JP2015021078A - Thermoplastic elastomer composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a thermoplastic elastomer composition which is excellent in all the characteristics comprising thermal aging resistance, acid resistance, moldability and fusibility at the same time and a molding obtained by using the composition.SOLUTION: An thermoplastic elastomer composition contains a (meth)acrylic elastomer (ingredient A) and a thermoplastic resin (ingredient B) of a melting point of 100-350°C having functional groups reactive with epoxy groups, in a mass ratio of ingredient A/ingredient B of 20/80 to 75/25, and additionally a compatibilizer (ingredient C) having averagely two or more epoxy groups per molecule, in a content of 0.1-30 pts. mass to 100 pts. mass of the combined content of ingredient A and ingredient B, and a crystalline thermoplastic elastomer (ingredient D), in a content of 35-400 pts. mass to 100 pts. mass of the combined content of ingredient A and ingredient B. A molding obtained by hot-forming the thermoplastic elastomer composition is also provided.

Description

  TECHNICAL FIELD The present invention relates to a thermoplastic elastomer composition used for electrical and electronic parts, automotive parts, sealing materials, packing, vibration damping members, tubes, and the like, and a molded body obtained by thermoforming the thermoplastic elastomer composition. .

  In recent years, with the advancement of electronic technology, an increase in power consumption due to high performance in electrical products and industrial machines and an increase in the density of devices due to downsizing have progressed. In the automobile field, movements aimed at improving the performance such as consideration for the environment by development of fuel cell vehicles, reduction of fuel consumption, weight reduction, etc. are accelerating. As one of the above-mentioned trends, resinization (metal, vulcanized rubber, hydrogenated nitrile rubber (HNBR), acrylic rubber, etc.) for parts used in a high temperature environment is being promoted. In addition, in the same resin component, a material that can be integrally molded is required to improve the molding cycle and reduce the molding processing cost. The main component of such resin parts is polycarbonate resin, and polyester-based elastomers and polyurethane-based elastomers are used as soft materials from the viewpoint of compatibility with resin parts at the time of fusion.

  Among them, polyester-based elastomers are excellent in heat resistance, bending fatigue resistance, chemical resistance, etc. among various thermoplastic elastomers, and are often used particularly in the fields of automobiles and electrical materials where heat resistance is required.

  In addition, a polyester elastomer having a triblock structure with a hard segment composed of crystalline aromatic dicarboxylic acid and the like and a soft segment composed of aliphatic polyether, aliphatic polyester, etc. Characteristic characteristics such as heat resistance and water resistance are developed for each grade by changing and adjusting the components and the composition ratio.

  Patent Document 1 includes (A) an acrylic rubber copolymerized with an acrylate ester containing an epoxy group, (B) a thermoplastic polyester resin, (C) an olefin polymer segment and a vinyl monomer. A composition obtained by dynamically crosslinking a graft copolymer to be formed or its precursor is described, and it is disclosed that it exhibits good moldability, heat resistance, and oil resistance.

  Patent Document 2 provides a molded article made of a resin composition excellent in molding processability, recyclability, flexibility, rubber properties, heat resistance, oil resistance, weather resistance, transparency, adhesion to a substrate, and the like. The acrylic block copolymer (A) comprising the methacrylic polymer block (a) and the acrylic polymer block (b), the thermoplastic resin (B), the thermoplastic elastomer (C), and the rubber. A resin composition containing (D) and at least one selected from the group consisting of thermosetting resins (E) is disclosed.

  Patent Document 3 discloses a composition comprising a polyester-based elastomer, a polyester resin, and an epoxy compound, and discloses that heat aging resistance is improved.

  Patent Document 4 discloses that by adding a polyester-based elastomer / polyurethane-based elastomer to a styrene block copolymer or a hydrogenated product thereof, heat-fusibility to a polar resin such as polycarbonate is improved. Yes.

JP 2007-45885 A JP 2009-79119 A JP-A-1-163259 Japanese Patent Laid-Open No. 9-12487

  However, in the description of Patent Document 1, as long as pre-crosslinked acrylic rubber is used, the molding processability is not so excellent, and it is limited to the extent that it is made into a sheet by extrusion, and can be applied to injection molding. Is far away.

  Although it is disclosed that the resin composition described in Patent Document 2 can be injection-molded, it is not known that a compatibilizer is used in combination, and such a resin is not sufficient in heat aging resistance. .

  The composition of the composition described in Patent Document 3 has a problem that the acid resistance is inferior, but no solution has been shown. Further, the composition of the composition described in Patent Document 4 has a problem that heat resistance is low.

  Therefore, as a prior art, a thermoplastic elastomer composition containing a crystalline thermoplastic elastomer in addition to an acrylic elastomer, a thermoplastic resin capable of reacting with an epoxy group, and an epoxy compound is not known, and a conventionally known elastomer is not known. There are advantages and disadvantages, and no composition is known that is excellent in all of the characteristics of heat aging resistance, acid resistance, moldability and fusing property.

  An object of the present invention is to provide a thermoplastic elastomer composition excellent in all the properties of heat aging resistance, acid resistance, moldability and fusion property, and a molded article obtained using the composition.

The present invention
[1] A (meth) acrylic elastomer (component A) and a thermoplastic resin (component B) having a melting point of 100 to 350 ° C. and having a functional group capable of reacting with an epoxy group are 20/80 to 75/25 A compatibilizer (component C) having a mass ratio (component A / component B) and having solubility in tetrahydrofuran and having an average of two or more epoxy groups in one molecule is combined with component A. 0.1 to 30 parts by mass with respect to 100 parts by mass of the total amount of Component B, and 35 to 400 parts by mass of crystalline thermoplastic elastomer (Component D) with respect to 100 parts by mass of the total amount of Component A and Component B A thermoplastic elastomer composition, and [2] a molded article obtained by thermoforming the thermoplastic elastomer composition described in [1].

  The thermoplastic elastomer composition of the present invention has the effect of being excellent in all of heat aging resistance, acid resistance, moldability, and fusing property as a material of a molded body.

  The thermoplastic elastomer composition of the present invention is a (meth) acrylic elastomer (component A), a thermoplastic resin having a functional group capable of reacting with an epoxy group (component B), and has a solubility in tetrahydrofuran. 2 contains a compatibilizer (component C) having an average of two or more epoxy groups and a crystalline thermoplastic elastomer (component D).

  The heat aging resistance is improved by the compatibilizing agent, and the fusibility is improved by the crystalline thermoplastic elastomer. In addition, in the thermoplastic elastomer composition of the present invention, it is an unexpected effect that the compatibilizer reacts with Component B to achieve both heat aging resistance and acid resistance.

  The (meth) acrylic elastomer (component A) preferably comprises two or more (meth) acrylic monomers and, if necessary, other copolymerizable vinyl monomers as constituent components. It can be obtained by increasing the molecular weight.

  Examples of the (meth) acrylic monomer include, for example, methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, phenyl (meth) acrylate, (meth) 2-ethylhexyl acrylate, cyclohexyl (meth) acrylate, (meth) acrylic acid, hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, glycidyl (meth) acrylate, methoxyethyl (meth) acrylate, Examples thereof include ethoxyethyl (meth) acrylate, butoxyethyl (meth) acrylate, phenoxyethyl (meth) acrylate, and the like. In this specification, unless otherwise specified, an alkyl group name without a subscript includes isomers such as n-, iso-, sec-, tert-, etc. And both acrylic.

  The amount of the (meth) acrylic monomer is preferably 20% by mass or more, more preferably 50% by mass or more, and still more preferably 80% by mass or more in the constituent components.

  Other copolymerizable vinyl monomers include styrene, α-methylstyrene, vinyl acetate, ethylene, propylene, butadiene, isoprene, maleic anhydride, etc. Among these, styrene, α-methylstyrene and Ethylene is preferred, and these vinyl monomers may be used in combination within a range that does not impair the object of the present invention (preferably 30% by mass or less, more preferably 20% by mass or less, and further preferably 10% by mass or less). Good.

  Examples of the monomer polymerization method for obtaining the (meth) acryl elastomer include a radical polymerization method, a living anion polymerization method, a living radical polymerization method, and the like. Examples of the polymerization form include a solution polymerization method, an emulsion polymerization method, a suspension polymerization method, and a bulk polymerization method.

  Component A is preferably a block copolymer composed of a hard segment and a soft segment. A block copolymer comprising two or more blocks constituting a hard segment and one or more blocks constituting a soft segment. A polymer is more preferable, and a triblock copolymer having two blocks constituting a hard segment on both sides of one block constituting a soft segment is further preferred. The proportion of the triblock copolymer in component A is preferably 60% by mass or more, and more preferably 70% by mass or more. Component A may contain a diblock copolymer and a multiblock copolymer in addition to the triblock copolymer.

  In order for the component A to exhibit the properties as a thermoplastic elastomer, it is preferable to have a hard segment having a glass transition temperature of room temperature or higher.

  The glass transition temperature of the block constituting the hard segment is preferably 20 to 200 ° C, more preferably 30 to 180 ° C, and even more preferably 50 to 150 ° C from the viewpoint of maintaining toughness in the normal temperature range of the composition. If the glass transition temperature of the block constituting the hard segment is too low, the resulting composition may have insufficient heat resistance, and it is difficult to obtain raw materials for blocks having a glass transition temperature exceeding 200 ° C.

  The vinyl monomer constituting the hard segment is preferably one or more of (meth) acrylic monomers. Such (meth) acrylic monomers include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, phenyl (meth) acrylate, (meth) acrylic. 2-ethylhexyl acid, cyclohexyl (meth) acrylate, (meth) acrylic acid, hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, glycidyl (meth) acrylate, methoxyethyl (meth) acrylate, ( Examples include ethoxyethyl (meth) acrylate, butoxyethyl (meth) acrylate, phenoxyethyl (meth) acrylate, and the like. In these, from a viewpoint of economical efficiency, methyl methacrylate, ethyl methacrylate, and butyl methacrylate are preferable, and methyl methacrylate is more preferable.

  The vinyl monomer constituting the hard segment preferably contains the (meth) acrylic monomer, but does not impair the object of the present invention (preferably 30% by mass or less, more preferably 20%). Or less, more preferably 10% by weight or less), and other monomers may be contained. Moreover, it can also be set as a hard segment by high molecular weight by a polymerization reaction.

  Examples of the copolymerizable vinyl monomer include ethylene, propylene, α-olefin, styrene, α-methylstyrene, acrylonitrile, parahydroxystyrene, vinyl alcohol, acrylic acid, methacrylic acid, acrylamide, methacrylamide, and methyl vinyl ether. , Vinyl benzoate, maleic acid, N-cyclohexylmaleimide, and the like. Among these, styrene, α-methylstyrene and ethylene are preferable.

  The glass transition temperature of the block constituting the soft segment is preferably −100 to 19 ° C., more preferably −80 to 10 ° C., and further preferably −70 to 0 ° C. If the glass transition temperature of the block constituting the soft segment is too high, the resulting composition may be insufficient in flexibility, and it is difficult to obtain raw materials for blocks having a glass transition temperature lower than −100 ° C.

  The vinyl monomer constituting the soft segment is preferably one or more of acrylic monomers. As such an acrylic monomer, ethyl acrylate, butyl acrylate, methoxyethyl acrylate, ethoxyethyl acrylate, benzyl acrylate, phenylethyl acrylate and the like are preferable because of high reactivity with the transesterification catalyst.

  Moreover, as an acrylic monomer which comprises the soft segment for the glass transition temperature of a soft segment to be 19 degrees C or less, acrylate acrylate, n-butyl acrylate, acrylate sec-butyl, acrylate acrylate At least one selected from the group consisting of hexyl, ethyl hexyl acrylate, n-heptyl acrylate, n-octyl acrylate, and phenylethyl acrylate is preferable, and it is difficult to be compatible with the hard segment and has a phase separation structure. From an easy viewpoint, at least one selected from the group consisting of n-propyl acrylate, n-butyl acrylate, n-hexyl acrylate, n-heptyl acrylate and n-octyl acrylate is more preferable, and acrylic acid n-Butyl is more preferred.

  The vinyl monomer constituting the soft segment preferably contains the acrylic monomer, but does not impair the object of the present invention (preferably 30% by mass or less, more preferably 20% by mass or less). And more preferably 10% by mass or less), and other monomers may be contained.

  As a method for measuring the glass transition temperature of a polymer, differential scanning calorimetry (DSC), dynamic viscoelasticity measurement, thermal expansion measurement (TMA) and the like are known. In the present invention, a hard segment and a soft segment are used. In block copolymers containing both, dynamic viscoelasticity measurement is a common method that can accurately measure both hard segment and soft segment values. A method for determining the glass transition temperature from the peak of the dielectric loss tangent Tan δ is known. Therefore, the glass transition temperature measured by dynamic viscoelasticity measurement is used for the glass transition temperature of the hard segment and the soft segment in the present invention.

  The mass ratio of the hard segment to the soft segment in component A (hard segment / soft segment) is preferably 10/90 to 70/30 from the viewpoint of imparting appropriate flexibility to component A, and 15/85 to 60/40. Is more preferable.

  Examples of commercially available products that can be used as Component A include Clarity from Kuraray Co., Ltd., Nanostrength from Arkema, and Nabster from Kaneka.

  The weight average molecular weight of Component A is preferably 20,000 or more, more preferably 30,000 or more, and further preferably 40,000 or more, from the viewpoint of mechanical properties such as tensile strength. Further, from the viewpoint of easy handling and maintaining a melt viscosity suitable for production of a molded article such as injection molding, it is preferably 1 million or less, more preferably 800,000 or less, and further preferably 700,000 or less. From these viewpoints, the weight average molecular weight of Component A is preferably 20,000 to 1,000,000, more preferably 30,000 to 800,000, and further preferably 40,000 to 700,000.

  Further, in the relationship between the weight average molecular weight (Mw) and the number average molecular weight (Mn), Mw / Mn is preferably 1 to 5, and more preferably 1.1 to 3.

  In the present invention, the component A may be one having a higher molecular weight than the polymerization average molecular weight of the component A in the raw material stage by a transesterification catalyst, a radical polymerization initiator, or the like. In this case, the distribution of the weight average molecular weight is broad or multimodal (having two or more peaks), and the weight average molecular weight is the average molecular weight.

  The A hardness of Component A is preferably 5 to 90, more preferably 10 to 80, from the viewpoint of the flexibility of the composition. In addition, A hardness means the durometer type A hardness prescribed | regulated to JISK6253. If the durometer type A hardness exceeds 90, the measurement accuracy will drop, so a comparison is also made using the durometer type D hardness, but the relative comparison that the value of the A hardness is higher is harder If it is the purpose of the above, it may be evaluated by A hardness.

  The flow start temperature of component A is preferably 80 ° C. or higher from the viewpoint of heat resistance of the composition, and preferably 220 ° C. or lower from the viewpoint of thermoplasticity (fluidity) of the composition. From these viewpoints, the flow start temperature of component A is preferably 80 to 220 ° C, and more preferably 100 to 200 ° C.

  Component B is a thermoplastic resin having a functional group capable of reacting with an epoxy group and is preferably crystalline in order to cause phase separation with Component A, and has a high melting point from the viewpoint of imparting heat resistance. A thermoplastic resin is preferable.

  The melting point of the thermoplastic resin is 100 ° C. or higher, preferably 180 ° C. or higher, more preferably 200 ° C. or higher, from the viewpoint of the heat resistance of the composition. Further, from the viewpoint of moldability, it is 350 ° C. or lower, preferably 300 ° C. or lower, more preferably 280 ° C. or lower. The melting point of the thermoplastic resin is 100 to 350 ° C, preferably 180 to 300 ° C, more preferably 200 to 280 ° C. The crystalline thermoplastic resin generally refers to a thermoplastic resin whose melting point is observed in a differential scanning calorimeter (DSC), and the melting point value is DSC. Although it also has a glass transition temperature, the glass transition temperature can be measured by DSC, but the dynamic viscoelasticity measurement can obtain a more precise value.

  In the present invention, examples of the functional group capable of reacting with an epoxy group include a hydroxyl group, a carboxyl group, an acid anhydride group, an amide group, an amino group, and the like. It has a seed or two or more kinds in the main chain or side chain of the thermoplastic resin.

  A thermoplastic resin that does not have a functional group capable of reacting with an epoxy group does not react with component C, which is a compatibilizing agent, and therefore, a thermoplastic elastomer that is poorly dispersed in component A and has good flexibility and heat resistance. Can't get.

  Specific examples of component B include nylon 6, nylon 6,6, nylon 12, polybutylene terephthalate (PBT), polyethylene terephthalate (PET), polyethylene naphthalate, polypropylene, polyethylene, polymethyl methacrylate, polystyrene, polymethacrylstyrene ( MS), acrylonitrile-butadiene-styrene (ABS) resin, acrylonitrile-styrene (AS) resin, polyacetal resin (POM), noryl resin (PPO), polyvinyl chloride (PVC), and the like. From the viewpoint of (high melting point) and incompatibility with component A, aromatic polyesters and / or polyamides are preferred. As the aromatic polyester, polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate and the like are preferable, and as the polyamide, nylon 6, nylon 6,6 and the like are preferable. Although it is preferable to use a plurality of these in combination, polyethylene terephthalate and / or polybutylene terephthalate are more preferable.

  When Component B is polyester, hydroxyl groups and carboxyl groups exist as functional groups at the molecular ends. In the present invention, the abundances of hydroxyl groups and carboxyl groups at the molecular terminals of the polyester used as component B in the present invention are not particularly limited, and general ones can be used. For example, component B is polyester. In this case, the acid value that is an index of the amount of the carboxyl group is preferably 0.1 to 100 meq / kg. More specifically, the acid value is preferably 0.1 meq / kg or more, more preferably 1 meq / kg or more, further preferably 3 meq / kg or more, and further preferably 5 meq / kg or more. Further, it is preferably 100 meq / kg or less, more preferably 80 meq / kg or less, further preferably 70 meq / kg or less, and further preferably 60 meq / kg or less. The acid value of the polyester resin was determined by dissolving 200 mg of a sufficiently dried sample in 10 ml of hot benzyl alcohol, cooling the solution, adding 10 ml of chloroform and phenol red, and adding 1/25 normal alcoholic potash solution (KOH Titration with methanol solution) and measurement. The hydroxyl value of the polyester is calculated by measuring the end group concentration which is the sum of the hydroxyl end group and the carboxyl end group of the polyester, and subtracting the acid value (carboxyl end group concentration) therefrom. The terminal group concentration is measured as the sum of the carboxyl terminal groups derived from succinic acid and the carboxyl groups of the polyester itself (= total acid value) by binding succinic acid to the hydroxyl terminal of the polyester. Calculated by hydroxyl value = total acid value−acid value.

When component B is polyamide, the molecular end functional groups are generally carboxyl groups and amino groups. The amount of each carboxyl group and amino group at the molecular end of the polyamide used as component B in the present invention is not particularly limited, and general ones can be used, but when component B is polyamide, The terminal amino group concentration is preferably 10 to 200 μmol / g. More specifically, the terminal amino group concentration is preferably 10 μmol / g or more, more preferably 15 μmol / g or more, further preferably 20 μmol / g or more, and further preferably 30 μmol / g or more. Further, it is preferably 200 μmol / g or less, more preferably 190 μmol / g or less, further preferably 180 μmol / g or less, and further preferably 170 μmol / g or less. The terminal amino group concentration and terminal carboxyl group concentration are determined from the integrated value of the characteristic signal corresponding to each terminal group by ¹ H-NMR.

  The mass ratio of component A to component B in the composition of the present invention is such that the more component A, the higher the acid resistance, and the more component B, the better the heat aging resistance. It is -75/25, Preferably it is 25 / 75-70 / 30, More preferably, it is 30 / 70-65 / 35.

  The total amount of component A and component B is preferably 10% by mass or more, more preferably 20% by mass or more, and further preferably 30% by mass or more in the thermoplastic elastomer composition.

The monomer unit constituting Component C is a monomer containing 50 mass% or more of two embodiments, that is, the first embodiment: a monomer unit (monomer unit c1) having an SP value of 17.5 to 25.0. Unit and second aspect: monomer unit containing at least 50% by mass of at least one monomer unit (monomer unit c2) selected from the group consisting of (meth) acrylic monomers, styrene and styrene derivatives (When the monomer unit c2 is composed of two or more types of monomer units, it means that the total amount is 50% by mass or more)
The monomer units c1 and c2 are common in that the affinity with the component A is good. The first embodiment and the second embodiment are separated for convenience, and some monomers are common to both. That is, (meth) acrylic monomers, styrene and styrene derivatives having an SP value of 17.5 to 25.0 correspond to any of the embodiments.

  In the first embodiment, the SP value for specifying the monomer unit c1 is widely known as a Solubility Parameter. The SP value (δ) in the present invention is determined by the following estimation formula.

VanKrevelen's formula
[VanKrevelen] Solubilityparameter: δ
δ = (Ecoh / V) 0.5
Ecoh = ΣEcoh, i
Unit: (J / cm ³ ) 0.5
Physical property values required for estimation
V: molar volume of constituent repeating unit (CRU) [cm ³ / mol]
Physical quantities calculated by group contribution method
Ecoh: molar cohesive energy of Hoftyzer & VanKrevelen [J / mol]
Group parameters
Ecoh, i: Group parameter for i-th molar cohesive energy [J / mol]

  As monomer units having an SP value of 17.5 to 25.0 (the values in parentheses are SP values), styrene (18.82), α-methylstyrene (19.55), methyl methacrylate (18.54), n-butyl acrylate (18.12) ), Ethyl acrylate (18.83), methyl acrylate (19.13), methoxyethyl acrylate (19.43), vinyl acetate (19.13) and the like.

  For example, olefins having an SP value of less than 17.5, such as ethylene and propylene, are not suitable as the main monomer unit of component C in the present invention. Examples of olefins having an SP value of less than 17.5 (the values in parentheses are SP values) include ethylene (16.00) and propylene (17.04).

  From the viewpoint of affinity with Component A, the SP value of the monomer unit c1 is 17.5 or more, preferably 17.8 or more, more preferably 18.0 or more. Moreover, it is 25.0 or less, Preferably it is 23.0 or less, More preferably, it is 22.0 or less, More preferably, it is 21.0 or less, More preferably, it is 20.0 or less. From these viewpoints, the SP value of the monomer unit c1 is 17.5 to 25.0, preferably 17.8 to 23.0, more preferably 18.0 to 22.0, still more preferably 18.0 to 21.0, and still more preferably. 18.0 to 20.0.

  When the proportion of the monomer unit c1 is 50% by mass or more in the monomer unit of the component C, the affinity with the component A is improved, and the component B can be more favorably dispersed in the component A. it can. The proportion of the monomer unit c1 is more preferably 60% by mass or more, further preferably 70% by mass or more, and more preferably 80% by mass or more.

  In the present invention, even a monomer unit whose SP value is difficult to specify can be used as the main monomer unit of Component C as long as it is a (meth) acryl monomer, styrene, or a styrene derivative.

  Therefore, the second embodiment of the monomer unit of component C includes at least one monomer unit (monomer unit c2) selected from the group consisting of (meth) acrylic monomers, styrene and styrene derivatives. It is a waste.

  Suitable (meth) acrylic monomers as the monomer unit c2 include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, and cyclohexyl (meth) acrylate. , Hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, glycidyl (meth) acrylate, methoxyethyl (meth) acrylate, ethoxyethyl (meth) acrylate, butoxyethyl (meth) acrylate, (meth ) Phenoxyethyl acrylate and the like are exemplified, and among these, from the viewpoint of affinity with Component A, alkyl (1-6) esters of (meth) acrylic acid and glycidyl (meth) acrylate are preferred. Since glycidyl (meth) acrylate has a strong hydrogen bond, it is difficult to specify the SP value, but it has a high affinity with Component A and is preferable as the monomer unit c2.

  Styrene derivatives are substituted with substituents such as lower alkyl groups having 1 to 4 carbon atoms, lower alkoxy groups having 1 to 4 carbon atoms, carboxyl groups, and halogen atoms at the alpha, ortho, meta, or para positions of styrene. Means the compound formed. The molecular weight (atomic weight) of the substituent is preferably 60 or less, more preferably 50 or less, and still more preferably 40 or less. Specific examples of the styrene derivative include α-methylstyrene and p-chlorostyrene.

  However, among the monomer unit c2 whose SP value is specified, that is, (meth) acrylic monomer, styrene and styrene derivatives, the SP value deviates from the SP value required for the monomer unit c1 of the first embodiment. Those having an SP value of less than 17.5 and more than 25.0 have low affinity with component A, and are excluded from the monomer unit c2 in the second embodiment. For example, those having an SP value of the monomer unit of less than 17.5 include alkyl esters of (meth) acrylic monomers having an alkyl group having 8 or more carbon atoms.

  When the proportion of the monomer unit c2 is 50% by mass or more in the monomer unit of the component C, the affinity with the component A is improved, and the component B can be more favorably dispersed in the component A. it can. The proportion of the monomer unit c2 is more preferably 60% by mass or more, further preferably 70% by mass or more, and more preferably 80% by mass or more.

  Hereinafter, in the present specification, unless otherwise specified, component C includes both component C of the first embodiment containing monomer unit c1 and component C of the second embodiment containing monomer unit c2. Applicable.

  The monomer unit constituting Component C preferably contains 10 to 90% by mass of (meth) acrylic monomer and 10 to 90% by mass of styrene or a styrene derivative. More preferably, it contains 15 to 80% by mass (more preferably 20 to 70% by mass) of (meth) acrylic monomer and 20 to 85% by mass (more preferably 30 to 80% by mass) of styrene or a styrene derivative. Since such a component C has a (meth) acryl monomer having a high affinity with the component A and styrene or a styrene derivative having a high affinity with the component B as constituent units, it is used as a compatibilizer for both AB components. It is preferable because it can work effectively.

  Component C needs to have solubility in tetrahydrofuran (THF), and is preferably a vinyl copolymer. A vinyl copolymer having no solubility in THF (for example, acrylic gel) has insufficient affinity with Component A, and Component B cannot be well dispersed in Component A. Specifically, having solubility in THF means that the solubility in THF at 25 ° C. is 5% by mass or more. The solubility is more preferably 10% by mass or more, and further preferably 15% by mass or more.

  Component C has an average of 2 or more, preferably 2.5 to 20, more preferably 3 to 10 epoxy groups per molecule. When the average number of epoxy groups is less than 2, the reactivity with the component B becomes low and the function as a compatibilizing agent is not achieved. As a result, the dispersion stability of component B decreases, and the problem cannot be solved. That is, a molded product having excellent flexibility and heat resistance can be provided, and a composition having a small molding temperature dependency for exhibiting excellent flexibility and heat resistance cannot be obtained.

  The epoxy value of component C is preferably 0.5 to 5 meq / g, more preferably 0.7 to 3 meq / g, from the viewpoint of the effect as a compatibilizing agent.

  Examples of commercially available products that can be used as component C include Alfon UG series manufactured by Toagosei Co., Ltd., Marproof G series manufactured by NOF Corporation, and Jonkrill ADR series manufactured by BASF.

  Component C needs to maintain an appropriate affinity for Component A and Component B, but if the weight average molecular weight of Component C exceeds 100,000, the compatibility with Component A decreases. On the other hand, if it is less than 1000, the compatibility with the component A becomes too high. From these viewpoints, the weight average molecular weight of Component C is preferably 1000 or more, more preferably 3000 or more, and further preferably 5000 or more. Moreover, 100,000 or less is preferable, 80,000 or less is more preferable, and 60,000 or less is more preferable. The weight average molecular weight of Component C is preferably 1,000 to 100,000, more preferably 3,000 to 80,000, and even more preferably 5,000 to 60,000.

  The number average molecular weight of Component C is preferably 500 to 50,000, more preferably 1,000 to 40,000, and even more preferably 2000 to 30,000 from the viewpoint of the dispersion stability of Component B in Component A as described above.

  The preferred content of component C is affected by the balance of the chemical composition and molecular weight of each of components A, B, and C. Furthermore, since component C has the effect of increasing the viscosity of component A and / or component B in addition to chemically increasing compatibility between component A and component B, it is difficult to predict by simple parameter calculation. It is preferable that the content of component C is 0.1 parts by mass or more with respect to 100 parts by mass of the total amount of component A and component B, because the resulting resin composition has high heat resistance, preferably 0.2 parts by mass or more, More preferably, it is 0.3 parts by mass or more. In addition, the content of component C is 30 masses with respect to the total amount of component A and component B of 100 parts by mass from the viewpoint of preventing the hardness of the composition and deterioration of heat aging resistance due to unreacted component C remaining. Part or less, preferably 20 parts by weight or less, more preferably 10 parts by weight or less. From these viewpoints, the content of component C is 0.1 to 30 parts by weight, preferably 0.2 to 20 parts by weight, more preferably 0.3 to 10 parts by weight, based on 100 parts by weight of the total amount of component A and component B. Part.

  Examples of the crystalline thermoplastic elastomer (component D) include polyester elastomers, polyurethane elastomers, polyamide elastomers, and the like. Among these, polyester elastomers and polyurethane elastomers are preferable. By including a crystalline thermoplastic elastomer in the composition of the present invention, flexibility and stretchability are imparted to the composition. It is also preferable to use a plurality of elastomers in combination, or to use an elastomer in combination with a crystalline thermoplastic resin other than the elastomer.

  The polyester elastomer preferably has an aromatic polyester block as a hard segment and a block copolymer having an aliphatic polyether block, an aliphatic polyester block, or an aliphatic polycarbonate block as a soft segment.

  Aromatic polyester blocks that are hard segments are phthalic acid, terephthalic acid, isophthalic acid, 1,4- or 2,6-naphthalenedicarboxylic acid, 4,4'-diphenyldicarboxylic acid, 4,4'-diphenylether dicarboxylic acid, One or more of aromatic dicarboxylic acids such as 4,4′-diphenylsulfone dicarboxylic acid or alkyl esters thereof, ethylene glycol, propylene glycol, trimethylene glycol, tetramethylene glycol, hexamethylene glycol, 1,4- Polycondensation with one or more diols such as cyclohexanediol, 1,4-cyclohexanedimethanol, 4,4'-dihydroxydibiphenyl, 2,2-bis (4'-β-hydroxyethoxydiphenyl) propane It is preferable that it is a body. Commercially available products include, for example, “Perprene P-series” (trade name, manufactured by Toyobo Co., Ltd.), “Hytrel” (trade name, manufactured by Toray DuPont Co., Ltd.), “Flexmer” (manufactured by Nippon Synthetic Chemical Industries, Ltd.). , Product name) and the like.

  More preferably, the aliphatic polyether block which is a soft segment is mainly composed of polyalkylene ether glycol. The mass average molecular weight of the aliphatic polyether block is usually preferably from 400 to 6000, and the content of the aliphatic polyether block is preferably from 60 to 90% by mass. The content of the aliphatic polyether block is converted from the raw material composition.

  Examples of the aliphatic polyester block that is a soft segment include polyε-caprolactone, polyenanthlactone, polycaprylolactone, polybutylene adipate, and the like. Examples of commercially available products include “Perprene S-series” (trade name, manufactured by Toyobo Co., Ltd.).

  The aliphatic polycarbonate block which is a soft segment is preferably composed mainly of an aliphatic diol residue having 2 to 12 carbon atoms. Examples of these aliphatic diols include ethylene glycol, 1,3-propylene glycol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,8-octanediol, 2, 2-dimethyl-1,3-propanediol, 3-methyl-1,5-pentanediol, 2,4-diethyl-1,5-pentanediol, 1,9-nonanediol, 2-methyl-1,8- And octanediol. An aliphatic diol having 5 to 12 carbon atoms is preferable from the viewpoint of flexibility and low temperature characteristics of the obtained crystalline thermoplastic elastomer. Examples of commercially available products include “Perprene C-series” (trade name, manufactured by Toyobo Co., Ltd.).

  As the polyurethane elastomer (TPU), those having a hard segment composed of diisocyanate and short-chain glycol and a soft segment composed of diisocyanate and long-chain polyol are preferred, and the formula [I]:

(In the formula, A represents a hard segment composed of a diisocyanate and a short-chain glycol, B represents a soft segment composed of a diisocyanate and a long-chain polyol, and Y represents a urethane linking A, which is a hard segment, and B, which is a soft segment. Represents a residue of a bonded diisocyanate compound, and as this type of diisocyanate compound, known ones such as phenylene diisocyanate, tolylene diisocyanate, xylene diisocyanate, 4,4'-diphenylmethane diisocyanate, hexamethylene diisocyanate are used. )
It is more preferable that it is a compound of the structure represented by these.

  Examples of the short chain glycol include ethylene glycol, propylene glycol, 1,4-butanediol, bisphenol A and the like.

  Long-chain polyols include poly (alkylene oxide) glycols having a molecular weight of 400 to 6,000 (eg, polyethylene glycol, poly (1,2- and 1,3-propylene oxide) glycol, poly (tetramethylene oxide) glycol, poly ( Polyether-based ones such as hexamethylene oxide) glycol and the like, or polyester-based ones such as polyalkylene adipate, polycaprolactone, polycarbonate and the like.

  It is known that crystalline thermoplastic elastomers have various hardnesses, and any of them can be used in the present invention, but the A hardness of the crystalline thermoplastic elastomer is preferably 10 to 95, 20-90 is more preferable.

  The greater the content of component D, the better the tensile elongation at break. Therefore, it is preferably 5 parts by mass or more, more preferably 10 parts by mass or more, and even more preferably 15 parts by mass or more with respect to 100 parts by mass of Component A. Moreover, since the one where it is few is excellent in a softness | flexibility, 1000 mass parts or less are preferable with respect to 100 mass parts of component A, 800 mass parts or less are more preferable, and 500 mass parts or less are more preferable. From these viewpoints, the content of component D is preferably 5 to 1000 parts by mass, more preferably 10 to 800 parts by mass, and still more preferably 15 to 500 parts by mass with respect to 100 parts by mass of component A.

  The greater the content of component D, the better the tensile elongation at break. Therefore, it is 35 parts by mass or more, preferably 50 parts by mass or more, and 90 parts by mass with respect to 100 parts by mass of the total amount of component A and component B. The above is more preferable. Moreover, from an acid-resistant viewpoint, it is 400 mass parts or less with respect to 100 mass parts of total amounts of the component A and the component B, 300 mass parts or less are preferable and 250 mass parts or less are more preferable. From these viewpoints, the content of Component D is 35 to 400 parts by mass, preferably 50 to 300 parts by mass, and more preferably 90 to 250 parts by mass with respect to 100 parts by mass of the total amount of Component A and Component B. preferable.

  In the composition of the present invention, when the reaction rate of the functional group of component B and the epoxy group of component C is slow, for example, when the composition of the present invention is produced with an extruder or the like, the degree of reaction is insufficient, The stability of the dispersion diameter of component B may be impaired. Therefore, the composition of the present invention preferably contains an aliphatic carboxylic acid metal salt (component E) as a catalyst for promoting the reaction between the functional group of component B and the epoxy group of component C. By adding Component E, Component B is effectively dispersed, and a composition with better dispersion stability is obtained. For example, even when the composition is placed under temperature conditions that exceed the melting point of Component B, good dispersion of Component B can be maintained for a longer time. The reason for having such an effect is presumed that the reaction between the component B and the component C is smoothed by the component E, and the component C functions more effectively as a compatibilizing agent.

  Examples of the aliphatic carboxylic acid metal salt include metal stearate such as sodium stearate, calcium stearate, aluminum stearate, zinc stearate, metal 12-hydroxystearate such as sodium 12-hydroxystearate and calcium 12-hydroxystearate. Examples include salts.

  The content of Component E is preferably 0.001 part by mass or more, and more preferably 0.005 part by mass or more with respect to 100 parts by mass of the total amount of Component A and Component B. Moreover, 10 mass parts or less are preferable, and 5 mass parts or less are more preferable. 0.001-10 mass parts is preferable with respect to 100 mass parts of total amounts of component A and component B, and, as for content of the component E, 0.005-5 mass parts is more preferable.

  In the present invention, it is further preferable to use a transesterification catalyst (component F) in combination.

  The thermoplastic elastomer composition of the present invention preferably further contains a transesterification catalyst. By blending the transesterification catalyst, the tensile strength at break of the resulting composition is improved. Specifically, in the tensile test, the tensile product (product of strength and elongation) is large, and the balance between strength and elongation becomes better. The reason for such an effect is that the molecular weight of component A can be increased by the transesterification catalyst, and in some cases, a partial crosslink is formed. It is presumed that the transesterification catalyst acts as a cross-linking agent, and that the composition becomes tougher by increasing the molecular weight of component A, which is the main component of the composition.

  A general polyester polymerization catalyst can be used as the esterification catalyst as a reaction catalyst for increasing the molecular weight of component A and partially crosslinking. Examples of such catalysts include antimony catalysts such as antimony trioxide, tin catalysts such as butyltin, octyltin, and stannoxane, titanium catalysts such as titanium aminates and titanium alkoxides, zirconium acetylacetonates, zirconium alkoxides, and the like. And zirconium-based catalysts. Among these, a titanium-based catalyst and a zirconium-based catalyst are preferable, and a titanium-based catalyst is more preferable.

  Specific examples of the titanium catalyst include titanium alkoxides such as tetraisopropyl titanate, tetranormal butyl titanate, butyl titanate dimer, tetraoctyl titanate, titanium acetylacetonate, titanium tetraacetylacetonate, titanium ethylacetoacetate, titanium phosphate compound , Organic solvent-soluble chelate compounds such as titanium octylene glycolate, titanium ethyl acetoacetate, titanium lactate ammonium salt, titanium lactate, titanium triethanolaminate, titanium tributanol aminate, titanium diethanolaminate, titanium aminoethylamino ethanol And water-soluble chelate compounds such as rate, and the like. Among these, water-soluble chelate compounds are preferred, and more preferred is tita. It is alkanol aminate

  The content of Component F is preferably 0.01 parts by mass or more, and more preferably 0.1 parts by mass or more with respect to 100 parts by mass of the total amount of Component A and Component B. Further, the content of the transesterification catalyst is preferably 10 parts by mass or less, and more preferably 5 parts by mass or less from the viewpoint of suppressing a decrease in thermoplasticity of the composition obtained by crosslinking of Component A. The content of Component F is preferably 0.01 to 10 parts by mass and more preferably 0.1 to 5 parts by mass with respect to 100 parts by mass of the total amount of Component A and Component B.

  The thermoplastic elastomer composition of the present invention may contain a thermal stabilizer from the viewpoint of suppressing changes in the properties of the composition of the present invention under heating conditions.

  Examples of the heat stabilizer include phosphorus-containing compounds, hydrazide compounds, organic sulfur-based antioxidants, phenol-based antioxidants, amine-based antioxidants, and other chelating agents with other transesterification catalysts (component F). Thus, compounds that reduce the activity of the catalyst can also be used. In this invention, since the tolerance with respect to the heat aging of a thermoplastic elastomer improves remarkably, a phosphorus containing compound and a hydrazide compound are preferable from a viewpoint which the freedom degree of use conditions becomes larger. These may be used in combination. The content of the heat stabilizer is preferably 0.01 to 15 parts by mass and more preferably 0.05 to 10 parts by mass with respect to 100 parts by mass of the total amount of component A and component B. Thermal aging mainly includes two phenomena, the first is a decrease in strength due to an increase in the proportion of low molecular weight components produced by thermal decomposition, and the second is free radicals produced by thermal decomposition. This is a decrease in elongation caused by the formation of active site crosslinks.

  The thermoplastic elastomer composition of the present invention includes acrylic rubber, silicone-modified acrylic rubber, butyl rubber, crosslinked rubber such as silicone-modified butyl rubber, acrylic rubber-g-methyl methacrylate, MAS (acrylic rubber-g-methyl methacrylate / styrene). Further, it may contain a graft copolymer such as MBS (butadiene rubber-g-methyl methacrylate / styrene), a block copolymer other than acrylic, such as a polyester block copolymer.

  Other additives include lubricants such as heavy metal deactivators and fatty acid esters; light stabilizers such as benzotriazole compounds, benzophenone compounds, benzoate compounds and hindered phenol compounds; hydrolysis of carbodiimide compounds and oxazoline compounds Inhibitors; Plasticizers such as phthalate compounds, polyester compounds, (meth) acryl oligomers, process oils; Inorganic foaming agents such as sodium bicarbonate and ammonium bicarbonate; Organics such as nitro compounds, azo compounds, and sulfonyl hydrazides Fillers such as carbon black, calcium carbonate, talc, glass fiber; flame retardants such as tetrabromophenol, ammonium polyphosphate, melamine cyanurate, magnesium hydroxide and aluminum hydroxide; silane coupling agents, tita Over preparative based coupling agents, compatibilizers, such as aluminate-based coupling agent or an acid-modified polyolefin resin; other pigments or dyes.

  The thermoplastic elastomer composition of the present invention includes at least a (meth) acrylic elastomer (component A), a thermoplastic resin (component B), a compatibilizer (component C), and a crystalline thermoplastic elastomer (component D), and further necessary. Depending on the method, raw material components containing an aliphatic carboxylic acid metal salt (component E), a transesterification catalyst (component F), a heat stabilizer, other additives and the like are obtained by a method of heat-kneading with an extruder or a kneader. Is preferred.

  When using a transesterification catalyst to increase the molecular weight of the (meth) acrylic elastomer (component A), it is preferable to use a heat stabilizer in combination to further stabilize the characteristics of the composition. The stabilizer is preferably added after the component A has been made high molecular weight (for example, after a raw material other than the heat stabilizer is kneaded for about 0.5 to 30 minutes at a kneading temperature of 180 to 350 ° C.). . If the heat stabilizer is added too early, component A may not be sufficiently high in molecular weight.

  Examples of the extruder include a single screw extruder, a parallel screw twin screw extruder, and a conical screw twin screw extruder. In the present invention, from the viewpoint of excellent mixing ability (the resulting mixture has good dispersibility), a twin screw extruder is preferable, and a co-rotating twin screw extruder is more preferable.

  The die attached to the discharge part of the extruder can be selected arbitrarily. For example, a strand die suitable for pellet production, a T die suitable for sheet or film production, a pipe die, a profile extrusion die, etc. Can be mentioned.

  Moreover, the extruder may be provided with a vent for venting gas connected to an air release portion or a decompression device, or may be provided with a plurality of raw material inlets.

  The kneader means a batch-type mixer capable of controlling the temperature, and examples include a Banbury mixer, a Brabender plastograph, and a lab plast mill.

  Each component may be charged into the extruder or kneader all at once, separately, or dividedly. However, the introduction of the heat stabilizer is as described above.

  Even if the temperature of the heat-kneading is less than the melting point of Component B, it is not impossible, and the lower the temperature, the higher the viscosity of the mixed system tends to be applied. Moreover, when it exceeds 350 degreeC, the (meth) acryl component of the component A will thermally decompose and the mechanical physical property of the composition obtained will fall. From these viewpoints, the preferred temperature for the heat-kneading is the lower limit of the melting point of component B—10 ° C., and the upper limit is 350 ° C. or less.

  The heating and kneading time depends on the heating temperature, the type and concentration of each component, and cannot be determined unconditionally. However, the heating and kneading time is appropriately determined in consideration of the quality variation control and productivity of the obtained thermoplastic elastomer composition. It is preferable. A typical heating and mixing time when using an extruder is, for example, 0.5 to 20 minutes, preferably 0.7 to 15 minutes, and more preferably 1 to 10 minutes.

  The thermoplastic elastomer composition of the present invention thus obtained preferably has a phase separation structure composed of a continuous phase and a dispersed phase. The continuous phase includes a component derived from a (meth) acrylic elastomer (component A), and the dispersed phase includes a component derived from a thermoplastic resin (component B). The thermoplastic elastomer composition of the present invention has a dispersed phase finely dispersed in a continuous phase, and can give a molded article excellent in flexibility and heat resistance. The molded article has excellent flexibility and heat resistance. The molding temperature dependency for exhibiting the properties is small (the allowable range of the molding temperature is wide), and the molding conditions are small in the processing of the molded body.

  Examples of the use of the thermoplastic elastomer composition of the present invention include the following.

[Automotive boots and covers, hoses and covers around the engine]
・ Car body door latch, control cable cover, boots, emblem, chassis, steering wheel, fuel hose,
Constant velocity joint boots, pinion & rack boots, strut suspension boots, ball joint bushes, dust seals, brake hoses,

-Around the engine Air duct hose, air duct, air intake hose, engine control system vacuum hose, intercooler hose, fuel line cover, various anti-vibration / damping materials, radiator hose, heater hose, oil cooler hose, power steering hose, various Various covers and cases such as gaskets, engine under hood, engine room cover

[Covering materials for electric wires and cables]
・ Wires for electronic / consumer devices Wire coverings for computers, office equipment, TVs, VTRs, etc. ・ Communication cables Communication wires ・ Optical fiber coating materials ・ Insulated wires ・ Communication cables ・ Electric wires ・ Automotive wire harnesses

[Industrial goods such as hoses, tubes, belts, soundproof and vibration-proof sheets]
Empty / hydraulic hose (tube), high-pressure hose (tube), fuel hose (tube), conveyor belt, V / round belt, timing belt, cushion grip, flex hammer, silencer gear, flexible coupling, gasoline tank seat, gasket, Packing, sealing material, O-ring, diaphragm, curl cord, accumulator interior, transport roller, compression spring, mandrel, tow rope jacket

[Sporting goods]
Golf ball skin, ski boots / climbing shoes cuffs, sports shoes outsole

  A molded body is obtained by appropriately heat-molding the thermoplastic elastomer composition of the present invention according to a conventional method. The use of the molded product obtained by thermoforming the thermoplastic elastomer composition of the present invention is not particularly limited, and general styrene elastomers, polyolefin elastomers, polyurethane elastomers, polyamide elastomers, acrylic elastomers And polyester elastomers can be used.

  Since the molded product obtained by molding the thermoplastic elastomer composition of the present invention has excellent heat resistance, for example, for applications that require heat resistance of 100 ° C. or higher (120 ° C. or higher, 150 ° C. or higher, depending on the design). Can also be suitably used.

  The temperature at the time of heat molding is preferably 180 ° C. or higher from the viewpoint of fluidity of the composition and molding processability resulting from it, from the viewpoint of preventing thermal decomposition of the (meth) acrylic component of component A in the composition, 350 ° C. or lower is preferable. From these viewpoints, the temperature during the heat molding is preferably 180 to 350 ° C, more preferably 200 to 320 ° C.

  Any molding machine capable of melt-molding the composition can be used as an apparatus used for producing a molded article using the thermoplastic elastomer composition of the present invention. Examples thereof include a kneader, an extrusion molding machine, an injection molding machine, a press molding machine, a blow molding machine, and a mixing roll.

  The molded body of the present invention can be obtained by thermoforming the above thermoplastic elastomer composition, but the A hardness of the molded body that is an index of flexibility is preferably 20 to 100, more preferably 30 to 85.

  EXAMPLES Hereinafter, although an Example demonstrates this invention, this invention is not limited to this.

[Production of compatibilizer C3]
The oil jacket temperature of a 1 liter pressurized stirred tank reactor equipped with an oil jacket was maintained at 200 ° C. On the other hand, a monomer mixture composed of 74 parts by mass of styrene, 20 parts by mass of glycidyl methacrylate, 6 parts by mass of n-butyl acrylate, 15 parts by mass of xylene and 0.5 parts by mass of ditertiary butyl peroxide (DTBP) as a polymerization initiator The raw material tank was charged. Continuous supply from the raw material tank to the reactor at a constant supply rate (48 g / min, residence time: 12 minutes), and the reaction liquid is continuously supplied from the outlet of the reactor so that the liquid content in the reactor is constant at approximately 580 g. Extracted. At that time, the internal temperature of the reactor was maintained at about 210 ° C.
After 36 minutes have passed since the temperature inside the reactor has stabilized, the extracted reaction solution is continuously removed by a thin-film evaporator maintained at a reduced pressure of 30 kPa and a temperature of 250 ° C. The free copolymer C3 was recovered. About 7 kg of compatibilizer C3 was recovered over 180 minutes.

[Production of compatibilizers C1 and C2]
Compatibilizer C1, in the same manner as the compatibilizer C3, except that a monomer mixture composed of a monomer having a composition shown in Table 3-1, 15 parts by mass of xylene, and 0.3 part by mass of DTBP was used. C2 was produced.

Examples 1 to 23 and Comparative Examples 1 to 18
After the raw material components having the composition ratios (parts by mass) shown in Tables 7 to 10 were dry-mixed, they were melt-kneaded and pelletized by an extruder (continuous kneader) under the following conditions.

・ Extruder (manufactured by Technobel, KZW32TW-60MG-NH)
Cylinder temperature: 200 ~ 260 ℃
Screw rotation speed: 300r / min

  The detail of the used resin raw material is shown to Tables 1-6.

  In addition, the physical property of each raw material component of Tables 1-5 was measured with the following method. Production of the raw material sheet was carried out in the same manner as the production of a press sheet of the composition described later. However, the press temperature was adjusted according to the raw material (a temperature at which a small amount of raw material was raised in advance and the temperature at which flow was visually confirmed was grasped).

[A hardness]
Measured according to JIS K 6253-3 “Durometer hardness”.

[Weight average molecular weight (Mw) and number average molecular weight (Mn)]
From a gel permeation chromatograph (hereinafter also referred to as GPC), THF is used as a solvent and is determined from polystyrene conversion.

(Glass transition temperature (Tg))
Using a dynamic viscoelasticity measuring device (RSAIII manufactured by TA Instruments Co., Ltd.), heat the test piece in the temperature range of -100 to 280 ° C, the heating rate of 5 ° C / min, and the frequency of 10Hz. The peak temperature of loss tangent (Tanδ) measured at the time is observed, and this temperature is defined as the glass transition temperature (Tg). A test piece having a thickness of 2 mm, a width of 12 mm, and a length of 30 mm is used.
In an elastomer having a plurality of blocks (soft segment and hard segment), a plurality of loss tangent peaks are usually observed. In this case, the peak on the low temperature side is derived from the soft segment, and the peak on the high temperature side is It comes from the hard segment.

[Flow start temperature]
A test piece of 12mm width x 30mm length is cut from the press sheet, and the dynamic viscoelasticity measuring device (TA Instruments RSA-II type) torsion mode (10gf load), frequency 10Hz, heating rate Measure the viscoelastic properties of each sample at 5 ° C / min and temperature 0-280 ° C.
The inflection point of the obtained storage modulus or the temperature at which measurement becomes impossible is defined as the flow start temperature. Although the inflection point of the storage elastic modulus appears near the glass transition temperature, it does not flow and therefore does not correspond to the flow start temperature.

[Melting point]
Place about 10mg of sample in an aluminum pan and crimp the aluminum lid. Install the aluminum pan in the instrument measuring section of the differential scanning calorimeter (Perkin Elmer DSC8000) and measure it in air at a heating rate of 20 ° C / min.

[Average number of epoxy groups per molecule (Fn)]
Calculated from the following formula.
Average number of epoxy groups (Fn) = a × b / 100c
In the above formula, a, b and c are as follows.
a: Ratio (% by mass) of vinyl monomer units having an epoxy group contained in the copolymer
b: number average molecular weight of copolymer c: molecular weight of vinyl monomer having epoxy group

[Epoxy value]
This is the number of milliequivalents of epoxy groups contained in 1 g of sample (equivalent number of epoxy groups contained in 1 kg of sample), which corresponds to the epoxy index of JISK7236.

[Evaluation 1]
The pellet-like compositions obtained in the examples and comparative examples were injection molded under the following conditions to produce a plate A having a thickness of 2 mm × width 125 mm × length 125 mm.

[Injection molding conditions]
Injection molding machine: 100MSIII-10E (trade name, manufactured by Mitsubishi Heavy Industries, Ltd.)
Injection molding temperature: 180 ~ 260 ℃
Mold temperature: 40 ℃

  Using plate A, the following characteristics were evaluated. The results are shown in Tables 7-10.

(1) Flexibility <A hardness>
Measure according to JIS K 6253A, except for the following conditions.
Measurement time: 1 second after the needle contacts the sample Load: 5kg

(2) Formability <Melt Mass Flow Rate (MFR)>
Measured in accordance with ASTM D 1238 at 250 ° C and 49N load. “> 100” means exceeding 100 g / 10 min. 0.1 g / 10 min or more is preferable.

(3) Heat aging resistance <Tensile strength retention>
Measured according to JIS K 6257.
That is, the tensile strength of a sample that was allowed to stand for 24 hours in a 23 ° C environment and a sample that was allowed to stand for 168 hours in a 150 ° C environment was measured in accordance with JIS K 6251, and the tensile strength retention rate was calculated from the following formula. . 70% or more is preferable.

(4) Acid resistance <Tensile strength retention>
The sample is immersed in 30% by mass hydrochloric acid and allowed to stand in a 23 ° C. environment for 168 hours, and then the tensile strength retention is measured in the same manner as in the evaluation of heat aging resistance. 60% or more is preferable.

[Evaluation 2: Fusion property]
A polycarbonate resin (manufactured by Mitsubishi Engineering Plastics Co., Ltd., Iupilon H-3000) was injection molded under the following conditions to prepare a test piece having a thickness of 6 mm × width 25 mm × length 125 mm.

[Injection molding conditions]
Injection molding machine: 100MSIII-10E (trade name, manufactured by Mitsubishi Heavy Industries, Ltd.)
Injection molding temperature: 220 ~ 230 ℃
Mold temperature: 40 ℃

  The obtained test piece was inserted into a mold, and the pellet-like compositions obtained in Examples and Comparative Examples were injection-molded under the same conditions as in Plate A, and the thickness was 6 mm × width 25 mm × length. A 125 mm weld specimen was prepared.

  Using the above-mentioned welding test piece according to JIS K 6854, the thermoplastic elastomer layer and the polycarbonate resin layer were subjected to a tensile test at 50 mm / min in the 180 ° direction at an ambient temperature of 23 ° C. The peel strength (unit: N / 25 mm) between the elastomer layer) and the base material layer (polycarbonate resin layer) was measured. 60N / 25mm or more is preferable.

  From the above results, it can be seen that in Examples 1 to 23, the molded article has excellent flexibility and moldability, and is excellent in heat aging resistance, acid resistance and fusion property. On the other hand, Comparative Examples 4, 5, 8, 10, and 11 are inferior in fusibility.

In Comparative Example 10, since component D is not blended, the adhesiveness is lacking as compared with Example 2.
In Comparative Example 15, since component C is not blended, the heat aging resistance and acid resistance are lacking as compared with Example 2. Since Comparative Example 16 uses a component that is not soluble in tetrahydrofuran, it lacks heat aging resistance.

  The molded body obtained from the thermoplastic elastomer composition of the present invention can be used in various fields such as electrical and electronic parts, automotive parts, sealing materials, packings, vibration damping members, and tubes.

Claims (12)

  A (meth) acrylic elastomer (component A) and a thermoplastic resin (component B) having a melting point of 100 to 350 ° C. and having a functional group capable of reacting with an epoxy group are mixed in a mass ratio of 20/80 to 75/25 ( Component A / Component B), and further having a solubility in tetrahydrofuran and having a compatibilizer (component C) having an average of two or more epoxy groups in one molecule of component A and component B 0.1 to 30 parts by mass with respect to 100 parts by mass in total, and 35 to 400 parts by mass of crystalline thermoplastic elastomer (component D) with respect to 100 parts by mass of the total amount of component A and component B, Thermoplastic elastomer composition.   Component C is selected from the group consisting of monomer units containing 50 mass% or more of monomer units (monomer units c1) having an SP value of 17.5 to 25.0, or a group consisting of (meth) acrylic monomers, styrene and styrene derivatives. The thermoplastic elastomer composition according to claim 1, wherein the thermoplastic elastomer composition is composed of monomer units containing at least 50% by mass of at least one monomer unit (monomer unit c2).   The thermoplastic elastomer composition according to claim 1 or 2, wherein the crystalline thermoplastic elastomer (component D) is a polyester elastomer and / or a polyurethane elastomer.   The monomer unit which comprises a compatibilizing agent (component C) contains 10-90 mass% of (meth) acrylic monomers, and contains 10-90 mass% of styrene or a styrene derivative, The any one of Claims 1-3 A thermoplastic elastomer composition.   The thermoplastic elastomer composition according to any one of claims 1 to 4, wherein the compatibilizing agent (component C) has a weight average molecular weight of 1,000 to 100,000.   The (meth) acryl elastomer (component A) is a block copolymer comprising two or more blocks constituting a hard segment and one or more blocks constituting a soft segment. A thermoplastic elastomer composition.   The thermoplastic elastomer composition according to claim 6, wherein the glass transition temperature of the block constituting the hard segment is 20 to 200 ° C, and the glass transition temperature of the block constituting the soft segment is -100 to 19 ° C.   The thermoplastic elastomer composition according to any one of claims 1 to 7, wherein the (meth) acrylic elastomer (component A) has a weight average molecular weight of 20,000 to 1,000,000.   The thermoplastic elastomer composition according to any one of claims 1 to 8, wherein the thermoplastic resin (component B) is an aromatic polyester and / or a polyamide.   The thermoplastic metal according to any one of claims 1 to 9, further comprising 0.001 to 10 parts by mass of the aliphatic carboxylic acid metal salt (component E) with respect to 100 parts by mass of the total amount of component A and component B. Elastomer composition.   The thermoplastic elastomer composition according to any one of claims 1 to 10, further comprising 0.01 to 10 parts by mass of the transesterification catalyst (component F) with respect to 100 parts by mass of the total amount of component A and component B. .   The molded object obtained by heat-molding the thermoplastic elastomer composition in any one of Claims 1-11.