JP6353338B2 - Thermoplastic elastomer composition - Google Patents

Description

  The present invention relates to a thermoplastic elastomer composition useful for various molded articles such as electronic materials, home appliances, electrical equipment, medical equipment, packaging materials, stationery and miscellaneous goods, and a molded body obtained using the composition.

  A thermoplastic elastomer composition containing a polyester elastomer and a styrene elastomer has been proposed as a useful composition for various molded products such as automobiles, electronic materials, home appliances, electrical equipment, medical equipment, packaging materials, stationery and miscellaneous goods. ing. The thermoplastic elastomer composition is required to have various physical properties depending on the use of the molded product. For example, for use in pen grips, it can be fused to a hard resin such as polycarbonate, flexible to obtain a good tactile sensation, transparency to confirm aesthetics and remaining ink amount, and can be used for a long time. A compression set (CS) or the like for preventing deformation is required.

For example, Patent Document 1 discloses the following (A) component and (B) component, (B) component, (A) component and ( B) A thermoplastic resin composition mixed so as to occupy 20 to 59% by weight of the total of the components is described, and it is disclosed that transparency is improved when an ionic copolymer is mixed with a polyester elastomer. Yes.
(A) (a) a dicarboxylic acid and / or an ester-forming derivative thereof, (b) a low molecular weight glycol and / or an ester-forming derivative thereof, and (c) a polyoxyalkylene glycol having an average molecular weight of 500 to 5000 and / or its A polyester elastomer obtained by polycondensing the three ester-forming derivatives so that the component (c) accounts for 10 to 90% of the weight of the polyester elastomer.
(B) An ionic copolymer containing 1 to 3 metal ions obtained by copolymerizing an α-olefin and a salt of an α · β-unsaturated carboxylic acid.

  Patent Document 2 discloses a high-melting-point crystalline polymer segment (a) mainly composed of crystalline aromatic polyester units (a) of 10 to 50% by weight and a low-melting-point polymer segment (b) mainly composed of aliphatic polyether units. 10 to 95% by weight of a polyester block copolymer (A) comprising 90 to 50% by weight as a main constituent, and hydrogenated styrene-based elastomer (B) and / or a crystalline polyolefin block having hydrogenation 0.2 to 20 parts by weight of an ethylene copolymer (D) having a carboxylate metal base in the side chain and 100 parts by weight in total with 90 to 5% by weight of the thermoplastic block copolymer (C) and / or Contains 0.01 to 3 parts by weight of carboxylic acid alkali metal salt (E) and / or 0.01 to 3 parts by weight of alkali metal salt (F) of an organic phosphate compound Te becomes, thickness haze value measured with a sheet of about 2 mm (cloudiness) is a thermoplastic elastomer resin composition having 85% or less of light-transmitting or transparent, is disclosed.

Japanese Patent Publication No.58-24459 JP 2004-143352 A

The thermoplastic resin composition having the composition described in Patent Document 1 cannot increase the flexibility so much, and the surface hardness of the composition shown in the examples is 34 to 40 in durometer D hardness, which is relatively hard. It is. The durometer D hardness is a method for measuring the surface hardness of a relatively hard rubber, and the D hardness 30 to 40 corresponds to the A hardness 80 to 90 in comparison with the durator A hardness which is a softer rubber surface hardness measurement method. It is known.
In addition, Patent Document 1 describes that various additives may be used in combination, but there is no disclosure about a method for increasing flexibility, and when polyester that is originally transparent is blended with a polyester elastomer. Since it is described that it becomes opaque, there is no disclosure or suggestion of a composition using a styrenic elastomer together.

  In Patent Document 2, it can be seen from the Examples that the thermoplastic elastomer resin composition in which paraffinic oil is blended has lower transparency than that in which it is not blended.

  An object of the present invention is to provide a thermoplastic elastomer composition which is excellent in compression set characteristics and flexibility while satisfying transparency, and further satisfies fusion properties, and a molded body obtained using the composition. It is to provide.

The present invention
[1] A thermoplastic styrenic elastomer A, a softening agent B, a thermoplastic polyester elastomer C, and an ionomer D,
The thermoplastic styrenic elastomer A has a weight average molecular weight of 200,000 to 500,000,
The kinematic viscosity of the softener B at 40 ° C. is 30 to 500 mm ² / s,
A mass ratio (A / B) of the thermoplastic styrenic elastomer A and the softener B is 50/50 to 75/25 ;
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 30/70,
The content of the thermoplastic polyester elastomer C is 50 to 250 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 ionomer D is 1 to 50 parts by mass with respect to 100 parts by mass of the total amount of the thermoplastic styrenic elastomer A and the softening agent B.
A thermoplastic elastomer composition,
[2] A molded article comprising the thermoplastic elastomer composition according to [1], and [3] 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 and compression set properties while satisfying transparency, and further has an effect of satisfying fusing properties.

  Conventionally, from the viewpoint of transparency, it is a common technical knowledge of those skilled in the art that a thermoplastic styrene-based elastomer contained in a thermoplastic elastomer composition preferably has a low weight average molecular weight. However, when the thermoplastic elastomer composition containing a thermoplastic styrene elastomer having a high weight average molecular weight, a thermoplastic polyester elastomer and an ionomer contains a softening agent, the flexibility is improved as compared with the case of not containing this. Of course, surprisingly, it has been found that the transparency becomes high, contrary to the above-mentioned common general knowledge. In addition, this composition has excellent compression set characteristics due to its high weight average molecular weight. Such a tendency has never been known before. As a result of intensive studies based on this epoch-making knowledge, the present inventors have completed the present invention.

  The thermoplastic elastomer composition of the present invention contains a thermoplastic styrene elastomer A, a softening agent B, a thermoplastic polyester elastomer C, and an ionomer D.

  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 part (hard segment) composed of block units (s1) and a soft part (soft segment) 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 -Measured by NMR spectrum or the like, and can be obtained from the measured value.

  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 200,000 or more, preferably 210,000 or more, more preferably 220,000 or more from the viewpoint of compression set. The weight average molecular weight of the thermoplastic styrene-based elastomer A is 500,000 or less, preferably 470,000 or less, more preferably 450,000 or less, from the viewpoint of moldability. From these viewpoints, the weight average molecular weight of the thermoplastic styrenic elastomer A is 200,000 to 500,000, preferably 210,000 to 470,000, and more preferably 220,000 to 450,000. When the thermoplastic elastomer A is composed of a plurality of elastomers, the weighted average value of the weight average molecular weight of each elastomer is within the above range.

  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 is unlikely to occur. From the viewpoint, 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 the bleeding resistance even better, and at 30 mm ² / s or more, preferably at least 40 mm ² / s, 50 mm ² / s or more is more preferable. Further, since the lower is easy to handle, not more than 500 mm ² / s, preferably not more than 450 mm ² / s, more preferably at most 400 mm ² / s. From these viewpoints, the kinematic viscosity of the softener B at 40 ° C. is 30 to 500 mm ² / s, preferably 40 to 450 mm ² / s, and more preferably 50 to 400 mm 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 if the thermoplastic styrenic elastomer A is too much, the dispersibility of various blended components decreases. / 10 or less, preferably 85/15 or less, more preferably 80/20 or less, and even more preferably 75/25 or less. Further, if the amount of the thermoplastic styrene elastomer A is too small, oil bleed occurs, leading to deterioration of physical properties, etc., so that it is 10/90 or more, preferably 15/85 or more, more preferably 20/80 or more, 25/75 or more is more preferable. From these viewpoints, the mass ratio (A / B) of the thermoplastic styrenic elastomer A and the softener B in the composition of the present invention is 10/90 to 90/10, preferably 15/85 to 85/15. More preferably, it is 20/80 to 80/20, and more preferably 25/75 to 75/25.

  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. Examples of commercially available products include “Keyflex” (trade name, manufactured by LG Chemical), “Perprene” (trade name, manufactured by Toyobo Co., Ltd.), “Hytrel” (trade name, manufactured by Toray DuPont Co., Ltd.), “ Flexmer "(manufactured by Nippon Synthetic Chemical Industry Co., Ltd., trade name) 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. As for the weight average molecular weight of the aliphatic polyether block which is a soft segment of a polyester-polyether block copolymer, 400-6000 are preferable.

  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 flexibility. 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 30/70, preferably 13/87 to 28/72, 15 / 85 to 25/75 is more preferable.

  The A hardness of the thermoplastic polyester elastomer C is preferably 50 to 98, more preferably 60 to 95, and still more preferably 70 to 90. In the present invention, the A hardness is a durometer type A hardness.

  The greater the content of the thermoplastic polyester elastomer C, the better the fusion with the polar resin. Therefore, it is 50 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 70 parts by mass or more, more preferably 90 parts by mass or more. Further, since the smaller one is superior in flexibility, it is 250 parts by mass or less, preferably 230 parts by mass or less, more preferably 220 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 50 to 250 parts by mass, preferably 70 to 230 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 90-220 mass parts.

  The ionomer D has an effect of improving the transparency of the composition. As the ionomer D, one in which a part of the carboxyl group of an acrylic copolymer containing acrylic acid or methacrylic acid is a metal salt is preferable, and a copolymer of ethylene and acrylic acid or methacrylic acid is more preferable. The ionomer D needs to be thermoplastic, and the concentration of the carboxyl group is preferably about 0.1 to 20 mol% per 1 mol of the ionomer D. It is preferable that 10 to 90%, preferably 20 to 70% of the carboxyl group is a metal salt. Examples of the metal salt include alkali metal, alkaline earth metal, zinc, and the like. Among these, an alkali metal salt is preferable, and a sodium salt is more preferable. Such a thing is marketed with names, such as high Milan and Surlyn, and can be used suitably.

  The melting point of the ionomer D is preferably 50 to 150 ° C., more preferably 70 to 130 ° C., from the viewpoint of kneadability.

  The higher the content of ionomer D, the better the transparency. However, if the content is too high, the transparency will reach its peak, and the crystallization speed and heat resistance may be adversely affected. It is 1-50 mass parts with respect to 100 mass parts of total amounts of A and the softening agent B, Preferably it is 10-45 mass parts.

  The total content of the thermoplastic styrenic elastomer A, softener B, thermoplastic polyester elastomer C and ionomer D is preferably 75% by mass or more, more preferably 80% by mass or more, and 85% by mass in the thermoplastic elastomer composition. % Or more is more preferable.

  The thermoplastic elastomer composition may further contain metal soap E. Transparency can be further improved by using a metal soap, that is, a metal salt of a carboxylic acid.

  Examples of the metal soap E include a metal salt of an aliphatic carboxylic acid, a metal salt of an alicyclic carboxylic acid, a metal salt of an aromatic carboxylic acid, and preferably a metal salt of an aliphatic carboxylic acid having 35 or less carbon atoms. More preferably, it is a metal salt of a monocarboxylic acid having 35 or less carbon atoms, more preferably a metal salt of a monocarboxylic acid having 10 to 32 carbon atoms. Examples of the metal salt include alkali metal, alkaline earth metal, zinc, and the like. Among these, an alkali metal salt is preferable, and a sodium salt is more preferable. A suitable specific example is sodium stearate.

  The content of the metal soap E is preferably 0.1 to 15 parts by mass and more preferably 0.5 to 10 parts by mass with respect to 100 parts by mass of the total amount of the thermoplastic styrenic elastomer A and the softening agent B.

  In the composition of the present invention, the transparency can be further improved by using a transparent nucleating agent in place of the metal soap or in combination with the metal soap. Among additives for synthetic resins, those known by the names of transparent nucleating agent, crystal nucleating agent, clarifying agent and the like include a metal salt type and a sorbitol type. In the present invention, a metal salt type is preferable, and a metal Examples of the salt include alkali metals such as sodium, potassium and lithium, salts of alkaline earth metals, zinc and the like, alkali metal salts are preferable, and sodium salts are more preferable. As the counter ion, an organic phosphate compound is preferable, and an aromatic phosphate compound is more preferable. Specific examples include the ADK STAB NA series manufactured by Asahi Denka Co., Ltd. When the transparent nucleating agent is included, the content is preferably 0.1 to 15 parts by weight, more preferably 0.5 to 10 parts by weight, based on 100 parts by weight of the total amount of the thermoplastic styrenic elastomer A and the softening agent B. The same applies when used together.

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

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

  Since the compatibilizing agent F is excellent in abrasion resistance and fusion property, the acid-modified hydrogenated thermoplastic styrene elastomer F1, the acid-modified olefin thermoplastic elastomer F2, and the graft polymer F3 of styrene elastomer and urethane elastomer. At least one elastomer selected from the group consisting of

  As the acid-modified hydrogenated thermoplastic styrene elastomer F1, a block copolymer comprising a polymer block unit (s2) comprising a styrene monomer and a polymer block unit (b2) comprising 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 part (hard segment) composed of block units (s2) and a soft part (soft segment) 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 F1 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 F1 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 styrene-based elastomer F1 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-based elastomer F1 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 F2 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 F1.

  The acid-modified amount of the acid-modified olefin-based thermoplastic elastomer F2 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 F2 is preferably 95 or less, more preferably 10 to 90, and still more preferably 20 to 90.

  As the graft polymer F3 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 F is 0.1 to 50 parts by mass 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 fusion property to other materials. Is preferable, 0.1 to 45 parts by mass is more preferable, and 1 to 40 parts by mass is further preferable.

  By blending the thickener G, since the stiffness of the resin is improved when the composition is melt-molded and cooled in the mold, the molded product can be taken out of the mold even in a short cooling time. The molding cycle time can be shortened.

  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.

  Since the thickener G content is more excellent in wear resistance, it is 0.1 parts by mass or more and 0.5 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. Preferably, 1 part by mass or more is more preferable. Further, since the moldability is better when the amount is smaller, the amount is preferably 30 parts by mass or less, more preferably 25 parts by mass or less, and more preferably 20 parts by mass with respect to 100 parts by mass of the total amount of the styrene elastomer A and the softener B The following is more preferable. From these viewpoints, the content of the thickener G is preferably 0.1 to 30 parts by mass, and 0.5 to 25 parts by mass with respect to 100 parts by mass of the polyester-based elastomer from the viewpoint of the balance between wear resistance and moldability. More preferred is 1 to 20 parts by mass.

  Polyolefin H is preferable from the viewpoint of moldability.

  Examples of the polyolefin H 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 H is preferably 50 parts by mass or less, more preferably 40 parts by mass or less, with respect to the total amount of 100 parts by mass of the styrene elastomer A and the softening agent B, since the smaller the content of polyolefin H is, the more flexible it is. Preferably, it is 30 parts by mass or less.

  The 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; insulating heat conductive fillers, lubricants, light stabilizers, antioxidants, ultraviolet absorbers, pigments, flame retardants, antistatic agents, release agents, tackifiers, crosslinking agents, crosslinking aids Various additives such as a foaming agent and a fragrance may be contained.

  The thermoplastic elastomer composition of the present invention comprises a thermoplastic styrenic elastomer A, a softening agent B, a thermoplastic polyester elastomer C and an ionomer D, and optionally a metal soap E, a compatibilizing agent F, a thickener G, It is obtained by mixing raw materials containing polyolefin H 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, a preferable melting temperature range when kneading is performed is −30 ° C. to + 100 ° C. with respect to the melting point, and 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 a strand, and cut into pellets such as a cylindrical shape or a rice grain 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 80 or less, more preferably 10 to 80, still more preferably 30 to 80, and even more preferably 50 to 80 from the viewpoint of flexibility.

  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, 50 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. 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. .

  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 with JIS K 6253 Type A.

[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). Ionomer D
[Concentration of carboxyl group]
Press the blend of base material and organic acid before modification with 0.1mm spacer and measure IR, then calibrate from absorption of characteristic carbonyl (1600-1900cm-1) and charge of organic acid. A line is prepared, and IR (IR measuring instrument: FT-210 manufactured by Horiba, Ltd.) is applied to the acid-modified press plate to calculate the concentration.

[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. Compatibilizer F
[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.

7). 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.

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.

Examples 1-14 and Comparative Examples 1-9 (Examples 9 and 12 are reference examples)
(1) Production of thermoplastic elastomer composition (pellet) The materials shown in Tables 2 to 4 other than paraffin oil were dry blended and impregnated with paraffin oil to produce 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 2-4 used by the Example and the comparative example is as follows.

[Thermoplastic styrenic elastomer]
SEBS-A: G1651 (Clayton Polymer Co., Ltd.), styrene monomer content 33% by mass, Mw 290,000
SEBS-B: G1650 (manufactured by Kraton Polymer Co., Ltd.), styrene monomer content 29% by mass, Mw 107,000
SEEPS: SEPTON4099 (manufactured by Kuraray Co., Ltd.), styrene monomer content 30% by mass, Mw 422,000

[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): Keyflex BT1028D (manufactured by LG Chemical), hard segment / soft segment 19/81, A hardness 81
TPEE-B (polyester polyether block copolymer): Keyflex BT1030D (manufactured by LG Chemical), hard segment / soft segment 23/77, A hardness 85
TPEE-C (polyester polyether block copolymer): KP3340 (manufactured by KOLON), hard segment / soft segment 39/61, A hardness 90

[Ionomer]
Himiran 1707 (Mitsui DuPont Polychemical Co., Ltd.), ethylene-methacrylic acid copolymer sodium salt, melting point 89 ° C

[Metal soap]
Sodium stearate

(Crystal nucleating agent)
NA-05 (Adeka Co., Ltd.): Nitrogen-containing phosphate ester compound

[Compatibilizer]
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

[Epoxy compound]
Epoxy compound A: composite, epoxy value 1.8 meq / g, St-MMA-GMA copolymer, GMA content 25% by mass, styrene monomer content 38% by mass, Fn 5.1, Mw 10,800
Acrylic modified polytetrafluoroethylene (PTFE): Methabrene A3000 (Mitsubishi Rayon Co., Ltd.)

(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 2-4.

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

2. Transparency (Haze)
A 2.0 mm thick plate was formed by injection molding and measured according to JIS K 7136.

3. Thermal fusion properties Insert the following polar resin into a 4mm thick x 25mm wide x 125mm long mold, injection molding the thermoplastic elastomer compositions obtained in the examples and comparative examples under the following conditions, A strip-shaped welding test piece was prepared.

4). Compression set (CS)
A plate with a thickness of 2 mm, a width of 125 mm, and a length of 125 mm was prepared by injection molding, and a punched sample with a diameter of 29 mm and a diameter of 2 mm was taken using a circular punching blade with a diameter of 29 mm. Of these, seven punched samples were stacked, and the thickness was 12.5 by compression. Using a test piece adjusted to mm, measurement was performed under the conditions of 70 ° C. × 24 hours in accordance with JIS K 6262.

5. Productivity [cycle time]
The total time from mold closing time to injection time to in-mold cooling time to mold opening time was defined as cycle time.

[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: 50%, injection speed: 50%, holding pressure: 20%, holding time: 10sec
Injection time: 2sec
Mold temperature: 40 ℃

  Using the above-mentioned welding test piece, a tensile test was carried out at 50 mm / min in the direction of 180 ° between the thermoplastic elastomer layer and the polar resin layer at an ambient temperature of 23 ° C., and the peel strength (unit: N / N) 25 mm) was measured.

  From the above results, the thermoplastic elastomer compositions of Examples 1 to 14 are excellent in transparency, flexibility, compression set characteristics and fusion properties as compared with the thermoplastic elastomer compositions of Comparative Examples 1 to 9. It can be seen that it is also useful as a molding material by injection molding.

From the comparison between Example 1 and Comparative Example 1, it can be seen that when the weight average molecular weight of the thermoplastic styrenic elastomer A is high, the transparency, flexibility, compression set characteristics and fusing property are improved.
In Example 11 and Comparative Example 9, thermoplastic styrene-based elastomers having different weight average molecular weights are used in combination, but it can be seen that Example 11 having a high weighted average value improves compression set characteristics and fusion properties.
From the comparison between Examples 1 and 2 and Comparative Example 2, it can be seen that when the amount of the hard segment of the plastic polyester elastomer C is small, the transparency, flexibility, compression set characteristics and fusion property are improved.
From the comparison between Example 1 and Comparative Example 3, it can be seen that when softener B is contained, the transparency, flexibility and compression set characteristics are improved.
From the comparison between Example 1 and Comparative Example 5, it can be seen that when ionomer D is contained, the transparency is remarkably improved.
From the comparison between Examples 1 and 3, it can be seen that when the metal soap E is contained, the transparency and flexibility are improved.
From the comparison between Examples 3 and 4, it can be seen that as the amount of the softener B increases, the transparency and flexibility are improved.
From the comparison between Examples 1 and 5, it can be seen that when the compatibilizing agent F is contained, the fusing property is improved.
From the comparison between Examples 1 and 6, it can be seen that when the thickener G is contained, the productivity is improved.
From the comparison with Examples 1 and 9, when the thermoplastic styrene-based elastomer A is contained more than the softening agent B, the transparency and the fusion property are excellent, and the thermoplastic styrene-based elastomer A is more than the softening agent B. When it is contained in a small amount, it can be seen that it is excellent in flexibility and compression set characteristics.
From the comparison between Examples 1 and 10, it can be seen that Example 1 having a low weight average molecular weight is excellent in transparency when the weight average molecular weight of the thermoplastic styrene elastomer A is in the range of 200,000 to 500,000.

  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 (7)

Containing thermoplastic styrene elastomer A, softener B, thermoplastic polyester elastomer C, and ionomer D;
The thermoplastic styrenic elastomer A has a weight average molecular weight of 200,000 to 500,000,
The kinematic viscosity of the softener B at 40 ° C. is 30 to 500 mm ² / s,
A mass ratio (A / B) of the thermoplastic styrenic elastomer A and the softener B is 50/50 to 75/25 ;
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 30/70,
The content of the thermoplastic polyester elastomer C is 50 to 250 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 ionomer D is 1 to 50 parts by mass with respect to 100 parts by mass of the total amount of the thermoplastic styrenic elastomer A and the softening agent B.
Thermoplastic elastomer composition.   The thermoplastic elastomer composition according to claim 1, wherein the A hardness is 80 or less.   Furthermore, the thermoplastic-elastomer composition of Claim 1 or 2 which contains 0.1-15 mass parts of metal soap E with respect to 100 mass parts of total amounts of the thermoplastic styrene-type elastomer A and the softening agent B.   The thermoplastic elastomer composition according to any one of claims 1 to 3, further comprising 0.1 to 50 parts by mass of the compatibilizer F with respect to 100 parts by mass of the total amount of the thermoplastic styrenic elastomer A and the softener B.   5. The thermoplastic elastomer composition according to claim 1, further comprising 0.1 to 30 parts by mass of the thickener G with respect to 100 parts by mass of the total amount of the thermoplastic styrene-based elastomer A and the softening agent B.   The molded object which consists of a thermoplastic-elastomer composition in any one of Claims 1-5.   A composite molded article obtained by welding the thermoplastic elastomer composition according to claim 1 to a member.