JP2015021050A - Thermoplastic elastomer composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a molding which has good flexibility and is excellent in oil resistance, especially high-temperature oil resistance (heat-resistant oil resistance) and an elastomer composition which can provide the molding.SOLUTION: A thermoplastic elastomer composition contains a (meth)acrylic elastomer (ingredient A) and a fluorine-based thermoplastic resin of a melting point of 100-300°C (ingredient B) in a mass ratio of ingredient A/ingredient B of 30/70 to 99/1. 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. .

  Patent Document 1 discloses a block copolymer (A) containing (meth) acrylic polymer block (a) and (meth) acrylic polymer block (b) ((a) and (b) are different). A thermoplastic elastomer composition for keypads having an essential component is disclosed and has two glass transition temperatures of −150 ° C. to 25 ° C. and 50 ° C. to 300 ° C., but the oil resistance is described. There is no description or suggestion about the combined use of a compatibilizing agent or a cross-linking agent. Although there is a description about heat resistance, since it is a keypad application, the test method is limited to visual inspection of deformation in an oven at 120 ° C, and it is not sufficient for use in severe industrial applications such as automobile applications. .

  Patent Document 2 contains a thermoplastic resin and a block copolymer (A) comprising (a) a (meth) acrylic polymer block and (b) an acrylic polymer block, and these are processed dynamically. The composition is disclosed, and there is a description that it is superior in heat resistance and oil resistance as compared with the polyester-based elastomer. And when the block copolymer (A) does not have a hydroxyl group, there is a description that a hydroxyl group-containing compound having a valence of 2 or more may be used as a crosslinking agent. The cross-linking agent is only titanium (IV) tetrabutoxide, and there is no description or suggestion of what effect other cross-linking agents have.

  Patent Document 3 discloses an acrylic block copolymer (A) composed of a methacrylic polymer block (a) and an acrylic polymer block (b), a thermoplastic polyurethane resin or a polyamide resin (B), and a styrene type. Although it is disclosed that the resin composition containing the thermoplastic elastomer (C) and the like is excellent in oil resistance, there is a description that the oil resistance test was performed at room temperature, and the oil resistance is not so excellent.

  Patent Document 4 discloses a compatibilizing agent that is a compound having at least one functional group selected from a thermoplastic polyester resin (A), an acrylic resin (B), a glycidyl group, an acid anhydride group, and a carboxyl group. Although the resin composition containing (C) is disclosed, there is no specific description regarding oil resistance, and there is no disclosure about the effect of the compatibilizer on oil resistance.

  Patent Document 5 discloses that a binder containing an elastomer component is used as a conductive resin composition for a fuel cell separator, and a block copolymer is disclosed as an example corresponding to the elastomer component. There is a description that it is preferable to include polyvinylidene fluoride and a soft acrylic resin from the viewpoint of aqueousness, and it is disclosed that a polymer alloy may be used in combination with a compatibilizing agent, but the structure of the soft acrylic resin is disclosed. The only Kuraray parapet SA disclosed in the examples is an acrylic rubber, and its chemical structure and physical properties are completely different from an acrylic thermoplastic elastomer exemplified by Kuraray clarity. That is, it can be said that there is no description or suggestion about the effect when the acrylic thermoplastic elastomer and the fluorine-based thermoplastic transfer resin are combined.

JP 2004-35637 A JP 2006-124724 A JP 2009-79119 A JP 2007-92038 A JP2012-15118A

  An object of the present invention is to provide a molded article having good flexibility and having excellent oil resistance, in particular, oil resistance at high temperature (heat resistance and oil resistance), and a thermoplastic elastomer composition capable of providing the molded article. It is to provide.

The present invention
[1] Containing (meth) acrylic elastomer (component A) and fluorine-based thermoplastic resin (component B) having a melting point of 100 to 300 ° C. in a mass ratio of 30/70 to 99/1 (component A / component B). And [2] a molded article obtained by thermoforming the thermoplastic elastomer composition described in [1].

  The thermoplastic elastomer composition of the present invention has excellent flexibility as a material of a molded body, and further has an effect of being excellent in oil resistance, particularly oil resistance at high temperatures (heat resistance and oil resistance).

  The thermoplastic elastomer composition of the present invention contains a (meth) acrylic elastomer (component A) and a fluorinated thermoplastic resin (component B) at a specific mass ratio. Oil resistance can be improved without impairing flexibility and heat resistance. The mechanism of action is not clear, but is estimated as follows.

  Fluorine-based thermoplastic resins, especially polyvinylidene fluoride resin, and their copolymers have good affinity with acrylic resins, and are partially compatible so that their good affinity is It is presumed that the thermoplastic resin exhibits a fine and uniform dispersion effect and contributes to the improvement of oil resistance of the resin composition.

  The (meth) acrylic elastomer (component A) is preferably composed of two or more (meth) acrylic monomers and other copolymerizable vinyl monomers as necessary.

  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) acrylic acid 2-ethylhexyl, cyclohexyl (meth) acrylate, (meth) acrylic acid, hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, glycidyl (meth) acrylate, methoxyethyl (meth) acrylate, (meth And ethoxyethyl 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 further 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 are included. Preferably, these vinyl monomers may be used in combination within a range that does not impair the object of the present invention (preferably 30% by weight or less, more preferably 20% by weight or less, and further preferably 10% by weight or less).

  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 comprising two or more blocks constituting a hard segment and one or more blocks constituting a soft segment, on both sides of one block constituting a soft segment, A triblock copolymer having two blocks constituting the hard segment is more preferable. 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.

  Vinyl monomers constituting the hard segment are methyl methacrylate, tert-butyl methacrylate, cyclohexyl methacrylate, phenyl methacrylate, hydroxyethyl methacrylate, isopropyl methacrylate and 2,2,2-trifluoroethyl methacrylate. At least one methacrylic monomer selected from the group consisting of is preferred, and methyl methacrylate is more preferred. The monomer constituting the hard segment preferably contains the methacrylic monomer, but other monomers can be used as long as the glass transition temperature of the hard segment is adjusted to a desired range. May be included.

  The glass transition temperature of the block constituting the hard segment is preferably 20 to 200 ° C, more preferably 30 to 180 ° C, and further preferably 50 to 160 ° C. 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.

  Examples of the vinyl monomer constituting the soft segment include acrylic monomers such as ethyl acrylate, butyl acrylate (BA), methoxyethyl acrylate, and ethoxyethyl acrylate. The monomer constituting the soft segment preferably contains the vinyl monomer, but other monomers can be used as long as the glass transition temperature of the soft segment is adjusted to a desired range. May be included.

  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.

  As a method for measuring the glass transition temperature of a polymer, differential scanning calorimetry (DSC), dynamic viscoelasticity measurement, thermal expansion measurement (TMA), etc. are known, but both hard segment and soft segment are included. In block copolymers, dynamic viscoelasticity measurement is generally used as a method for accurately measuring both hard segment and soft segment values. Viscoelasticity measurement is performed at different temperatures, and the loss tangent Tanδ peak is measured. Methods for determining the glass transition temperature are 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 50/50. Is more preferable.

  Examples of commercially available products that can be used as Component A include Clarity manufactured by Kuraray Co., Ltd., Nano Strength manufactured by Arkema Co., Ltd., and Nabster manufactured by Kaneka Co., Ltd.

  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 still more 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.

  From the viewpoint of the flexibility of the composition, the hardness of Component A is preferably 1 to 85, more preferably 2 to 75, and still more preferably 3 to 70 in terms of D hardness. The D hardness means durometer type D hardness defined in JIS K 6253.

  The fluorine-based thermoplastic resin (component B) in the present invention has a specific melting point. The melting point of the fluorinated thermoplastic resin is 100 ° C. or higher, and preferably 110 ° C. or higher, from the viewpoint of increasing the heat resistance of the resulting resin composition. Further, from the viewpoint of suppressing thermal decomposition in the step of melt mixing with the (meth) acryl elastomer, it is 300 ° C. or lower, and preferably 290 ° C. or lower.

  Fluorine-based thermoplastic resins, as represented by polyvinylidene fluoride resin, are excellent in chemical resistance, heat resistance, and hygiene, such as valves and caps for semiconductor and liquid crystal manufacturing equipment, guide rails and rollers for industrial machinery. It is used for bolts and linings of chemical industry, piping parts for food processing machine parts, medical equipment and the like.

  Examples of the monomer constituting the fluorine-based thermoplastic resin include tetrafluoroethylene, 1,1-difluoroethylene, chlorotrifluoroethylene, hexafluoropropylene, and the like. Among these, one or two or more are used. be able to. 1,1-difluoroethylene and hexafluoropropylene are preferred. Moreover, the copolymerizable monomer may be used in the range which does not impair the effect of this invention. Examples of the copolymerizable monomer include ethylene, propylene, styrene, methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, styrene, α -Methylstyrene etc. are mentioned, Among these, ethylene is preferable.

As a specific example of the fluorine-based thermoplastic resin,
ETFE (melting point: 260-270 ° C.): ethylene-tetrafluoroethylene copolymer,
PVDF (melting point: 150-170 ° C.): polyvinylidene fluoride polymer,
PVDF copolymer (melting point: 115-170 ° C.): HFP (hexafluoropropylene) copolymer,
ECTFE (melting point: 220-250 ° C.): ethylene / chlorotrifluoroethylene copolymer,
VDF-CTFE (melting point: 169 ° C.): Fukkavinylidene / chlorotrifluoroethylene copolymer,
PCTFE (melting point: 210-216 ° C.): polychlorotrifluoroethylene,
FEP (melting point: 260-280 ° C.): tetrafluoroethylene / hexafluoropropylene copolymer,
EFEP (melting point: 215 to 270 ° C.): ethylene / tetrafluoroethylene / hexafluoropropylene copolymer and the like.

  The weight average molecular weight of the fluorinated thermoplastic resin is preferably 50,000 or more, more preferably 100,000 or more, and further preferably 200,000 or more, from the viewpoint of mechanical properties as a molded product. Further, from the viewpoint of controlling the viscosity at the time of melt molding and easily obtaining a molded product having a desired shape, it is preferably 2 million or less, more preferably 1.5 million or less, and even more preferably 1 million or less.

  The melt viscosity of the fluorinated thermoplastic resin is preferably from 100 to 10,000 Pa · sec, more preferably from 200 to 8,000 Pa · sec, still more preferably from 300 to 7,000 Pa · sec.

  If the amount of the fluorine-based thermoplastic resin is too small, the heat resistance and oil resistance become insufficient, which is not preferable. If the amount is too large, the elastic modulus and the altitude are too high. From these viewpoints, in the thermoplastic elastomer composition of the present invention, the mass ratio of component A to component B (component A / component B) is 30/70 to 99/1, and 60/40 to 98/2 is Preferably, 50/50 to 97/3 is more preferable.

  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 thermoplastic elastomer composition of the present invention preferably further contains a carbodiimide compound (component C) from the viewpoint of oil resistance. It is known that carbodiimide compounds can be used in polyester resins and polylactic acid resins to improve heat resistance and durability, but there are no examples of use in (meth) acrylic elastomers. There is also no known effect on the elastomer.

  The carbodiimide compound (component C) has the formula (I):

(In the formula, n R may be different from each other, a divalent aliphatic hydrocarbon group having 1 to 18 carbon atoms, a divalent heterocyclic group having 3 to 12 carbon atoms, or a 6 to 14 carbon atoms. A divalent aromatic hydrocarbon group, a divalent alicyclic hydrocarbon group having 3 to 13 carbon atoms, or a terminal hydroxyl group, and n is an integer of 1 to 15)
It preferably has a skeleton represented by: It can react with an amine or carboxylic acid to cause a crosslinking reaction.

  In the formula (I), those in which n is 1 include dicyclohexylcarbodiimide, diisopropylcarbodiimide, N, N′-phenylcarbodiimide, N, N′-dicyclohexylcarbodiimide, N, N′-di-2,6-diisopropylphenylcarbodiimide 1-ethyl-3- (3-dimethylaminopropyl) carbodiimide (EDC) and its hydrochloride, 1-ethyl-3- (tert-butyl) carbodiimide (BEC), 1-cyclohexyl-3- (2-morpholinoethyl ) Carbodiimide (CMC) and the like.

  In the formula (I), a linear polymer called polycarbodiimide is known as n having 2 or more. As the organic diisocyanate which is a synthetic raw material in the production of the polycarbodiimide compound, aromatic diisocyanate, aliphatic diisocyanate, alicyclic diisocyanate and mixtures thereof can be used.

  Examples of aromatic diisocyanates include 1,5-naphthalene diisocyanate, 4,4′-diphenylmethane diisocyanate, 4,4′-diphenyldimethylmethane diisocyanate, 1,3-phenylene diisocyanate, 1,4-phenylene diisocyanate, 2,4 -Tolylene diisocyanate, 2,6-tolylene diisocyanate, mixture of 2,4-tolylene diisocyanate and 2,6-tolylene diisocyanate, xylylene diisocyanate, tetramethylxylylene diisocyanate, 2,6-isopropylphenyl diisocyanate, 1 1,3,5-triisopropylbenzene-2,4-diisocyanate and the like.

  Examples of the aliphatic diisocyanate include hexamethylene diisocyanate. Examples of the alicyclic diisocyanate include cyclohexane-1,4-diisocyanate, isophorone diisocyanate, dicyclohexylmethane-4,4′-diisocyanate, and methylcyclohexane diisocyanate.

  The polycarbodiimide compound is obtained by, for example, using a monoisocyanate or a polyisocyanate as a raw material, and subjecting to a decarboxylation condensation reaction in a solvent-free or inert solvent at a temperature of about 70 ° C. or more in the presence of an organic phosphorus compound or an organometallic compound. It is obtained by doing.

  The polycarbodiimide includes an aliphatic polycarbodiimide in which R is an aliphatic group and an aromatic polycarbodiimide in which R has an aromatic group. The aliphatic polycarbodiimide is more bleed than the aromatic polycarbodiimide. The aliphatic group is preferably linear rather than branched. The molecular weight of the polycarbodiimide is preferably 100 or more and 100,000 or less, more preferably 500 or more and 10,000 or less, from the viewpoint of safety and ease of handling.

  Commonly available commercially available aliphatic polycarbodiimide compounds include carbodilite LA-1 (poly (4,4′-dicyclohexylmethanecarbodiimide), number average molecular weight 2,000, carbodiimide equivalent 247 g / mol), carbodilite HMV-8CA ( Number average molecular weight of about 3,000, carbodiimide equivalent 278 g / mol), carbodilite HMV-15CA (carbodiimide equivalent 262 g / mol) containing no isocyanate group (Nisshinbo Chemical Co., Ltd.). Commercially available aromatic polycarbodiimide compounds include stavaxol P (poly (1,3,5-triisopropylbenzene) polycarbodiimide, number average molecular weight 3,500) and stavaxol P-400 (poly (1,3,5) -Triisopropylbenzene) polycarbodiimide, number average molecular weight of about 20,000), stavaxol I (N, N'-di-2,6-diisopropylphenylcarbodiimide, number average molecular weight 450) (above, manufactured by Rhein Chemie) It is done.

  The content of Component C is preferably 0.01 parts by mass or more, more preferably 1 part by mass or more, and even more preferably 1.5 parts by mass or more with respect to 100 parts by mass of the total amount of Component A and Component B from the viewpoint of oil resistance. . Moreover, from a heat resistant viewpoint, 10 mass parts or less are preferable with respect to 100 mass parts of total amounts of the component A and the component B, 5 mass parts or less are more preferable, and 3 mass parts or less are more preferable. From these viewpoints, the content of component E is preferably 0.01 to 10 parts by mass, more preferably 1 to 5 parts by mass, and further more preferably 1.5 to 3 parts by mass with respect to 100 parts by mass of the total amount of component A and component B. preferable.

  It is preferable that the thermoplastic elastomer composition of the present invention further contains a transesterification catalyst (component D). The transesterification catalyst has a function of promoting the progress of the crosslinking reaction of the (meth) acryl elastomer and improving the heat resistance by increasing the molecular weight.

  Component D is preferably an organometallic compound such as an organotin catalyst, an organotitanium catalyst, or an organozirconium catalyst.

  Examples of the organotin catalyst include dibutyltin dilaurate, dibutyltin oxide, tributyltin chloride, tributyltin fluoride, and tributyltin oxide.

  Examples of organotitanium catalysts include tetraisopropyl titanate, tetranormal butyl titanate, butyl titanate dimer, tetraoctyl titanate, titanium ethyl acetoacetate, titanium lactate ammonium salt, titanium lactate, titanium triethanolaminate, etc. Dinormal butanol bis (triethanolaminate), tetrastearyl titanate and the like can be mentioned. Among these, titanium alkanolaminate is preferable, and titanium triethanolaminate is more preferable.

  Examples of the organic zirconium catalyst include normal propyl zirconate, normal butyl zirconate, zirconium tetraacetyl acetonate, zirconium ethyl acetoacetate and the like.

  Component D is preferably titanium triethanolamate, titanium dinormalbutanol bis (triethanolaminate) and zirconium tetraacetylacetonate from the viewpoint of reactivity with component A.

  The content of Component D is preferably 0.01 parts by mass or more, more preferably 0.02 parts by mass or more, and 0.03 parts by mass or more with respect to 100 parts by mass of the total amount of Component A and Component B from the viewpoint of improving heat resistance. Further preferred. Further, from the viewpoint of suppressing a decrease in thermoplasticity of the resulting composition, the amount is preferably 10 parts by mass or less, more preferably 8 parts by mass or less, with respect to 100 parts by mass of the total amount of Component A and Component B. More preferred is less than or equal to parts by weight. From these viewpoints, the content of component C is preferably 0.01 to 10 parts by mass, more preferably 0.02 to 8 parts by mass, and further 0.03 to 5 parts by mass with respect to 100 parts by mass of the total amount of component A and component B. preferable.

  The thermoplastic elastomer composition of the present invention preferably further contains a crystalline thermoplastic resin (component E) having a high melting point from the viewpoint of imparting heat resistance to the composition. The melting point of the crystalline thermoplastic resin is preferably 100 ° C. or higher, more preferably 180 ° C. or higher, and further preferably 200 ° C. or higher. Further, from the viewpoint of ease of production, 350 ° C. or lower is preferable, 300 ° C. or lower is more preferable, and 280 ° C. or lower is further preferable. The melting point of the crystalline thermoplastic resin is preferably 100 to 350 ° C, more preferably 180 to 300 ° C, and further preferably 200 to 280 ° C.

  In the present invention, the crystalline thermoplastic resin refers to a thermoplastic resin whose melting temperature based on JIS K 7121 is observed in a differential scanning calorimeter (DSC).

  Examples of the crystalline thermoplastic resin include aromatic polyester resins, polyacetal resins, polyamide resins, and the like. Examples of the aromatic polyester resin include polyethylene terephthalate, polybutylene terephthalate, and polyethylene naphthalate. Examples of the polyacetal resin include polyoxymethylene resin. Examples of the polyamide resin include nylon 6, nylon 66, and the like. Among these, aromatic polyester resins and polyamide resins are preferable from the viewpoint of heat resistance (high melting point) and incompatibility with Component A. It is also preferable to use a plurality of these in combination.

  Crystalline thermoplastic elastomers are also a category of crystalline thermoplastic resins, and examples thereof include polyester elastomers and polyamide elastomers. 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 a crystalline thermoplastic resin other than the elastomer and the elastomer in combination.

  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 6,000, 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.).

  The content of Component E is preferably 10 parts by mass or more, more preferably 20 parts by mass or more, and even more preferably 30 parts by mass or more with respect to 100 parts by mass of the total amount of Component A and Component B from the viewpoint of heat resistance. . From the viewpoint of flexibility, the amount is preferably 400 parts by mass or less, more preferably 300 parts by mass or less, and further preferably 250 parts by mass or less with respect to 100 parts by mass of the total amount of Component A and Component B. From these viewpoints, the content of Component E is preferably 10 to 400 parts by mass, more preferably 20 to 300 parts by mass, and further 30 to 250 parts by mass with respect to 100 parts by mass of the total amount of Component A and Component B. preferable.

  The thermoplastic elastomer composition of the present invention preferably further contains a polycarbonate resin (component F), which is an amorphous thermoplastic resin, from the viewpoint of imparting heat resistance at high temperatures to the composition.

  The polycarbonate resin is generally obtained by interfacial polycondensation in a solvent using bisphenol A and phosgene as raw materials. Alternatively, bisphenol A and diphenyl carbonate can be heated and melted without a solvent, and obtained by a polycondensation reaction by transesterification under reduced pressure.

  The polycarbonate resin is preferably a bisphenol A monomer and linked by a carbonate bond using phosgene, but a polycarbonate copolymer using any diol component as long as the effects of the present invention are not impaired. It may be.

  Specific examples of the polycarbonate resin include, for example, hydroquinone, resorcinol, 4,4′-biphenol, 1,1-bis (4-hydroxyphenyl) cyclohexane (bisphenol Z), 1,1-bis (4-hydroxyphenyl) ethane. (Bisphenol E), 2,2-bis (4-hydroxyphenyl) propane (bisphenol A), 2,2-bis (4-hydroxy-3-methylphenyl) propane (bisphenol C), 2,2-bis (4 -Hydroxyphenyl) butane, 1,1-bis (4-hydroxyphenyl) -1-phenylethane, 1,1-bis (4-hydroxyphenyl) -3,3,5-trimethylcyclohexane, 2,2-bis ( 4-hydroxyphenyl) pentane, 4,4 '-(p-phenylenediisopropylidene) diphenol, 4,4'-(m-phenylenediisopropylidene) diphenol (bisphenol M), 1,1-bis (4 -Hydroxyphenyl) -4-isopropyl Hexane, bis (4-hydroxyphenyl) oxide, bis (4-hydroxyphenyl) sulfide, bis (4-hydroxyphenyl) sulfoxide, bis (4-hydroxyphenyl) sulfone, bis (4-hydroxyphenyl) ketone, bis (4 -Hydroxyphenyl) ester, 2,2-bis (3,5-dibromo-4-hydroxyphenyl) propane, bis (3,5-dibromo-4-hydroxyphenyl) sulfone, bis (4-hydroxy-3-methylphenyl) ) Sulfide, 9,9-bis (4-hydroxyphenyl) fluorene, 9,9-bis (4-hydroxy-3-methylphenyl) fluorene, etc., among which bisphenol Z, bisphenol E, bisphenol A, bisphenol C And bisphenol M are preferred, and bisphenol Z and bisphenol A are more preferred. These may be used alone or in combination of two or more.

  Moreover, not only a linear chain but also a polycarbonate resin having a branched structure can be used. A polycarbonate having a branched structure can be obtained by polymerization using a branching agent. Preferred branching agents include 2,2-bis [4,4-bis (4-hydroxyphenyl) cyclohexyl] propane, 2,2-bis. And [4,4-bis (4-hydroxy-3-methylphenyl) cyclohexyl] propane.

  The weight average molecular weight of the polycarbonate resin is preferably 10,000 to 300,000, and more preferably 20,000 to 200,000. 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 1.5 to 3.

  The content of Component F is preferably 1 part by mass or more, more preferably 2 parts by mass or more, and 5 parts by mass or more with respect to 100 parts by mass of the total amount of Component A and Component B from the viewpoints of heat resistance and oil resistance. Is more preferable. From the viewpoint of flexibility, the amount is preferably 200 parts by mass or less, more preferably 150 parts by mass or less, and still more preferably 100 parts by mass or less with respect to 100 parts by mass of the total amount of Component A and Component B. From these viewpoints, the content of component D is preferably 1 to 200 parts by mass, more preferably 2 to 150 parts by mass, and further 5 to 100 parts by mass with respect to 100 parts by mass of the total amount of component A and component B. preferable.

  The thermoplastic elastomer composition of the present invention may appropriately contain known additives as necessary. Additives include heat stabilizers; lubricants such as heavy metal deactivators and fatty acid esters; light stabilizers such as benzotriazole compounds, benzophenone compounds, benzoate compounds and hindered phenol compounds; epoxy compounds and oxazoline compounds Hydrolysis inhibitors of phthalates; plasticizers such as phthalate compounds, polyester compounds, (meth) acryl oligomers, process oils; inorganic foaming agents such as sodium bicarbonate and ammonium bicarbonate; nitro compounds, azo compounds, sulfonyl hydrazides Organic foaming agents such as carbon black, calcium carbonate, talc, glass fiber, etc .; Flame retardants such as tetrabromophenol, ammonium polyphosphate, melamine cyanurate, magnesium hydroxide and aluminum hydroxide; Silane coupling Agent, titane DOO-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 comprises at least a (meth) acrylic elastomer (component A) and a fluorine-based thermoplastic resin (component B), and if necessary, a carbodiimide compound (component C), a transesterification catalyst (component). It is preferable to obtain a raw material component containing D), a crystalline thermoplastic resin (component E), a polycarbonate resin (component F), other additives and the like by heating and kneading with an extruder or a kneader.

  From the viewpoint of moldability, the heat kneading temperature is preferably 100 ° C. or higher, more preferably 120 ° C. or higher, and further preferably 150 ° C. or higher. Further, from the viewpoint of preventing thermal deterioration during heating and kneading, it is preferably 320 ° C. or lower, more preferably 310 ° C. or lower, and further preferably 300 ° C. or lower.

  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 preferred, and a co-rotating twin screw extruder is more preferred.

  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 and a Brabender.

  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.

  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 is excellent in flexibility, heat resistance and oil resistance, and in the field of thermoplastic elastomer materials, it is used in the same fields of use as thermoplastic polyester elastomers and thermoplastic polyamide elastomers. Can do.

  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 product of the present invention obtained by thermoforming a thermoplastic elastomer composition preferably has an A hardness of 30 to 100, more preferably 40 to 95, which is an index of flexibility. Moreover, it is preferable that D hardness is 5-60, and 10-50 are more preferable.

Further, the storage elastic modulus at 25 ° C. of the molded body of the present invention is preferably 3.0 × 10 ^{5 to} 6,000 × 10 ^{5, and} more preferably 5.0 × 10 ^{5 to} 5,000 × 10 ⁵ from the viewpoint of flexibility.

  EXAMPLES The present invention will be specifically described below with reference to examples, but the present invention is not limited to these examples.

Examples 1-17 and Comparative Examples 1-7
Raw material components are charged at a composition ratio (parts by mass) shown in Tables 1 to 3 in a batch kneader (Plastograph EC50 type, manufactured by Brabender, Inc.) heated to 260 ° C, and the raw material is melted at a rotation speed of 60 r / min Kneaded. In a kneading time of 10 minutes, the entire kneaded material in a molten state was taken out and cooled at room temperature to obtain a composition.

  Details of the raw materials used are as follows.

<Component A>
・ (Meth) acrylic elastomer a: Clarity LA3320 (manufactured by Kuraray Co., Ltd.)
PMMA-PBA-PMMA triblock copolymer, MMA / BA = 15/85 (mass ratio), Mw: 128,901, Mn: 99,999, Mw / Mn: 1.29, Tg: hard segment (PMMA) = 139 ° C, soft segment (PBA) =-27 ℃, A hardness: 28, D hardness: 2
・ (Meth) acrylic elastomer b: Clarity LA2330 (manufactured by Kuraray Co., Ltd.)
PMMA-PBA-PMMA triblock copolymer, MMA / BA = 20/80 (mass ratio), Mw: 99,394, Mn: 81,982, Mw / Mn: 1.21, Tg: hard segment (PMMA) = 137 ° C, soft segment (PBA) =-23 ° C, A hardness: 32, D hardness: 5
・ (Meth) acrylic elastomer c: Clarity LA4285 (Kuraray Co., Ltd.)
PMMA-PBA-PMMA triblock copolymer, MMA / BA = 50/50 (mass ratio), Mw: 58,000, Mn: 51,527, Mw / Mn: 1.13, Tg: hard segment (PMMA) = 141 ° C, soft segment (PBA) =-29 ° C, A hardness: 98, D hardness: 59
[(P) MMA: (poly) methyl methacrylate, (P) BA: (poly) n-butyl acrylate]

<Component A '>
・ PMMA resin: Sumipex LG21 (manufactured by Sumitomo Chemical Co., Ltd.)
Mw: 59,048, Mn: 31,952, Mw / Mn: 1.85, Tg: 113 ° C

<Component B>
-Polyvinylidene fluoride a: Kyner 710 (manufactured by Arkema Co., Ltd.)
Vinylidene fluoride homopolymer, melting point: 165 to 172 ° C., melt viscosity (232 ° C., 100 sec ⁻¹ ): 400 to 800 Pa · sec
・ Polyvinylidene fluoride b: Kyner 760 (manufactured by Arkema Co., Ltd.)
Vinylidene fluoride homopolymer, melting point: 165-272 ° C, melt viscosity (232 ° C, 100sec-1): 2300-2900Pa · sec

<Component C>
・ Carbodiimide compound: Carbodilite LA-1 (Nisshinbo Chemical Co., Ltd.)
Poly (4,4'-dicyclohexylmethanecarbodiimide), Mn: 2,000, carbodiimide equivalent: 247 g / mol

<Component D>
・ Organic titanium catalyst: ORGATICS TC-400 (Matsumoto Fine Chemical Co., Ltd.)
Titanium triethanolamate

<Component E>
・ PBT (polybutylene terephthalate): Toraycon 1401x04 (manufactured by Toray Industries, Inc.)
Melting point: 225 ° C
・ PET (polyethylene terephthalate): SA-1206 (manufactured by Unitika Ltd.)
Melting point: 255 ° C
・ Copolymerized PET (polyethylene terephthalate): MA-1346P (manufactured by Unitika Ltd.)
Melting point: 230 ° C

<Component F>
・ Polycarbonate resin: Lexan 141R (manufactured by Subic Innovative Plastics)
Bisphenol A polycarbonate, Mw: 40,428, Mn: 18,091, Mw / Mn: 2.23

  In addition, the physical property of each raw material component was measured with the following method.

(Weight average molecular weight (Mw) and number average molecular weight (Mn))
From a gel permeation chromatograph (GPC), the following apparatus, column and solvent are used and determined from polystyrene conversion.
・ Equipment: Tosoh HLC-8120
・ Column: Inertsil WF300
・ Solvent: Tetrahydrofuran

[Glass transition temperature (Tg) and melting point]
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 the loss tangent (Tan δ) measured at the time is taken as the glass transition temperature (Tg). The temperature at which the elastic modulus cannot be measured due to the melting of the test piece is defined as the melting point (Tm). A test piece having a thickness of 2 mm, a width of 12.5 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.

[A hardness]
Measure according to JIS K 6253-3.

[D hardness]
Measure according to JIS K 6253-3.

[Melt viscosity]
In accordance with JIS K 7199, a capillary rheometer is used to measure at 232 ° C. and a shear rate of 100 sec ⁻¹ .

  The composition obtained in Examples and Comparative Examples was subjected to a mold of 2 mm thick × 10 cm wide × 10 cm long using a 50 t hot press machine of a hot press machine (manufactured by Toho Co., Ltd.) heated to 260 ° C. After being used and hot-press molded for 5 minutes, a cold press was applied for 5 minutes to produce a 2 mm-thick press sheet as a test piece.

  The following characteristics were measured and evaluated using a 2 mm thick press sheet. The results are shown in Tables 1-3.

(1) Flexibility <A hardness>
A 2mm thick press sheet is allowed to stand in a constant temperature and humidity chamber (temperature 23 ° C, relative humidity 50%) for at least 24 hours to stabilize the sheet.
Three sheets of 2 mm thick press sheets are stacked and measured according to JIS K 6253-3 “Durometer Hardness Test Method”.

<D hardness>
Measured in accordance with JIS K 6253-3 “Durometer Hardness Test Method” as with A hardness.

<Storage modulus>
Using a dynamic viscoelasticity measuring device (RSA III manufactured by TA Instruments Co., Ltd.), the storage elastic modulus at 25 ° C. is measured. As a test piece, a 2 mm-thick press sheet is punched into a width of 12.5 mm and a length of 30 mm.

<Tensile strength and elongation at break>
As a test piece, a 2 mm thick press sheet is used by punching into a No. 3 dumbbell mold described in JIS K 6251. Using a tensile tester, pull a test piece placed at room temperature 23 ° C for 24 hours or more at a tensile speed of 500 mm / min, record the stress when the test piece breaks as the tensile strength, and calculate the following from the elongation at break: The elongation at break is calculated from the equation.
Elongation at break (%) = (L−L ₀ ) / L ₀ × 100
(L ₀ indicates the length of the test piece before the test, and L indicates the length of the test piece when it breaks)

(2) Oil resistance <Oil resistance immersion test>
It conforms to the test method specified in JIS K 6258. The test piece is a 2 mm thick press sheet punched into a No. 3 dumbbell mold. After immersing the test piece in IRM # 903 oil (formerly ASTM No. 3 oil) at 23 ° C., 120 ° C. or 150 ° C. for 168 hours, the mass change rate (%) is calculated by the following formula.

Mass change rate (%) = (m3−m1) / m1 × 100
m1: Mass of test piece in air before immersion (mg)
m3: Mass of test specimen in air after immersion (mg)

<Transparency>
Using a 2mm thick press sheet, leave it in a constant temperature room at 23 ° C for 24 hours, and then measure the light transmittance and HAZE. Measure HAZE by the method according to JIS K 7361 (How to determine haze of plastic transparent material) by the method according to JIS K 7361 (Test method for total light transmittance of plastic transparent material). . The equipment is HAZE-GARDII manufactured by Toyo Seiki Seisakusho.

  In the case where a crystalline thermoplastic resin is used, the crystalline thermoplastic resin is inferior in compatibility with other components and thus the transparency is lowered, but the oil resistance is not affected.

  From the above results, it can be seen that the thermoplastic elastomer compositions of the examples are excellent in flexibility and also have good oil resistance.

  In Examples 1 to 3, (meth) acryl elastomer / fluorine-based thermoplastic resin is blended at 60/40 to 85/15, and the oil resistance is higher than that of Comparative Example 1 that does not include a fluorine-based thermoplastic resin. It has improved. Moreover, it is excellent in flexibility as compared with the hardness (storage modulus) of the fluorinated thermoplastic resin of Comparative Example 2.

  In Example 4, although the kind of fluorine-type thermoplastic resin is changed, it is excellent in heat and oil resistance, and has a softness | flexibility similarly to Examples 1-3.

  In Example 5, a (meth) acryl elastomer c having a high hardness is blended. The hardness is lower and the flexibility is better than that of the fluorinated thermoplastic resin of Comparative Example 2.

  In Examples 6 and 7, a transesterification catalyst is blended, and the flexibility and oil resistance are good as in Examples 1 to 5. In Comparative Example 7, a transesterification catalyst is blended with respect to Comparative Example 1, but the heat and oil resistance is improved, but since no fluorine-based thermoplastic resin is blended, the oil resistance at 23 ° C is improved. can not see.

  In Example 8, the (meth) acryl elastomer a having a low hardness is blended and a transesterification catalyst is blended, and the heat and oil resistance is excellent.

  In Examples 9 to 10, two types of (meth) acrylic elastomers a and c are blended, and the heat and oil resistance is particularly improved.

  In Examples 11 and 12, two types of (meth) acrylic elastomers b and c are blended and a carbodiimide compound is blended, and the oil resistance is particularly excellent.

  In Examples 13 to 16, a crystalline thermoplastic resin is blended, and the transparency is lost, but the heat and oil resistance is excellent.

  In Example 17, a polycarbonate resin is blended, and the oil resistance is excellent.

  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 (6)

  Heat comprising (meth) acrylic elastomer (component A) and fluoroplastic resin (component B) having a melting point of 100 to 300 ° C. in a mass ratio of 30/70 to 99/1 (component A / component B) Plastic elastomer composition.   Furthermore, the thermoplastic elastomer composition of Claim 1 which contains 0.01-10 mass parts of carbodiimide compounds (component C) with respect to 100 mass parts of total amounts of the component A and the component B.   Furthermore, the thermoplastic elastomer composition of Claim 1 or 2 which contains 0.01-10 mass parts of transesterification catalysts (component D) with respect to 100 mass parts of total amounts of the component A and the component B.   Furthermore, the crystalline thermoplastic resin (component E) whose melting | fusing point is 100-350 degreeC is contained in 10-400 mass parts with respect to 100 mass parts of total amounts of the component A and the component B, The any one of Claims 1-3 A thermoplastic elastomer composition.   Furthermore, 1-200 mass parts of polycarbonate resins (component F) are contained with respect to 100 mass parts of total amounts of the component A and the component B, The thermoplastic elastomer composition in any one of Claims 1-4.   The molded object obtained by heat-molding the thermoplastic elastomer composition in any one of Claims 1-5.