compound and conjugated diene compound (SBS): Kraton D-KX405 (manufactured by Kraton Polymer Japan) Styrene: 24%, solution viscosity 25 ° C. (25 wt% toluene) Solution): 1200 cps, hardness: 55 (Shore A), specific gravity: 0.94
Comparative component (3) Random copolymer of non-hydrogenated aromatic vinyl compound and conjugated diene compound (SBR): SL552 (manufactured by JSR) Styrene: 24%, Mooney viscosity ML _{1 + 4} (100 ° C.): 55, vinyl bond Amount: 39%, specific gravity: 0.94
Comparative Component (4) Rosin: Rosin resin (Haristar DS-110S, manufactured by Harima Kasei Kogyo Co., Ltd.)
Comparative component (5) partially hydrogenated polybutadiene (partially hydrogenated BR): hydrogenation rate 53%, (remaining main chain double bond amount 46%, remaining side chain double bond amount 7%),
(C-1) Polar ethylene-based copolymer (EVA): EVAFLEX EV-270 (manufactured by Mitsui DuPont Polychemical Co., Ltd.), MFR (190 ° C., 21.18 N load): 1.0 dg / min, VA Content: 28 wt%, hardness: 82 (Shore A), specific gravity: 0.95
(C-2) Ethylene / methacrylic acid copolymer (EMAA): Nucrel 0903HC (Mitsui DuPont Polychemical Co., Ltd.) Specific gravity: 0.93, MFR: 3 dg / min, MAA content: 9 wt%
(D) Polypropylene resin (R-TPO): Adflex X500F (reactor TPO polymerized by Cataloy process (multi-stage polymerization in reactor): manufactured by Sun Allomer), melting point: 162 ° C., specific gravity: 0.89, flexural modulus : 470 (MPa), MFR (230 ° C., 21.18 N load): 9 dg / min, weight average molecular weight: 130,000
(E) Hydrogenated block copolymer (SEPS): Septon 4077 (trademark; manufactured by Kuraray Co., Ltd.), styrene content: 30% by weight, isoprene content: 70% by weight, number average molecular weight: 260,000, weight average Molecular weight: 320,000, molecular weight distribution: 1.23, hydrogenation rate: 90% or more (f) Non-aromatic hydrocarbon rubber softener (Oil): Diana Process Oil PW-90 (manufactured by Idemitsu Kosan Co., Ltd.) Type: paraffinic oil, weight average molecular weight: 540, aromatic component content: 0.1% or less, viscosity (37.8 ° C.): 30.85 cSt, viscosity (100 ° C.): 5.3 cSt, pour point: -15 ° C, flash point: 270 ° C
(G) Calcium carbonate (CaCO ₃ ): NS400 (manufactured by Sankyo Seimitsu Co., Ltd.)
(H) Antioxidant: Hindered phenol / phosphite / lactone complex antioxidant: HP2215 (trademark; manufactured by Ciba Specialty Chemicals)

  The partially hydrogenated polybutadiene as the comparative component (5) can be obtained by partially hydrogenating polybutadiene rubber by a known hydrogenation method. For example, F.A. L. Ramp, etal, J. et al. Amer. Chem. Soc. , 83, 4672 (1961), a method of hydrogenation using a triisobutylborane catalyst, Hung Yu Chen, J. et al. Polym. Sci. Polym. Letter Ed. , 15, 271 (1977), hydrogenation using a toluenesulfonyl hydrazide, or an organic cobalt-organic aluminum catalyst or an organic nickel-organic aluminum catalyst described in Japanese Patent Publication No. 42-8704. The method of adding etc. can be mentioned. Here, particularly preferable hydrogenation methods are disclosed in Japanese Patent Application Laid-Open Nos. 59-133203 and 60-220147 or an inert organic solvent using a catalyst capable of hydrogenation under mild conditions of low temperature and low pressure. In which a bis (cyclopentadienyl) titanium compound is brought into contact with hydrogen in the presence of a catalyst comprising a hydrocarbon compound having a sodium atom, a potassium atom, a rubidium atom or a cesium atom. This is the method shown in the publication. And the control of the endothermic peak heat quantity, which is an index of the crystallinity of the hydrogenated rubber, is performed by adding a polar compound such as tetrahydrofuran or controlling the polymerization temperature. Decreasing the endothermic peak heat is achieved by increasing the polar compound or decreasing the polymerization temperature to increase the 1,2-vinyl bond.

Moreover, the measuring method of the said hydrogenation rate (%) was measured with the following method.
The measurement was performed by NMR according to the following procedure. First, the polybutadiene rubber before hydrogenation is dissolved in deuterated chloroform and subjected to chemical shift by FT-NMR (270 mega, manufactured by JEOL). 7-5.2 ppm (signal C0) of 1,2-vinyl protons (= CH ₂ ) and chemical shifts 5.2-5.8 ppm (signal D0) vinyl protons (= CH ₂ ) From the integrated intensity, the following formula was used.
(V) = [0.5C0 / {0.5C0 + 0.5 (D0−0.5C0)}] × 100

Next, the polybutadiene rubber after partial hydrogenation was dissolved in deuterated chloroform, and similarly, by FT-NMR, a chemical shift of 0.6 to 1.0 ppm (referred to as signal A1) by hydrogenated 1,2 bonds. Methyl group proton (—CH ₃ ), chemical shift 4.7 to 5.2 ppm (signal C1) unhydrogenated 1,2-vinyl proton (= CH ₂ ), chemical shift 5.2 to 5 It was calculated by the following equation from the integrated intensity of non-hydrogenated vinyl proton (= CH-) of .8 ppm (referred to as signal D1).
First, p = 0.5C0 / (0.5C1 + A1 / 3), A11 = pA1, C11 = pC1, D11 = pD1,
Hydrogenation rate of 1,2-vinyl bond part (B)
(B) = [(A11 / 3) / {A11 / 3 + C11 / 2}] × 100
Hydrogenation rate of 1,4-double bond part (C)
(C) = [{0.5 (D0−0.5C0) −0.5 (D11−0.5C11)} / 0.5 (D0−0.5C0)] × 100
Hydrogenation rate of the entire butadiene part (A)
(A) = (V) × (B) / 100 + [100− (V)] × (C) × 100

Microstructure The symbols defined above are described below.
1,2-vinyl bond before hydrogenation = (V) × (B) / 100 (%)
1,4 bond before hydrogenation = {100− (V)} × (C) / 100 (%)
1,2-vinyl bond after hydrogenation = (V) × {100- (B)} / 100 (%)
1,4-bond after hydrogenation = {100- (V)} × {100- (B)} / 100 (%)

(Examples 1-9, Comparative Examples 1-9)
The composition ratios shown in Tables 1 and 2 were charged into a twin screw extruder having an L / D of 47, and melt kneaded at a kneading temperature of 180 ° C. and a screw rotation speed of 350 rpm to form pellets. Next, the obtained pellet was injection-molded to prepare a test piece, which was used for each test. The evaluation results are shown in Tables 1 and 2.

As is clear from Examples 1 to 9 in Table 1, the thermoplastic elastomer composition of the present invention had good characteristics.
In Comparative Examples 1 and 2 in Table 2, the blending amount of the component (b) is out of the scope of the present invention. When there is little component (b), heat-fusibility with an ionomer resin will deteriorate. When there are many components (b), extrusion moldability and heat aging property will deteriorate.
Comparative Example 3 uses a block copolymer (SBS) of a non-hydrogenated aromatic vinyl compound and a conjugated diene compound in place of the partially hydrogenated block copolymer of component (b), and has a tensile strength. In addition, the elongation, the heat fusion property with the ionomer resin, and the extrusion moldability were inferior.
Comparative Example 4 is an example in which the component (b) was not used at all, and the heat fusion property with the ionomer resin was inferior.
It can be seen that even if SEPS or SEEPS is contained instead of the component (b) as in Comparative Examples 1 and 4, there is no effect of improving the heat-fusibility with the ionomer resin.
Comparative Example 5 uses a random copolymer (SBR) of a non-hydrogenated aromatic vinyl compound and a conjugated diene compound in place of the partially hydrogenated block copolymer of component (b), and an ionomer resin. The heat-fusibility with was poor.
In Comparative Example 6, rosin was used in place of the partially hydrogenated block copolymer of the component (b), and the elongation and thermal fusion with the ionomer resin were inferior.
In Comparative Example 7, partially hydrogenated polybutadiene was used instead of the partially hydrogenated block copolymer of the component (b), and the heat-fusibility with the ionomer resin was inferior.
In Comparative Example 8, the component (a) was not used, and the heat fusion property and the extrusion moldability with the ionomer resin were inferior.
In Comparative Example 9, very low density polyethylene (VLDPE) was used as the component (a), and the heat-fusibility with the ionomer resin was inferior.

  The thermoplastic elastomer composition of the present invention is excellent in heat-fusability and / or compositeness with an ionomer resin or the like, excellent in heat resistance, has an appropriate hardness, and / or adhesiveness with a urethane sealant and / or Because of excellent composite properties, composite molded products with thermoplastic elastomer compositions and polar resins can be used in various applications such as automobile members, building members, and weak electrical products.

Claims (12)

(A) 100 parts by weight of an ethylene resin polymerized by a metallocene catalyst and having a density of 0.85 to 0.91 g / cm ³ , and (b) an aromatic vinyl compound having a hydrogenation rate of 3 to 90% A thermoplastic elastomer composition comprising 5 to 180 parts by weight of a partially hydrogenated block copolymer with a conjugated diene compound.   Furthermore, (c) 1-200 weight part of polar ethylene-type copolymers are contained, The thermoplastic-elastomer composition of Claim 1 characterized by the above-mentioned.   3. The thermoplastic elastomer composition according to claim 2, wherein the polar ethylene-containing copolymer has a polar group-containing comonomer content of 5 to 55% by weight.   The thermoplastic elastomer composition according to claim 2 or 3, wherein the (c) polar ethylene copolymer is an ethylene-vinyl acetate copolymer.   The thermoplastic elastomer composition according to any one of claims 1 to 4, further comprising (d) 1 to 400 parts by weight of a polypropylene-based resin.   Further, (e) 1 to 400 parts by weight of a block compound copolymer of an aromatic vinyl compound and a conjugated diene compound having a hydrogenation rate exceeding 95% is contained. The thermoplastic elastomer composition according to Item.   The thermoplastic elastomer composition according to any one of claims 1 to 6, further comprising (f) 1 to 250 parts by weight of a softener for a non-aromatic hydrocarbon rubber.   A thermoplastic elastomer composition for extrusion molding comprising the thermoplastic elastomer composition according to any one of claims 1 to 7.   A thermoplastic elastomer composition for composite molding with a urethane sealant comprising the thermoplastic elastomer composition according to any one of claims 1 to 8.   A thermoplastic elastomer composition for composite molding with an ionomer resin comprising the thermoplastic elastomer composition according to any one of claims 1 to 9.   The molded article which consists of a thermoplastic elastomer composition of any one of Claims 1-10.   A laminated molded article comprising a layer comprising the thermoplastic elastomer composition according to any one of claims 1 to 11.