JP2016079227A - Thermoplastic elastomer composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a thermoplastic elastomer composition excellent in flexibility, moldability, fusion property and slidability and having good abrasion resistance and bloom resistance and a molded body obtained by using the composition.SOLUTION: There is provided a thermoplastic elastomer composition containing a thermoplastic styrenic elastomer A, a softener B, a thermoplastic polyester-based elastomer C and a silicone modified (meth)acryl polymer D, where a mass ratio of the thermoplastic styrenic elastomer A and the softener B (A/B) is 25//75 to 95/5 and the thermoplastic polyester-based elastomer C contains a hard segment and a soft segment with a mass ratio (hard segment/soft segment) of 10/90 to 60/40.SELECTED DRAWING: None

Description

  The present invention has excellent adhesiveness to various materials, and is useful for various molded products such as automobiles, electronic materials, home appliances, electrical equipment, medical tools, packaging materials, stationery and miscellaneous goods, and grips. The present invention relates to a thermoplastic elastomer composition used for various members such as tubes, packings, gaskets, cushions, films, sheets, and the like, and a molded body obtained using the composition.

  Patent Document 1 discloses an invention relating to a thermoplastic elastomer composition in which a hydrogenated derivative of a styrene-butadiene block copolymer, a rubber softener, and a polyester elastomer are blended.

Patent Document 2 discloses a thermoplastic elastomer having a partially or completely crosslinked rubber dispersed in a polyolefin resin, a general formula A-B-A (where A is a polymer block of a monovinyl-substituted aromatic hydrocarbon, B is an elastomeric polymer block of a conjugated diene) with respect to 100 parts by weight of an elastomer composition containing a hydrogenated derivative of a block copolymer represented by the formula:
An invention relating to a thermoplastic elastomer composition to which at least one of a higher fatty acid amide, a polyorganosiloxane, and an acrylic-silicone copolymer resin is added is disclosed.

JP-A-1-193352 JP 2001-200118 A

  Conventionally, in order to improve the slidability of the resin composition, the resin component itself is hardened, or as a lubricant, a long-chain organic acid compound such as an organic acid ester, an organic acid salt, or an organic acid amide, or a silicone oil In particular, in a soft composition, it is necessary to add a large amount of lubricant in order to exhibit sufficient slidability. However, when a large amount of lubricant is blended, the dispersibility of the lubricant is not so good, so once the lubricant is dispersed, the composition melts, flows, or is exposed to high temperatures In addition, the lubricant is separated and gathers near the surface, and problems such as bleeding, delamination, and bloom are likely to occur. In addition, long-chain organic acid compounds are likely to be denatured at high temperatures, and have a problem that they tend to cause discoloration and foreign matter called burns and burnt during melt molding.

  On the other hand, there is a known method to improve the slidability by adding solid particles that do not melt even at high temperatures, such as silicone powder and Teflon powder, but the solid particles act as fillers, which adversely affects moldability and surface properties. In addition, since the adhesiveness with the resin component of the composition is not good, peeling is likely to occur from the interface, and when used in a large amount, there is a problem that the strength of the composition itself is lowered.

  In response to such problems, a copolymer having both a structural part familiar with the resin component and a structural part that improves slidability has been developed and has been tried to be applied to various thermoplastic resins. On the other hand, while the effect of increasing heat resistance and weather resistance appears, there is often a drawback that melt flowability and moldability are worsened. This may be because, for example, a graft copolymer or block copolymer having different structures acts as a pseudo-crosslinking point of a thermoplastic resin. Further, as a property similar to the slidability required for the thermoplastic elastomer composition, there is wear resistance, but both do not always show the same tendency.

  An object of the present invention is to provide a thermoplastic elastomer composition having excellent flexibility, moldability, fusing property, and slidability, and having good wear resistance and bloom resistance, and a molded product obtained using the composition. Is to provide.

  As a result of investigations by the present inventors, it is possible to obtain a fusion property as compared with other lubricants by adding a silicone-modified acrylic polymer to a thermoplastic elastomer composition containing a styrene elastomer, a softener, and a polyester elastomer. The inventors have found that the abrasion resistance of the composition is remarkably improved without damaging the present invention, and have completed the present invention.

The present invention
[1] A thermoplastic styrenic elastomer A, a softening agent B, a thermoplastic polyester elastomer C, and a silicone-modified (meth) acrylic polymer D,
The mass ratio (A / B) of the thermoplastic styrenic elastomer A and the softener B is 25/75 to 95/5,
The thermoplastic polyester elastomer C includes a hard segment and a soft segment in a mass ratio (hard segment / soft segment) of 10/90 to 60/40,
The content of the thermoplastic polyester elastomer C is 75 to 1000 parts by mass with respect to 100 parts by mass of the total amount of the thermoplastic styrene elastomer A and the softener B,
The content of the silicone-modified (meth) acrylic polymer D is 1 to 35 parts by mass with respect to 100 parts by mass of the thermoplastic polyester elastomer C.
A thermoplastic elastomer composition,
[2] A molded article comprising the thermoplastic elastomer composition according to [1],
[3] The present invention relates to a composite molded article obtained by welding the thermoplastic elastomer composition according to [1] to a member.

  The thermoplastic elastomer composition of the present invention is excellent in flexibility, moldability, fusing property, and slidability, and has the effect of having good wear resistance and bloom resistance.

  The thermoplastic elastomer composition of the present invention contains a thermoplastic styrenic elastomer A, a softening agent B, a thermoplastic polyester elastomer C, and a silicone-modified (meth) acrylic polymer D. A combination of a thermoplastic polyester elastomer C and a silicone-modified (meth) acrylic polymer D containing a hard segment and a soft segment in a predetermined ratio has never been attempted before. Hydrophobic polysiloxane part as typified by polydimethylsiloxane is excellent in slidability but is not compatible with most carbon polymers, and acrylic polymer as typified by poly (meth) acrylate In view of its SP value, the portion is considered to be excellent in affinity with the soft segment portion of the thermoplastic elastomer composition, but is unlikely to affect the hard segment portion. Therefore, the silicone-modified (meth) acrylic polymer D is a polyester. The bleed phenomenon is not caused by being fixed to the soft segment portion of the system elastomer, but the pseudo segment is not caused in the hard segment portion. Therefore, it is considered that the effect of not impairing the flexibility of the composition is exhibited.

  In view of this, in the present invention, when the silicone-modified (meth) acrylic polymer D is used for the thermoplastic polyester elastomer A, the slidability is improved, while the flexibility of the composition, the melt fluidity, Although it can be understood that there is no adverse effect on moldability, the effect of wear resistance obtained in the present invention is remarkable, which cannot be explained only by simply improving the slidability.

  The thermoplastic styrenic elastomer A is composed of a polymer block unit (s1) composed of a styrene monomer and a polymer block unit (b1) composed of a conjugated diene compound from the viewpoints of flexibility and moldability. A block copolymer (Z1) is preferred.

  Styrene monomers constituting the block unit (s1) include styrene, o-methylstyrene, p-methylstyrene, p-tert-butylstyrene, 1,3-dimethylstyrene, α-methylstyrene, vinylnaphthalene, And vinyl anthracene.

  The block copolymer (Z1) consists of a hard segment (hard portion) composed of block units (s1) and a soft segment (soft portion) composed of block units (b1), from the viewpoint of determining the overall physical properties. The content of the styrene monomer in the block copolymer (Z1) is preferably 5 to 80% by mass, more preferably 10 to 70% by mass, and still more preferably 15 to 40% by mass.

  Examples of the conjugated diene compound constituting the block unit (b1) include butadiene, isoprene, 1,3-pentadiene and the like.

The block copolymer (Z1) is preferably partially or wholly hydrogenated because unsaturated bonds are reduced by hydrogenation and heat resistance, weather resistance and mechanical properties are improved. . The hydrogenation rate is preferably 80% or more, and more preferably 90% or more. In the present invention, the hydrogenation rate refers to the content of the carbon-carbon double bond derived from the conjugated diene unit in the block copolymer, before and after hydrogenation, by iodine value measurement, infrared spectrophotometer, ¹ H -It can be determined from the measured value by measuring with NMR spectrum or the like.

  Specific examples of hydrogenated block copolymer (Z1) include styrene-ethylene-butylene-styrene block copolymer, styrene-ethylene-propylene-styrene block copolymer, styrene-ethylene-ethylene-propylene-styrene. Block copolymer, styrene-butadiene rubber, acrylonitrile-butadiene rubber, pyridine-butadiene rubber, styrene-isoprene rubber, styrene-ethylene copolymer, styrene-butadiene-styrene block copolymer, styrene-isoprene-styrene block copolymer Polymer, poly (α-methylstyrene) -polybutadiene-poly (α-methylstyrene), poly (α-methylstyrene) -polyisoprene-poly (α-methylstyrene), ethylene-propylene copolymer, styrene-chloroprene rubber Etc. These may be used singly or as a mixture of two or more. From the viewpoint of raw material preparation and workability, styrene-ethylene-butylene-styrene block copolymer (SEBS), styrene-ethylene-propylene. It is preferably at least one selected from the group consisting of a styrene block copolymer (SEPS) and a styrene-ethylene-ethylene-propylene-styrene block copolymer (SEEPS).

  The thermoplastic styrenic elastomer A is preferably not acid-modified from the viewpoint of being readily available in large quantities and having various characteristics.

  The weight average molecular weight of the thermoplastic styrenic elastomer A is preferably 10,000 or more, more preferably 50,000 or more, further preferably 100,000 or more, and further preferably 200,000 or more from the viewpoint of heat resistance and mechanical properties. Further, from the viewpoint of ease of flow during heating, that is, from the viewpoint of moldability during production, 500,000 or less is preferable, 400,000 or less is more preferable, and 350,000 or less is more preferable. From these viewpoints, the weight average molecular weight of the hydrogenated thermoplastic styrenic elastomer A is preferably 10,000 to 500,000, more preferably 50,000 to 400,000, further preferably 100,000 to 350,000, and further preferably 200,000 to 350,000.

  Examples of the softening agent B include rubber softening agents such as paraffin oil, naphthene oil, and aromatic oil. Among these, the affinity with the hydrogenated thermoplastic elastomer is good, and bleeding occurs. From the viewpoint of difficulty, paraffin oil is preferable.

Kinematic viscosity at 40 ° C. of softening agent B is higher it is, to prevent volatilization during heating and melting, since even better bleeding resistance, preferably at least 10 mm ² / s, more preferably at least 20 mm ² / s, 25 mm ² / s or more is more preferable, and 30 mm ² / s or more is more preferable. Further, since the lower is easy to handle, preferably 1000 mm ² / s or less, more preferably less 700 mm ² / s, more preferably not more than 500 mm ² / s. From these viewpoints, kinematic viscosity at 40 ° C. of softening point B is preferably from 10 to 1000 mm ² / s, more preferably 25~700mm ² / s, more preferably 30~500mm ² / s.

  The mass ratio (A / B) of the thermoplastic styrenic elastomer A and the softening agent B in the composition of the present invention is such that the dispersibility of various blending components decreases if the softening agent content is too small. 5 or less, preferably 67/33 or less, more preferably 65/35 or less, and even more preferably 62.5 / 37.5 or less. Further, if the content of the softening agent is too large, oil bleeding occurs, leading to deterioration of physical properties and the like, so that it is 25/75 or more, and preferably 26/74 or more. From these viewpoints, the mass ratio (A / B) of the thermoplastic styrenic elastomer A and the softening agent B in the composition of the present invention is 25/75 to 95/5, preferably 25/75 to 67/33. 26/74 to 65/35, more preferably 26/74 to 62.5 / 37.5.

  The thermoplastic polyester elastomer C preferably includes a hard segment (hard portion) and a soft segment (soft portion), has an aromatic polyester block as a hard segment, and a polyester having an aliphatic polyether block as a soft segment -More preferably, it is a polyether block copolymer.

  The aromatic polyester block, which is a hard segment of the polyester-polyether block copolymer, is phthalic acid, terephthalic acid, isophthalic acid, 1,4- or 2,6-naphthalenedicarboxylic acid, 4,4′-diphenyldicarboxylic acid, One or more aromatic dicarboxylic acids such as 4,4'-diphenyl ether dicarboxylic acid, 4,4'-diphenylsulfone dicarboxylic acid or alkyl esters thereof, and ethylene glycol, propylene glycol, trimethylene glycol, tetramethylene glycol 1 of diols such as hexamethylene glycol, 1,4-cyclohexanediol, 1,4-cyclohexanedimethanol, 4,4'-dihydroxydibiphenyl, 2,2-bis (4'-β-hydroxyethoxydiphenyl) propane It is preferable that it is a polycondensate with a seed | species or 2 or more types. Commercially available products include, for example, “Perprene” (trade name, manufactured by Toyobo Co., Ltd.), “Hytrel” (trade name, manufactured by Toray DuPont Co., Ltd.), “Flexmer” (trade name, manufactured by Nippon Synthetic Chemical Industry Co., Ltd.). ) And the like.

  The aliphatic polyether block which is a soft segment of the polyester-polyether block copolymer is preferably mainly composed of polyalkylene ether glycol. The weight average molecular weight of the aliphatic polyether block is preferably 400 to 6000.

  Although it is known that the thermoplastic polyester elastomer C has various hardnesses, it is preferable that the thermoplastic polyester elastomer C has a relatively low hardness from the viewpoint of fusibility. From this viewpoint, the mass ratio of the hard segment to the soft segment (hard segment / soft segment) in the thermoplastic polyester elastomer C is 10/90 to 60/40, preferably 20/80 to 55/45, 30 / 70-50 / 50 is more preferable.

  The A hardness of the thermoplastic polyester elastomer C is preferably 50 to 98, more preferably 60 to 97, and still more preferably 70 to 94. In the present invention, A hardness is durometer type A hardness, and D hardness described later is durometer type D hardness.

  The greater the content of the thermoplastic polyester elastomer C, the better the fusion with the polar resin. Therefore, it is 75 parts by mass or more with respect to 100 parts by mass of the total amount of the styrene elastomer A and the softener B. The amount is preferably 80 parts by mass or more, more preferably 100 parts by mass or more. Further, since the smaller one is superior in flexibility, it is 1000 parts by mass or less, preferably 800 parts by mass or less, more preferably 500 parts by mass with respect to 100 parts by mass of the total amount of the styrene elastomer A and the softening agent B. It is as follows. From these viewpoints, the content of the thermoplastic polyester elastomer C is 75 to 1000 parts by mass, preferably 80 to 800 parts by mass with respect to 100 parts by mass of the total amount of the styrene elastomer A and the softener B. More preferably, it is 100-500 mass parts.

  The silicone-modified (meth) acrylic polymer D has a structure including at least one polysiloxane portion and at least one (meth) acrylic acid polymer portion. For example, (Acrylates / Ethylhexyl acrylate / (Methacrylate methacrylate) copolymer (trade name: KP578), wax type (acrylates / stearyl acrylate / dimethicone methacrylate) copolymer (trade name: KP561P), (acrylates / behenyl acrylate / methacrylate methacrylate) copolymer (KP562P), Those having various structures and properties such as Saimak of Toagosei Co., Ltd. and Charine of Nissin Chemical Industry Co., Ltd. are known.

  Among these, a polyalkylsiloxane having a radical polymerization reactive group, SH group or both in the side chain and a (co) polymer of (meth) acrylic acid ester and / or (meth) acrylic acid hydroxyalkyl ester are included. Polymerized block copolymers and / or graft copolymers are preferred. Such a copolymer is, for example, a polyalkylsiloxane having a radical polymerization reactive group, SH group or both in the side chain, and a (co) copolymer of (meth) acrylic acid ester and / or (meth) acrylic acid hydroxyalkyl ester. The polymer is obtained by graft polymerization in the presence of a known polymerization catalyst. In addition, when the polyalkylsiloxane part is produced, the number of starting points of the (meth) acrylic graft can be adjusted by appropriately adding a silane monomer having an unsaturated group, and the polysiloxane part is also a (meth) acrylic part. Also, it may be linear or branched. (Meth) acrylic acid ester and (meth) acrylic acid hydroxyalkyl ester may be used in combination, or only one of them may be used.

  Examples of the alkyl of the polyalkylsiloxane component include an alkyl group having 1 to 20 carbon atoms and an aromatic group. Among these, methyl, butyl and phenyl are preferable, and methyl is more preferable.

  More specifically preferred polyalkylsiloxanes include those of formula (I):

[Wherein R ¹ , R ² and R ³ are the same or different hydrocarbon groups or halogenated hydrocarbon groups having 1 to 20 carbon atoms, Y is an organic group having a radical polymerization reactive group, an SH group or both. , X ¹ and X ² are the same or different hydrogen atoms, lower alkyl groups having 1 to 20 carbon atoms, or formula (II):

(In the formula, R ⁴ and R ⁵ are the same or different, respectively, a hydrocarbon group or halogenated hydrocarbon group having 1 to 20 carbon atoms, R ⁶ is a hydrocarbon group or halogenated hydrocarbon group having 1 to 20 carbon atoms, It is an organic group having a radical polymerization reactive group, an SH group or both)
And m is an integer of 1 to 10,000, n is an integer of 1 or more, preferably 1 to 50]
The compound represented by these is mentioned.

  Examples of the radical polymerization reactive group include a vinyl group, an acryloyl group, a methacryloyl group, and an allyl group.

  In a copolymer of a polyalkylsiloxane having a radical polymerization reactive group, SH group or both in the side chain, and a (co) polymer of (meth) acrylic acid ester and / or (meth) acrylic acid hydroxyalkyl ester, The higher the ratio of the polysiloxane part, the better the slidability of the composition. On the other hand, the ratio of (co) polymer of (meth) acrylic acid ester and / or (meth) acrylic acid hydroxyalkyl ester Higher tends to improve the dispersibility in the composition. From these viewpoints, the polymerization ratio between the polyalkylsiloxane and the (co) polymer (polyalkylsiloxane / (co) polymer) is preferably 5/95 to 85/15 in terms of mass ratio, -80/20 is more preferable, and 20 / 80-75 / 25 is more preferable.

  In the (co) polymer of (meth) acrylic acid ester and / or (meth) acrylic acid hydroxyalkyl ester, either a methacrylic acid compound and an acrylic acid compound may be used in combination. It is preferable to use more because the heat resistance of the composition becomes higher. Examples of the ester component include alkyl esters having 1 to 20 carbon atoms such as methyl, ethyl, butyl, 2-ethylhexyl, isobutyl, hexyl, octyl, lauryl and stearyl, and alkoxyalkyls having 1 to 20 carbon atoms such as methoxyethyl and butoxyethyl. Examples include esters, cyclohexyl, phenyl, benzyl esters and the like. Examples of the hydroxyalkyl ester component include hydroxyethyl (meth) acrylate and hydroxypropyl (meth) acrylate. These ester components can be used alone or in combination of two or more.

  The higher the melting point of the silicone-modified (meth) acrylic polymer D, the higher the wear resistance tends to be, and it is preferably 50 ° C. or higher, more preferably 100 ° C. or higher. Further, when the composition is melt-kneaded, it is preferable that the silicone-modified (meth) acrylic polymer D is also melted and mixed more uniformly with the components of the composition, so that it is preferably 220 ° C. or less, more preferably 200 ° C. or less. is there. From these viewpoints, the melting point of the silicone-modified acrylic polymer B is preferably 50 to 220 ° C, more preferably 100 to 200 ° C.

  When the silicone-modified (meth) acrylic polymer D is solid at normal temperature (23 ° C.), it is preferably granular. The area-based average particle diameter of the primary particles is preferably 0.5 to 150 μm, more preferably 1 to 120 μm, further preferably 5 to 100 μm, and further preferably 30 to 70 μm. The shape of the primary particles can be directly observed by electron microscope observation, and at least 30 arbitrary particles are selected, the major axis and minor axis are measured, normalized to an ellipse, and the sectional area is calculated by calculating the cross-sectional area. The average particle size can be calculated. Such calculation can be easily performed from image data obtained by electron microscope observation by using an image processing program. When the silicone-modified (meth) acrylic polymer D has such a particle shape, it is easy to handle as a powder raw material, but when kneaded into the composition of the present invention, the dispersibility is good, so the composition It quickly disperses in the product and provides good slidability to the composition.

  Examples of such particulate silicone-modified acrylic polymer D include those known as Sharine R-170S and R-181S manufactured by Nissin Chemical Industry, and these can be used. What was manufactured by the method as described in 182987 gazette can also be used.

  The content of the silicone-modified (meth) acrylic polymer D is 1 to 35 parts by mass and more preferably 1.5 to 20 parts by mass with respect to 100 parts by mass of the thermoplastic polyester elastomer C.

  Along with the silicone-modified (meth) acrylic polymer D, other lubricants may be used in combination. Since the silicone-modified (meth) acrylic polymer D is compatible not only with the resin component but also with any organic silicone-based lubricant, problems such as bleeding and discoloration due to other lubricants can be suppressed. However, if there are too many other lubricants, the effect of the silicone-modified (meth) acrylic polymer D is reduced, so the amount used when other lubricants are used in combination is 100 parts by mass of the silicone-modified (meth) acrylic polymer D. Is preferably 100 parts by mass or less, and more preferably 5 to 60 parts by mass.

  The total content of thermoplastic styrenic elastomer A, softener B, thermoplastic polyester elastomer C and silicone-modified (meth) acrylic polymer D is preferably 50% by mass or more, and 60% by mass or more in the thermoplastic elastomer composition. Is more preferable, and 80% by mass or more is more preferable.

  The thermoplastic elastomer composition of the present invention may further contain a stabilizer. Various stabilizers for the resin composition are known. In the present invention, an antioxidant is preferable from the viewpoint of improving heat aging resistance, and a light stabilizer is preferable from the viewpoint of improving weather resistance. .

  As the antioxidant, a highly effective sulfur-based antioxidant E is preferable, and a thiopropionic acid ester-based antioxidant that is a divalent sulfur compound is more preferable. In particular, a linear structure such as dilauryl-3,3-thiodipropionate is more dispersible than a branched structure such as pentaerythrityl ester, and the composition can be added even in a small amount. It is preferable because it has a high antioxidant effect because it is uniformly dispersed.

  The content of the antioxidant, preferably the sulfur-based antioxidant E, is preferably 0.05 to 0.8 parts by mass with respect to 100 parts by mass of the thermoplastic polyester-based elastomer A from the viewpoint of significantly improving heat aging resistance, preferably 0.1 to 0.7 parts by mass is more preferable.

  As the light stabilizer, a highly effective hindered amine light stabilizer F is preferable. Examples of hindered amine light stabilizers include pentaerythrityl tetrakis (3-laurylthiodipropionate), bis (2,2,6,6, -tetramethyl-4-piperidinyl) ester, bis (2,2, 6,6, -tetramethyl-4-piperidyl) sebacate, 2- (3,5-di-t-butyl-4-hydroxybenzyl) -2-n-butylmalonate bis (1,2,2,6, 6-pentamethyl-4-piperidyl), dimethyl succinate 1- (2-hydroxyethyl) -4-hydroxy-2,2,6,6-tetramethylpiperidine polycondensate, poly [{6- (1,1 , 3,3-tetramethylbutyl) amino-1,3,5-triazine-2,4-diyl} {(2,2,6,6-tetonimethyl-4-piperidyl) imino} hexamethylene {(2,2 , 6,6-tetramethyl-4-piperidyl) imino}], N, N′-bis (3-aminopropyl) ethylenediamine · 2,4-bis [N-butyl-N- (1,2,2,6 , 6-Pentamethyl-4-piperidyl) amino] -6-chloro-1,3,5-triazine condensate, 2- (3,5- -t-Butyl-4-hydroxybenzyl) -2-n-butylmalonate bis (1,2,2,6,6-pentamethyl-4-piperidyl), poly [{6- (1,1,3,3 -Tetramethylbutyl) amino-1,3,5-triazine-2,4-diyl} {(2,2,6,6-tetonimethyl-4-piperidyl) imino} hexamethylene {(2,2,6,6 -Tetramethyl-4-piperidyl) imino}] and the like. Ultraviolet absorbers can also be used as light stabilizers.

  The content of the light stabilizer, preferably the hindered amine light stabilizer F, is preferably 0.05 to 0.8 parts by weight with respect to 100 parts by weight of the thermoplastic polyester elastomer A, from the viewpoint of significantly improving the weather resistance. -0.7 mass part is more preferable.

  The thermoplastic elastomer composition of the present invention may further contain a thickener G, a compatibilizer H, polyolefin I and the like. These may be used alone or in combination.

  By blending the thickener G, the viscosity of the thermoplastic polyester elastomer C is increased, and the raw materials are sufficiently mixed to improve transparency and moldability.

  As the thickener G, any one can be used as long as it has an effect of increasing the melt tension in the molding process of the thermoplastic resin. Among them, an epoxy thickener, an acrylic thickener, etc. Is preferred.

  The epoxy thickener is preferably an epoxy compound that is a polymer having a styrene structure in the skeleton.

  The higher the epoxy value of the epoxy compound, the higher the reactivity, so that it is preferably 0.10 meq / g or more, more preferably 0.50 meq / g or more. Further, it is preferably 5.0 meq / g or less, more preferably 3.0 meq / g or less because of easy production. From these viewpoints, the epoxy value of the epoxy compound is preferably 0.10 to 5.0 meq / g, and more preferably 0.5 to 3.0 meq / g.

  The epoxy compound is preferably composed of monomer units containing glycidyl (meth) acrylate and styrene and / or a styrene derivative.

  Glycidyl acrylate is very reactive with the terminal functional group of the polyester elastomer, and by blending an epoxy compound containing glycidyl (meth) acrylate in a predetermined amount or more, the thermoplastic polyester elastomer phase The viscosity ratio of the polyester elastomer phase and the styrene elastomer phase is reduced at the time of kneading, so that it can be dispersed more finely and mechanical strength such as wear can be improved. . From these viewpoints, the content of glycidyl (meth) acrylate is preferably 15 to 70% by mass, more preferably 17 to 60% by mass, and further preferably 20 to 50% by mass in the monomer unit. In addition, in this invention, content in a monomer unit means content of the said unit in all the monomer units which comprise the polymer.

  As the styrene derivative, the alpha, ortho, meta, or para position of styrene is substituted with a substituent such as a lower alkyl group having 1 to 4 carbon atoms, a lower alkoxy group having 1 to 4 carbon atoms, a carboxyl group, or a halogen atom. The compounds obtained are preferred. 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.

  The content of styrene and / or styrene derivative is preferably 20% by mass or more, and more preferably 30% by mass or more in the monomer unit.

  As the monomer units other than glycidyl (meth) acrylate, styrene, and styrene derivatives, (meth) acrylic monomers other than glycidyl (meth) acrylate are preferable because they are easily copolymerized and easily manufactured.

  (Meth) acrylic monomers include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, cyclohexyl (meth) acrylate, hydroxyethyl (meth) acrylate , Hydroxypropyl (meth) acrylate, methoxyethyl (meth) acrylate, ethoxyethyl (meth) acrylate, butoxyethyl (meth) acrylate, phenoxyethyl (meth) acrylate, and the like.

  The number of epoxy groups in the epoxy compound is preferably 2 or more on average per molecule, more preferably 2.5 to 20 and even more preferably 3 to 10 from the viewpoint of compatibility with the polyester elastomer.

  The weight average molecular weight of the epoxy compound is preferably 1,000 or more, more preferably 3,000 or more, and even more preferably 5,000 or more because larger ones can suppress volatilization at high temperatures. Moreover, since the lower one becomes more reactive, it is preferably 100,000 or less, more preferably 80,000 or less, and even more preferably 50,000 or less. From these viewpoints, the weight average molecular weight of the epoxy compound is preferably 1,000 to 100,000, more preferably 3,000 to 80,000, and further preferably 5,000 to 50,000.

  Examples of commercially available epoxy compounds include Alfon UG series manufactured by Toagosei Co., Ltd., Marproof G series manufactured by NOF Corporation, and Jonkrill ADR series manufactured by BASF.

  As acrylic thickeners, acrylic polymeric processing aids, acrylic-modified polytetrafluoroethylene, and the like are known. In the present invention, acrylic-modified polytetrafluoroethylene is preferred. Acrylic-modified polytetrafluoroethylene is thermoplastic because polytetrafluoroethylene, which has been improved in compatibility with thermoplastic resins by acrylic modification, is fibrillated by melt kneading to form a fibrous network. The moldability can be improved by increasing the melt viscosity of the resin composition.

  The content of the thickener G is preferably greater than 0.1 parts by weight, more preferably 0.5 parts by weight or more, and more preferably 1 part by weight with respect to 100 parts by weight of the thermoplastic polyester elastomer C because the higher the content, the better the wear resistance. Part or more is more preferable. Further, since the moldability is better when the amount is smaller, the amount is preferably 15 parts by mass or less, more preferably 10 parts by mass or less, and further preferably 3 parts by mass or less with respect to 100 parts by mass of the thermoplastic polyester elastomer C. From these viewpoints, the content of the thickener G is preferably 0.1 to 15 parts by mass with respect to 100 parts by mass of the thermoplastic polyester elastomer C from the viewpoint of the balance between wear resistance and moldability. Mass parts are more preferred, and 1-3 mass parts are even more preferred.

  The compatibilizing agent H is preferable from the viewpoint of fusibility.

  As the compatibilizing agent H, since it has excellent wear resistance and fusion property, it is an acid-modified hydrogenated thermoplastic styrene elastomer H1, an acid-modified olefin thermoplastic elastomer H2, and a graft polymer of a styrene elastomer and a urethane elastomer. At least one elastomer selected from the group consisting of H3 is preferred.

  The acid-modified hydrogenated thermoplastic styrene elastomer H1 is a block copolymer composed of a polymer block unit (s2) composed of a styrene monomer and a polymer block unit (b2) composed of a conjugated diene compound. The hydrogenated product of (Z2) is preferably acid-modified.

  Styrene monomers constituting the block unit (s2) include styrene, o-methylstyrene, p-methylstyrene, p-tert-butylstyrene, 1,3-dimethylstyrene, α-methylstyrene, vinylnaphthalene, And vinyl anthracene.

  Examples of the conjugated diene compound constituting the block unit (b2) include butadiene, isoprene, 1,3-pentadiene and the like.

  The block copolymer (Z2) consists of a hard segment (hard portion) composed of block units (s2) and a soft segment (soft portion) composed of block units (b2), from the viewpoint of determining the overall physical properties. The content of the styrene monomer in the block copolymer (Z2) is preferably 5 to 70% by mass, more preferably 10 to 60% by mass, and still more preferably 20 to 50% by mass.

  The block copolymer (Z2) may be partially or wholly hydrogenated, but by adding hydrogen, unsaturated bonds are reduced, and heat resistance, weather resistance and mechanical properties are obtained. It is done. From these viewpoints, the hydrogenation rate is preferably 80% or more, and more preferably 90% or more.

  Specific examples of the hydrogenated block copolymer (Z2) include styrene-ethylene-butylene-styrene block copolymer, styrene-ethylene-propylene-styrene block copolymer, styrene-ethylene-ethylene-propylene-styrene. Block copolymer, styrene-ethylene-butylene (styrene controlled distribution) -styrene block copolymer, styrene-isobutylene-styrene block copolymer, styrene-butadiene rubber, acrylonitrile-butadiene rubber, pyridine-butadiene rubber, styrene-isoprene Rubber, styrene-ethylene copolymer, styrene-butadiene-styrene block copolymer, styrene-isoprene-styrene block copolymer, poly (α-methylstyrene) -polybutadiene-poly (α-methylstyrene), poly (α -Methyl Styrene) -polyisoprene-poly (α-methylstyrene), ethylene-propylene copolymer, styrene-chloroprene rubber and the like. These may be used singly or as a mixture of two or more. From the viewpoint of raw material preparation and workability, styrene-ethylene-butylene-styrene block copolymer (SEBS), styrene-ethylene-propylene. -Styrene block copolymer (SEPS), Styrene-ethylene-ethylene-propylene-styrene block copolymer (SEEPS), Styrene-ethylene-butylene (styrene control distribution) -Styrene block copolymer (SEB (S) S) And at least one selected from the group consisting of a styrene-isobutylene-styrene block copolymer (SIBS).

  The acid modification of the hydrogenated product of the block copolymer (Z2) is not particularly limited, but can be performed, for example, by introducing a carboxyl group or an acid anhydride group into the hydrogenated product. The introduction of the carboxyl group or acid anhydride group can be performed according to a method known per se. Specifically, for example, hydrogenated products and unsaturated monocarboxylic acids exemplified by acrylic acid, methacrylic acid, etc .; unsaturated dicarboxylic acids exemplified by maleic acid, fumaric acid, hymic acid, itaconic acid, etc .; An unsaturated dicarboxylic acid anhydride exemplified by maleic acid, hymic anhydride, itaconic anhydride, etc. is heated in the presence of an organic peroxide in the presence or absence of a solvent to cause a graft reaction. Can be obtained. It can also be obtained commercially.

  The acid-modified amount of the acid-modified hydrogenated thermoplastic styrenic elastomer H1 is preferably 0.5 to 5% by mass, more preferably 0.7 to 4.0% by mass, and further preferably 1.0 to 3.0% by mass from the viewpoints of compatibility and workability. .

  The weight average molecular weight of the acid-modified hydrogenated thermoplastic styrene elastomer H1 is preferably 50,000 or more from the viewpoint of heat resistance, and is preferably 400,000 or less from the viewpoint of fluidity of the melt and rubber elasticity. From these viewpoints, the weight average molecular weight of the acid-modified hydrogenated thermoplastic styrenic elastomer H1 is preferably 50,000 to 400,000, more preferably 70,000 to 350,000, and further preferably 80,000 to 300,000. Only one type of acid-modified hydrogenated thermoplastic styrene elastomer H1 may be used, or two or more types different in weight average molecular weight, 1,2-vinyl bond amount, and the like may be used in combination. When two or more kinds are used in combination, the weighted average value is preferably within the above range, and more preferably within the above range.

  Examples of the acid-modified olefin-based thermoplastic elastomer H2 include ethylene-propylene copolymers, α-olefin copolymer elastomers such as ethylene, propylene, 1-butene, 1-pentene, 1-hexene and 1-octene, Examples thereof include copolymer elastomers with conjugated dienes, mixtures of two or more of these, and at least some of these are acid-modified. Among these, an acid-modified product of ethylene-α-olefin copolymer and an acid-modified product of propylene-α-olefin copolymer are preferable.

  The acid modification treatment can be performed in the same manner as the acid-modified hydrogenated thermoplastic styrene elastomer H1.

  The acid-modified amount of the acid-modified olefin-based thermoplastic elastomer H2 is preferably 0.5 to 5% by mass and more preferably 0.7 to 4.0% by mass from the viewpoints of compatibility and workability.

  The A hardness of the acid-modified olefinic thermoplastic elastomer H2 is preferably 95 or less, more preferably 10 to 90, and still more preferably 20 to 90.

  As the graft polymer H3 of styrene elastomer and urethane elastomer, even if it is a diblock copolymer having one styrene elastomer block and one polyurethane elastomer block, the total of styrene elastomer and polyurethane elastomer block is 3 or 4 or more linked polyblock copolymers may be used, but from the standpoint of excellent heat resistance and no foul odor when heated and melted, 1 styrene elastomer and 1 polyurethane elastomer block are combined. Diblock copolymers made are preferred. Examples of commercially available products include Kuramylon (registered trademark) TU polymer manufactured by Kuraray Co., Ltd.

  The content of the compatibilizing agent H is 200 parts by mass or less with respect to 100 parts by mass of the total amount of the styrenic elastomer A and the softening agent B from the viewpoint of improving the wear resistance and the fusing property to other materials. The amount is preferably 100 parts by mass or less, and more preferably 1 to 60 parts by mass.

  Polyolefin I is preferable from the viewpoint of moldability.

  Examples of the polyolefin I include polyethylene, polypropylene, and ethylene-propylene copolymer.

  The polyolefin may be acid-modified. Examples of acids used for modification include maleic acid, halogenated maleic acid, itaconic acid, cis-4-cyclohexene-1,2-dicarboxylic acid, endo-cisbicyclo (2,2,1) -5-heptene-2,3 -Dicarboxylic acids such as dicarboxylic acids and anhydrides, esters, amides, imides, etc. of dicarboxylic acids, monocarboxylic acids such as acrylic acid, methacrylic acid, crotonic acid, and esters, amides of the monocarboxylic acids.

  The content of polyolefin I is preferably less than 50 parts by mass and more preferably 40 parts by mass or less with respect to 100 parts by mass of the total amount of styrene elastomer A and softener B, since the smaller the content of polyolefin I, the better the flexibility. Preferably, it is 30 parts by mass or less.

  The thermoplastic elastomer composition of the present invention may contain other thermoplastic resins and thermoplastic elastomers as long as the effects of the present invention are not impaired.

  The thermoplastic elastomer composition of the present invention may contain a polar elastomer for the purpose of modifying the polar resin. The polar elastomer is not particularly limited, and examples thereof include NBR (nitrile rubber), polyurethane rubber, epichlorohydrin rubber, polyurethane-based thermoplastic elastomer, polyamide-based thermoplastic elastomer, and the like.

  The thermoplastic elastomer composition of the present invention is, as necessary, a reinforcing agent such as carbon black, silica, carbon fiber, glass fiber, etc. within a range not impairing the effects of the present invention; calcium carbonate, talc, clay, titanium oxide, Fillers such as mica; contains various additives such as insulating heat conductive fillers, pigments, flame retardants, antistatic agents, mold release agents, tackifiers, crosslinking agents, crosslinking aids, foaming agents, fragrances, etc. May be.

  The thermoplastic elastomer composition of the present invention comprises a thermoplastic styrenic elastomer A, a softening agent B, a thermoplastic polyester elastomer C and a silicone-modified (meth) acrylic polymer D, and if necessary, a sulfur-based antioxidant E, It is obtained by mixing raw materials containing a hindered light stabilizer F, a thickener G, a compatibilizer H, polyolefin I and the like and solidifying by cooling.

  “Mixing” as used in the present invention is not particularly limited as long as various components are mixed well, and various components may be dissolved and mixed in a soluble organic solvent, or by melt kneading. However, when an epoxy compound is used as the thickener G, it is preferable to react at least a part of the thermoplastic polyester elastomer C and the epoxy compound. It is preferable to carry out under the condition that the polyester elastomer C melts, and the molecular weight of the thermoplastic polyester elastomer C increases and the viscosity increases due to the reaction with the terminal functional group of the thermoplastic polyester elastomer C. Even when a thickener other than an epoxy compound is used, a thickening effect is exhibited by kneading at the melting temperature of the thermoplastic polyester elastomer C. Therefore, it is preferable to continue kneading at the melting temperature of the raw material until the viscosity increases. By increasing the viscosity, pressure is easily applied even when the composition is used for heat fusion, and the fusion strength is increased. In addition, the problem of sink marks at the time of molding is improved. Therefore, the thermoplastic elastomer composition of the present invention is preferably composed of a reaction product obtained by mixing raw materials constituting the composition under conditions where the thermoplastic polyester elastomer C melts.

  The conditions under which the thermoplastic polyester elastomer C melts can be defined based on, for example, the melting point of the thermoplastic polyester elastomer C that can be determined by viscoelasticity measurement. Although it is a condition, in the melt-kneading method, it is not necessarily the melting point measured in a stationary state, it may melt at a temperature lower than the melting point, and the higher the temperature, the smaller the melt viscosity becomes, and the easier it is to mix. If it is too high, thermal decomposition may occur. From these viewpoints, the preferred melting temperature range when kneading is -30 ° C to + 100 ° C with respect to the melting point, more preferably -20 ° C to + 50 ° C with respect to the melting point.

  When melt-kneading, a general extruder can be used, and it is preferable to use a twin-screw extruder for improving the kneading state. Supply to the extruder may be made by mixing various components in advance using a mixing device such as a Henschel mixer from one hopper, or each component is charged into two hoppers and fixed with a screw under the hopper. You may offer while.

  The product obtained by mixing the raw materials constituting the thermoplastic elastomer composition can be in the form of pellets, powders, sheets, etc., depending on the application. For example, it is melt-kneaded by an extruder, extruded into strands, and cut into pellets such as cylindrical or rice grains by a cutter while cooling in cold water. The obtained pellets are usually formed into a predetermined sheet-like molded product or a molded product by injection molding or extrusion molding. Further, the melt-kneaded product can be formed into pellets with a ruder or the like and used as a forming raw material. It is good also as an intermediate product which stuck the mount etc. to the sheet-like thermoplastic elastomer composition.

  The A hardness of the thermoplastic elastomer composition of the present invention is preferably 10 to 90, more preferably 20 or more, and further preferably 40 or more, from the viewpoint of flexibility. The D hardness is preferably 60 or less, more preferably 10 to 50, and even more preferably 15 to 40.

  The melt mass flow rate at 230 ° C. and 21.2 N of the thermoplastic elastomer composition of the present invention is preferably 0.1 to 40 g / 10 min, more preferably 0.1 to 30 g / 10 min, and more preferably 1.0 to 20 g from the viewpoint of adhesiveness and fluidity. / 10 min is more preferable.

  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.

  The apparatus used for manufacturing a molded body using the thermoplastic elastomer composition of the present invention can be any molding machine capable of melting a molding material. 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 thermoplastic elastomer composition of the present invention can also be used as a composite molding material and can be suitably used for bonding members made of different materials because it is welded to various materials. For example, it is used for welding to at least one member selected from the group consisting of metals, ceramics, glass, olefin resins and polar resins, and particularly exhibits good adhesion to polar resins and the like.

  The metal is not particularly limited, and examples thereof include aluminum, aluminum alloy, stainless steel, iron, copper, galvanized steel, magnesium, magnesium alloy, and various plated products.

  Examples of the olefin resin include polypropylene resin, polyethylene resin, polybutene resin, polymethylpentene resin, cyclic olefin resin, and ethylene-cyclic olefin copolymer resin, and even those that are melt-kneaded are mixed in the polymerization machine. Reactor type thermoplastic olefin (TPO) may also be used. The olefinic thermoplastic elastomer may be dynamically crosslinked.

  Examples of polar resins include polycarbonate, polyester resins, poly (meth) acrylate resins such as polymethyl methacrylate, polyethylene oxide resins, polypropylene oxide resins, polyvinyl acetate resins, polyamide resins, polyurethane resins, Polystyrene resins such as ABS resin, polyvinyl ether resins, polyvinyl alcohol resins, polyphenylene ether resins, polyphenylene sulfide resins, polysulfone resins, polyether imide resins, polyether ketone resins, polyether ether ketone resins, LCP (liquid crystal polymers ), Polar resins such as ionomers, and mixtures of two or more thereof.

  When the thermoplastic elastomer composition of the present invention is welded to at least one member selected from the group consisting of metals, ceramics, glass, olefin resins, and polar resins, the peel strength from the members is the adhesive property. From the viewpoint, 90 N / 25 mm or more is preferable.

  In the present invention, welding is a phenomenon in which heat is applied at a temperature equal to or higher than the melting point of the thermoplastic elastomer composition of the present invention to form a melt, and then solidified at a temperature equal to or lower than the melting point, thereby fixing to the interface to be welded. Say. In order to apply heat, a hot press machine, a heated roll machine, a hot air generator, heated steam, an ultrasonic welder, a high frequency welder, a laser, or the like can be used. Therefore, even if the interface of the welded portion has a complicated three-dimensional shape, it can be well blended and integrated into the complicated three-dimensional shape.

  Therefore, the thermoplastic elastomer composition of the present invention can be integrated not only with members but also into a composite molded body. Accordingly, it is possible to bond a member having a complicated joint surface or a member having joint surfaces having different shapes.

  The composite molded body in which the thermoplastic elastomer composition of the present invention is welded to a member is injection molding, injection compression molding, insert molding, multicolor molding, vacuum molding, pressure molding, blow molding, hot press molding, foam molding, laser welding. The thermoplastic elastomer composition of the present invention is not tacky like an adhesive and is easy to handle, although it can be obtained by molding by a method such as molding or extrusion molding. It can also be applied to injection molding.

  The composite molded body in which the thermoplastic elastomer composition of the present invention is welded to the member is at least one selected from the group consisting of metals, ceramics, glass, olefin resins, and polar resins in the molded body composed of the thermoplastic elastomer composition. An insert molded body in which the above member is inserted, a thermoplastic elastomer composition, and a composite molded body obtained by multicolor molding of at least one member selected from the group consisting of an olefin resin or a polar resin. .

  EXAMPLES The present invention will be specifically described below with reference to examples, but the present invention is not limited to these examples. Various physical properties of the raw materials used in Examples and Comparative Examples were measured by the following methods.

1. Thermoplastic styrene elastomer A
[Styrene monomer content]
Measurement is performed using a nuclear magnetic resonance apparatus (manufactured by BRUKER, Germany, DPX-400).

(Weight average molecular weight (Mw))
Under the following measurement conditions, the molecular weight is measured in terms of polystyrene by gel permeation chromatography, and the weight average molecular weight is determined.

Measuring device and pump: JASCO (JASCO Corporation), PU-980
・ Column oven: Showa Denko KK, AO-50
・ Detector: Hitachi, RI (differential refractometer) detector L-3300
・ Column type: Showa Denko Co., Ltd. “K-805L (8.0 × 300mm)” and “K-804L (8.0 × 300mm)” each used in series ・ Column temperature: 40 ℃
・ Guard column: KG (4.6 × 10mm)
・ Eluent: Chloroform ・ Eluent flow rate: 1.0 ml / min ・ Sample concentration: Approximately 1 mg / ml
・ Sample solution filtration: 0.45μm pore size disposable filter made of polytetrafluoroethylene ・ Standard sample for calibration curve: Polystyrene made by Showa Denko KK

2. Softener B
(Kinematic viscosity)
Measured at a temperature of 40 ° C. according to JIS Z 8803.

3. Thermoplastic polyester elastomer C
(Weight average molecular weight of aliphatic polyether block (Mw))
Similarly to the thermoplastic styrenic elastomer A, the molecular weight is measured in terms of polystyrene by gel permeation chromatography, and the weight average molecular weight is obtained.

[Hard segment / Soft segment (mass ratio)]
The mass ratio of the hard segment to the soft segment was measured by proton NMR measurement at 25 ° C in a 3-5 vol% concentration in deuterated chloroform solvent using a nuclear magnetic resonance apparatus (manufactured by BRUKER, Germany, DPX-400). It calculates from the signal intensity ratio of the methylene peak adjacent to various oxygen in the structure.

[A hardness]
Measure according to the method specified in JIS K 6253.

[Melting point]
Using a differential scanning calorimetry (DSC) apparatus, the melting peak temperature obtained by raising the temperature at 10 ° C./min according to the method specified in JIS K 7121 is defined as the melting point. When a plurality of melting peaks appear, the melting peak appearing at a lower temperature is taken as the melting point.

4). Silicone-modified (meth) acrylic polymer D
[Average particle size]
Measurement is performed using a scanning electron microscope (SEM) apparatus.
The shape of the primary particles can be directly observed by scanning electron microscope observation. Select 30 arbitrary particles, measure the major axis and minor axis, normalize to ellipse, and calculate the cross-sectional area to calculate the area standard The average particle diameter is calculated.

Measuring device / SEM: VE-8800 (manufactured by KEYENCE)
・ Acceleration voltage: 1.3kV

[Melting point]
Using a differential scanning calorimetry (DSC) apparatus, the melting peak temperature obtained by raising the temperature at 10 ° C./min according to the method specified in JIS K 7121 is defined as the melting point. When a plurality of melting peaks appear, the melting peak appearing at a lower temperature is taken as the melting point.

5. Thickener G
[Epoxy value]
Epoxy value means the number of moles of epoxy group contained in 100 g of resin, and the epoxy equivalent measured by the method of JIS K 7236 is defined as the mass of resin containing 1 equivalent of epoxy group, Calculated as epoxy value (meq / g) = 1000 / epoxy equivalent.

[Average number of epoxy groups contained per molecule of epoxy compound (Fn)]
The number average molecular weight of one molecule is multiplied by the monomer composition, and GMA is calculated as one epoxy group.

(Content of glycidyl acrylate (GMA))
When the epoxy compound does not contain a compound having an epoxy group other than GMA, the content of GMA is calculated from the concentration of the epoxy group measured by the method specified in JIS K 7236, similarly to the epoxy value. When a compound having an epoxy group is included in addition to GMA, proton NMR measurement is performed with a nuclear magnetic resonance apparatus (manufactured by BRUKER, Germany, DPX-400), and the content of GMA is determined by quantifying the characteristic group of GMA. Determine the amount.

[Content of styrene and / or styrene derivative (styrene monomer)]
Proton NMR measurement is performed with a nuclear magnetic resonance apparatus (manufactured by BRUKER, Germany, DPX-400), and the content of styrene and / or styrene derivatives is determined by quantifying the characteristic groups of styrene.

(Weight average molecular weight (Mw) and number average molecular weight (Mn))
Similarly to the thermoplastic styrene-based elastomer A, the molecular weight is measured in terms of polystyrene by gel permeation chromatography, and the weight average molecular weight and number average molecular weight are determined.

6). Compatibilizer H
[Styrene monomer content]
Measurement is performed using a nuclear magnetic resonance apparatus (manufactured by BRUKER, Germany, DPX-400).

(Weight average molecular weight (Mw))
Under the following measurement conditions, the molecular weight is measured in terms of polystyrene by gel permeation chromatography, and the weight average molecular weight is determined.

Measuring device and pump: JASCO (JASCO Corporation), PU-980
・ Column oven: Showa Denko KK, AO-50
・ Detector: Hitachi, RI (differential refractometer) detector L-3300
・ Column type: Showa Denko Co., Ltd. “K-805L (8.0 × 300mm)” and “K-804L (8.0 × 300mm)” each used in series ・ Column temperature: 40 ℃
・ Guard column: KG (4.6 × 10mm)
・ Eluent: Chloroform ・ Eluent flow rate: 1.0 ml / min ・ Sample concentration: Approximately 1 mg / ml
・ Sample solution filtration: 0.45μm pore size disposable filter made of polytetrafluoroethylene ・ Standard sample for calibration curve: Polystyrene made by Showa Denko KK

[A hardness]
Measure according to the method specified in JIS K 6253.

[Amount of acid modification]
Press the blend of the base material and organic acid before modification with a 0.1 mm spacer and measure IR, then the calibration curve from the characteristic carbonyl (1600-1900 cm ^-1 ) absorption and organic acid charge Then, IR measurement (IR measuring instrument: FT-210 manufactured by Horiba, Ltd.) is performed on the acid-modified press plate, and the amount of modification is determined.

Production Example of Silicone Modified (Meth) acrylic Polymer A 98 parts by mass of methyl acrylate, 2 parts by mass of 2-hydroxyethyl methacrylate and formula (III):

A mixture of 233 parts by mass of a polyalkylsiloxane represented by formula (1) with a radically reactive surfactant (Aqualon HS-10 and RN-20 (both manufactured by Daiichi Kogyo Seiyaku Co., Ltd.)) at 1/3 mass ratio (HS- 10 / RN-20) and emulsified in 4 parts by mass in 50 parts by mass of deionized water. 1/30 of the obtained emulsion was collected, and in a nitrogen atmosphere at 60 ° C., 100 parts by mass of deionized water and a t-butyl hydroperoxide polymerization initiator (t-butyl hydroperoxide (pure content 70 30 mass parts) 0.3 parts by mass), 0.17 parts by mass of Rongalite, 0.3 parts by mass of a 1% by mass aqueous solution of disodium ethylenediaminetetraacetate, and 0.1 parts by mass of a 1% by mass aqueous solution of ferrous sulfate) After a minute, the remaining emulsion was dropped and polymerized over 3 hours while maintaining the internal temperature at 80 ° C., and further aged for 1 hour to complete the reaction. The obtained emulsion was dried by a spray drying method to obtain a powdery silicone-modified (meth) acrylic polymer A. The average primary particle size was 50 μm and the melting point was 120 ° C.

Production Example of Silicone Modified (Meth) Acrylic Polymer B 98 parts by mass of methyl acrylate, 2 parts by mass of 2-hydroxyethyl methacrylate and 100 parts by mass of polyalkylsiloxane represented by the formula (III) were converted into silicone modified (meth) acrylic polymer A. Emulsion polymerization was carried out in the same manner as in the above production example, followed by drying by a spray drying method to obtain a powdery silicone-modified (meth) acrylic polymer B. The average primary particle size was 55 μm and the melting point was 125 ° C.

Production Example of Epoxy Compound A The oil jacket temperature of a 1 liter pressurized stirred tank reactor equipped with an oil jacket was kept at 200 ° C.
On the other hand, a monomer mixture consisting of 38 parts by mass of styrene (St), 8 parts by mass of butyl acrylate (BA), 25 parts by mass of glycidyl methacrylate (GMA) and 29 parts by mass of methyl methacrylate (MMA) Part by mass and 0.3 part by mass of ditertiary butyl peroxide were mixed and charged into a raw material tank. The monomer mixture is continuously fed from the raw material tank to the reactor at a constant feed rate (48 g / min, average residence time in the reactor: 12 minutes), so that the mass of the reactor content is constant at approximately 580 g. The reaction solution was continuously withdrawn from the outlet of the reactor. 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 was recovered. About 7 kg of copolymer (epoxy compound A) was recovered over 180 minutes.
Table 1 shows the number average molecular weight (Mn) and weight average molecular weight (Mw) of the epoxy compound A, and the average number (Fn) of epoxy groups contained per molecule of the epoxy compound.

Production Example of Epoxy Compound B An epoxy compound was prepared in the same manner as Epoxy Compound B except that a monomer mixture having the composition shown in Table 1 was used and the amount of ditertiary butyl peroxide was changed to 0.5 parts by mass. B was obtained.

Examples 1-29 and Comparative Examples 1-9
(1) Preparation of thermoplastic elastomer composition (pellet) The materials shown in Tables 2 to 5 other than paraffin oil were dry blended and impregnated with paraffin oil to prepare a mixture. Thereafter, the mixture was melt-kneaded with an extruder under the following conditions, extruded into strands, cooled to about 3 mm in diameter and about 3 mm in thickness with a cutter while cooled in cold water, and pellets of the thermoplastic elastomer composition were formed. Manufactured.

[Melting and kneading conditions]
Extruder: KZW32TW-60MG-NH (trade name, manufactured by Technobel Co., Ltd.)
Cylinder temperature: 180 ~ 220 ℃
Screw rotation speed: 300r / min

  The detail of the raw material of Tables 2-5 used by the Example and the comparative example is as follows.

[Thermoplastic styrenic elastomer]
SEBS-A: G1651 (manufactured by Kraton Polymer Co., Ltd.), styrene monomer content 33% by mass, Mw 290,000
SEBS-B: G1641 (manufactured by Kraton Polymer Co., Ltd.), styrene monomer content 32% by mass, Mw 240,000
SEEPS: SEPTON4055 (manufactured by Kuraray Co., Ltd.), styrene monomer content 30% by mass, Mw 300,000

[Softener]
Paraffin oil: PW90 (made by Idemitsu Kosan Co., Ltd.), kinematic viscosity (40 ° C) 95.54mm ² / s

[Thermoplastic polyester-based elastomer]
TPEE-A (polyester polyether block copolymer): tetramethylene glycol / polybutylene glycol / terephthalic acid polycondensate, hard segment / soft segment (mass ratio) = 19/81, A hardness 78, melting point 160 ° C.
TPEE-B (polyester polyether block copolymer): terephthalic acid / isophthalic acid / tetramethylene glycol / polytetramethylene glycol copolymer, hard segment / soft segment (mass ratio) = 39/61, A hardness 91, melting point 155 ° C.

[Lubricant]
Silicone-modified (meth) acrylic polymer A: synthetic, average particle size 50 μm, melting point 120 ° C.
Silicone-modified (meth) acrylic polymer B: synthetic, average particle size 55 μm, melting point 125 ° C.
Oleic acid amide: Neutron (Nippon Seika Co., Ltd.)
Silicone oil: SH200 oil (manufactured by Toray Dow Corning), kinematic viscosity (25 ° C) 500mm ² / s
Acrylic external lubricant: Metablen L-1000 (Mitsubishi Rayon)

〔Antioxidant〕
Sulfur-based antioxidant A: SUMILIZER TPL-R (manufactured by Sumitomo Chemical), dilauryl-3,3-thiodipropionate, Mw: 515
Sulfur-based antioxidant B: SUMILIZER TP-D (manufactured by Sumitomo Chemical), pentaerythrityl tetrakis (3-laurylthiodipropionate), Mw: 1162
Phenol antioxidant: irgnox1010 (BASF)

(Light stabilizer)
Hindered amine light stabilizer: Tinuvin 144 (BASF)
UV absorber: Tinuvin 326 FL (manufactured by BASF)

[Thickener]
Epoxy compound A: synthetic product, epoxy value 1.8 meq / g, St-MMA-GMA copolymer, GMA content 25% by mass, styrene monomer content 38% by mass, Fn5.1, Mw10,800
Epoxy compound B: composite, epoxy value 1.4 meq / g, St-GMA copolymer, GMA content 20% by mass, styrene monomer content 74% by mass, Fn4.5, Mw9800
Epoxy compound C: Marproof G-0250SP (manufactured by NOF Corporation), epoxy value 0.32meq / g, St-GMA copolymer, GMA content 50 mass%, styrene monomer content 50 mass%, Mw20,000 Acrylic modified polytetrafluoroethylene (PTFE): Methabrene A3000 (Mitsubishi Rayon Co., Ltd.)

[Compatibilizer]
Acid-modified SEBS: FG1901X (manufactured by Kraton Polymer), maleic anhydride-modified SEBS, styrene monomer content 30% by mass, A hardness 71, maleic anhydride content 1.7% by mass
Acid-modified ethylene-α-olefin copolymer: Amplify GR216 (manufactured by Dow Chemical Company), maleic anhydride-modified ethylene-α-olefin copolymer, A hardness 77, maleic anhydride content 0.5-1.0 mass%

[Polyolefin]
PP (polypropylene): PX600N (manufactured by Sun Allomer), flexural modulus of 1650 MPa
Acid-modified PP: Yumex 1010 (manufactured by Sanyo Chemical Industries), maleic acid-modified, Mw 30,000, acid value 52

(2) Production of molded body of thermoplastic elastomer composition The pellets were injection molded under the following conditions to produce a plate 2 mm thick x 125 mm wide x 125 mm long.

[Injection molding conditions]
Injection molding machine: 100MSIII-10E (trade name, manufactured by Mitsubishi Heavy Industries, Ltd.)
Injection molding temperature: 200 ℃
Injection pressure: 30%
Injection time: 3sec
Mold temperature: 40 ℃

  The following evaluation was performed about the composition obtained by the Example and the comparative example. The results are shown in Tables 2-5.

(1) Flexibility Measure A hardness (value after 1 second from the start of the test) according to JIS K 6253 for a sample of 3 mm-thick molded body samples with a thickness of 2 mm (total 6 mm). did. The measurement was carried out after conditioning for one day in a room at a temperature of 23 ° C. and a humidity of 50%.

(2) Fusing property The following polar resin is inserted into a 4 mm thick x 25 mm wide x 125 mm long mold, and the thermoplastic elastomer compositions obtained in the examples and comparative examples are injection molded under the following conditions. Then, a strip-shaped welding test piece was prepared.

[Insert material (polar resin)]
(1) Size: 2mm thick x 25mm wide x 120mm long
(2) Type
PC (polycarbonate): Iupilon H-3000 manufactured by Mitsubishi Engineering Plastics

[Injection molding conditions]
Injection molding machine: 100MSIII-10E, manufactured by Mitsubishi Heavy Industries, Ltd.
Injection molding temperature: 240 ℃
Injection pressure: 30%
Injection time: 2sec
Mold temperature: 40 ℃

  Using the above-mentioned welding test piece by a method compliant with JIS K 6854, a tensile test is performed at a temperature of 23 ° C with a thermoplastic elastomer layer and a polar resin layer at a rate of 50 mm / min in the 180 ° direction, and the skin material layer and the substrate The peel strength (unit: N / 25 mm) of the layer was measured.

◎: Peel strength 150N / 25mm or more ○: Peel strength 90N / 25mm or more, less than 150N / 25mm △: Peel strength 50N / 25mm or more, less than 90N / 25mm ×: Peel strength less than 50N / 25mm

(3) Abrasion resistance (Taber abrasion test)
Using injection-molded plate (125mm square plate), JIS K 7204, 23 ° C, wear wheel: H-22, rotation speed: 72r / min, number of rotations: 1,000 times, load: 1000g, wear loss (1000g mg).

○: Wear loss is less than 100 mg ×: Wear loss is 100 mg or more

(4) Sliding property
The coefficient of static friction was measured by a method based on JIS K-7125.
-Specimen: An injection molded sample with a thickness of 2 mm, cut to a width of 80 mm and a length of 125 mm.
・ N number: 3
・ Measuring device: Friction tester (Toyo Seiki Seisakusho)
〔Measurement condition〕
・ Test speed: 100mm / min, load range: 10N, thread weight: 200N (initial load 0.4 to 0.5N)
・ Displacement: 60mm
・ Material: Felt [Measuring method]
-In advance, measure E-D27N as a blank at the start of the test and confirm that the coefficient of dynamic friction is in the range of 0.85 to 1.10.
-Double-sided tape was applied to the upper and lower ends of the test piece, the test piece was attached to a metal plate, the test piece was fixed so that it did not move, and the static friction coefficient was measured under the above conditions.

(5) Melt mass flow rate (MFR)
According to ASTM D1238, the measurement was performed at 230 ° C. and 21.2 N.

(6) Formability Formability was evaluated with respect to sink marks, flow marks, and mold releasability problems when preparing test pieces for heat-fusibility with polar resins by injection molding.

◎: No molding defects and good releasability ○: No molding defects but slightly poor mold release △: Some defects in moldability ×: Problems in moldability

(7) Bloom resistance After leaving the injection-molded plate (125mm square plate) in a 40 ° C and 80% relative humidity environment for one week, lightly wipe the sheet surface with black paper with a load of 3N (about 300g). The presence or absence of deposits such as rubbing, powder blowing and oil on the sheet surface was visually observed.

(8-1) Contrast Test Tensile No. 3 dumbbell-shaped test pieces (thickness 2 mm) were left in a 63 ° C. gear oven without light irradiation for 500 hours. The tensile strength before and after standing was measured by a method based on JIS K 6257, and the tensile strength retention was calculated by the following formula.

(8-2) Heat Aging Resistance A tensile No. 3 dumbbell-shaped test piece (thickness 2 mm) was left in a gear oven at 130 ° C. for 500 hours. The tensile strength before and after standing was measured by a method based on JIS K 6257, and the tensile strength retention was calculated by the same formula as the comparison test.

(8-3) Weather resistance A tensile No. 3 dumbbell-shaped test piece (thickness 2 mm) was allowed to stand at 63 ° C. for 500 hours under light irradiation. The tensile strength before and after standing was measured by a method based on JIS K 6257, and the tensile strength retention was calculated by the same formula as the comparison test.

From the above results, the thermoplastic elastomer compositions of Examples 1 to 29 are flexible, fusion with polar resins, slidability, wear resistance, moldability, as compared with Comparative Examples 1 to 9. In addition, both the bloom resistance and the bloom resistance are good, and it can be seen that it is also useful as a molding material by injection molding.
From the results of Examples 21 to 29, it can be seen that those containing an antioxidant and / or a light stabilizer are further improved in heat aging resistance and / or weather resistance.

  The thermoplastic elastomer composition of the present invention is useful for various molded articles such as automobiles, electronic materials, home appliances, electrical equipment, medical equipment, packaging materials, stationery and miscellaneous goods, and further grips, tubes, packings, gaskets, Used for various members such as cushions, films and sheets.

Claims (10)

A thermoplastic styrenic elastomer A, a softening agent B, a thermoplastic polyester elastomer C, and a silicone-modified (meth) acrylic polymer D;
The mass ratio (A / B) of the thermoplastic styrenic elastomer A and the softener B is 25/75 to 95/5,
The thermoplastic polyester elastomer C includes a hard segment and a soft segment in a mass ratio (hard segment / soft segment) of 10/90 to 60/40,
The content of the thermoplastic polyester elastomer C is 75 to 1000 parts by mass with respect to 100 parts by mass of the total amount of the thermoplastic styrene elastomer A and the softener B,
The content of the silicone-modified (meth) acrylic polymer D is 1 to 35 parts by mass with respect to 100 parts by mass of the thermoplastic polyester elastomer C.
Thermoplastic elastomer composition.   The silicone-modified (meth) acrylic polymer D is a (copolymer) of a polyalkylsiloxane having a radical polymerization reactive group, an SH group, or both in the side chain and a (meth) acrylic ester and / or a (meth) acrylic hydroxyalkyl ester. The heat according to claim 1, which is a block copolymer and / or a graft copolymer polymerized with a mass ratio of 5/95 to 85/15 (polyalkylsiloxane / (co) polymer). Plastic elastomer composition.   The thermoplastic elastomer composition according to claim 1 or 2, wherein the silicone-modified (meth) acrylic polymer D has a melting point of 50 to 220 ° C.   The thermoplastic elastomer composition according to any one of claims 1 to 3, wherein the silicone-modified (meth) acrylic polymer D is a granular solid having an area-based average particle size of primary particles of 0.5 to 150 µm.   In addition to 100 parts by mass of the thermoplastic polyester elastomer A, 0.05 to 0.8 parts by mass of the sulfur-based antioxidant E and / or 0.05 to 0.8 parts by mass of the hindered amine light stabilizer F are contained. The thermoplastic elastomer composition according to any one of claims 1 to 4.   Furthermore, 0.1-15 mass parts of thickening agents G are contained with respect to 100 mass parts of thermoplastic polyester-type elastomer C, The thermoplastic elastomer composition in any one of Claims 1-5.   The thermoplastic elastomer composition according to any one of claims 1 to 6, further comprising a compatibilizing agent H.   Furthermore, the thermoplastic elastomer composition in any one of Claims 1-7 containing polyolefin I.   The molded object which consists of a thermoplastic-elastomer composition in any one of Claims 1-8.   A composite molded article obtained by welding the thermoplastic elastomer composition according to claim 1 to a member.