JP2005325229A - Thermoplastic elastomer composition and molding - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To obtain a thermoplastic elastomer resin composition that has no blocking between pellets but has excellent handleability in spite of being flexible and has no folding habit even by repeated folding, excellent moldability and appearance of molding and excellent thermal adhesiveness to a nonpolar hard resin and a molding using the same. <P>SOLUTION: The thermoplastic elastomer resin composition is obtained by mixing a polyester block copolymer with a modified hydrogenated styrene block copolymer having a specific chemical structure and has high thermal adhesiveness to a polypropylene resin. The molding is obtained from the thermoplastic elastomer resin composition. <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

  Since the present invention is flexible but has no blocking between pellets, it has excellent handling properties, and it has excellent resilience. To provide a composite molded body with a non-polar hard resin such as polypropylene resin because it has excellent surface appearance and bleed-out so that the surface appearance of the molded product is excellent, and because it has excellent thermal adhesiveness with a non-polar hard resin The present invention relates to a thermoplastic elastomer resin composition capable of being molded and a molded article using the same.

  Polyester block copolymers with a crystalline aromatic polyester unit as a hard segment and an aliphatic polyether unit such as poly (alkylene oxide) glycol as a soft segment have rubber properties such as flexibility and high resilience. It is a molding material with high mechanical properties, high temperature characteristics, low temperature characteristics, oil resistance, chemical resistance, etc. It has expanded to industrial materials such as automobiles, electrical / electronic parts, and consumer goods.

  However, there is a limit when trying to make it more flexible while retaining the characteristics of such a polyester block copolymer, and there is a limit to its application development. Further, the flexible polyester block copolymer has a problem that the thermal adhesiveness with a hard resin, particularly the thermal adhesiveness with a polypropylene resin is insufficient.

  In order to improve the flexibility of the polyester block copolymer, many attempts have been made in the past to incorporate a thermoplastic elastomer more flexible into the polyester block copolymer. For example, a styrene-butadiene block copolymer A composition comprising a hydrogenated derivative, a rubber softener, and a polyester elastomer (for example, see Patent Document 1) is known.

  In addition, attempts have been made to increase the thermal adhesiveness with a hard resin, and a hydrogenated styrene block copolymer or a block copolymer obtained by modifying a carboxylic acid with a styrene block copolymer has a melting point of 80 ° C to 180 ° C. Thermal fusion of a thermoplastic elastomer such as a hydrogenated SBS block copolymer and a hard resin made of a polyester elastomer having a thermal adhesive property with a hard resin made of a thermoplastic polyester in the range (see, for example, Patent Document 2) A composition having excellent adhesion (see, for example, Patent Document 3), a hard block comprising a block elastic body comprising a polystyrene block and a hydrogenated or non-hydrogenated polyisoprene block, and a condensation polymerization block elastic body such as a polyester elastomer. Composition excellent in heat-fusibility with resin (for example, see Patent Document 4), specific polyether ester and styrene-based elastomer A composition excellent in heat-fusibility with a hard resin made of an elastic polymer such as (see, for example, Patent Document 5), and excellent in heat-fusibility with a hard resin made of a specific styrene-based elastomer and a polyester elastomer The composition (for example, refer patent document 6) etc. are known.

  According to the above-mentioned conventional proposal, it is possible to obtain a flexible resin composition as compared with the conventional polyester block copolymer, but even with these techniques, the adverse effects caused by the softening become obvious. Result. For example, since the softening has increased the stickiness and the pellets will be blocked, handling in processes such as pelletization and drying of pellets will be a problem, and paper bags that will contain about 20 kg after drying will be separated. When wrapped and stacked in a warehouse, the pellets are integrated into a large lump that is not easily loosened, which is a serious problem especially in summer. Furthermore, when an injection molding is attempted, the mold release property is lowered due to the softening, so that the molding cycle may become longer or the molded product may be deformed. In addition, in the case of the above-mentioned conventional proposal, the surface of the molded product is peeled off, which is a drawback of the polymer blend system, and the surface of the molded product is peeled off. For this reason, there is a current situation that becomes a problem when used as an actual product. In addition, according to the above-described conventional proposal, although the thermal adhesiveness to polar hard resins such as ABS resin, polycarbonate resin, and polybutylene terephthalate resin is improved, thermal adhesion to nonpolar hard resin such as polypropylene resin is improved. Sex was insufficient.

  Among these problems, in order to solve the problem of stickiness of molded products and poor releasability at the time of molding, certain styrenic elastomers and hard resins made of thermoplastic elastomers such as paraffinic oils and polyester elastomers There has been proposed a composition (see, for example, Patent Document 7) that has excellent heat-fusibility and has no sticky feeling and excellent releasability. However, since paraffinic oil is also used in this technique, bleeding out may occur and the surface appearance of the molded product may be remarkably deteriorated, which causes a problem when used as an actual product.

  In addition, for the purpose of improving thermal adhesion to nonpolar hard resins such as polypropylene resin, a composition comprising a thermoplastic elastomer such as a specific styrene elastomer and a polyester elastomer (for example, see Patent Document 8) has been proposed. Yes. Although the resin composition according to this proposal has certainly improved thermal adhesiveness to polypropylene resin, it has not been excellent in resilience when repeatedly bent.

  Furthermore, a composition having a high viscosity and excellent bending fatigue resistance, which is composed of a polyester elastomer and a hydrogenated styrene elastomer having an acid at the end of the graft product and an epoxy compound, is also known (see, for example, Patent Document 9). The resin composition was a resin composition having a high melt viscosity suitable for blow molding, and was not a resin composition excellent in both injection moldability and thermal adhesiveness with polypropylene resin.

  In this way, it is flexible but has no blocking between pellets, has excellent handling properties, and has excellent resilience, so it does not fold even when it is bent repeatedly. There is a limit to obtaining a material that is excellent in appearance of a molded product because it does not peel or bleed out, and has excellent thermal adhesion to a nonpolar hard resin such as polypropylene resin. In particular, when a polypropylene resin and one end thereof are combined and used for automobile interiors, there is a part that can be freely deformed because it is not thermally fused with the polypropylene resin. A material having a performance that can be used for covers that are used for bending deformation has not yet been found.

On the other hand, a block copolymer in which a molecular unit containing either an alkoxysilyl group, an amino group, or both an alkoxysilyl group and an amino group is bonded to a block copolymer composed of a styrene block and a conjugated diene block is hydrogenated. An added modified hydrogenated conjugated diene polymer is known, and it has also been proposed to blend a polyester elastomer with this polymer (for example, see Patent Document 10). And, by blending both the modified hydrogenated conjugated diene polymer and the polyester elastomer, it has been disclosed to give a molded article having an excellent balance of impact resistance, strength, moldability, and adhesiveness. This prior art does not suggest any improvement in the balance between the flexibility and the tackiness of the polyester block copolymer, the maintenance of the restoring property, and the improvement of the thermal adhesiveness with the polypropylene resin.
JP-A-1-193352 Japanese Patent Laid-Open No. 1-230660 Japanese Patent Laid-Open No. 3-100045 JP-A-6-65467 Japanese Patent Laid-Open No. 10-80977 JP-A-10-130451 JP-A-8-72204 Japanese Patent Laid-Open No. 9-12487 Japanese Patent Laid-Open No. 2-276533 JP 2003-246817 A

  The present invention has an object to solve the above-described problems in the prior art, and the object is to repeat it because it is flexible, has no blocking between pellets, has excellent handling properties, and has good resilience. Even if it is bent, there is no crease, and it has excellent moldability such as injection molding because it has good releasability. The surface appearance of the molded product is beautiful because it does not cause surface peeling or bleed-out. An object of the present invention is to provide a thermoplastic elastomer resin composition excellent in adhesiveness with a polar hard resin and a molded body using the same.

  As a result of intensive investigations to achieve the above-mentioned object, the present inventors have found that the polyester block copolymer has a styrenic block copolymer with an alkoxysilyl group, an amino group, an alkoxysilyl group, and an amino group. One or more of a modified hydrogenated styrene block copolymer obtained by hydrogenating a block copolymer having a molecular unit bonded containing any one selected from the above, or the modified hydrogenated styrene block copolymer and a hydrogenated styrene block The inventors have found that the above object can be effectively achieved by a composition blended with a copolymer, and have reached the present invention.

  That is, according to the present invention, the high-melting-point crystalline polymer segment (a) mainly composed of crystalline aromatic polyester units and the low-melting-point polymer segment (b) mainly composed of aliphatic polyether units are the main constituent components. A block copolymer comprising 50 to 85% by weight of the polyester block copolymer (A), at least one vinyl aromatic compound polymer block (c) and at least one conjugated diene block (d). A block copolymer (B1) obtained by hydrogenating a block copolymer to which molecular units containing groups are bonded, at least one vinyl aromatic compound polymer block (c) and at least one conjugated diene block (d) A block copolymer in which molecular units containing amino groups are bonded to the block copolymer is hydrogenated. Molecules containing an alkoxysilyl group and an amino group in a block copolymer (B2) and a block copolymer comprising at least one vinyl aromatic compound polymer block (c) and at least one conjugated diene block (d) Heat blended with 50 to 15% by weight of one or more modified hydrogenated styrene block copolymers (B) selected from block copolymers (B3) obtained by hydrogenating block copolymers having bonded units Plastic elastomer resin composition, and 50 to 85% by weight of the polyester block copolymer (A), 5 to 45% by weight of the modified hydrogenated styrene block copolymer (B), and at least one vinyl aromatic compound weight Hydrogenated styrene block copolymer comprising a combined block (c) and at least one conjugated diene block (d) and hydrogenated C) 5 to 45% by weight so that the total amount of (B) + (C) is 50 to 15% by weight and the total amount of (A) + (B) + (C) is 100% by weight A thermoplastic elastomer resin composition blended in is provided.

In the thermoplastic elastomer resin composition of the present invention,
10% tensile strength measured according to the method described in JIS K7113 is 0.5 to 6 MPa,
The residual deformation measured by the following method is 6 mm or less,
(Measuring method: A rectangular test piece of 125 mm length, 75 mm width, 2 mm thickness was injection-molded, and a strip-shaped test piece of 80 mm length, 20 mm width, 2 mm thickness punched from the square plate test piece was measured as the distance between chucks. The sample was set on a 60 mm dematcher bending fatigue tester and subjected to 3000 times bending deformation by moving 30 mm between chucks at a distance of 60 mm at a cycle of 5 Hz at room temperature, and then the test piece was removed from the dematcher bending fatigue tester and deformed. The test piece is placed on a flat surface so that it becomes a mountain shape, and after 5 minutes of release, the distance from the flat surface to the lower side of the test piece at the apex deformed to the mountain shape of the test piece is measured to determine the amount of residual deformation.
The thermal adhesive force with respect to the polypropylene resin measured by the following method is 1 MPa or more (measurement method: a JIS No. 2 dumbbell test piece defined by JIS K7113 using a polypropylene resin is formed by injection molding, A test piece was cut into half length at the center, and one of the test pieces was set in a cavity in a mold for molding a JIS No. 2 type dumbbell test piece, and then the thermoplastic elastomer resin composition was used. Then, injection molding is performed at a cylinder temperature of 230 ° C. and a mold temperature of 50 ° C. The obtained molded product is allowed to stand at room temperature for 1 day, and then the weld strength is measured by pulling at a strain rate of 60% / min. (It is the thermal adhesive strength to the resin.)
(Measuring method: JIS No. 2 dumbbell test piece defined by JIS K7113 is made by injection molding using polypropylene resin, this test piece is cut in half at the center, and one of the test pieces is cut. After setting in a cavity in a mold for molding a JIS No. 2 type dumbbell test piece, the thermoplastic elastomer resin composition is used for injection molding at a cylinder temperature of 230 ° C. and a mold temperature of 50 ° C. The product is allowed to stand at room temperature for 1 day, and then the weld strength is measured by pulling at a strain rate of 60% / min. This weld strength is defined as the thermal adhesive force to the polypropylene resin.)
However, both are preferable conditions, and by applying these conditions, it can be expected to obtain a more excellent effect.

The molded article of the present invention is characterized by being formed by injection molding the above thermoplastic elastomer resin composition,
Being a composite molded body,
A composite molded body comprising a hard resin and the thermoplastic elastomer resin composition;
A composite molded body comprising a polypropylene resin and the thermoplastic elastomer resin composition;
Being a molded product for automobiles,
Being a molded body for automobile interiors, and that the molded body is a cover,
Are mentioned as preferable conditions.

  According to the present invention, as described below, it is flexible but has no blocking between pellets, so it is excellent in handling properties and is excellent in restorability, so that it does not fold even when it is repeatedly folded, and has good release properties. Therefore, it is excellent in moldability such as injection molding, surface peeling and bleed-out do not occur, and the molded product surface appearance is excellent, and furthermore, it has excellent thermal adhesiveness with nonpolar hard resin and nonpolar hard resin such as polypropylene resin It is possible to obtain a thermoplastic elastomer resin composition capable of providing a composite molded body of the above and a molded body using the same.

  Hereinafter, the present invention will be described in detail.

  The high melting point crystalline polymer segment (a) 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, etc. 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.

  Specific examples of the diol include diols having a molecular weight of 400 or less, for example, aliphatic diols such as 1,4-butanediol, ethylene glycol, trimethylene glycol, pentamethylene glycol, hexamethylene glycol, neopentyl glycol, decamethylene glycol, , 1-cyclohexanedimethanol, 1,4-dicyclohexanedimethanol, alicyclic diols such as tricyclodecane dimethanol, and xylylene glycol, bis (p-hydroxy) diphenyl, bis (p-hydroxy) diphenylpropane, 2,2′-bis [4- (2-hydroxyethoxy) phenyl] propane, bis [4- (2-hydroxyethoxy) phenyl] sulfone, 1,1-bis [4- (2-hydroxyethoxy) phenyl] cyclohexane Aromatic diols such as 4,4′-dihydroxy-p-terphenyl and 4,4′-dihydroxy-p-quarterphenyl are preferred, and such diols are in the form of ester-forming derivatives, such as acetyl compounds and alkali metal salts. But it can be used.

  Two or more of these dicarboxylic acids, derivatives thereof, diol components and derivatives thereof may be used in combination. An example of a preferable high-melting crystalline polymer segment (a) is a polybutylene terephthalate unit derived from terephthalic acid and / or dimethyl terephthalate and 1,4-butanediol. Also preferred are those comprising polybutylene terephthalate units derived from terephthalic acid and / or dimethyl terephthalate and polybutylene isophthalate units derived from isophthalic acid and / or dimethyl isophthalate and 1,4-butanediol. .

  The low melting point polymer segment (b) of the polyester block copolymer (A) used in the present invention is an aliphatic polyether, and specific examples of the aliphatic polyether include poly (ethylene oxide) glycol, poly (propylene). Oxide) glycol, poly (tetramethylene oxide) glycol, poly (hexamethylene oxide) glycol, copolymers of ethylene oxide and propylene oxide, ethylene oxide adducts of poly (propylene oxide) glycol, and copolymers of ethylene oxide and tetrahydrofuran, etc. Can be mentioned. Of these, poly (tetramethylene oxide) glycol and / or poly (propylene oxide) glycol ethylene oxide adducts and / or copolymers of ethylene oxide and tetrahydrofuran are preferred. The number average molecular weight of these low-melting polymer segments is preferably about 300 to 6000 in the copolymerized state.

  The copolymerization amount of the low melting point polymer segment (b) of the polyester block copolymer (A) used in the present invention is usually 10 to 90% by weight, preferably 30 to 85% by weight, more preferably 50 to 80%. % By weight.

  The polyester block copolymer (A) used in the present invention can be produced by a known method. Specific examples thereof include, for example, a method of subjecting a lower alcohol diester of dicarboxylic acid, an excessive amount of low molecular weight glycol and a low melting point polymer segment component to a transesterification reaction in the presence of a catalyst, and polycondensing the resulting reaction product, Any method such as a method in which an acid, an excessive amount of glycol and a low melting point polymer segment component are esterified in the presence of a catalyst and the resulting reaction product is polycondensed may be used.

  At least one vinyl aromatic compound polymer block (c) of the modified hydrogenated styrene block copolymer (B) used in the present invention is composed of styrene, α-methylstyrene, vinyltoluene, p-methylstyrene, pt. -Blocks polymerized from butyl styrene, o-ethyl styrene, o, p-dichlorostyrene, etc. Among them, styrene is preferably used.

  At least one conjugated diene block (d) of the modified hydrogenated styrene block copolymer (B) used in the present invention is butadiene, isoprene, butadiene / isoprene copolymer, 2,3-dimethyl-1,3-butadiene. , 1,3-pentadiene, 2-methyl-1,3-pentadiene, 1,3-hexadiene, 4,5-diethyl-1,3-octadiene, 3-butyl-1,3-octadiene, and chloroprene Of these, among these, styrene-butadiene block copolymers, styrene-isoprene block copolymers, and styrene-isoprene / butadiene block copolymers are preferably used.

  The modified hydrogenated styrene block copolymer (B) used in the present invention comprises at least one vinyl aromatic compound polymer block (c) as described above and at least one conjugated diene block (d) as described above. In addition, one or more selected from molecular units containing an alkoxysilyl group, an amino group, and both an alkoxysilyl group and an amino group are bonded and hydrogenated. That is, the modified hydrogenated styrene block copolymer (B) used in the present invention comprises at least one vinyl aromatic compound polymer block (c) as described above and at least one conjugated diene block (d) as described above. ), Wherein the molecular unit containing the alkoxysilyl group is bonded and hydrogenated (B1), and at least one vinyl aromatic compound polymer block (c) as described above At least one conjugated diene block (d) as described above, in which molecular units containing amino groups are bonded and hydrogenated (B2), and at least one vinyl aromatic as described above Composed of a compound polymer block (c) and at least one conjugated diene block (d) as described above, alkoxysilyl And after being bound molecular units containing both amino groups are those of 1 or more selected from among (B3) which is hydrogenated.

  The modified hydrogenated styrene block copolymer (B) used in the present invention is disclosed in, for example, JP-A No. 2003-155385. In order to bond molecular units containing alkoxysilyl groups, tetraethoxysilane, tetramethoxysilane, methyltriethoxysilane, methyltrimethoxysilane, dimethyldimethoxysilane, dimethyldiethoxysilane, methyltriphenoxysilane, dimethyldiphenoxy Silane, 1-trimethylsilyl-2-dimethoxy-1-aza-2-silanecyclopentane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropylmethyldiethoxysilane, γ-methacryloxypropylmethyldimethoxysilane, γ-methacryloxypropylmethylmethoxysilane, trimethylsiloxytriphenoxysilane, trimethylsiloxytrimethoxysilane, trimethylsiloxytriethoxysilane, trimethylsiloxy tribute Shishiran and, like 1,1,3,3-tetramethyl-1-phenoxymethyl Siji siloxanes are used. In addition, in order to bind a molecular unit containing an amino group, a conjugated diene and an aromatic vinyl compound are combined with 3-lithio-1- [N, N-bis (trimethylsilyl)] aminopropane, 2-lithio-1- In the presence of an organic alkali metal compound having an amino group such as [N, N-bis (trimethylsilyl)] aminoethane or 3-lithio-2,2-dimethyl-1- [N, N-bis (trimethylsilyl)] aminopropane. Polymerization method, conjugated diene and p- [N, N-bis (trimethylsilyl) amino] styrene, p- [N, N-bis (trimethylsilyl) aminomethyl] styrene, p- {2- [N, N-bis ( An unsaturated monomer having an amino group such as trimethylsilyl) amino] ethyl} styrene or an aromatic vinyl compound thereof and an organic alkali metal compound A method of polymerizing in the presence, and conjugated diene or conjugated diene and aromatic vinyl compound are polymerized in the presence of an organic alkali metal compound, and the resulting conjugated diene polymer is converted to N-benzylidenemethylamine, N-benzylidenebutylamine, A method of reacting N-benzylideneaniline or the like is used.

  The modified hydrogenated styrene block copolymer (B) used in the present invention is obtained by bonding an alkoxysilyl group, an amino group, or a molecular unit containing both an alkoxysilyl group and an amino group by the above method. , Hydrogenated.

  The modified hydrogenated styrene block copolymer (B) used in the present invention is a block copolymer comprising at least one vinyl aromatic compound polymer block (c) and at least one conjugated diene block (d). This is a block copolymer obtained by hydrogenating a block copolymer in which an alkoxysilyl group, an amino group, or a molecular unit containing both an alkoxysilyl group and an amino group is bonded. May be. Examples of such polyolefin blocks include polyethylene blocks, polypropylene blocks, and polyethylene / polypropylene copolymer blocks.

  At least one vinyl aromatic compound polymer block (c) of the hydrogenated styrene block copolymer (C) which is another component used in the present invention is the modified hydrogenated styrene block copolymer (B) described above. This is the same as the polymer block (c).

  In addition, at least one conjugated diene block (d) of the hydrogenated styrene block copolymer (C) used in the present invention is also the polymer block (c) of the modified hydrogenated styrene block copolymer (B) described above. It is the same.

  The hydrogenated styrene block copolymer (C) used in the present invention comprises at least one vinyl aromatic compound polymer block (c) as described above and at least one conjugated diene block (d) as described above. It is further hydrogenated.

  In the thermoplastic elastomer resin composition of the present invention, a high melting point crystalline polymer segment (a) mainly composed of crystalline aromatic polyester units, and a low melting point polymer segment (b) mainly composed of aliphatic polyether units, 50 to 85% by weight, preferably 55 to 80% by weight, more preferably 60 to 75% by weight, of at least one vinyl aromatic compound polymer block (c), ) And at least one conjugated diene block (d), a block copolymer (B1) obtained by hydrogenating a block copolymer in which a molecular unit containing an alkoxysilyl group is bonded, at least one vinyl An aromatic polymer block (c) and at least one conjugated diene block (d). A block copolymer (B2) obtained by hydrogenating a block copolymer in which a molecular unit containing an amino group is bonded to the block copolymer, at least one vinyl aromatic compound polymer block (c), and at least one conjugated diene One or more selected from block copolymers (B3) obtained by hydrogenating a block copolymer in which molecular units containing an alkoxysilyl group and an amino group are bonded to the block copolymer comprising the block (d) The modified hydrogenated styrene block copolymer (B) is blended in an amount of 50 to 15% by weight, preferably 45 to 20% by weight, and more preferably 40 to 25% by weight. When the blending amount of the polyester block copolymer (A) is less than the above range, not only the heat resistance, chemical resistance, blocking resistance, restoring property, releasability, etc. of the resin composition become insufficient, but also surface peeling. This is not preferable because the appearance of the molded product is deteriorated. Moreover, when the compounding quantity of a polyester block copolymer (A) exceeds said range, since a softness | flexibility will fall and thermal adhesiveness with respect to a polypropylene resin becomes inadequate, it is unpreferable.

  In the case of blending the polyester block copolymer (A), the modified hydrogenated styrene block copolymer (B), and the hydrogenated styrene block copolymer (C) in the thermoplastic elastomer resin composition of the present invention. The polyester block copolymer (A) 50 to 85% by weight, the modified hydrogenated styrene block copolymer (B) 5 to 45% by weight, and at least one vinyl aromatic compound polymer block (c) Hydrogenated styrene block copolymer (C) comprising at least one conjugated diene block (d) and hydrogenated in an amount of 5 to 45% by weight, and the total amount of (B) + (C) is 50 to 15% by weight. So that the total amount of (A) + (B) + (C) is 100% by weight. When the blending amount of the polyester block copolymer (A) is less than the above range, not only the heat resistance, chemical resistance, blocking resistance, restoring property, releasability, etc. of the resin composition become insufficient, but also surface peeling. This is undesirable because the appearance of the molded product is poor. Moreover, when the compounding quantity of a polyester block copolymer (A) exceeds said range, since a softness | flexibility will fall and thermal adhesiveness with respect to a polypropylene resin becomes inadequate, it is unpreferable.

  In the thermoplastic elastomer resin composition of the present invention, the 10% tensile strength measured according to the method described in JIS K7113 is preferably 0.5 to 6 MPa, and more preferably 0.5 to 4 MPa. Further, it is preferably 0.5 to 2 MPa.

  In the thermoplastic elastomer resin composition of the present invention, the amount of residual deformation measured by the following method is preferably 6 mm or less, more preferably 4 mm or less, and further preferably 2 mm or less. .

  (Measuring method: A rectangular test piece of 125 mm length, 75 mm width, 2 mm thickness was injection-molded, and a strip-shaped test piece of 80 mm length, 20 mm width, 2 mm thickness punched from the square plate test piece was measured as the distance between chucks. The sample was set on a 60 mm dematcher bending fatigue tester and subjected to 3000 times bending deformation by moving 30 mm between chucks at a distance of 60 mm at a cycle of 5 Hz at room temperature. The test piece is placed on a flat surface so that it becomes a mountain shape, and after 5 minutes of release, the distance from the flat surface to the lower side of the test piece at the apex deformed to the mountain shape of the test piece is measured to determine the amount of residual deformation.

  In the thermoplastic elastomer resin composition of this invention, it is preferable that the thermal adhesive force with respect to the polypropylene resin measured by the following method is 1 Mpa or more.

  (Measuring method: JIS No. 2 dumbbell test piece defined by JIS K7113 is made by injection molding using polypropylene resin, this test piece is cut in half at the center, and one of the test pieces is cut. After being set in a cavity in a mold for molding a JIS No. 2 type dumbbell test piece, injection molding is performed at a cylinder temperature of 230 ° C. and a mold temperature of 50 ° C. using the thermoplastic elastomer resin composition of the present invention. The molded product is allowed to stand at room temperature for 1 day, and then the weld strength is measured by pulling at a strain rate of 60% / min. The weld strength is defined as the thermal adhesive force to the polypropylene resin.

  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, talc, phthalic acid ester-based , Plasticizers such as benzoate, trimellitic acid ester and pyromellitic ester, rubber softeners such as paraffinic and naphthenic oils, colorants such as dyes and pigments, UV blocking such as titanium oxide and carbon black Agent, glass fiber, carbon fiber, potassium titanate Reinforcing agents, such as whiskers, flame retardants, foaming agents, adhesives, adhesion promoters, fluorescent agents, crosslinking agents, and surfactants can be allowed to optionally contain the like.

  Since the thermoplastic elastomer resin composition of the present invention is flexible but has no blocking between pellets, it has excellent handling properties and excellent resilience. Excellent moldability such as injection molding, surface peeling and bleed-out do not occur, excellent surface appearance of molded products, and excellent thermal adhesiveness with non-polar hard resin, and with non-polar hard resin such as polypropylene resin Because it can provide composite molded products, it is useful for thermal automobiles, electronic / electrical equipment, precision equipment, and various molded products for general consumer goods. Furthermore, grips, tubes, packings, gaskets, cushion bodies It is also suitable for films, sheets, and the like.

  It is also useful to obtain a composite molded product obtained by laminating a layer made of the thermoplastic elastomer resin composition of the present invention and a hard resin layer. The hard resin constituting the hard resin layer is not particularly limited as long as it is a resin that retains the rigidity of the composite molded product and has the desired mechanical strength. It is done. The composite molded body is manufactured by a coextrusion molding method, a multicolor injection molding method including two-color molding, an overmolding by an insert molding method, or the like. Since the thermoplastic elastomer resin composition of the present invention is excellent in adhesiveness with polypropylene resin, the molded body of the present invention, particularly the composite molded body, includes various cases, covers, connectors, grips, rollers, casters, hoses, It can be applied to multilayer tubes. The thermoplastic elastomer resin composition of the present invention is particularly excellent in thermal adhesiveness with polypropylene resin, so it is used in automobiles, particularly in automobile interiors, specifically, a part thereof is thermally bonded to polypropylene resin by composite molding, The other is suitable for use as a cover that can be freely deformed and repeatedly bent and deformed.

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

[Melting point]
Using a differential scanning calorimeter (DSC-910, manufactured by Du Pont), the top temperature of the melting peak when heated at a heating rate of 10 ° C./min in a nitrogen gas atmosphere was measured.

[Melt viscosity index (MFR)]
Measurement was performed at a temperature of 200 ° C. and a load of 2160 g in accordance with ASTM D-1238.

[Blocking properties]
200 g of pellets are put into an assembling box-shaped container having an internal dimension of 15 cm long × 7 cm wide × 6 cm high, a plate of 15 cm long × 7 cm wide is placed on the pellet, and a load of 16 kg is applied thereto. In that state, heat treatment is performed in a hot air oven at 80 ° C. for 20 hours. After the test, the side wall of the box-type container was removed and a load was applied, and the maximum load at which the blocking state collapsed was measured.

[Surface peeling]
The pellets dried at 80 ° C. for 3 hours were injection-molded at a temperature of 200 ° C. to obtain a molded product having a length of 115 mm, a width of 60 mm, and a thickness of 2 mm. The surface of the molded product was observed with the naked eye to determine whether surface peeling occurred.

[Hardness (Durometer D)]
Measured according to ASTM D-2240.

[Mechanical properties]
According to JIS K7113, the tensile strength at break and the tensile elongation at break were measured.

[10% tensile strength]
It measured according to JIS K7113.

[Residual deformation]
A rectangular plate test piece of length 125mm, width 75mm, thickness 2mm is injection-molded, and a strip-shaped test piece 80mm length, width 20mm, thickness 2mm punched from the square plate test piece is bent by a dematcher with a distance between chucks of 60mm. Set on a fatigue tester and give 3000 times of bending deformation by moving from chuck distance 60mm to 30mm at a cycle of 5Hz at room temperature. Then, remove the test piece from the Dematcher bending fatigue tester. The mold was placed on a flat surface so as to form a mold, and after 5 minutes of release, the distance from the flat surface to the lower side of the test piece at the apex deformed into a mountain shape of the test piece was measured to determine the amount of residual deformation.

[Releasability]
When each of the pellets dried at 80 ° C. for 3 hours is used to injection-mold a square plate test piece having a length of 125 mm, a width of 75 mm, and a thickness of 2 mm at a cylinder temperature of 230 ° C. and a mold temperature of 50 ° C. The ease of removal from the mold was evaluated, and the following determination was made.
○: The entire surface of the square plate specimen is released.
Δ: A part of the square plate test piece is in close contact with the mold.
X: The entire surface of the square plate test piece is in close contact with the mold.

[Thermal adhesive strength]
A JIS No. 2 dumbbell test piece defined in JIS K7113 was prepared by injection molding using “Grand Polypro” J703W (manufactured by Grand Polymer Co., Ltd.) as a polypropylene resin. Then, one of the test pieces was set in a cavity in a mold for molding a JIS No. 2 type dumbbell test piece, and then the cylinder temperature was 230 ° C. and the mold temperature was 50 ° C. using the evaluation resin composition. Was injection molded. The obtained molded article was allowed to stand at room temperature for 1 day, and was then pulled at a strain rate of 60% / min to measure the weld strength. This weld strength was defined as the thermal adhesive force to the polypropylene resin.

[Reference example]
[Production of Polyether Ester Block Copolymer (A-1)]
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, are stirred with a helical ribbon. 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 Phenolic Antioxidant manufactured by Ciba Geigy) to the reaction mixture, the temperature was raised to 245 ° C., and then the pressure in the system was increased to 27 Pa over 50 minutes. The polymerization was carried out for 1 hour and 50 minutes under the reduced pressure. The obtained polymer was discharged into water in the form of strands and pelletized by cutting.

[Production of Polyether Ester Block Copolymer (A-2)]
329 parts of terephthalic acid, 96 parts of isophthalic acid, 403 parts of 1,4-butanediol, and 467 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 Phenolic Antioxidant manufactured by Ciba Geigy) to the reaction mixture, the temperature was raised to 245 ° C., and then the pressure in the system was changed to 27 Pa over 50 minutes. The pressure was reduced and polymerization was carried out for 2 hours and 45 minutes under the 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.

[Modified hydrogenated styrene block copolymer (B)]
The contents of the modified hydrogenated styrene block copolymer used in the following examples are shown in Table 2.

[Hydrogenated styrene block copolymer (C)]
The contents and trade names of the hydrogenated styrene block copolymers used in the following examples are shown in Table 3.

[Examples 1 to 8]
To the polyester block copolymers (A-1) and (A-2) obtained in Reference Examples, the modified hydrogenated styrene block copolymers (B-1), (B-2), (B-3), If necessary, the hydrogenated styrene block copolymers (C-1), (C-2), and (C-3) are mixed using a V-blender at the blending ratio (% by weight) shown in Table 4. Using a twin screw extruder having a diameter of 45 mm and a triple thread type screw, the mixture was melt-kneaded at 230 ° C. and pelletized.

  Using these pellets, the load that breaks blocking, surface layer peeling, bleed out, melting point, hardness, tensile breaking strength, tensile breaking elongation, 10% tensile strength, residual deformation, releasability, heat with polypropylene resin The results of evaluating the adhesive strength are also shown in Table 4.

[Comparative Examples 1 to 7]
It was melt-kneaded and pelletized at the blending ratios (% by weight) shown in Table 4 in the same manner as in Examples 1-8. The results of evaluating physical properties in the same manner as in Examples 1 to 8 are also shown in Table 4.

  From the above results, the thermoplastic elastomer resin compositions of the present invention shown in Examples 1 to 8 are flexible, have no blocking between pellets, have a small residual deformation, excellent releasability, surface peeling and Does not cause bleed out. Furthermore, it is excellent in thermal adhesiveness with polypropylene resin. On the other hand, the resin compositions shown in Comparative Examples 1 and 2 were flexible and did not block between pellets, and the residual deformation amount was small, but they were not thermally bonded to polypropylene resin. Moreover, although the resin composition shown to Comparative Examples 3-5 was flexible and heat adhesiveness with a polypropylene resin was recognized to some extent, the blocking between pellets was large and the mold release property was also bad. Furthermore, since the compatibility was inferior, surface layer peeling occurred on the surface of the molded product, and when attempting to measure the amount of residual deformation, severe layer peeling occurred at the bent portion. In the resin compositions shown in Comparative Examples 6 to 7, although layer peeling was not observed, the blocking between pellets was large and the releasability was poor.

  The thermoplastic elastomer resin composition of the present invention is useful for thermal automobiles, electronic / electrical equipment, precision equipment, and various molded articles for 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 product obtained by laminating a layer made of the thermoplastic elastomer resin composition of the present invention and a hard resin layer, particularly a composite molded product of polypropylene resin, has various housings, covers, connectors, grips, rollers, casters. It can be applied to hoses and multilayer tubes.

Claims (12)

A polyester block copolymer comprising a high-melting-point crystalline polymer segment (a) mainly composed of crystalline aromatic polyester units and a low-melting-point polymer segment (b) mainly composed of aliphatic polyether units as main components ( A) A molecular unit containing an alkoxysilyl group is bonded to a block copolymer comprising 50 to 85% by weight, at least one vinyl aromatic compound polymer block (c) and at least one conjugated diene block (d). A block copolymer (B1) obtained by hydrogenating the block copolymer, an amino group in a block copolymer comprising at least one vinyl aromatic compound polymer block (c) and at least one conjugated diene block (d) Block copolymer (B2) obtained by hydrogenating a block copolymer having molecular units bonded to each other A block copolymer in which molecular units containing an alkoxysilyl group and an amino group are bonded to a block copolymer comprising at least one vinyl aromatic compound polymer block (c) and at least one conjugated diene block (d) A thermoplastic elastomer resin composition containing 50 to 15% by weight of at least one modified hydrogenated styrene block copolymer (B) selected from the block copolymer (B3) obtained by hydrogenating the above. 50 to 85% by weight of the polyester block copolymer (A), 5 to 45% by weight of the modified hydrogenated styrene block copolymer (B), at least one vinyl aromatic compound polymer block (c) and at least A hydrogenated hydrogenated styrene block copolymer (C) consisting of one conjugated diene block (d) (C) in an amount of 5 to 45% by weight, and a total amount of (B) + (C) of 50 to 15% by weight. A thermoplastic elastomer resin composition blended so that the total amount of (A) + (B) + (C) is 100% by weight. The thermoplastic elastomer resin composition according to claim 1 or 2, which has a 10% tensile strength of 0.5 to 6 MPa measured according to a method described in JIS K7113. The thermoplastic elastomer resin composition according to any one of claims 1 to 3, wherein the residual deformation measured by the following method is 6 mm or less.
(Measuring method: A rectangular test piece of 125 mm length, 75 mm width, 2 mm thickness was injection-molded, and a strip-shaped test piece of 80 mm length, 20 mm width, 2 mm thickness punched from the square plate test piece was measured as the distance between chucks. The sample was set on a 60 mm dematcher bending fatigue tester and subjected to 3000 times bending deformation by moving 30 mm between chucks at a distance of 60 mm at a cycle of 5 Hz at room temperature, and then the test piece was removed from the dematcher bending fatigue tester and deformed. The test piece is placed on a flat surface so that it becomes a mountain shape, and after 5 minutes of release, the distance from the flat surface to the lower side of the test piece at the apex deformed to the mountain shape of the test piece is measured to determine the amount of residual deformation. The thermoplastic elastomer resin composition according to any one of claims 1 to 4, wherein the thermal adhesive force with respect to the polypropylene resin measured by the following method is 1 MPa or more.
(Measuring method: JIS No. 2 dumbbell test piece defined by JIS K7113 is made by injection molding using polypropylene resin, this test piece is cut in half at the center, and one of the test pieces is cut. After setting in a cavity in a mold for molding a JIS No. 2 type dumbbell test piece, the thermoplastic elastomer resin composition is used for injection molding at a cylinder temperature of 230 ° C. and a mold temperature of 50 ° C. The product is allowed to stand at room temperature for 1 day, and then the weld strength is measured by pulling at a strain rate of 60% / min. This weld strength is defined as the thermal adhesive force to the polypropylene resin.) The molded object formed by injection-molding the thermoplastic elastomer resin composition of any one of Claims 1-5. The molded article according to claim 6, which is a composite molded article. The molded body according to claim 7, wherein the composite molded body is a composite molded body made of a hard resin and the thermoplastic elastomer resin composition according to claim 1. The molded body according to claim 7 or 8, wherein the hard resin is a polypropylene resin. The molded article according to any one of claims 6 to 9, which is for automobiles. The molded article according to any one of claims 6 to 9, which is used for automobile interior. It is a cover, The molded object of any one of Claims 6-9.