JP2018035298A - Thermoplastic elastomer composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a thermoplastic elastomer composition which is excellent in flexibility and heat fusibility with a polar resin such as a polycarbonate resin, an ABS resin, an ASA resin and an acrylic resin.SOLUTION: A thermoplastic elastomer composition contains following components (A), (B) and (C), and contains 30-70 pts.mass of the component (A), 10-50 pts.mass of the component (B) and 5-50 pts.mass of the component (C) with respect to 100 pts.mass of the total composition. A component (A): a polyurethane-based thermoplastic elastomer containing following components (A-1) and/or (A-2), a component (A-1): a polyether-based thermoplastic polyurethane elastomer and a component (A-2): a polycarbonate-based thermoplastic polyurethane elastomer, a component (B): a styrenic elastomer and/or a hydrogenated product of the styrenic elastomer, and a component (C): a softening agent for hydrocarbon-based rubber.SELECTED DRAWING: None

Description

The present invention relates to a thermoplastic elastomer composition that is excellent in flexibility and excellent in heat-fusibility with polar resins such as polycarbonate resin, ABS resin, ASA resin, and acrylic resin.
The present invention also relates to a molded article obtained by molding the thermoplastic elastomer composition, a composite molded article using the thermoplastic elastomer composition, and an automobile member.

  In the fields of automotive parts, OA equipment, home appliance parts, sporting goods, daily necessities, toys, etc., not only the design and appearance are improved, but also the touch is good, the touch is good, and In order to provide anti-slip and sealing properties, a laminated molded body may be obtained by laminating a soft thermoplastic elastomer layer on a relatively hard thermoplastic resin layer such as polycarbonate resin, ABS resin, ASA resin, or acrylic resin. As the thermoplastic elastomer, a styrene thermoplastic elastomer is usually used.

  There are two methods for stacking and integrating these layers of dissimilar materials, such as using an adhesive, and fitting each layer with unevenness, all of which are in terms of production efficiency, manufacturing cost, and product design flexibility. It is not preferable.

  If these layers can be laminated and integrated by heat fusion, a composite molded body can be molded in one step without the need for a separate bonding step, processing for forming irregularities, and a fitting step. Elastomers have a problem that they are inferior in heat-fusibility with polar resins such as polycarbonate resin, ABS resin, ASA resin or acrylic resin.

Conventionally, what blended the following components AC as a styrenic thermoplastic elastomer used for a heat fusion compound molding with polycarbonate resin and acrylic resin is proposed (patent documents 1).
Component A: Hydrogenated product of styrene / conjugated diene block copolymer, whose conjugated diene is a mixture of isoprene and butadiene Component B: Paraffinic oil component C: Polyester thermoplastic elastomer, polyamide thermoplastic elastomer And at least one thermoplastic elastomer selected from the group of polyurethane-based thermoplastic elastomers

Patent Document 1 mentions a polyurethane-based thermoplastic elastomer as Component C, but the polyurethane-based thermoplastic elastomer used in the examples of Patent Document 1 (“Elastollan” manufactured by Takeda Birdish Urethane Kogyo Co., Ltd.). Is an adipate-based thermoplastic polyurethane elastomer and does not fall under the component (A-1) or component (A-2) of the present invention.
The conjugated diene component of the styrene / conjugated diene block copolymer of component A used in Patent Document 1 is a mixture of isoprene and butadiene.

JP-A-8-72204

According to the study of the present inventor, it has been found that the styrenic thermoplastic elastomer of Patent Document 1 has insufficient heat-fusibility with a polar resin such as polycarbonate resin, ABS resin, ASA resin, or acrylic resin. .
Specifically, in Patent Document 1, evaluation of heat-fusibility is performed by a method similar to the method described in the Examples section below. For example, heat-fusibility to a polycarbonate resin (molding temperature) The peel strength at 240 ° C.) is 2.2 to 9.1 kg / 25 mm (= 2.16 to 89 N / 25 mm), which is clearly inferior to the peel strength achieved in the examples of the present invention. is there.

An object of the present invention is to provide a thermoplastic elastomer composition that is excellent in flexibility and excellent in heat-fusibility with polar resins such as polycarbonate resin, ABS resin, ASA resin, and acrylic resin.
The present invention also provides a molded article formed by molding the thermoplastic elastomer composition, a composite molded article using the thermoplastic elastomer composition, and an automobile member.

As a result of intensive studies to solve the above problems, the present inventor, as a polyurethane-based thermoplastic elastomer to be blended with a styrene-based thermoplastic elastomer composition, particularly a polyether-based thermoplastic polyurethane elastomer and / or a polycarbonate-based thermoplastic. It has been found that by using a polyurethane elastomer, a thermoplastic elastomer composition excellent in flexibility and heat fusion with a polar resin can be obtained.
That is, the gist of the present invention is as follows.

[1] At least the following components (A), (B) and (C) are contained, and 30 to 70 parts by mass of component (A) and component (B) with respect to 100 parts by mass of the total composition in the composition. 10 to 50 parts by mass and 5 to 50 parts by mass of the component (C).
Component (A): Polyurethane thermoplastic elastomer containing the following components (A-1) and / or (A-2) Component (A-1): Polyether thermoplastic polyurethane elastomer Component (A-2): Polycarbonate Thermoplastic polyurethane elastomer component (B): Styrenic elastomer and / or hydrogenated component of styrene elastomer (C): Softener for hydrocarbon rubber

（上記式（１）中のＡはジイソシアネート化合物とグリコールとからなるハードセグメントを表し、Ｂはジイソシアネート化合物と長鎖グリコールからなるソフトセグメントを表し、Ｙはウレタン結合のジイソシアネート化合物の残基を表す。） [2] The component (A) is a polyurethane-based thermoplastic elastomer represented by the following general formula (1), and the component (A-1) has a long-chain glycol in the following general formula (1) having a molecular weight of 500 to 500. The thermoplastic elastomer composition according to [1], which is composed of 10,000 alkylene glycol, and the component (A-2) is a long-chain glycol in the following general formula (1) composed of polycarbonate.

(A in the above formula (1) represents a hard segment composed of a diisocyanate compound and glycol, B represents a soft segment composed of a diisocyanate compound and a long-chain glycol, and Y represents a residue of a urethane-bonded diisocyanate compound. )

[3] The thermoplastic elastomer composition according to [1] or [2], wherein the component (B) is a styrene / conjugated diene block copolymer and / or a hydrogenated product thereof, and the conjugated diene is butanediene. .

[4] The thermoplastic elastomer composition according to any one of [1] to [3], wherein the component (C) is a paraffinic oil having a kinematic viscosity at 40 ° C. of 20 to 800 centistokes.

[5] A molded article obtained by molding the thermoplastic elastomer composition according to any one of [1] to [4].

[6] A composite molded product obtained by heat-sealing the molded product according to [5] with polycarbonate resin, ABS resin, ASA resin, or acrylic resin.

[7] An automotive member comprising the composite molded article according to [6].

[8] The automobile member according to [7], which is an automobile exterior member.

The thermoplastic elastomer composition of the present invention is excellent in flexibility and heat fusion property with polar resins such as polycarbonate resin, ABS resin, ASA resin and acrylic resin.
Therefore, according to the thermoplastic elastomer composition of the present invention, a thermoplastic elastomer composition layer having excellent flexibility is formed on the surface of a polar resin layer such as a polycarbonate resin, an ABS resin, an ASA resin, and an acrylic resin. Thus, the composite molded body can be manufactured with high productivity by integral molding by heat fusion.

Hereinafter, embodiments of the present invention will be described in detail.
The present invention is not limited to the following description, and can be arbitrarily modified and implemented without departing from the gist of the present invention. In addition, in this specification, when expressing by putting a numerical value or a physical-property value before and behind using "-", it shall use as what includes the value before and behind.

[Thermoplastic elastomer composition]
The thermoplastic elastomer composition of the present invention contains at least the following components (A), (B) and (C), and the component (A) is 30 to 70 with respect to 100 parts by mass of the total composition in the composition. It contains 10 to 50 parts by mass of component (B) and 5 to 50 parts by mass of component (C).
Component (A): Polyurethane thermoplastic elastomer containing the following components (A-1) and / or (A-2) Component (A-1): Polyether thermoplastic polyurethane elastomer Component (A-2): Polycarbonate Thermoplastic polyurethane elastomer component (B): Styrenic elastomer and / or hydrogenated component of styrene elastomer (C): Softener for hydrocarbon rubber

<Mechanism>
The thermoplastic elastomer composition of the present invention containing the component (A), the component (B), and the component (C) in a predetermined ratio provides excellent heat-fusibility with a polar resin while imparting flexibility. Although the details of the mechanism are not clear, the polycarbonate component or the polyether component of the polyurethane thermoplastic elastomer of component (A) increases the molecular entanglement with the polar resin at the time of thermal fusion, This is considered to be due to the improvement of the wearing strength. That is, in the thermoplastic elastomer composition of the present invention, the polyether thermoplastic polyurethane elastomer of component (A-1) and / or the polycarbonate of component (A-2) is used as the polyurethane thermoplastic elastomer of component (A). By using a thermoplastic polyurethane elastomer, it is possible to obtain a higher thermal fusion property with respect to a polar resin than Patent Document 1 using an adipate-based thermoplastic polyurethane elastomer as a polyurethane-based thermoplastic elastomer.

<Component (A)>
In the present invention, as the polyurethane-based thermoplastic elastomer of component (A), from the viewpoint of ensuring good adhesion with a polar resin, molding processability, and rubbery feel, a diisocyanate compound and a glycol having a molecular weight of about 50 to 500 are used. A polyether-based thermoplastic polyurethane elastomer, such as a polyalkylene glycol having a molecular weight of about 500 to 10,000, and a hard segment composed of a diisocyanate compound and a long-chain glycol. (Component (A-1)) and / or a polycarbonate thermoplastic polyurethane elastomer (component (A-2)) in which the long-chain glycol is polycarbonate is used.

  Here, as the diisocyanate compound, known and commonly used compounds such as phenylene diisocyanate, trigen diisocyanate, xylene diisocyanate, 4,4-diphenylmethane diisocyanate, hexamethylene diisocyanate are preferably used. These diisocyanate compounds may be the same or different in each of the soft segment and the hard segment.

  This type of component (A) polyurethane-based thermoplastic elastomer is represented by the following general formula (1).

(A in the above formula (1) represents a hard segment composed of a diisocyanate compound and glycol, B represents a soft segment composed of a diisocyanate compound and a long-chain glycol, and Y represents a residue of a urethane-bonded diisocyanate compound. )

  The component (A) preferably has a durometer A hardness (type A durometer hardness) measured in accordance with JIS K6253 of 60 to 95, preferably 70 to 94, from the viewpoint of flexibility and heat aging resistance. More preferred.

  Commercially available polyurethane thermoplastic elastomers of component (A) include “Elastollan (registered trademark)” (manufactured by BASF), “Pandex (registered trademark)” (manufactured by DIC Bayern), “Resamine (registered trademark)”. "(Manufactured by Dainichi Seika Kogyo Co., Ltd.).

  As the polyurethane thermoplastic elastomer of component (A), only the polyether thermoplastic polyurethane elastomer of component (A-1) may be used, or only the polycarbonate thermoplastic polyurethane elastomer of component (A-2) is used. The component (A-1) and the component (A-2) may be mixed and used.

<Component (B)>
Examples of the component (B) styrene elastomer used in the present invention include styrene-butadiene copolymer rubber and styrene-isoprene copolymer rubber. Among these, from the viewpoint of heat resistance and flexibility, styrene-based elastomer is used. The block copolymer is preferably a styrene-based block copolymer having a polymer block composed of vinyl aromatic hydrocarbon units and a polymer block composed of conjugated diene units, and the following formula (2) and / or Copolymer of vinyl aromatic hydrocarbon represented by formula (3) and conjugated diene block and hydrogenated product thereof (hydrogenated derivative) (hereinafter sometimes referred to as “hydrogenated block copolymer”) It is particularly preferable that a hydrogenated product of a copolymer of a vinyl aromatic hydrocarbon and a conjugated diene block represented by the following formula (2) and / or formula (3): It is most preferred that.

S- (DS) m (2)
(SD) n (3)
(In the formula, S represents a polymer block composed of vinyl aromatic hydrocarbon units, D represents a polymer block composed of conjugated diene units, and m and n represent integers of 1 to 5).

  The block copolymer described above may be linear, branched and / or radial.

As the monomeric vinyl aromatic hydrocarbon constituting the polymer block of S, a styrene derivative such as styrene or α-methylstyrene is preferable.
As the conjugated diene monomer constituting the polymer block of D, butadiene and / or isoprene are preferable, and butanediene is particularly preferable.

  When the block copolymer represented by the formula (2) and / or the formula (3) is a hydrogenated block copolymer, and the polymer block of D is composed only of butadiene, The 1,2-addition structure is preferably 20 to 70% by mass in order to maintain the properties as an elastomer after hydrogenation.

  m and n are preferably large in the sense of lowering the order-disorder transition temperature, but are preferably small in terms of ease of production and cost. As a block copolymer (including a hydrogenated block copolymer), since it is excellent in rubber elasticity, the block copolymer represented by the formula (3) (including the hydrogenated block copolymer) is more preferable than the formula ( The block copolymer represented by 2) (including a hydrogenated block copolymer) is preferred, and the block copolymer represented by the formula (2) wherein m is 3 or less (including a hydrogenated block copolymer). ) Is more preferable, and a block copolymer (including a hydrogenated block copolymer) represented by the formula (2) in which m is 2 or less is particularly preferable.

  The ratio of “polymer block of S” in the block copolymer (including hydrogenated block copolymer) represented by the formula (2) and / or the formula (3) depends on the mechanical strength of the thermoplastic elastomer and The larger one is preferable from the viewpoint of heat-sealing strength, and the smaller one is preferable from the viewpoint of flexibility, profile extrusion moldability, and difficulty of bleeding out. Specifically, the ratio of the “polymer block of S” in the block copolymer (including the hydrogenated block copolymer) of the formula (2) is preferably 10% by mass or more, and 15% by mass. More preferably, it is more preferably 20% by mass or more, and on the other hand, it is preferably 50% by mass or less, more preferably 45% by mass or less, and 40% by mass or less. It is particularly preferred.

  The weight average molecular weight (Mw) of a styrene elastomer such as a block copolymer (including a hydrogenated block copolymer) represented by the formula (2) and / or the formula (3) is large in terms of mechanical strength. However, the smaller one is preferable in terms of molding appearance and fluidity. Specifically, the weight average molecular weight of the styrene elastomer is preferably 10,000 or more, more preferably 30,000 or more, and on the other hand, preferably 450,000 or less, and 400,000 or less. More preferably, it is more preferably 200,000 or less, and most preferably 180,000 or less. Here, the weight average molecular weight (Mw) is a polystyrene equivalent weight average molecular weight measured under the following conditions by gel permeation chromatography (hereinafter sometimes abbreviated as GPC).

(Measurement condition)
Equipment: “150CALC / GPC” manufactured by Nihon Millipore
Column: Showa Denko "AD80M / S" 3 detectors: FOXBORO infrared spectrophotometer "MIRANIA" measurement Wavelength 3.42 [mu] m
Solvent: o-dichlorobenzene Temperature: 140 ° C
Flow rate: 1 cm ³ / min Injection volume: 200 microliters Concentration: 2 mg / cm ³
Addition of 0.2 mass% 2,6-di-t-butyl-p-phenol as an antioxidant

  As a manufacturing method of the above-mentioned block copolymer, any method may be used as long as the above-described structure and physical properties are obtained, and a known manufacturing method can be used.

  Commercially available products of such hydrogenated block copolymers include “Typol (registered trademark)” manufactured by TSRC, “Clayton (registered trademark) G” manufactured by Kraton Polymer, and “Septon (registered trademark)” manufactured by Kuraray. ) "," Tuftec (registered trademark) "manufactured by Asahi Kasei Corporation.

  The styrene-based elastomer and / or hydrogenated product thereof as the component (B) may be used alone or in combination of two or more.

  In addition, the quantity of the block copolymer represented by the said Formula (2) and / or Formula (3) contained in a component (B) and / or its hydrogenated block copolymer is 20 mass% or more. It is preferably 30% by mass or more, more preferably 40% by mass or more, and the upper limit is usually 100% by mass.

<Ingredient (C)>
The component (C), the hydrocarbon rubber softener used in the present invention is effective in improving the flexibility and fluidity of the thermoplastic elastomer composition of the present invention.

  As the hydrocarbon rubber softener, a mineral oil softener and a synthetic resin softener are preferable, and a mineral oil softener is more preferable because of its high affinity for the component (B).

  Mineral oil softeners are generally a mixture of aromatic hydrocarbons, naphthenic hydrocarbons and paraffinic hydrocarbons, with paraffinic oils in which 50% or more of all carbon atoms are paraffinic hydrocarbons, Those in which about 30 to 45% of all carbon atoms are naphthenic hydrocarbons are called naphthenic oils, and those in which 35% or more of all carbon atoms are aromatic hydrocarbons are called carbon atom aromatic oils. ing. The hydrocarbon rubber softener used as component (C) may be any one of the above-mentioned various softeners or a mixture of a plurality of kinds. Among these, since the hue is good, the paraffin type Oil is preferred. Examples of the synthetic resin softener include polybutene and low molecular weight polybutadiene.

  The kinematic viscosity at 40 ° C. of the hydrocarbon rubber softener is preferably lower in terms of improving the fluidity of the thermoplastic elastomer composition of the present invention, but higher in terms of the difficulty of fogging and the like. . Specifically, it is preferably 20 centistokes or more, more preferably 50 centistokes or more, and on the other hand, it is preferably 800 centistokes or less, and preferably 600 centistokes or less. The flash point (COC method) of the hydrocarbon rubber softener is preferably 200 ° C. or higher, more preferably 250 ° C. or higher. Furthermore, the pour point of the hydrocarbon rubber softener is preferably 20 ° C. or higher, and is preferably −10 ° C. or lower. The aniline point of the hydrocarbon rubber softener is preferably 110 ° C. or higher and 150 ° C. or lower.

<Combination ratio>
The thermoplastic elastomer composition of the present invention is composed of 30 to 70 parts by weight of component (A), 10 to 50 parts by weight of component (B), and 100 parts by weight of component (C) with respect to 100 parts by weight of the total composition. ) Is contained in an amount of 5 to 50 parts by mass.
When the content of the component (A) in 100 parts by mass of the total composition is less than 30 parts by mass, the effect of improving the heat-fusibility is not sufficient, and when it exceeds 70 parts by mass, the components (B) and When the content of the component (C) is reduced, flexibility and fluidity are lowered.
When the content of the component (B) in 100 parts by mass of the total composition is less than 10 parts by mass, the flexibility and rubber elasticity decrease, and when it exceeds 50 parts by mass, the components (A) and (C) By reducing the content, the heat-fusibility and fluidity become insufficient.
When the content of the component (C) in 100 parts by mass of the total composition is less than 5 parts by mass, the effect of improving the flexibility and fluidity by blending the component (C) is not sufficient, and 50 parts by mass When it exceeds, content of a component (A) and a component (B) will decrease relatively, and heat bondability and mechanical strength will fall.

  The thermoplastic elastomer composition of the present invention is composed of 30 to 70 parts by weight of component (A), 10 to 50 parts by weight of component (B), and 100 parts by weight of component (C) with respect to 100 parts by weight of the total composition. ) Is preferably contained in an amount of 5-50 parts by weight, particularly preferably 40-60 parts by weight of component (A), 20-40 parts by weight of component (B), and 20-40 parts by weight of component (C). preferable.

<Other ingredients>
The thermoplastic elastomer composition of the present invention is a component other than the above components (A) to (C) (in the present specification, simply referred to as “other components”) within a range not impairing the object of the present invention. May be included). Examples of other components include resins other than components (A) and (B) (sometimes referred to simply as “other resins” in this specification) and various additives.

  Examples of other resins that can be contained in the thermoplastic elastomer composition of the present invention include polyolefin resins, polyester resins, polyamide resins, styrene resins, acrylic resins, polycarbonate resins, and polyvinyl chloride resins. Other resins mentioned above may contain only one type or two or more types.

  Examples of the polyolefin resin include homopolymers having 2 to 4 carbon atoms such as ethylene, propylene, and 1-butene, and copolymers having these as main components. Specifically, these polyolefin resins are not limited to homopolymers such as polyethylene, polypropylene, poly-1-butene, and the like, as long as the main component is an α-olefin having 2 to 4 carbon atoms. It also includes a copolymer with ~ 20 α-olefin or a vinyl compound such as vinyl acetate, vinyl chloride, acrylic acid, methacrylic acid or styrene. Further, it may be a graft copolymer graft-modified with an unsaturated carboxylic acid such as maleic anhydride, maleic acid, acrylic acid or a derivative thereof. Furthermore, these polyolefin resins may be a mixture.

  Polyester resins include terephthalic acid, isophthalic acid, diphenyl ether-4,4-dicarboxylic acid, aromatic dicarboxylic acids such as naphthalene-1,4- or 2,6-dicarboxylic acid, oxalic acid, succinic acid, adipic acid, sebacin Acid, aliphatic dicarboxylic acid such as undecadicarboxylic acid, acid component of dicarboxylic acid such as alicyclic dicarboxylic acid such as cyclohexanedicarboxylic acid, and ethylene glycol, propylene glycol, 1,4-butanediol, neopentyl glycol, etc. Polycondensates with aliphatic glycols, cycloaliphatic glycols such as cyclohexanedimethanol, and glycol components such as aromatic diols such as bisphenol A. Specifically, polyethylene terephthalate (PET), copolymerized PET, polybutylene Terephthalate, polyethylene naphth , Poly cyclohexylene terephthalate, and the like. In addition, polycarboxylic acid such as polylactic acid, polyglycolic acid, poly-β-hydroxybutyrate, poly-β-hydroxyvalerate, poly-γ-butyrolactone, poly-δ-valerolactone, poly-ε-caprolactone, etc. A condensate is also mentioned. Among these, PET and copolymerized PET are particularly preferable.

  Polyamide resins include aliphatic diamines such as hexamethylene diamine and decamethylene diamine, diamines such as alicyclic diamine and aromatic diamine, aliphatic dicarboxylic acids such as adipic acid and sebacic acid, and fats such as cyclohexane dicarboxylic acid. Polyamides obtained by polycondensation with dicarboxylic acids such as aromatic dicarboxylic acids such as cyclic dicarboxylic acid, terephthalic acid and isophthalic acid; Polyamides obtained by condensation of aminocarboxylic acids such as ε-aminocaproic acid; ε-caprolactam and the like Examples thereof include polyamides obtained from lactams and copolymerized polyamides composed of these components. Specifically, nylon 6, nylon 66, nylon 610, nylon 9, nylon 11, nylon 12, nylon 6/66 copolymer, nylon 66/610 copolymer, nylon 6/11 copolymer and the like can be mentioned. Among these, nylon 6 and nylon 66, which are excellent in melting point, rigidity and the like, are preferable.

  The styrene resin is a resin mainly composed of styrene such as a homopolymer of styrene, a copolymer of styrene and acrylonitrile, methyl (meth) acrylate, or a modified rubber thereof, and more specifically, polystyrene, High impact polystyrene (rubber compounded polystyrene), styrene-acrylonitrile copolymer (SAN), styrene-methyl methacrylate copolymer, acrylonitrile-butadiene-styrene copolymer rubber (ABS), styrene-maleic anhydride copolymer ( SMA) and the like. However, the styrene resin mentioned here does not include those corresponding to the component (B).

  Acrylic resins include polymethyl acrylate, polyethyl acrylate, polybutyl acrylate, poly-2-ethylhexyl acrylate, polymethyl methacrylate, polyacrylonitrile, polymethacrylonitrile, methyl methacrylate-acrylonitrile copolymer, Examples thereof include methyl methacrylate-α-methylstyrene copolymer and acrylonitrile-methyl acrylate-butadiene copolymer. Of these, polyacrylonitrile is preferred.

  Examples of the polycarbonate resin include various polycarbonates obtained by reacting a dihydroxy compound with phosgene or diphenyl carbonate by a known method. Examples of the dihydroxy compound include hydroquinone, resorcinol, 4,4′-dihydroxydiphenylmethane, 4,4′-dihydroxydiphenylethane, 4,4′-dihydroxydiphenyl-n-butane, 4,4′-dihydroxydiphenyl-2,2- Propane (bisphenol A), 4,4′-dihydroxydichlorodiphenyl-2,2-propane, 4,4′-dihydroxydiphenyl-1,1-cyclohexane, 4,4′-dihydroxydiphenylethylphenylmethane, 2,2 ′ -Dihydroxydiphenyl, 2,6-dihydroxynaphthalene, 4,4'-dihydroxydiphenyl ether and the like are used. Of these, polycarbonate using 4,4'-dihydroxy-phenyl-2,2-propane (bisphenol A) is preferred because of its excellent mechanical performance and transparency.

  Examples of the polyvinyl chloride resin include a homopolymer or a copolymer of vinyl chloride. Further included are homopolymers or copolymers of vinylidene chloride. Although the monomer copolymerizable with a polyvinyl chloride resin is not limited, For example, ethylene, propylene, acrylonitrile, vinyl acetate, maleic acid or its ester, acrylic acid or its ester, methacrylic acid or its ester, etc. are mentioned. Further, a polymer blend of a polyvinyl chloride resin, for example, a polymer blend composed of a polyvinyl chloride resin and polyvinylidene chloride may be used.

  When the thermoplastic elastomer composition of the present invention contains these other resins, the effects of flexibility, heat-fusibility, and fluidity due to the inclusion of components (A) to (C) at a predetermined ratio are sufficient. Therefore, the content of other resins with respect to 100 parts by mass of the total composition is preferably 20 parts by mass or less, particularly preferably 10 parts by mass or less.

  Additives that can be contained in the thermoplastic elastomer composition of the present invention include antioxidants, molding aids such as crystal nucleating agents and lubricants, UV stabilizers, light stabilizers such as hindered amine compounds, and hydrolysis resistance improvers. And coloring agents such as pigments and dyes, antistatic agents, conductive agents, flame retardants, reinforcing agents, fillers, plasticizers, mold release agents and the like.

  Among these, as the antioxidant, a dithiocarbamate-based antioxidant, a hindered phenol-based antioxidant, a sulfur-based antioxidant, a phosphorus-based antioxidant, or the like can be used.

  As the dithiocarbamate antioxidant, a metal salt of dialkyldithiocarbamate is preferable, among which nickel dialkyldithiocarbamate is preferable, and nickel dibutyldithiocarbamate is particularly preferable because it has a large effect of improving heat aging resistance.

Specific examples of hindered phenol antioxidants include 2,4-dimethyl-6-t-butylphenol, 2,6-di-t-butylphenol, 2,6-di-t-butyl-p-cresol, hydroxy Methyl-2,6-di-t-butylphenol, 2,6-di-t-α-dimethylamino-p-cresol, 2,5-di-t-butyl-4-ethylphenol, 4,4′-bis (2,6-di-t-butylphenol), 2,2'-methylene-bis-4-methyl-6-t-butylphenol, 2,2'-methylene-bis (4-ethyl-6-t-butylphenol) 4,4′-methylene-bis (6-tert-butyl-o-cresol)
4,4′-methylene-bis (2,6-di-t-butylphenol), 2,2′-methylene-bis (4-methyl-6-cyclohexylphenol), 4,4′-butylidene-bis (3 -Methyl-6-tert-butylphenol), 4,4′-thiobis (6-tert-butyl-3-methylphenol), bis (3-methyl-4-hydroxy-5-tert-butylbenzyl) sulfide, 4, 4'-thiobis (6-t-butyl-o-cresol), 2,2'-thiobis (4-methyl-6-t-butylphenol), 2,6-bis (2'-hydroxy-3'-t-) Butyl-5′-methylbenzyl) -4-methylphenol, 3,5-di-tert-butyl-4-hydroxybenzenesulfonic acid diethyl ester, 2,2′-dihydroxy-3,3′-di (α-methyl) (Cyclohexyl)- 5,5′-dimethyl-diphenylmethane, α-octadecyl-3 (3 ′, 5′-di-t-butyl-4′-hydroxyphenyl) propionate, 6- (hydroxy-3,5-di-t-butylanilino) -2,4-bis-octyl-thio-1,3,5-triazine, hexamethylene glycol-bis [β- (3,5-di-t-butyl-4-hydroxyphenol) propionate], N, N ' Hexamethylene-bis (3,5-di-t-butyl-4-hydroxyhydrocinnamic acid amide), 2,2-thio [diethyl-bis-3 (3,5-di-t-butyl-4-hydroxy Phenyl) propionate], 3,5-di-t-butyl-4-hydroxybenzenephosphonic acid dioctadecyl ester, tetrakis [methylene-3 (3,5-di-t-butyl-4-hydro) Cyphenyl) propionate] methane, 1,3,5-trimethyl-2,4,6-tris (3,5-di-t-butyl-4-hydroxybenzyl) benzene, 1,1,3-tris (2-methyl -4-hydroxy-5-di-t-butylphenyl) butane, tris (3,5-di-t-butyl-4-hydroxyphenyl) isocyanurate, tris [β- (3,5-di-t-butyl) -4 hydroxyphenyl) propionyl-oxyethyl] isocyanurate and the like.
Among these, the use of those having a molecular weight of 500 or more such as tetrakis [methylene-3 (3,5-di-t-butyl-4-hydroxyphenyl) propionate] methane is preferable.

  The sulfur-based antioxidant is a compound containing sulfur such as thioether, dithioate, mercaptobenzimidazole, thiocarbanilide, and thiodipropion ester. However, those corresponding to the above dithiocarbamate antioxidants are not included. Among these, thiodipropion ester compounds are particularly preferable.

  Examples of phosphorus antioxidants include phosphorus-containing compounds such as phosphoric acid, phosphorous acid, hypophosphorous acid derivatives, phenylphosphonic acid, polyphosphonate, dialkylpentaerythritol diphosphite, and dialkylbisphenol A diphosphite.

  These antioxidants may be used alone or in combination of two or more.

  In the thermoplastic elastomer composition of the present invention, the content of the antioxidant is preferably 0.01 to 5 parts by mass per 100 parts by mass in total of the components (A) to (C). If the content is less than 0.01 parts by mass, the effect of improving the heat aging resistance tends to be insufficient. On the other hand, even if it is used in excess of 5 parts by mass, an effect commensurate with the increase in the addition amount is obtained. Not only is it not economical, but it may cause problems such as bleeding, and the mechanical strength of the composition may decrease.

  The total content of the additives in the thermoplastic elastomer composition of the present invention is preferably 10 parts by mass or less, more preferably 5 parts by mass or less, with respect to 100 parts by mass of the total composition. .

<Method for producing thermoplastic elastomer composition>
The method for producing the thermoplastic elastomer composition of the present invention is not particularly limited, and components (A) to (C) and other components added as necessary are dry blended according to a conventional method. Then, it can manufacture by melt-kneading.
In addition, it is preferable in terms of workability to handle the component (C) that is a liquid component at normal temperature (23 ° C.) after mixing the component (B) and the component (C) in advance and then mixing with other components.

<Physical properties of thermoplastic elastomer composition>
The flexibility of the thermoplastic elastomer of the present invention can be evaluated as a duro A hardness as shown in the examples below. This duro A hardness is evaluated to have a lower value as being excellent in flexibility, preferably 95 or less, and more preferably 90 or less.

  The heat-fusibility of the thermoplastic elastomer composition of the present invention with a polar resin such as polycarbonate resin, ABS resin, ASA resin, and acrylic resin can be evaluated by a peel test shown in the following examples. It is evaluated that the larger the value of the peel strength is, the better the heat fusion property with the polar resin is, and this value is preferably 60 N / 25 mm or more, and more preferably 70 N / 25 mm or more.

[Molded body]
By molding the thermoplastic elastomer composition of the present invention, it can be used as various molded products. Specific examples of the molded body include an injection molded body, an extrusion molded body, and a press molded body. In the thermoplastic elastomer composition of the present invention, various injection methods such as a normal injection molding method, extrusion molding method, press molding method and the like can be used, and if necessary, a gas injection molding method, an injection compression molding method, By using various molding methods such as a short shot foam molding method, a molded body can be obtained.

In particular, the molding conditions for injection molding the thermoplastic elastomer composition of the present invention are as follows.
The molding temperature is generally 150 to 300 ° C, preferably 180 to 280 ° C. The injection pressure is usually 5 to 100 MPa, preferably 10 to 80 MPa. The mold temperature is usually 0 to 80 ° C, preferably 20 to 60 ° C.

[Composite molded body]
The molded body formed by molding the thermoplastic elastomer composition of the present invention can be used as a composite molded body by heat-sealing to a polar resin such as polycarbonate resin, ABS resin, ASA resin, or acrylic resin.

  Among the polar resins that are thermally fused with the thermoplastic elastomer composition of the present invention, the polycarbonate resin is produced by reacting an aromatic hydroxy compound or a small amount thereof with a phosgene. It can also be produced by transesterifying an aromatic dihydroxy compound or a small amount of a polyhydroxy compound with a carbonic acid diester. If necessary, a trifunctional or higher functional compound of a branching agent and a molecular weight modifier are provided for the reaction. This aromatic polycarbonate resin is a thermoplastic aromatic polycarbonate resin that may or may not be branched.

  Specific examples of the aromatic dihydroxy compound include 2,2-bis (4-hydroxyphenyl) propane (hereinafter sometimes simply referred to as “bisphenol A”), tetramethylbisphenol A, tetrabromobisphenol A, bis (4 -Hydroxyphenyl) -p-isopropylbenzene, hydroquinone, resorcinol, 4,4'-dihydroxyphenyl, bis (4-hydroxyphenyl) methane, bis (4-hydroxyphenyl) ether, bis (4-hydroxyphenyl) sulfone, bis (4-hydroxyphenyl) sulfoxide, bis (4-hydroxyphenyl) sulfide, bis (4-hydroxyphenyl) ketone, 1,1-bis (4-hydroxyphenyl) ethane, 1,1-bis (4-hydroxyphenyl) Cyclohexane, etc. It can be mentioned. Among these, it is particularly preferable to use bisphenol A.

  The branched aromatic polycarbonate resin may be phloroglucin, 4,6-dimethyl-2,4,6-tri (4-hydroxyphenyl) heptene-2, 4,6-dimethyl-2,4,6-tri (4 -Hydroxyphenyl) heptane, 2,6-dimethyl-2,4,6-tri (4-hydroxyphenyl) heptene-3, 2,6-dimethyl-2,4,6-tri (4-hydroxyphenyl) heptane, Polyhydroxy compounds exemplified by 1,3,5-tri (4-hydroxyphenyl) benzene, 1,1,1-tri (4-hydroxyphenyl) ethane, and 3,3-bis (4-hydroxyaryl) ) Oxindole [= isatin (bisphenol A)], 5-chloroisatin, 5,7-dichloroisatin, 5-bromoisatin, etc. Some of the compounds, for example, can be obtained by replacing 0.1 to 2 mol% polyhydroxy compound. Furthermore, monovalent aromatic hydroxy compounds suitable for adjusting the molecular weight include m- and p-methylphenol, m- and p-propylphenol, p-bromophenol, p-tertiary-butylphenol, and Examples include p-long chain alkyl-substituted phenol.

  A suitable aromatic polycarbonate resin is a polycarbonate mainly composed of bis (4-hydroxyphenyl) alkane-based compound, particularly preferably bisphenol A. A suitable example is a polycarbonate copolymer obtained by using two or more aromatic dihydroxy compounds in combination and a branched polycarbonate resin obtained by using a small amount of a trivalent phenol compound (Japanese Patent Laid-Open No. Sho 63). No. -30524, JP-A-56-55328, JP-B-55-414, JP-B-60-25049, and JP-B-3-49930). The aromatic polycarbonate resin may be used as a mixture of two or more. The molecular weight of the preferred polycarbonate resin is in the range of 10,000 to 150,000 in terms of polystyrene-converted weight average molecular weight measured by GPC from the balance of heat resistance, mechanical strength, moldability, etc. A range of 100,000 is preferred, and a range of 35,000 to 80,000 is particularly preferred. Examples of commercially available products include “Europylon” manufactured by Mitsubishi Engineering Plastics and “Novalex” manufactured by Mitsubishi Engineering Plastics.

  An acrylic resin is a resin obtained by polymerizing and copolymerizing acrylic acid and its derivatives. Specific examples include polymers and copolymers such as acrylic acid, acrylic acid ester, acrylamide, acrylonitrile, methacrylic acid, and methacrylic acid ester. Among these, polymers such as methacrylic acid esters such as methyl methacrylate and ethyl methacrylate are preferable, and it is particularly preferable to use a polymer of methyl methacrylate (polymethyl methacrylate resin). Examples of commercially available products include “Acrypet” manufactured by Mitsubishi Rayon Co., Ltd.

The ABS resin is a resin produced by an emulsion polymerization method, a mass / suspension polymerization method, or a mass polymerization method, for example, a resin having a composition of 10 to 30% by mass of acrylonitrile, 5 to 45% by mass of butadiene, and 50 to 85% by mass of styrene. There are also those using α-methylstyrene instead of styrene.
Similarly, AES resin is a resin having a composition of acrylonitrile 10 to 30% by mass, ethylene / propylene rubber 5 to 45% by mass, and styrene 50 to 85% by mass, and using α-methylstyrene instead of styrene. Is also included.

  These resins include rubber components, talc, calcium carbonate, mica, glass fiber fillers, plasticizers such as paraffin oil, antioxidants, heat stabilizers, light stabilizers, UV absorbers, Various additives such as a compatibilizer, a lubricant, a lubricant, an antifogging agent, an antiblocking agent, a slipping agent, a dispersant, a coloring agent, an antibacterial agent, and a fluorescent brightening agent can be blended.

As a method for producing a composite molded body, a T-die laminate molding method, a co-extrusion molding method, a blow molding method, an insert injection molding method, a two-color injection molding method, a core back injection molding method, a sandwich injection molding method, an injection press molding method Various molding methods such as these can be used. Among the molding methods described above, the insert injection molding method is a method in which a core material (polar resin) is injection-molded in advance, and the molded product is inserted into a mold, and then between the molded product and the mold. It is a molding method in which a surface layer material (thermoplastic elastomer composition of the present invention) is injection-molded in a void. The two-color injection molding method is a core material (polar resin) using two or more injection molding machines. After the injection molding, the mold cavity is exchanged by rotating or moving the mold, and a gap is formed between the molded product and the mold, and the surface layer material (the thermoplastic material of the present invention) This is a molding method in which an elastomer composition) is injection molded. In addition, the core back injection molding method uses a single injection molding machine and a single mold to inject a core material (polar resin), and then expands the cavity volume of the mold. This is a molding method in which a surface layer material (the thermoplastic elastomer composition of the present invention) is injection-molded in a gap between a product and a mold.
The core material may be molded by using a normal injection molding method or by gas injection molding.

The injection molding conditions for the polar resin as the core material are generally a molding temperature of 100 to 300 ° C., preferably 150 to 280 ° C., and an injection pressure of 50 to 1,000 kg / cm ² , preferably 100 to 800 kg / cm ^2. Adopted.
The average thickness of the core layer in this injection-molded product is preferably 0.6 to 6 mm, and if it exceeds the above range, sink marks occur in the core layer and the smoothness of the surface of the molded product is inferior. If the amount is less than the above range, for example, mechanical properties such as rigidity and strength, heat resistance, and durability that are required for use in automotive parts may not be satisfied. Moreover, it is preferable that the average thickness of a surface material layer is 1-5 mm, and the thing exceeding the said range is inferior to a soft feeling, and the thing below the said range worsens the adhesiveness of a core material and surface material. Further, the injection molding conditions for the surface material layer are generally 150 to 300 ° C., preferably 200 to 290 ° C., particularly preferably 220 to 280 ° C., 50 to 1,000 kg / cm ² , preferably 100 to 800 kg. An injection pressure of / cm ² is employed. Also, runners, spools, etc. consisting only of the surface material are used as the surface material, only the core material, or runners, spools, etc. consisting of the core material and the surface material, and defective molded products are recycled to the core material. You can also.

[Usage]
A composite molded body in which a layer made of the thermoplastic elastomer composition of the present invention and a layer made of a polar resin such as polycarbonate resin, ABS resin, ASA resin, or acrylic resin are integrated by heat-sealing is used as various industrial parts. be able to. Specifically, instrument panels, center panels, center console boxes, door trims, pillars, assist grips, steering wheels, automotive interior parts such as airbag covers, automotive exterior parts such as malls, vacuum cleaner bumpers, remote control switches, OA equipment Home appliance parts such as various key tops, underwater use products such as underwater glasses and underwater camera covers, various cover parts, industrial parts with various packings for the purpose of sealing, waterproofing, soundproofing, vibration proofing, racks & It can be used for automotive functional members such as pinion boots, suspension boots, constant velocity joint boots, etc., curled cord wire coverings, belts, hoses, tubes, silencing gears and other electrical and electronic parts, toys, sports equipment and the like.

  In particular, the composite molded article of the present invention is suitable for automobile members, particularly automobile exterior members, because of the flexibility of the thermoplastic elastomer composition of the present invention and the high adhesion to the polar resin layer.

  Hereinafter, although the specific aspect of this invention is demonstrated in detail using an Example, this invention is not limited by a following example, unless the summary is exceeded. In addition, the values of various production conditions and evaluation results in the following examples have meanings as preferable values of the upper limit or the lower limit in the embodiment of the present invention, and the preferable range is the above-described upper limit or lower limit value. A range defined by a combination of values of the following examples or values of the examples may be used.

  In the following examples and comparative examples, the raw materials used for the production of the thermoplastic elastomer composition and the evaluation methods of the obtained thermoplastic elastomer composition are as follows.

[Raw materials]
Component (A) (polyether-based or polycarbonate-based thermoplastic polyurethane elastomer)
(A-1): Pandex (registered trademark) T-8190 manufactured by DIC Bayern
Polyether-based thermoplastic polyurethane elastomer
Duro A hardness: 90
(A-2): Pandex (registered trademark) T-9290 manufactured by DIC Bayern
Polycarbonate thermoplastic polyurethane elastomer
Duro A hardness: 90

Component (B) (styrene elastomer and / or hydrogenated product of styrene elastomer)
(B-1): Typole (registered trademark) 6151 manufactured by TSRC
Hydrogenated styrene-butadiene-styrene block copolymer
Weight average molecular weight: 250,000
Styrene content: 32% by mass
1,2-addition structure in the microstructure of the butadiene block: 30% by mass

Component (C) Hydrocarbon rubber softener (c-1): “Diana Process Oil PW90” manufactured by Idemitsu Kosan Co., Ltd.
Paraffinic oil
Kinematic viscosity (40 ° C): 90 centistokes

Other thermoplastic elastomer (d-1): Pandex (registered trademark) T-1180 manufactured by DIC Bayern
Adipate thermoplastic polyurethane elastomer
Duro A hardness: 81

(E-1): Polyester thermoplastic elastomer
Polybutylene terephthalate-polytetramethylene ether block copolymer
Number average molecular weight of polytetramethylene ether unit: 1000
Polytetramethylene ether unit content: 52% by mass
Content of polybutylene terephthalate unit: 48% by mass
Melting point (measured with DSC apparatus): 185 ° C
Duro A hardness: 95

<Evaluation method>
1) Flexibility: Duro A hardness The pellets of the thermoplastic elastomer composition obtained in each example, using an injection molding machine, at an injection temperature of 240 ° C. and a mold temperature of 40 ° C., a sheet of 100 mm × 100 mm × 2 mm Was measured, and the duro A hardness was measured according to JIS K6253. The duro A hardness indicates that the smaller the value is, the better the flexibility is, and the flexibility material is preferably 95 or less.

2) Thermal fusion property: peel strength Using an injection molding machine, polycarbonate resin ("Novalex (registered trademark) H-3000" manufactured by Mitsubishi Engineering Plastics), ABS resin ("Techno ABS (registered trademark) manufactured by Technopolymer)" Trademark) 150 ”, ASA resin (“ Diarack (registered trademark) S201B ”manufactured by UMG ABS), and acrylic resin (“ Acrypet (registered trademark) IRK304 ”manufactured by Mitsubishi Rayon Co., Ltd.)) are each 100 mm × 100 mm × 2 mm Then, the obtained sheet was inserted into a sheet mold of 100 mm × 100 mm × 4 mm, and the thermoplastic elastomer composition obtained in each example was inserted into the gap between the molded sheet and the mold. Pellets are injected using an injection molding machine at an injection temperature of 240 ° C and a mold temperature of 40 ° C to perform heat fusion molding. The obtained two-layer molded sheet was cut into strip-shaped test pieces of 25 mm × 100 mm, and the surface layer material layer (thermoplastic elastomer composition) and the core material layer (polar resin) were pulled in the 180 ° C. direction at a pulling rate of 200 mm / The peel strength of the surface material layer / core material layer was measured in minutes, and the greater the value, the better the thermal fusion with the polar resin, and the fusion strength is 60 N / 25 mm or more. However, it is most preferable that the material breaks (the test piece breaks without peeling between the layers).

[Example / Comparative Example]
<Example 1>
(A-1) 50 parts by mass, (b-1) 30 parts by mass, (c-1) 20 parts by mass, antioxidant (trade name Irganox (registered trademark) 1010 manufactured by BASF Japan) 0.1 part by mass , 0.2 parts by weight of a weathering agent (trade name Tinuvin (registered trademark) XT855FF, manufactured by BASF Japan), 1.5 parts by weight of a carbon master batch (PC40B, manufactured by Dainichi Seika Kogyo Co., Ltd.) is blended for 1 minute using a Henschel mixer, The same direction twin screw extruder (“TEX30α” manufactured by Kobe Steel, L / D = 45, number of cylinder blocks = 13) is charged at a rate of 20 kg / h, and the temperature is raised in the range of 180 to 210 ° C. to perform melt-kneading. To produce pellets of the thermoplastic elastomer composition. Evaluation of said 1) -2) was performed about the pellet of the obtained thermoplastic elastomer composition. The evaluation results are shown in Table-1.

[Examples 2-5, Comparative Examples 1-2]
Each component was mix | blended with the compounding quantity shown in Table 1, and it knead | mixed similarly to Example 1 and obtained the pellet of the thermoplastic elastomer composition. In addition, as in Example 1, the evaluations 1) to 2) were performed. The evaluation results are shown in Table-1.

From Table 1, according to the thermoplastic elastomer composition of the present invention containing the component (A), the component (B), and the component (C) in a predetermined ratio, excellent flexibility with the polar resin can be achieved. Thermal fusion can be obtained. In contrast, Comparative Example 1 using an adipate-based thermoplastic polyurethane elastomer as a polyurethane-based thermoplastic elastomer and Comparative Example 2 using a polyester-based thermoplastic elastomer have extremely poor heat-fusibility with a polar resin. It becomes.
The details of the mechanism for improving the heat-fusibility to the polar resin are not clear, but the polycarbonate component or the polyether component of the polyurethane-based thermoplastic elastomer of the component (A) is entangled with the polar resin during the heat-sealing. It is considered that the peel strength is improved accordingly.

Claims (8)

It contains at least the following components (A), (B) and (C), and 30 to 70 parts by mass of component (A) and 10 to 10 parts of component (B) with respect to 100 parts by mass of the total composition in the composition. A thermoplastic elastomer composition comprising 50 parts by mass and 5 to 50 parts by mass of the component (C).
Component (A): Polyurethane thermoplastic elastomer containing the following components (A-1) and / or (A-2) Component (A-1): Polyether thermoplastic polyurethane elastomer Component (A-2): Polycarbonate Thermoplastic polyurethane elastomer component (B): Styrenic elastomer and / or hydrogenated component of styrene elastomer (C): Softener for hydrocarbon rubber The component (A) is a polyurethane-based thermoplastic elastomer represented by the following general formula (1), and the component (A-1) has a long-chain glycol in the following general formula (1) having a molecular weight of 500 to 10,000. The thermoplastic elastomer composition according to claim 1, wherein the long-chain glycol in the following general formula (1) is a polycarbonate.

(A in the above formula (1) represents a hard segment composed of a diisocyanate compound and glycol, B represents a soft segment composed of a diisocyanate compound and a long-chain glycol, and Y represents a residue of a urethane-bonded diisocyanate compound. ) Component (B) is a styrene / conjugated diene block copolymer and / or a hydrogenated product thereof,
The thermoplastic elastomer composition according to claim 1 or 2, wherein the conjugated diene is butanediene.   The thermoplastic elastomer composition according to any one of claims 1 to 3, wherein the component (C) is a paraffinic oil having a kinematic viscosity at 40 ° C of 20 to 800 centistokes.   The molded object formed by shape | molding the thermoplastic elastomer composition of any one of Claim 1 thru | or 4.   A composite molded product obtained by heat-sealing the molded product according to claim 5 with a polycarbonate resin, ABS resin, ASA resin, or acrylic resin.   The member for motor vehicles which consists of a composite molded object of Claim 6.   The member for motor vehicles according to claim 7 which is a member for car exteriors.