JP5458429B2 - Thermoplastic elastomer resin composition and molded body - Google Patents

Description

  The present invention relates to a thermoplastic elastomer resin composition that is flexible but has no stickiness, has excellent handling properties, and at the same time has excellent mechanical properties, molding processability, and two-color moldability with a hard resin, and a molded body using the same. Is.

  A polyester block copolymer having a crystalline aromatic polyester unit as a hard segment and an aliphatic polyether unit such as poly (alkylene oxide) glycol or an aliphatic polyester unit such as polylactone as a soft segment has molding processability, It has excellent mechanical properties such as impact resistance, elastic recovery, flexibility, high temperature characteristics, adhesiveness, etc., and these (molding processability, mechanical properties, heat resistance) are well balanced. Applications have been expanded to industrial materials such as sheets, films, fibers, automobiles, and electrical / electronic components.

  Theoretically, the polyester block copolymer can be softened by increasing the weight ratio of the soft segment, but the characteristics such as good moldability (solidification speed, mold release) and heat resistance are drastically reduced. . In practice, the surface Shore D hardness of 30 is the limit, and flexibility is positioned as the hardest elastomer among engineering plastic elastomers and general-purpose elastomers, and is limited by its application development.

  In order to improve the flexibility of the polyester block copolymer, many attempts have been made in the past to incorporate a thermoplastic resin and an elastomer that are more flexible into the polyester block copolymer, such as a styrene-butadiene block, or A composition comprising a hydrogenated derivative of a styrene-isoprene block copolymer and a plasticizer and a polyester elastomer (see, for example, Patent Documents 1 and 2) has been proposed.

  On the other hand, a composition comprising a core-shell copolymer obtained by copolymerizing a core polymer mainly composed of butyl acrylate with a polymer mainly composed of styrene and acrylonitrile as a shell and a polyester elastomer (see, for example, Patent Document 3) ) Has been proposed.

  According to the above-described conventional technique (see Patent Document 1), it is possible to obtain a flexible resin composition as compared with a conventional polyester block copolymer. However, there are problems such as stickiness when touched, blocking of pellets, and reduction in work efficiency due to adhesion between molded products.

  In addition, according to the above-described conventional technology (see Patent Document 2), a resin composition that is flexible and does not feel sticky and has excellent heat-fusibility with a hard resin can be obtained. Addition is indispensable, and there are problems of bleed out and deterioration of physical properties.

  Furthermore, in the above-described conventional technique (see Patent Document 3), a flexible resin composition can be obtained as compared with the conventional polyester block copolymer, but the resin composition has poor flowability and has a problem in moldability. It was.

  Therefore, the conventional technology is flexible but does not feel sticky and has excellent handling properties, and there is no deterioration in the appearance of the molded product due to bleeding out, and at the same time, it has excellent mechanical properties, molding processability, and two-color moldability with hard resin. It was difficult to obtain an elastomer resin composition.

JP-A-10-130451 JP-A-8-72204 JP 2000-302940 A

  The present invention has been achieved as a result of studying the solution of the problems in the prior art described above as an issue.

  Therefore, the object of the present invention is to be flexible but not sticky and excellent in handling properties, and not to deteriorate the appearance of the molded product due to bleed-out, and at the same time, mechanical properties, molding processability, two-color moldability with hard resin It is an object of the present invention to provide an elastomer resin composition excellent in the above-mentioned properties and a molded product comprising the same.

  As a result of sincere studies to achieve the above-mentioned object, the present inventors have found that a polyester block copolymer includes a core polymer mainly composed of butyl acrylate and a polymer mainly composed of styrene and acrylonitrile as a shell. The inventors have found that the above object can be achieved for the first time by simultaneously blending a polymerized core / shell copolymer and a specific hydrogenated styrene block copolymer, and have reached the present invention.

That is, according to the present invention, the high melting point crystalline polymer segment (a1) mainly composed of crystalline aromatic polyester and the low melting point polymer segment (a2) mainly composed of aliphatic polyether units and / or aliphatic polyester units. And 50% to 90% by weight of the polyester block copolymer (A) having a main component as a constituent component, butyl acrylate alone or a mixture of butyl acrylate and 2-ethylhexyl acrylate (b1), having an alkyl group having 1 to 4 carbon atoms At least one compound (b2) selected from alkyl acrylates and alkyl methacrylates, vinyl cyanide compound (b3), maleic acid monoalkyl ester compound (b4) represented by the following structural formula (I), and crosslinking agent Polymer obtained by emulsion polymerization of (b5) Core-shell copolymer (B) having 5 to 35% by weight with a polymer obtained by polymerizing aromatic vinyl compound (b6), vinylcyan compound (b3), and crosslinking agent (b5) as a core And hydrogenated styrene block copolymer (C) 5 to 40% by weight comprising at least one vinyl aromatic compound polymer block (c1) and at least one conjugated diene block (c2). What is claimed is: 1. A thermoplastic elastomer resin composition comprising: a composite molded product formed by injection molding of a mixed resin of an ABS resin and a polycarbonate resin; and a strain rate of 50 mm / min. There is provided a thermoplastic elastomer resin composition having a fusion adhesive strength of 180 N / 20 mm or more when a tensile test is performed under conditions .

  (In the formula, the substituent R represents a saturated aliphatic hydrocarbon group having 10 to 24 carbon atoms, an unsaturated aliphatic hydrocarbon group, or an aromatic hydrocarbon group.)

  In the thermoplastic elastomer resin composition of the present invention, the surface hardness measured according to the method described in JIS K7215 is preferably 85 A or less, and by applying these conditions, it is more excellent. You can expect to get the effect.

  In addition, the molded article of the present invention is formed by injection molding the above thermoplastic elastomer resin composition, and exhibits the best effect particularly in the case of a composite molded article.

  According to the present invention, a polyester-block copolymer (A) and a core-shell copolymer obtained by copolymerizing a core polymer mainly composed of butyl acrylate with a polymer mainly composed of styrene and acrylonitrile as a shell (B) When the hydrogenated styrene block copolymer (C) is blended at the same time, it is flexible but has no stickiness and excellent handling properties, and there is no deterioration in the appearance of the molded product due to bleed-out. An elastomer resin composition excellent in moldability and two-color moldability with a hard resin can be obtained.

It is the top view (I) and side view (B) which show the schematic shape of the heat-fusion-molded article of an Example and a comparative example. It is a figure which shows the outline of a deformation | transformation amount measurement. It is a side view which shows the schematic shape for measuring heat sealing | bonding adhesive force. It is the top view (I) and side view (B) which show the outline of an adhesive test.

  Hereinafter, the present invention will be described in detail.

  The high melting point crystalline polymer segment (a1) of the polyester block copolymer (A) used in the present invention is mainly formed from an aromatic dicarboxylic acid or an ester-forming derivative thereof and a diol or an ester-forming derivative thereof. Specific examples of aromatic dicarboxylic acids that are polyesters include terephthalic acid, isophthalic acid, phthalic acid, naphthalene-2,6-dicarboxylic acid, naphthalene-2,7-dicarboxylic acid, anthracene dicarboxylic acid, diphenyl-4,4. Examples include '-dicarboxylic acid, diphenoxyethanedicarboxylic acid, 4,4'-diphenyl ether dicarboxylic acid, 5-sulfoisophthalic acid, and sodium 3-sulfoisophthalate. Although aromatic dicarboxylic acid is mainly used, if necessary, a part of the aromatic dicarboxylic acid may be converted to alicyclic dicarboxylic acid such as 1,4-cyclohexanedicarboxylic acid, cyclopentanedicarboxylic acid, 4,4′-dicyclohexyldicarboxylic acid. Alternatively, it may be substituted with an aliphatic dicarboxylic acid such as adipic acid, succinic acid, oxalic acid, sebacic acid, dodecanedioic acid, and dimer acid. Of course, ester-forming derivatives of dicarboxylic acids such as lower alkyl esters, aryl esters, carbonates, and acid halides can be used equally. As the diol, a diol having a molecular weight of 400 or less, for example, an aliphatic diol such as 1,4-butanediol, ethylene glycol, trimethylene glycol, pentamethylene glycol, hexamethylene glycol, neopentyl glycol, decamethylene glycol, 1,1- Cycloaliphatic diols such as cyclohexanedimethanol, 1,4-dicyclohexanedimethanol, tricyclodecane dimethanol, xylylene glycol, bis (p-hydroxy) diphenyl, bis (p-hydroxyphenyl) propane, 2,2- Bis [4- (2-hydroxyethoxy) phenyl] propane, bis [4- (2-hydroxy) phenyl] sulfone, 1,1-bis [4- (2-hydroxyethoxy) phenyl] cyclohexane, 4,4 ′ − Dihydroxy Aromatic diols such as -p-terphenyl and 4,4'-dihydroxy-p-quarterphenyl are preferred, and such diols can also be used in the form of ester-forming derivatives such as acetyl compounds and alkali metal salts.

  Two or more of these dicarboxylic acids and their derivatives or diol components may be used in combination.

  An example of the most preferred high melting crystalline polymer segment (a2) is polybutylene terephthalate derived from terephthalic acid and / or dimethyl terephthalate and 1,4-butanediol.

  The low-melting point polymer segment (a1) of the polyester block copolymer (A) used in the present invention is an aliphatic polyether and / or an aliphatic polyester, and examples of the aliphatic polyether include poly (ethylene oxide) glycol, Poly (propylene oxide) glycol, poly (tetramethylene oxide) glycol, poly (hexamethylene oxide) glycol, copolymer of ethylene oxide and propylene oxide, ethylene oxide adduct of poly (propylene oxide) glycol, copolymer of ethylene oxide and tetrahydrofuran Etc. Examples of the aliphatic polyester include poly (ε-caprolactone), polyenantlactone, polycaprylolactone, and polybutylene adipate. Poly (tetramethylene oxide) glycol, poly (propylene oxide) glycol ethylene oxide adduct, poly (ε-caprolactone) from the elastic properties of polyester block copolymers obtained from these aliphatic polyethers and / or aliphatic polyesters ), Polybutylene adipate and the like are preferable, and among these, an ethylene oxide adduct of poly (propylene oxide) glycol is particularly preferable.

  The copolymerization amount of the low-melting point polymer segment (a1) of the polyester block copolymer (A) used in the present invention is usually 10 to 90% by weight, preferably 15 to 85% by weight, and more preferably 20 to 80%. % By weight. In particular, if it is 10% by weight or less, the flexibility is insufficient, and if it is 90% by weight or more, the crystallinity is low and the moldability is deteriorated.

  Two or more kinds of polyester block copolymers having different compositions may be used in combination.

  The polyester block copolymer (A) used in the present invention can be produced by a known method. For example, a method in which a lower alcohol diester of dicarboxylic acid, an excessive amount of low molecular weight glycol, and a low melting point polymer segment component are transesterified in the presence of a catalyst and the resulting reaction product is polycondensed, or an excess amount of dicarboxylic acid A method of subjecting the resulting glycol and low melting point polymer segment component to an esterification reaction in the presence of a catalyst and polycondensing the resulting reaction product, or preparing a high melting point crystalline segment in advance, A method of adding and randomizing by transesterification, a method of linking a high melting point crystalline segment and a low melting point polymer segment with a chain linking agent, and a poly (ε-caprolactone) in the low melting point polymer segment Do not add ε-caprolactone monomer to the melting crystalline segment. However, either method may be taken.

  The core-shell copolymer (B) used in the present invention comprises butyl acrylate alone or a mixture of butyl acrylate and 2-ethylhexyl acrylate (b1), an alkyl acrylate ester having 1 to 4 carbon atoms and a methacrylic ester. Emulsifying at least one compound (b2) selected from acid alkyl esters, vinylcyan compound (b3), maleic acid monoalkyl ester compound (b4) represented by the following structural formula (I) and crosslinking agent (b5) A core-shell copolymer having a polymer as a core and a polymer obtained by polymerizing an aromatic vinyl compound (b6), a vinylcyan compound (b3), and a crosslinking agent (b5) as a shell. However, there is an alkyl group having 1 to 4 carbon atoms constituting the core of the core-shell copolymer (B). Examples of lylic acid ester and methacrylic acid ester (b2) include methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, methyl methacrylate, ethyl methacrylate, propyl methacrylate, and butyl methacrylate. Ethyl methacrylate can be preferably used.

  (In the formula, the substituent R represents a saturated aliphatic hydrocarbon group having 10 to 24 carbon atoms, an unsaturated aliphatic hydrocarbon group, or an aromatic hydrocarbon group.)

  As the vinylcyan compound (b3) constituting the core-shell copolymer (B) used in the present invention, acrylonitrile, methacrylonitrile and the like can be used.

  The maleic acid monoalkyl ester compound (b4) constituting the core-shell copolymer (B) used in the present invention is represented by the structural formula (I), and the saturated aliphatic hydrocarbon group includes a lauryl group, Examples include undecanyl group, myristyl group, palmityl group, heptadecanyl group, stearyl group, arachidyl group, and behenyl group. Examples of the unsaturated aliphatic hydrocarbon group include a palmitoleyl group, a heptadecenyl group, an oleyl group, an eicosenyl group, an erucyl group, a linole group, and a linolenic group. Examples of the aromatic hydrocarbon group include a phenylpropane group, a phenylsulfone group, a xylyl group, and a naphthyl group. Further, examples of the alkali metal include sodium and potassium.

  Examples of the crosslinking agent (b5) constituting the core-shell copolymer (B) used in the present invention include ethylene glycol, diethylene glycol, triethylene glycol, 1,3 propanediol, 1,4 butanediol, glycerin and the like. Examples thereof include aromatic divinyl compounds such as diacrylates and / or triacrylates of polyhydric alcohols, dimethacrylates and / or trimethacrylates of similar polyhydric alcohols, divinylbenzene, and divinyltoluene.

  Examples of the aromatic vinyl compound (b6) constituting the core-shell copolymer (B) used in the present invention include styrene, α-methylstyrene, o-methylstyrene, m-methoxystyrene, N, N-dimethyl- Examples thereof include p-aminostyrene and divinylbenzene.

  The amount of copolymerization of the butyl acrylate simple substance or the mixture of butyl acrylate and 2-ethylhexyl acrylate (b1) constituting the core / shell copolymer (B) used in the present invention is the core / shell copolymer (B) 100. It is preferable that it is 40 to 80 weight% per weight%. When the copolymerization amount of butyl acrylate alone or a mixture of butyl acrylate and 2-ethylhexyl acrylate (b1) is less than 40% by weight, the flexibility of the core-shell copolymer (B) is insufficient. It is not possible to sufficiently achieve softening of the polyester block copolymer composition. Further, when the copolymerization amount of the butyl acrylate alone or the mixture (b1) of 2-ethylhexyl acrylate exceeds 80% by weight, the tackiness of the core-shell copolymer (B) becomes remarkably high. The polymer composition has adhesiveness, and the desired handling property cannot be improved or good touch feeling can be achieved.

  The amount of 2-ethylhexyl acrylate in the butyl acrylate simple substance or the mixture (b1) of butyl acrylate and 2-ethylhexyl acrylate constituting the core-shell copolymer (B) used in the present invention is 40% by weight or less. Is preferred. When the amount of 2-ethylhexyl acrylate exceeds 40% by weight, the tackiness of the core-shell copolymer (B) becomes remarkable, so that the polyester block copolymer composition of the present invention has tackiness. It is difficult to achieve improved handling and good touch when touched.

  The shell constituting the core-shell copolymer (B) used in the present invention is composed of 6 to 20 parts by weight of the aromatic vinyl compound (b6) and vinylcyan compound (b3) with respect to 100 parts by weight of the core polymer. 3 to 12 parts by weight, and 0.05 to 1 part by weight of the crosslinking agent (b5) is preferably polymerized. When the amount of the aromatic vinyl compound (b6) or vinylcyan compound (b3) constituting the shell polymer is small, the dispersion of the core-shell copolymer (B) into the polyester block copolymer (A) is poor, The strength of the polyester block copolymer composition comprising them is significantly reduced. Further, when the amount of the aromatic vinyl compound (b6) or the vinylcyan compound (b3) constituting the shell polymer is large, the flexibility of the core / shell copolymer (B) is insufficient, which is an object of the present invention. Softening of the polyester block copolymer composition cannot be achieved sufficiently.

  Two or more kinds of core / shell copolymers (B) having different compositions may be used in combination.

  The core-shell copolymer (B) used in the present invention can be produced by a known two-stage reaction. For example, butyl acrylate alone or a mixture of butyl acrylate and 2-ethylhexyl acrylate (b1), at least one compound (b2) selected from an alkyl acrylate ester and an alkyl methacrylate ester consisting of an alkyl group having 1 to 4 carbon atoms, Vinyl cyanide compound (b3), maleic acid monoalkyl ester (b4) and cross-linking agent (b5) as a solvent such as water, surfactant such as sodium alkylbenzenesulfonate, and radical initiation such as di-t-butyl peroxide Together with the agent, the reaction vessel is charged and subjected to an emulsion polymerization reaction at a predetermined temperature to obtain a core polymer latex. Furthermore, an aromatic vinyl compound (b6), a vinylcyan compound (b3), and a crosslinking agent (b5) are added to the reaction vessel containing the core polymer latex and reacted to obtain the desired core-shell copolymer. Can do. The obtained core / shell copolymer (B) latex is added with a coagulant such as calcium chloride, washed and dried to isolate the core / shell copolymer (B).

  The hydrogenated styrene-butadiene block copolymer (C) used in the present invention is a hydrogenated styrene-butadiene block copolymer, and the styrene-butadiene block copolymer is a styrene block, Examples thereof include a diblock copolymer composed of a butadiene block, a triblock copolymer, and a radial block copolymer.

  At least one vinyl aromatic compound polymer block (c1) of the hydrogenated styrene block copolymer (C) used in the present invention is styrene, α-methylstyrene, vinyltoluene, p-methylstyrene, pt −. This is a block polymerized from butyl styrene, o-ethyl styrene, o, p-dichlorostyrene, etc., among which styrene is preferably used.

  At least one conjugated diene block (c2) of the hydrogenated styrene block copolymer (C) used in the present invention is butadiene, isoprene, butadiene / isoprene copolymer, 2,3-dimethyl-1,3-butadiene, Polymerized from 1,3-pentadiene, 2-methyl-1,3-pentadiene, 1,3-hexadiene, 4,5-diethyl-1,3-octadiene, 3-butyl-1,3-octadiene, chloroprene, etc. Among these, a styrene-butadiene block copolymer, a styrene-isoprene block copolymer, and a styrene-isoprene / butadiene block copolymer are preferably used.

  As the hydrogenated styrene block copolymer (C), one modified with an unsaturated carboxylic acid or an anhydride thereof, or an epoxy group-containing monomer may be used. Specifically, modified styrene-hydrogenated butadiene diblock copolymer, modified styrene-hydrogenated butadiene-styrene triblock copolymer (modified styrene-ethylene-butylene-styrene block copolymer: modified SEBS) and the like. Can be mentioned.

  Furthermore, two or more types of hydrogenated styrene-butadiene block copolymers (C) having different compositions may be used.

The blending ratio of each component in the thermoplastic elastomer resin composition of the present invention is such that the high-melting crystalline polymer segment (a1) mainly composed of a crystalline aromatic polyester, and mainly an aliphatic polyether unit and / or an aliphatic polyester unit. The polyester block copolymer (A) comprising as a main component a low melting point polymer segment (a2) comprising 50 to 90% by weight, preferably 55 to 85% by weight, more preferably 60 to 80% by weight, Butyl acrylate alone or a mixture of butyl acrylate and 2-ethylhexyl acrylate (b1), at least one compound (b2) selected from alkyl acrylates and alkyl methacrylates having an alkyl group having 1 to 4 carbon atoms, vinylcyan Compound (b3), the above structural formula (I ), A polymer obtained by emulsion polymerization of a maleic acid monoalkyl ester compound (b4) and a crosslinking agent (b5), and an aromatic vinyl compound (b6), a vinylcyan compound (b3), and a crosslinking agent. (b5) is polymerized comprising a core-shell copolymer the polymer was a shell (B) 5 to 35 wt%, good Mashiku is a 5 to 25% by weight, at least one vinyl aromatic compound polymer block (c1) and at least one conjugated diene block (c2) and color Nari hydrogenated styrene block copolymer is hydrogenated (C) 5 to 40 wt%, the good Mashiku 10 to 25 wt% .

  In the thermoplastic elastomer resin composition of the present invention, the surface hardness measured according to the method described in JIS K7215 is preferably 85 A or less, and more preferably 80 A or less.

  In addition, the thermoplastic elastomer resin composition of the present invention is a known hindered phenol-based, phosphite-based, thioether-based, amine-based antioxidant, benzophenone-based, and the like as long as the object of the present invention is not impaired. , Benzotriazole-based, hindered amine-based light-proofing agent, polyolefin-based wax, aliphatic amide compound, aliphatic ester compound, anti-blocking agent such as fatty acid metal salt, crystallization nucleating agent such as calcium carbonate and talc, dye and pigment, etc. Colorants, UV blocking agents such as titanium oxide, carbon black, reinforcing agents such as glass fibers and carbon fibers, potassium titanate whiskers, flame retardants, foaming agents, adhesives, adhesion aids, fluorescent agents, crosslinking agents, and A surfactant or the like can be optionally contained.

  These additives and fillers may be blended in advance in the polyester block copolymer, may be blended in the polyester block copolymer together with the composition of the present invention, or after the formation of the composition of the present invention. It may be added.

  The effects of the present invention will be described below with reference to examples. All percentages and parts in the examples are based on weight unless otherwise specified. The physical properties shown in the examples were measured as follows.

[Tensile properties]
Measurement was performed according to JIS K7113 using a JIS-2 injection test piece.

[Surface hardness]
It measured according to JIS K7215.

[Melt viscosity index (MFR)]
Measurement was performed at a temperature of 220 ° C. and a load of 2,160 g according to ASTM D-1238.

[Deformation amount]
First, using a blend of ABS resin and polycarbonate resin, an L-shape with a width of 20 mm, a length of 60 mm, and a thickness of 3 mm shown in FIG. 1 is injection molded under the conditions of a cylinder temperature of 260 ° C. and a mold temperature of 50 ° C. The molded L-shaped molded product (B) was set in a mold having the shape shown in FIG. 2, and then the evaluation resin composition was subjected to a cylinder temperature of 200 ° C. and a mold temperature of 50 ° C. Injection molding was performed under conditions to obtain a composite molded product in which a molded product (A) made of a thermoplastic elastomer composition and the molded product (B) were joined. After leaving this at 23 ° C. and 50% Rh for 1 day, the amount of strain was measured according to the standard shown in FIG.

[Heat adhesion strength]
First, using a mixed resin of ABS resin and polycarbonate resin, an L-shape with a width of 20 mm, a length of 60 mm, and a thickness of 3 mm shown in FIG. 2 is injection molded under the conditions of a cylinder temperature of 260 ° C. and a mold temperature of 50 ° C. The molded L-shaped molded product (B) was set in a mold having the shape shown in FIG. 2, and then the evaluation resin composition was subjected to a cylinder temperature of 200 ° C. and a mold temperature of 50 ° C. Injection molding was performed under conditions to obtain a composite molded product in which a molded product (A) made of a thermoplastic elastomer composition and the molded product (B) were joined. This was allowed to stand at 23 ° C. and 50% Rh for 1 day, and then subjected to a tensile test under the condition of a strain rate of 50 mm / min by the method shown in FIG.

[Adhesion test]
A strip test piece having a width of 25 mm and a length of 125 mm was produced by punching from a square plate test piece having a length of 125 mm, a width of 75 mm, and a thickness of 2 mm, which had been injection-molded under conditions of a cylinder temperature of 200 ° C. and a mold temperature of 50 ° C. Next, as shown in FIG. 4, the strip test pieces were overlapped by 50 mm and pressed with a 2 kg weight for 1 minute, and then the adhesive shear load was measured.

[appearance]
The surface state of a square plate test piece obtained by injection molding under conditions of a cylinder temperature of 200 ° C. and a mold temperature of 50 ° C. was confirmed with the naked eye and evaluated in the following three stages.
◎ ・ ・ ・ No bleed-out and very good appearance
○ ・ ・ ・ Bleed-out is hardly observed and appearance is good.
X: Bleeding out is remarkable or / and appearance is poor.

[Reference example]
[Production of Polyether Ester Block Copolymer (A-1)]
Helical ribbon type stirring of 273 parts of dimethyl terephthalate, 120 parts of 1,4-butanediol and 723 parts of poly (tetramethylene oxide) glycol having a number average molecular weight of about 2000 together with 3 parts of titanium tetrabutoxide and 3 parts of trimellitic anhydride The reaction vessel equipped with a blade was charged and heated at 210 ° C. for 2 hours and 30 minutes, and 95% of the theoretical methanol amount was distilled out of the system. After adding 0.5 parts of “Irganox” 1330 (Hindered phenol antioxidant manufactured by Ciba Geigy) to the reaction mixture, the temperature was raised to 245 ° C., and then the pressure in the system was reduced to 27 Pa over 50 minutes. And polymerization was carried out for 1 hour and 50 minutes under these conditions. The obtained polymer was discharged into water in the form of strands and pelletized by cutting.

[Production of Polyether Ester Block Copolymer (A-2)]
340 parts of terephthalic acid, 100 parts of isophthalic acid, 394 parts of 1,4-butanediol and 495 parts of poly (tetramethylene oxide) glycol having a number average molecular weight of about 1400 were equipped with a helical ribbon stirring blade together with 2 parts of titanium tetrabutoxide. The reaction vessel was charged and heated at 190 to 225 ° C. for 3 hours to conduct esterification while distilling the reaction water out of the system. After adding 0.5 parts of “Irganox” 1098 (hindered phenol antioxidant manufactured by Ciba Geigy) to the reaction mixture, the temperature was raised to 245 ° C., and then the pressure in the system was reduced to 27 Pa over 50 minutes. The polymerization was carried out for 2 hours and 45 minutes under these conditions. The obtained polymer was discharged into water as a strand and cut into pellets.

  Table 1 shows the compositions and physical properties of A-1 and A-2.

[Production of core-shell copolymer (B)]
37.3 kg of water, 0.46 kg of hexadecyl maleate monoester, 0.16 kg of 50% aqueous potassium hydroxide, 0.031 kg of sodium dodecylbenzenesulfonate, 9 kg of butyl acrylate, 2.6 kg of methyl acrylate, 1.3 kg of acrylonitrile, 1 , 4-butanediol dimethacrylate 0.19 kg, t-dodecyl mercaptan 0.039 kg and potassium persulfate 0.029 kg were charged in a reaction vessel and reacted at 60 ° C. for 2 hours 30 minutes to obtain a core polymer latex. Furthermore, 301.7 kg of styrene, 0.74 kg of acrylonitrile, 0.025 kg of divinylbenzene, and 0.005 kg of t-dodecyl mercaptan were added to the reaction vessel, and the reaction was carried out to obtain a core-shell copolymer (B). The obtained latex of the core / shell copolymer (B) was broken by salting out, washed and dried to obtain a powder.

[Hydrogenated styrene block copolymer (C1 to C4)]
Table 2 shows the contents and trade names of the styrene block copolymers used in the following examples and comparative examples.

[Examples 1 to 5]
The polyester block copolymers (A-1) and (A-2) obtained in Reference Examples were added to the core / shell copolymer (B), the hydrogenated styrene block copolymer (C-1), and (C- 2), (C-3), and (C-4) are mixed using a V-blender at a blending ratio (% by weight) shown in Table 3, and twin screw extrusion having a diameter of 45 mm and a triple thread type screw The mixture was melt-kneaded at 180 ° C. using a machine and pelletized.

  Using these pellets, the results of evaluation of tensile physical properties, surface hardness, melt viscosity index, deformation, heat-bonding adhesive strength between ABS resin and polycarbonate resin, adhesiveness, and appearance of molded products This is also shown in Table 3.

[Comparative Examples 1-5]
At the blending ratio (% by weight) shown in Table 3, it was melt-kneaded and pelletized in the same manner as in Examples 1-5. The results of evaluating the physical properties in the same manner as in Examples 1 to 5 are also shown in Table 3.

  As described above, the polyester block copolymer alone (Comparative Example 1) cannot fulfill its purpose in terms of flexibility. In addition, the composition of the polyester block copolymer and the core / shell block copolymer (Comparative Example 2) does not have a hydrogenated styrene block copolymer, and therefore can achieve its purpose in terms of melt viscosity index and deformation. In addition, since the composition of the polyester block copolymer and the hydrogenated styrene block copolymer (Comparative Example 3 or 4) does not have a core / shell copolymer, the adhesive strength and molding with a hard resin can be reduced. The purpose cannot be achieved in terms of appearance and stickiness of the product. The same applies to the composition (Comparative Example 5 or 6) in which the ratio of the core / shell copolymer or the hydrogenated styrene block copolymer is large as compared with the Examples.

  From the above results, only Examples 1 to 5 which are the compositions of the present invention have good moldability (high fluidity and good appearance) without bleed out while being flexible, and two colors with a hard resin. It can be seen that it has formability (high heat-bonding adhesive strength, low deformation amount) and a smooth feel without stickiness (low tackiness).

  The thermoplastic elastomer composition of the present invention is effective for various applications such as thermal automobiles, electronic / electric equipment, precision equipment, and general consumer goods, taking advantage of the above-described excellent characteristics. It is also suitable for tubes, packings, gaskets, cushion bodies, films, and sheets.

  Further, a molded article made of the thermoplastic elastomer resin composition of the present invention, in particular, a composite molded article formed by laminating a layer made of the thermoplastic elastomer resin composition of the present invention and a hard resin layer, has various casings and covers. It can be applied to connectors, grips, rollers, casters, hoses, multilayer tubes and the like.

(A) Molded product made of thermoplastic elastomer composition for composite molding (B) Molded product made of mixed resin of ABS resin and polycarbonate resin

Claims (4)

Main components are a high-melting-point crystalline polymer segment (a1) mainly composed of a crystalline aromatic polyester and a low-melting-point polymer segment (a2) mainly composed of an aliphatic polyether unit and / or an aliphatic polyester unit. Polyester block copolymer (A) 50 to 90% by weight, butyl acrylate alone or a mixture of butyl acrylate and 2-ethylhexyl acrylate (b1), alkyl acrylate ester having 1 to 4 carbon atoms and methacrylic acid At least one compound (b2) selected from alkyl esters, vinylcyan compound (b3), maleic acid monoalkyl ester compound (b4) represented by the following structural formula (I) and crosslinking agent (b5) are emulsion-polymerized. With the polymer as a core and aromatic A core-shell copolymer (B) having a shell made of a polymer obtained by polymerizing a nil compound (b6), a vinylcyan compound (b3), and a crosslinking agent (b5), and at least one vinyl aroma A hydrogenated styrene block copolymer (C) consisting of an aromatic compound polymer block (c1) and at least one conjugated diene block (c2) is blended in an amount of 5 to 40% by weight. A tensile test was performed on a composite molded product obtained by injection molding of a mixed resin of an ABS resin and a polycarbonate resin, under the condition of a strain rate of 50 mm / min. A thermoplastic elastomer resin composition having a fusion adhesive strength of 180 N / 20 mm or more .

(In the formula, the substituent R represents a saturated aliphatic hydrocarbon group having 10 to 24 carbon atoms, an unsaturated aliphatic hydrocarbon group, or an aromatic hydrocarbon group.) The thermoplastic elastomer resin composition according to claim 1, wherein the surface hardness measured by the method described in JIS K7215 is 85 A or less. Molded body characterized by being obtained by injection molding the thermoplastic elastomer composition according to claim 1 or 2. The molded body according to claim 3, wherein the molded body is a composite molded body.

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