JPWO2009004939A1 - Thermoplastic resin composition and molded article - Google Patents

Abstract

The problem to be solved by the present invention is to provide a thermoplastic resin composition that imparts flexibility to a thermoplastic polyurethane resin and has improved oil resistance, which has been a conventional problem. A thermoplastic resin composition comprising 1 to 60% by weight of an acrylic block copolymer (A) and 99 to 40% by weight of a thermoplastic polyurethane resin (B), wherein the thermoplastic polyurethane resin (B) is It can be achieved by a thermoplastic resin composition characterized by being either a polyether-based thermoplastic polyurethane resin or a polyester-based thermoplastic polyurethane resin.

Description

  The present invention relates to a thermoplastic resin composition having improved oil resistance, which has been a problem in conventional thermoplastic polyurethane resins imparted with flexibility.

  Thermoplastic polyurethane resins are widely used as molding materials because they have excellent characteristics such as impact resistance, flex resistance, wear resistance, and low temperature characteristics. Moreover, in recent years, its soft texture and moist touch have attracted attention, and its use is further expanding as flexible injection-molded products such as watch bands, shoe soles, camera grips, and electric / precision machines. When obtaining such a flexible thermoplastic polyurethane resin, it is softened so as to have an appropriate hardness by blending a plasticizer. However, the thermoplastic polyurethane containing a plasticizer has a drawback that the plasticizer bleeds out of the composition (Patent Document 1).

Also, in order to improve the above-mentioned drawbacks, a composition blended with a thermoplastic polyurethane resin using a block copolymer comprising an aromatic vinyl polymer block and a conjugated diene polymer block as a modifier has been proposed. (Patent Document 2). Although it is disclosed that the polyurethane-based resin composition is given flexibility by blending the block copolymer, the compatibility between the thermoplastic polyurethane-based resin and the modifier is greatly different, so that the compatibility is insufficient. Thus, the molded body obtained from this resin composition has a problem that the mechanical properties of the tensile machine are lowered and the oil resistance is deteriorated.
JP 2004-300300 A JP 09-78242 A

  The present invention provides a thermoplastic resin composition that imparts flexibility to a thermoplastic polyurethane resin and has improved oil resistance, which has been an important issue for thermoplastic polyurethane resins.

  As a result of intensive studies in order to solve the above-mentioned problems, the present inventors add an acrylic block copolymer containing a methacrylic polymer block and an acrylic polymer block to the thermoplastic polyurethane resin. As a result, it has been found that oil flexibility can be greatly improved while providing flexibility, and the present invention has been completed.

That is, the present invention is a thermoplastic resin composition comprising 1 to 60% by weight of an acrylic block copolymer (A) and 99 to 40% by weight of a thermoplastic polyurethane resin (B),
The thermoplastic polyurethane resin (B) relates to a thermoplastic resin composition characterized in that it is either a polyether thermoplastic polyurethane resin or a polyester thermoplastic polyurethane resin.

  In a preferred embodiment, the acrylic block copolymer (A) is selected from the group represented by the general formula (ab) n, the general formula (ab) na (n is an integer of 1 or more). It is related with the thermoplastic resin composition characterized by being at least 1 type.

  A preferred embodiment relates to a thermoplastic resin composition characterized in that the acrylic block copolymer (A) is a triblock copolymer represented by the general formula aba.

  In a preferred embodiment, the acrylic block copolymer (A) is from 0.1 to 50% by weight of the methacrylic polymer block (a) and from 99.9 to 50% by weight of the acrylic polymer block (b). It is related with the thermoplastic resin composition characterized by becoming.

  In a preferred embodiment, the acrylic block copolymer (A) is from 0.1 to 40% by weight of the methacrylic polymer block (a) and from 99.9 to 60% by weight of the acrylic polymer block (b). A thermoplastic resin composition characterized by comprising:

  In a preferred embodiment, the acrylic block copolymer (A) comprises 10 to 40% by weight of the methacrylic polymer block (a) and 90 to 60% by weight of the acrylic polymer block (b). It relates to a thermoplastic resin composition.

  In a preferred embodiment, the acrylic polymer block (b) is an acrylic ester 50 containing at least one monomer selected from the group consisting of n-butyl acrylate, ethyl acrylate, and 2-methoxyethyl acrylate. The present invention relates to a thermoplastic resin composition comprising -100% by weight and vinyl monomer 50-50% by weight.

  In a preferred embodiment, the acrylic block copolymer (A) has an acid anhydride group, a carboxyl group, and at least one of the methacrylic polymer block (a) and the acrylic polymer block (b). The present invention relates to a thermoplastic resin composition having at least one functional group selected from the group consisting of a hydroxyl group and an epoxy group.

  A preferred embodiment relates to a thermoplastic resin composition, wherein the acrylic block copolymer (A) comprises a block copolymer produced by an atom transfer radical polymerization method.

  A preferred embodiment relates to a thermoplastic resin composition characterized in that the thermoplastic polyurethane resin (B) comprises a polyether thermoplastic polyurethane resin.

  Another embodiment of the present invention relates to a molded article containing the thermoplastic resin composition.

  According to the present invention, a thermoplastic resin composition can be obtained in which flexibility is imparted to a thermoplastic polyurethane resin and oil resistance is greatly improved.

The present invention is a thermoplastic resin composition comprising 1 to 60% by weight of an acrylic block copolymer (A) and 99 to 40% by weight of a thermoplastic polyurethane resin (B),
The thermoplastic polyurethane resin (B) is a thermoplastic thermoplastic resin composition characterized in that it is either a polyether thermoplastic polyurethane resin or a polyester thermoplastic polyurethane resin.

<Acrylic block copolymer (A)>
The acrylic block copolymer (A) constituting the thermoplastic elastomer composition comprises a methacrylic polymer block (a) that is a hard segment and an acrylic polymer block (b) that is a soft segment. The acrylic polymer block (a) imparts shape retention during molding, and the acrylic polymer block (b) imparts elasticity as an elastomer and meltability during molding. In the acrylic block copolymer (A), the ratio of the methacrylic polymer block (a) and the acrylic polymer block (b) is not particularly limited, but the methacrylic polymer block (a) The proportion is preferably 0.1 to 50% by weight, and the proportion of the acrylic polymer block (b) is preferably 99.9 to 50% by weight. Furthermore, the proportion of the methacrylic polymer block (a) is preferably 0.1 to 40% by weight, and the proportion of the acrylic polymer block (b) is preferably 99.9 to 60% by weight. In particular, the proportion of the methacrylic polymer block (a) is preferably 10 to 40% by weight, and the proportion of the acrylic polymer block (b) is preferably 90 to 60% by weight. If the proportion of the methacrylic polymer block (a) is smaller than 0.1% by weight and the proportion of the acrylic polymer block (b) is larger than 99.9% by weight, the shape is not retained during molding, and the methacrylic When the proportion of the polymer block (a) is larger than 50% by weight and the proportion of the acrylic polymer block (b) is smaller than 50% by weight, the elasticity as an elastomer and the meltability at the time of molding are lowered. .

  In addition, when the ratio of the methacrylic polymer block (a) is small, the hardness is lowered. On the other hand, when the proportion of the acrylic polymer block (b) is small, the hardness tends to increase. For this reason, the composition ratio between the methacrylic polymer block (a) and the acrylic polymer block (b) needs to be appropriately set in consideration of the required hardness of the elastomer composition. Further, when the proportion of the methacrylic polymer block (a) is small, the viscosity is low, and when the proportion of the acrylic polymer block (b) is small, the viscosity tends to be high. For this reason, the composition ratio of the methacrylic polymer block (a) and the acrylic polymer block (b) needs to be appropriately set in consideration of required processing characteristics.

  The molecular weight of the acrylic block copolymer (A) is adjusted so that the number average molecular weight measured by gel permeation chromatography is 30,000 to 200,000. If the molecular weight is smaller than 30,000, sufficient mechanical properties as an elastomer may not be exhibited, and if the molecular weight is larger than 200,000, processing properties may be deteriorated. In particular, when powder slush molding is performed, the resin needs to flow even under no pressure. Therefore, when the molecular weight is large, the melt viscosity tends to increase and the moldability tends to deteriorate.

  Moreover, the ratio (Mw / Mn) of the weight average molecular weight (Mw) and the number average molecular weight (Mn) measured by gel permeation chromatography of the acrylic block copolymer (A) may be 1.8 or less. Preferably, it is 1.5 or less. If Mw / Mn exceeds 1.8, the uniformity of the acrylic block copolymer may deteriorate.

  The acrylic block copolymer (A) may be a linear block copolymer, a branched (star) block copolymer, or a mixture thereof. The structure of such a block copolymer is appropriately selected according to the required physical properties of the acrylic block copolymer (A). However, in terms of cost and ease of polymerization, linear block copolymer Coalescence is preferred.

  The linear block copolymer may have any structure (arrangement), but from the viewpoint of the physical properties of the linear block copolymer or the composition, the methacrylic polymer block (a ) Is expressed as a, and the acrylic polymer block (b) is expressed as b, (ab) n type, b- (ab) n type, and (ab) na type (n is 1). It is preferably made of at least one acrylic block copolymer selected from the group consisting of the above integers (for example, an integer of 1 to 3). Among these, from the viewpoint of physical properties of the composition, an ab type diblock copolymer and an abb type triblock copolymer are preferable, and the ab- An a-type triblock copolymer is more preferable.

  The relationship between the glass transition temperatures of the methacrylic polymer block (a) and the acrylic polymer block (b) constituting the acrylic block copolymer (A) is the glass transition of the methacrylic polymer block (a). When the temperature is Tga and the glass transition temperature of the acrylic polymer block (b) is Tgb, it is preferable to satisfy the relationship of the following formula in terms of mechanical strength, rubber elasticity, and the like.

Tga> Tgb
The glass transition temperature (Tg) of the methacrylic polymer block (a) and the acrylic polymer block (b) can be measured by DSC (differential scanning calorimetry) or tan δ peak of dynamic viscoelasticity. .

<Methacrylic polymer block (a)>
The methacrylic polymer block (a) is a block obtained by polymerizing a monomer having a methacrylic acid ester as a main component, and is 50 to 100% by weight of the methacrylic acid ester and a vinyl type copolymerizable therewith. It preferably consists of 0 to 50% by weight of monomer. When the proportion of the methacrylic acid ester is less than 50% by weight, the weather resistance, which is a feature of the methacrylic acid ester, may be impaired.

  Examples of the methacrylic acid ester constituting the methacrylic polymer block (a) include, for example, methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, N-pentyl methacrylate, n-hexyl methacrylate, n-heptyl methacrylate, n-octyl methacrylate, 2-ethylhexyl methacrylate, nonyl methacrylate, decyl methacrylate, dodecyl methacrylate, Examples thereof include methacrylic acid aliphatic hydrocarbons (eg, alkyl having 1 to 18 carbon atoms) such as stearyl methacrylate. These can be used alone or in combination of two or more. Among these, methyl methacrylate is preferable in terms of processability, cost, and availability.

  Examples of vinyl monomers copolymerizable with the methacrylic acid ester constituting the methacrylic polymer block (a) include, for example, acrylic acid esters, aromatic alkenyl compounds, vinyl cyanide compounds, conjugated diene compounds, And halogen-containing unsaturated compounds.

  Examples of the acrylate ester include methyl acrylate, ethyl acrylate, n-propyl acrylate, n-butyl acrylate, isobutyl acrylate, n-pentyl acrylate, n-hexyl acrylate, n-heptyl acrylate, Acrylic acid aliphatic hydrocarbon (eg, alkyl having 1 to 18 carbon atoms) ester such as n-octyl acrylate, 2-ethylhexyl acrylate, nonyl acrylate, decyl acrylate, dodecyl acrylate, stearyl acrylate, etc. Can do.

  Examples of the aromatic alkenyl compound include styrene, α-methylstyrene, p-methylstyrene, p-methoxystyrene, and the like.

  Examples of the vinyl cyanide compound include acrylonitrile and methacrylonitrile.

  Examples of the conjugated diene compound include butadiene and isoprene.

  Examples of the halogen-containing unsaturated compound include vinyl chloride, vinylidene chloride, perfluoroethylene, perfluoropropylene, and vinylidene fluoride.

  These compounds listed as vinyl monomers can be used alone or in combination of two or more. These vinyl monomers are appropriately selected in consideration of the glass transition temperature of the methacrylic polymer block (a) described later, the compatibility with the acrylic block (b), and the like.

  The glass transition temperature of the methacrylic polymer block (a) is preferably 25 ° C. or higher, more preferably 40 ° C. or higher. If the glass transition temperature is less than 25 ° C., rubber elasticity at high temperatures tends to decrease. The glass transition temperature of the methacrylic polymer block (a) can be set by setting the weight ratio of the monomer in the polymer portion according to the Fox formula.

<Acrylic polymer block (b)>
The monomer that constitutes the acrylic polymer block (b) is an acrylic acid ester monomer, and is copolymerized with it from the viewpoint of easily obtaining a composition having desired physical properties, cost, and availability. It is preferably composed of possible vinyl monomers.

  The acrylic ester monomer constituting the acrylic polymer block (b) is a vinyl monomer copolymerizable with the methacrylic ester monomer constituting the methacrylic polymer block (a). The same specific example as an acrylic ester monomer can be given. Moreover, at least one of these can be used.

  Among these, ethyl acrylate, acrylic acid-n-butyl and acrylic acid-2-methoxyethyl are preferable.

  When acrylic acid-n-butyl is used, the molded body produced from the thermoplastic resin composition of the present invention exhibits good rubber elasticity and low temperature characteristics. When ethyl acrylate is used, it exhibits good mechanical properties such as good oil resistance and tensile strength. In addition, when 2-methoxyethyl acrylate is used, good low-temperature characteristics and oil resistance are exhibited, and the surface tackiness of the resin is improved. These are used alone or in combination of two or more according to the required properties. In addition, a softness | flexibility and oil resistance may be impaired as the ratio of these acrylic acid esters is less than 50 weight%.

  Examples of vinyl monomers copolymerizable with the acrylic ester constituting the acrylic polymer block (b) include methacrylic ester, aromatic alkenyl compound, vinyl cyanide compound, conjugated diene compound, halogen, and the like. Examples thereof include an unsaturated compound containing silicon, an unsaturated compound containing silicon, an unsaturated carboxylic acid compound, and an unsaturated dicarboxylic acid compound.

  Specific examples thereof are the same as those described above as the monomer component used in the methacrylic polymer block (a). These vinyl monomers can be used alone or in combination of two or more. These vinyl monomers have a glass transition temperature and oil resistance required for the acrylic polymer block (b), compatibility with the methacrylic polymer block (a), and compatibility with the thermoplastic polyurethane resin. It is preferable to select a preferable one in consideration of balance such as tolerability.

  Here, the ratio of the acrylate monomer is preferably 50% by weight or more, and more preferably 70% by weight or more in the whole acrylic polymer block (b). If it is less than 50% by weight, the physical properties of the composition, particularly impact resistance and flexibility, which are characteristics when using an acrylic ester, tend to be impaired. Moreover, 0-50 weight% is preferable and, as for the ratio of the other vinyl monomer which can be copolymerized, More preferably, it is 0-25 weight%.

  The acrylic polymer block (b) comprises 50 to 100% by weight of an acrylic ester containing at least one monomer selected from the group consisting of n-butyl acrylate, ethyl acrylate, and 2-methoxyethyl acrylate. The vinyl monomer is preferably composed of 50 to 0% by weight.

  From the viewpoint of rubber elasticity of the acrylic block copolymer (A), the glass transition temperature of the acrylic polymer block (b) is preferably 50 ° C. or less, and more preferably 0 ° C. or less. When the glass transition temperature of the acrylic polymer block (b) is higher than the temperature of the environment in which the elastomer composition is used, flexibility and rubber elasticity are hardly exhibited.

<Functional group>
Among the methacrylic polymer block (a) and the acrylic polymer block (b), at least one polymer block main chain includes an acid anhydride group, a carboxyl group, a hydroxyl group, and an epoxy group. It is preferable to contain at least one selected functional group in terms of improving compatibility with the thermoplastic polyurethane resin.

  The acid anhydride group is an anhydride group of a carboxyl group, and is introduced into the main chain from the ease of introduction into the methacrylic polymer block (a) and the acrylic polymer block (b). More specifically, it is represented by the general formula (1). General formula (1):

(In the formula, R ¹ is hydrogen or a methyl group, and two R ^{1 s} may be the same or different from each other. N is an integer of 0 to 3, and m is an integer of 0 or 1.)
N in General formula (1) is an integer of 0-3, Preferably it is 0 or 1, More preferably, it is 1. When n is 4 or more, polymerization tends to be complicated, and cyclization of the acid anhydride group tends to be difficult.

  As a method for introducing the acid anhydride group, it is preferable that the acid anhydride group is introduced into the acrylic block copolymer in the form of a precursor of the acid anhydride group and then cyclized. In particular, the general formula (2):

(Wherein R ² represents hydrogen or a methyl group; R ³ represents hydrogen, a methyl group or a phenyl group; at least two of the three R ³ are selected from a methyl group and / or a phenyl group; R ³ may be the same or different from each other. It is preferable to melt-knead an acrylic block copolymer having at least one unit represented by

  Introduction of the unit represented by the general formula (2) into the methacrylic polymer block (a) and the acrylic polymer block (b) is an acrylate ester derived from the general formula (2) or methacrylic acid. This can be done by copolymerizing an ester monomer. Examples of the monomer include t-butyl (meth) acrylate, isopropyl (meth) acrylate, α, α-dimethylbenzyl (meth) acrylate, α-methylbenzyl (meth) acrylate, It is not limited to these. Among these, (meth) acrylic acid-t-butyl is preferable from the viewpoints of availability, ease of polymerization, and ease of formation of acid anhydride groups. In the present application, (meth) acrylic acid means acrylic acid and methacrylic acid.

  The formation of the acid anhydride group is preferably performed by heating the acrylic block copolymer having a precursor of the acid anhydride group at a high temperature, and is preferably heated at 180 to 300 ° C. When the temperature is lower than 180 ° C., the acid anhydride group is likely to be insufficiently generated. When the temperature is higher than 300 ° C., the acrylic block copolymer itself having a precursor of the acid anhydride group may be decomposed.

  The carboxyl group may be introduced into the main chain of the methacrylic polymer block (a) or the acrylic polymer block (b) or may be introduced into the side chain. In view of ease of introduction into the combined block (a) and the acrylic polymer block (b), it is preferably introduced into the main chain.

  When the monomer having a carboxyl group does not deactivate the catalyst under the polymerization conditions, the introduction of the carboxyl group is preferably introduced by direct polymerization. In the case of deactivation, it is preferable to introduce a carboxyl group by functional group conversion.

  In the method of introducing a carboxyl group by functional group conversion, the carboxyl group is introduced into the acrylic block copolymer in a form protected with an appropriate protective group or in the form of a functional group that is a precursor of the carboxyl group. The functional group can be generated by a known chemical reaction. By this method, a carboxyl group can be introduced.

  For example, an acrylic block copolymer containing a monomer having a functional group that becomes a precursor of a carboxyl group such as t-butyl (meth) acrylate and trimethylsilyl (meth) acrylate is synthesized and hydrolyzed. Alternatively, a method of generating a carboxyl group by a known chemical reaction such as acid decomposition (JP-A-10-298248, JP-A-2001-234146), for example, (meth) acrylic acid-t-butyl, (meth) acrylic A method of synthesizing and melt-kneading an acrylic block copolymer containing unit amounts such as isopropyl acid, α, α-dimethylbenzyl (meth) acrylate, and α-methylbenzyl (meth) acrylate (JP 2006-104419 A) No.).

  The epoxy group is not particularly limited as long as it is an organic group containing an epoxy ring. For example, 1,2-epoxyethyl group, 2,3-epoxypropyl group (that is, glycidyl group), 2,3-epoxy-2- Examples thereof include an aliphatic hydrocarbon (eg, alkyl) group having an epoxy ring such as methylpropyl group; an alicyclic hydrocarbon group having an epoxy ring such as 3,4-epoxycyclohexyl group. These may be selected from desired reactivity, reaction rate, availability, cost, and the like, and are not particularly limited. Among these, glycidyl groups are most preferable from the viewpoint of availability.

  Examples of the monomer having an epoxy group include methacrylic acid such as glycidyl methacrylate, 2,3-epoxy-2-methylpropyl methacrylate, (3,4-epoxycyclohexyl) methyl methacrylate, and an epoxy ring. Esters with organic group-containing alcohols to be included; glycidyl acrylate, 2,3-epoxy-2-methylpropyl acrylate, (3,4-epoxycyclohexyl) methyl acrylate and other organic group-containing alcohols containing an epoxy ring And an epoxy group-containing unsaturated compound such as 4-vinyl-1-cyclohexene 1 and 2 epoxide. These may be selected from desired reactivity, reaction rate, availability, cost, and the like, and there is no particular limitation. Among these, glycidyl methacrylate and glycidyl acrylate are preferred because of availability. preferable.

  The hydroxyl group may be polymerized directly from the (meth) acrylic monomer containing a hydroxyl group at the time of polymerization of the acrylic block copolymer (A). After the acrylic block copolymer (A) is polymerized, You may introduce | transduce using esterification reaction or transesterification. From the viewpoint of easy reaction, it is preferable that a (meth) acrylic monomer containing a hydroxyl group is directly polymerized during the polymerization of the acrylic block copolymer (A). Here, in this application, (meth) acryl means acryl or methacryl.

  Specific (meth) acrylic monomers include (meth) acrylic acid-2-hydroxyethyl, (meth) acrylic acid-2-hydroxypropyl, (meth) acrylic acid-3-hydroxypropyl, (meth) acrylic acid- 4-hydroxybutyl, Blemmer E series (Nippon Yushi Co., Ltd.), Blemmer PE series (Nippon Yushi Co., Ltd.), Blemmer AE series (Nippon Yushi Co., Ltd.), Blemmer P series (Nippon Yushi Co., Ltd.), Blemmer PP series (Nippon Yushi Co., Ltd.), Blemmer AP series (Nippon Yushi Co., Ltd.), Blemmer PEP series (Nippon Yushi Co., Ltd.), Blemmer AEP series (Nippon Yushi Co., Ltd.), Blemmer PET series (Nippon Yushi ( ), Blemmer AET series (Nippon Yushi Co., Ltd.), Blemmer PPT series (Japan) Oils and fats Co., Ltd.), Brenmer APT series (Nippon Oil & Fats Co., Ltd.), and the like.

  These compounds can be used alone or in combination of two or more. Among these, (meth) acrylic acid-2-hydroxyethyl, (meth) acrylic acid-2-hydroxypropyl, and (meth) acrylic acid-4-hydroxybutyl are easy in terms of polymerization and are easily available. This is preferable.

  The content of the monomer unit having a functional group is the structure and composition of the acrylic block copolymer (A), the number of blocks constituting the acrylic block copolymer (A), the glass transition temperature, In addition, it varies depending on the site and manner in which the functional group is contained and the compatibility with the thermoplastic polyurethane resin. Therefore, it may be set as necessary, but is preferably 0.1% by weight or more, and more preferably 0.5% by weight or more in the entire acrylic block copolymer (A). If it is less than 0.1% by weight, the effect of improving the compatibility between the acrylic block copolymer (A) and the thermoplastic polyurethane resin (B) tends to be insufficient.

<Method for producing acrylic block copolymer (A)>
The method for producing the acrylic block copolymer (A) is not particularly limited, but it is preferable to use controlled polymerization using an initiator. Examples of controlled polymerization include living anionic polymerization, radical polymerization using a chain transfer agent, and recently developed living radical polymerization. Especially, it is preferable to manufacture by the living radical polymerization method from the point of control of the molecular weight and structure of an acryl-type block copolymer.

  The living radical polymerization method is a radical polymerization method in which the activity at the polymerization terminal is maintained without being lost. In the narrow sense, living polymerization refers to polymerization in which the terminal always has activity, but generally includes pseudo-living polymerization in which the terminal is inactivated and the terminal is in equilibrium. . The definition here is also the latter.

  As the living radical polymerization method, a method using a chain transfer agent such as polysulfide, cobalt porphyrin complex (J. Am. Chem. Soc., 1994, 116, 7943). ) And nitroxide compounds (Macromolecules, 1994, 27, 7228), atom transfer radicals using organic halides as initiators and transition metal complexes as catalysts Examples thereof include a polymerization method (Atom Transfer Radical Polymerization: ATRP). In the present invention, any of these methods is not particularly limited, but the atom transfer radical polymerization method described in International Publication No. 2004/13192 pamphlet is used from the viewpoint of easy control. Is preferred.

<Thermoplastic polyurethane resin (B)>
Examples of the thermoplastic polyurethane-based resin (B) include (a) a thermoplastic polyurethane-based resin composed of an organic diisocyanate, (b) a chain extender, and (c) a polymer polyol. The thermoplastic polyurethane-based resin (B) may be produced by any method. For example, the component (b) and the component (b) and the component (c), which have been mixed uniformly in advance, are mixed at high speed. It is produced by casting on a mold-treated bat and reacting at a temperature of 200 ° C. or lower as necessary, or by adding (a) and (b) components to a prepolymer of a terminal isocyanate group After that, the component (c) is added and stirred at high speed, and this is cast on a release-treated vat and, if necessary, produced by reacting at a temperature of 200 ° C. or lower. Known techniques can be used.

  As the thermoplastic polyurethane-based resin (B), ester-based and ether-based thermoplastic urethane-based resins can be preferably used. From the viewpoint of compatibility with the acrylic block copolymer (A), a polyether-based resin can be used. A polyurethane resin is more preferable.

  As the organic diisocyanate (i), conventionally known ones can be appropriately used. For example, hexamethylene diisocyanate, lysine diisocyanate, isophorone diisocyanate, xylene diisocyanate, cyclohexane diisocyanate, 4,4′-dicyclohexylmethane diisocyanate, hydrogen Xylylene diisocyanate, toluidine diisocyanate, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, 4,4'-diphenylmethane diisocyanate, p-phenylene diisocyanate, m-phenylene diisocyanate, 1,5-naphthalene diisocyanate, 3, , 3′-dichloro-4,4′-diphenylmethane diisocyanate, etc. alone or in combination of two or more thereof. It can be. Further, as the organic isocyanate compound, a tri- or higher functional polyvalent isocyanate compound such as triphenylmethane triisocyanate can be used in combination as desired.

  The chain extender (b) is not particularly limited, and any chain extender conventionally used in the production of ordinary thermoplastic polyurethanes may be used, but an active hydrogen atom capable of reacting with an isocyanate group. It is preferable to use a low molecular compound having 2 or more in the molecule, and it is particularly preferable to use a dihydroxy compound having a molecular weight of less than 500. For example, ethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, 2,3-butylene glycol, 1,4-butanediol, 2,2′-dimethyl-1,3 -Propanediol, diethylene glycol, 1,5-pentanediol, 1,6-hexanediol, cyclohexane-1,4-diol, cyclohexane-1,4-dimethanol, 1,4-bis (β-hydroxyethoxy) benzene, Diols such as 1,4-cyclohexanedimethanol, bis (β-hydroxyethyl) terephthalate, and xylylene glycol can be used alone or in combination of two or more thereof.

  As the polymer polyol (c), it is preferable to use a dihydroxy compound having an average molecular weight of 500 to 4000, and it is preferable to use a polyester polyol or a polyether polyol. In addition, other polymer polyols may be used by mixing them, and examples thereof include polycarbonate polyols, polyester polycarbonate polyols, polyolefin polyols, conjugated diene polymer polyols, castor oil polyols, and silicone resins. Examples include polyols and vinyl polymer-based polyols.

  Said polyester polyol can be manufactured by the well-known polycondensation method by the esterification method or the transesterification method, using a dicarboxylic acid component, a diol component, and other components as needed. The polyester polyol can also be produced by ring-opening polymerization of a lactone in the presence of a diol component.

  Examples of the dicarboxylic acid component used in the production of the polyester polyol include dicarboxylic acid components commonly used in the production of polyester, such as succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, Carbons such as dodecanedioic acid, methylsuccinic acid, 2-methylglutaric acid, 3-methylglutaric acid, trimethyladipic acid, 2-methyloctanedioic acid, 3,8-dimethyldecanedioic acid, 3,7-dimethyldecanedioic acid Aliphatic dicarboxylic acids of 4 to 12; cycloaliphatic dicarboxylic acids such as cyclohexanedicarboxylic acid, dimer acid, and hydrogenated dimer acid; aromatic dicarboxylic acids such as terephthalic acid, isophthalic acid, orthophthalic acid, and naphthalenedicarboxylic acid; Trifunctional or higher polyvalent carboxylic acids such as acid and pyromellitic acid; , And the like et esters or ester forming derivatives such as their anhydrides. These dicarboxylic acid components may be used alone or in combination of two or more.

  Examples of the diol component used in the production of the polyester polyol include those commonly used in the production of polyester, such as ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, 1,3-propanediol, and 2-methyl-1. , 3-propanediol, 2,2-diethyl-1,3-propanediol, 1,3-butanediol, 1,4-butanediol, 2-methyl-1,4-butanediol, neopentyl glycol, 1, 5-pentanediol, 3-methyl-1,5-pentanediol, 1,6-hexanediol, 1,7-heptanediol, 1,8-octanediol, 2-methyl-1,8-octanediol, 2, 7-dimethyl-1,8-octanediol, 1,9-nonanedio Aliphatic diols having 2 to 15 carbon atoms such as 1, 2-methyl-1,9-nonanediol, 2,8-dimethyl-1,9-nonanediol, 1,10-decanediol; Cycloaliphatic diols such as cyclohexanedimethanol and cyclooctanedimethanol; aromatic diols such as 1,4-bis (β-hydroxyethoxy) benzene; trimethylolpropane, trimethylolethane, glycerin, 1,2,6- Examples thereof include polyhydric alcohols having 3 or more hydroxyl groups per molecule such as hexanetriol, pentaerythritol, and diglycerin. In producing the polyester polyol, one kind of these diol components may be used, or two or more kinds may be used in combination.

  Examples of the polylactone diol obtained by ring-opening polymerization of a lactone in the presence of a diol component include polypropiolactone diol, polycaprolactone diol, and polyvalerolactone diol.

  Polyether polyols include polyether diols and glycols (for example, ethylene glycol, propylene glycol, 1, and the like) obtained by ring-opening polymerization of cyclic ethers (for example, ethylene oxide, propylene oxide, trimethylene oxide, tetrahydrofuran, methyltetrahydrofuran, etc.). 4-butanediol, neopentyl glycol, 1,6-hexanediol, 3-methyl-1,5-pentanediol, 2-methyl-1,8-octanediol, 1,9-nonanediol, 1,10-decane And polyether diols obtained by polycondensation of diols). Examples thereof include polypropylene ether glycol, polytetramethylene ether glycol, polyhexamethylene ether glycol, and other copolymer polyether glycols. As the polyether polyol, one type may be used, or two or more types may be used in combination.

  Examples of the polycarbonate polyol include those obtained by a reaction between a diol component and a carbonate compound such as dialkyl carbonate, alkylene carbonate, or diaryl carbonate. As the diol component constituting the polycarbonate polyol, the diol component exemplified above as the constituent component of the polyester polyol can be used. Examples of the dialkyl carbonate include dimethyl carbonate and diethyl carbonate. Examples of the alkylene carbonate include ethylene carbonate. Examples of the diaryl carbonate include diphenyl carbonate. Can do. For example, polyhexamethylene carbonate diol, diol obtained by ring-opening addition polymerization of lactone to polyhexamethylene carbonate diol, co-condensation of polyhexamethylene carbonate diol with other polyester diols, polyether diols, polyether ester diols Thing etc. are mentioned. One type of polycarbonate polyol may be used, or two or more types may be used in combination.

  The number average molecular weight of the thermoplastic polyurethane resin (B) of the present invention is not particularly limited, but is preferably 5,000 to 1,000,000, and particularly preferably 10,000 to 500,000. If the number average molecular weight is less than 5,000, the mechanical properties tend to be insufficient, and if it exceeds 1,000,000, the moldability tends to decrease.

<Thermoplastic resin composition>
The thermoplastic resin composition of the present invention comprises an acrylic block copolymer (A) and a thermoplastic polyurethane resin (B), and comprises the acrylic block copolymer (A) and the thermoplastic polyurethane resin (B). , (A) :( B) = 1: 99 to 60:40 are preferably contained in a weight ratio, and (A) :( B) = 5: 95 to 55:45 are preferably contained in a weight ratio. Preferably, (A) :( B) is contained in a weight ratio of 25:75 to 50:50. When the content of the acrylic block copolymer (A) is more than 60% by weight, the heat resistance of the resulting thermoplastic resin composition is lowered. Moreover, when content of an acrylic block copolymer (A) is less than 1 weight%, the softness | flexibility improvement effect of the thermoplastic resin composition obtained will fall.

  If necessary, a thermoplastic resin may be added to the thermoplastic resin composition of the present invention. By adding this thermoplastic resin, the mechanical strength and other characteristics of the thermoplastic resin composition can be improved.

  Examples of the thermoplastic resin include polyvinyl chloride resin, polyethylene resin, polypropylene resin, cyclic olefin copolymer resin, polymethyl methacrylate resin, polystyrene resin, polyphenylene ether resin, polyphenylene sulfide resin, and polysulfone resin. , Polyimide resin, and polyamideimide resin. At least one of these can be used. However, the thermoplastic resin is not limited to these, and various thermoplastic resins can be used, and styrene elastomers, olefin elastomers, ester elastomers, vinyl chloride elastomers, amide elastomers, etc. can also be used. Can do.

  Various thermoplasticity imparting agents may be added to the thermoplastic resin composition of the present invention as necessary. By adding a flexibility-imparting agent, it can be expected that the thermoplastic resin composition has low hardness and improved elongation.

  The thermoplastic resin composition of the present invention includes a stabilizer, a flame retardant, a pigment, an antistatic agent, a release agent, a lubricant, an antibacterial anti-resistant for the purpose of adjusting the physical properties of the thermoplastic resin composition and the molded article obtained. A mold agent or the like may be further added. Among these, examples of the stabilizer include an antioxidant, a light stabilizer, and an ultraviolet absorber. These additives may be appropriately selected according to the required physical properties and the intended use.

<Method for producing thermoplastic resin composition>
The thermoplastic resin composition of the present invention is produced using the above-mentioned acrylic block copolymer (A) and the thermoplastic polyurethane resin (B).

  As the kneader used for the production of the composition, various devices capable of performing heating and kneading at the same time can be used. For example, Banbury, kneader, uniaxial or multiaxial used for ordinary rubber processing can be used. Examples include an extruder. Furthermore, if necessary, the composition can be molded using a press, an injection molding machine or the like. The kneading temperature for producing the composition is preferably 100 to 350 ° C, more preferably 150 to 300 ° C. When the temperature is lower than 100 ° C., the thermoplastic polyurethane resin is insufficiently melted, resulting in uneven kneading. When the temperature is higher than 350 ° C., the acrylic block copolymer (A) and the thermoplastic polyurethane resin itself tend to decompose.

  The thermoplastic resin composition of the present invention can be molded using a molding method and molding apparatus generally used for thermoplastic resins, such as extrusion molding, injection molding, press molding, blow molding, calendar molding, vacuum, and the like. Molding can be performed by any molding method such as molding or foam molding.

  EXAMPLES Although this invention is demonstrated further in detail based on an Example, this invention is not limited only to these Examples. The molecular weight, injection molding, hardness, mechanical strength, and oil resistance described in the examples were performed according to the following methods.

<Molecular weight measurement method>
The molecular weight shown in this example was measured by the GPC analyzer shown below, and the molecular weight in terms of polystyrene was determined using chloroform as the mobile phase. As a system, a GPC system manufactured by Waters was used, and Shodex (registered trademark) K-804 (polystyrene gel) manufactured by Showa Denko KK was used for the column.

<Injection molding>
For the injection molding shown in this example, Toshiba's injection molding machine IS80EPN was used. The mold was a center gate plate (length 120 mm * width 120 mm * thickness 2 mm). The measurement position was 55 mm, the molding cycle was 2 seconds for injection, and 30 seconds for cooling, and the molded body was taken out from the mold in a semi-automatic mode. Further, the dumbbell described below was punched out in the TD direction (perpendicular to the injection direction) and the mechanical strength of the molded body taken out was measured.

<Hardness>
According to JIS K6253, the hardness at 23 ° C. (immediately after, JIS A) was measured with a type A durometer.

<Mechanical strength>
Measurements were made using an autograph AG-10TB model manufactured by Shimadzu Corporation, applying the method described in JIS K7113. Measurement was performed at n = 3, and the average value of strength (MPa), elongation (%), and modulus of elasticity (MPa) when the test piece broke was adopted. A test piece having a shape of 2 (1/3) shape and a thickness of about 2 mm was used. The test was conducted at 23 ° C. and a test speed of 500 mm / min. In principle, the test piece was conditioned for 48 hours or more at a temperature of 23 ± 2 ° C. and a relative humidity of 50 ± 5% before the test.

<Oil resistance>
In accordance with ASTM D638, ASTM Oil No. 1 in which the molded product of the composition was kept at room temperature or 100 ° C. 3 was immersed for 72 hours, and the weight change rate (% by weight) was determined.

(Production Example 1)
<Synthesis of acrylic block copolymer (A)>
A 500-liter reactor purged with nitrogen was charged with 87.1 kg of butyl acrylate and 2.23 kg of t-butyl acrylate, followed by 625 g of cuprous bromide and stirring was started. Thereafter, a solution prepared by dissolving 628 g of diethyl 2,5-dibromoadipate in 7.84 kg of acetonitrile was charged, and the jacket was heated and held at an internal temperature of 75 ° C. for 30 minutes. Thereafter, 76 g of pentamethyldiethylenetriamine was added to initiate polymerization of the acrylic polymer block. A small amount of the polymerization solution was withdrawn at regular intervals from the start of polymerization, and the conversion of butyl acrylate was determined by gas chromatogram analysis. The polymerization rate was controlled by adding pentamethyldiethylenetriamine as needed.

  When the conversion of butyl acrylate reached 95%, 106.5 kg of toluene, 431 g of cuprous chloride, 76 g of pentamethyldiethylenetriamine, and 38.4 kg of methyl methacrylate were added to polymerize the methacrylic polymer block. Started. When the conversion rate of methyl methacrylate reached 90%, 220 kg of toluene was added to dilute the reaction solution, and the reactor was cooled to stop the polymerization. When the GPC analysis of the obtained acrylic block copolymer was conducted, the number average molecular weight (Mn) was 108,900 and the molecular weight distribution (Mw / Mn) was 1.34.

  Toluene was added to the resulting acrylic block copolymer solution to make the polymer concentration 22% by weight. To this solution, 1.49 kg of p-toluenesulfonic acid monohydrate was added and stirred at 30 ° C. for 3 hours. The reaction solution was sampled to confirm that the solution was colorless and transparent, and 2.47 kg of Radiolite # 3000 manufactured by Showa Chemical Industry was added. Thereafter, pressure filtration was performed at 0.1 to 0.4 MPaG using a pressure filter equipped with polyester felt as a filter medium to separate a solid content.

  The filtered acrylic block copolymer solution was charged into a 500 L reactor and heated at 150 ° C. for 4 hours. After cooling, 6.18 kg of Kyowa Chemical Kyoward 500SH was added and stirred for 1 hour. The reaction solution was sampled to confirm that the solution was neutral, and the reaction was completed. This converted t-butyl acrylate (tBA) units to acrylic acid (AA) units. The content of acrylic acid units in the entire block copolymer was 1.7% by weight. Then, using a pressure filter equipped with polyester felt as a filter medium, pressure filtration was performed at 0.1 to 0.4 MPaG to separate a solid content, and a polymer solution was obtained.

  After adding 0.6 parts by weight of Irganox 1010 (manufactured by Ciba Specialty Chemicals Co., Ltd.) to 100 parts by weight of the polymer to the obtained polymer solution, SCP100 (Kurimoto Corporation) The solvent component was evaporated using a heat transfer area of 1 m2). The heating medium oil at the evaporator inlet was 180 ° C., the evaporator vacuum was 0.01 MPa or less, the screw rotation speed was 60 rpm, and the polymer solution supply rate was 32 kg / h. The polymer was made into a strand through a φ4 mm die, cooled in a water tank, and then an acrylic block copolymer pellet having a carboxylic acid functional group was obtained by a pelletizer.

(Examples 1-2)
The block copolymer prepared in Production Example 1, a thermoplastic polyurethane resin (Elastollan C60D: manufactured by BASF Japan) and Irganox 1010 as a stabilizer were hand-blended in the ratio shown in Table 1, and 200 ° C. (cylinder part 8 points (C1 ~ C8, from the bottom of the hopper to the die side in the order of C1 to C8)) using a twin-screw extruder (32mmφ, L / D = 22.5, manufactured by Nippon Steel Works, product name TEX30HSS) Melt kneading was performed at a rotational speed of 300 rpm. The obtained sample was injection-molded to obtain a sheet of 120 mm square and 2 mm thickness. Using this sheet, hardness measurement and oil resistance test were performed. The evaluation results are shown in Table 1.

(Comparative Example 1)
An ester-based thermoplastic polyurethane-based resin (Elastollan C60D: manufactured by BASF Japan) was injection-molded to obtain a 120 mm square sheet having a thickness of 2 mm. Using this sheet, hardness measurement and oil resistance test were performed. The evaluation results are shown in Table 1.

(Comparative Examples 2-3)
Styrene elastomer (Septon 2063: manufactured by Kuraray) and thermoplastic polyurethane resin (Elastollan C60D: manufactured by BASF Japan) were hand-blended at the ratio shown in Table 1, and 200 ° C. (cylinder part 8 points (C1 to C8, hopper). Using a twin screw extruder (32 mmφ, L / D = 22.5, manufactured by Nippon Steel Works Co., Ltd., product name TEX30HSS) from bottom to die side in the order of C1 to C8) Melt kneaded. Moreover, the obtained sample was injection-molded to obtain a sheet of 120 mm square and 2 mm thickness. Using this sheet, hardness measurement and oil resistance test were performed. The evaluation results are shown in Table 1.

  From the comparison between Examples 1 and 2 and Comparative Example 1, it is understood that the thermoplastic polyurethane resin added with the acrylic block copolymer has improved flexibility relative to the thermoplastic polyurethane resin alone. . Further, from the comparison between Example 1 and Comparative Example 2 and the comparison between Example 2 and Comparative Example 3, when the blending amounts are the same, those using an acrylic block copolymer as a modifier are styrene elastomers. It can be seen that it has better oil resistance than those using.

(Example 3)
The polymer pellets obtained in Production Example 1, the polyether-based thermoplastic polyurethane resin (PANDEX T-8180N: manufactured by DIC Bayer Polymer Co., Ltd.) and the stabilizer: Irganox 1010 in the proportions shown in Table 1 Using a mill (manufactured by Toyo Seiki Co., Ltd.), melt-kneading was performed at 200 ° C. to obtain a block sample. The obtained sample was hot press molded at a set temperature of 200 ° C. to obtain a molded body for evaluation having a thickness of 2 mm. This molded body was used for hardness measurement, mechanical strength, and oil resistance test. The evaluation results are shown in Table 2.

Example 4
Labo plast mill with the polymer pellets obtained in Production Example 1, polyester thermoplastic polyurethane resin (PANDEX T-1180: manufactured by DIC Bayer Polymer Co., Ltd.) and stabilizer: Irganox 1010 in the proportions shown in Table 1. Using a Toyo Seiki Co., Ltd. melt kneaded at 200 ° C., a block sample was obtained. The obtained sample was hot press molded at a set temperature of 200 ° C. to obtain a molded body for evaluation having a thickness of 2 mm. This molded body was used for hardness measurement, mechanical strength, and oil resistance test. The evaluation results are shown in Table 2.

(Comparative Example 4)
Polyether-based thermoplastic polyurethane resin (PANDEX T-8180N: manufactured by DIC Bayer Polymer Co., Ltd.) and stabilizer: Irganox 1010 in the ratio shown in Table 1, using Labo Plast Mill (manufactured by Toyo Seiki Co., Ltd.) Were melt-kneaded at 200 ° C. to obtain block samples. The obtained sample was hot press molded at a set temperature of 200 ° C. to obtain a molded body for evaluation having a thickness of 2 mm. This molded body was used for hardness measurement, mechanical strength, and oil resistance test. The evaluation results are shown in Table 2.

(Comparative Example 5)
Polyester-based thermoplastic polyurethane-based resin (PANDEX T-1180: manufactured by DIC Bayer Polymer Co., Ltd.) and stabilizer: Irganox 1010 in the ratio shown in Table 1, using Labo Plast Mill (manufactured by Toyo Seiki Co., Ltd.) A block sample was obtained by melt-kneading at 200 ° C. The obtained sample was hot press molded at a set temperature of 200 ° C. to obtain a molded body for evaluation having a thickness of 2 mm. This molded body was used for hardness measurement, mechanical strength, and oil resistance test. The evaluation results are shown in Table 2.

(Comparative Example 6)
Styrene elastomer (Septon 2063: manufactured by Kuraray Co., Ltd.) and polyether thermoplastic polyurethane resin (PANDEX T-8180N: manufactured by DIC Bayer Polymer Co., Ltd.) and stabilizer: Irganox 1010 in the ratios shown in Table 1. Using a Laboplast mill (manufactured by Toyo Seiki Co., Ltd.), it was melt kneaded at 200 ° C. to obtain a block sample. The obtained sample was hot press molded at a set temperature of 200 ° C. to obtain a molded body for evaluation having a thickness of 2 mm. This molded body was used for hardness measurement, mechanical strength, and oil resistance test. The evaluation results are shown in Table 2.

(Comparative Example 7)
Styrene-based elastomer (Septon 2063: manufactured by Kuraray Co., Ltd.), polyester-based thermoplastic polyurethane resin (PANDEX T-1180: manufactured by DIC Bayer Polymer Co., Ltd.) and stabilizer: Irganox 1010 in the ratios shown in Table 1, Using a Laboplast mill (manufactured by Toyo Seiki Co., Ltd.), melt-kneading was performed at 200 ° C. to obtain a block sample. The obtained sample was hot press molded at a set temperature of 200 ° C. to obtain a molded body for evaluation having a thickness of 2 mm. This molded body was used for hardness measurement, mechanical strength, and oil resistance test. The evaluation results are shown in Table 2.

  From the comparison between Examples 3 and 4 and Comparative Examples 4 and 5, the addition of an acrylic block copolymer to a thermoplastic polyurethane resin has improved flexibility relative to the thermoplastic polyurethane resin alone. I understand. From the comparison between Example 3 and Example 4, the addition of an acrylic block copolymer to a polyester thermoplastic polyurethane resin is the addition of an acrylic block copolymer to a polyether thermoplastic polyurethane resin. It can be seen that it has better oil resistance than.

  Further, from the comparison between Example 3 and Comparative Example 6 and the comparison between Example 4 and Comparative Example 7, when the blending amounts are the same, those using an acrylic block copolymer as a modifier are styrene elastomers. It can be seen that it has better oil resistance and mechanical properties than those used.

  The thermoplastic resin composition comprising the acrylic block copolymer (A) and the thermoplastic polyurethane resin (B) obtained in the present invention has the characteristics inherent to the acrylic block copolymer and the thermoplastic polyurethane resin. Since the flexibility, oil resistance, etc. are improved while maintaining, it can be used more suitably as an automobile or an electric / electronic component.

  Specifically, packing materials, sealing materials, gaskets, sealing materials such as plugs, CD dampers, architectural dampers, automotive exterior members, vibration control materials such as vibration control materials for vehicles and home appliances, vibration isolation materials, Automotive interior materials, cushion materials, daily necessities, electrical components, electronic components, sports materials, grips or cushioning materials, wire coating materials, packaging materials, sheets, skins, film materials, base polymers for adhesives, resin modifiers, various types It can be used effectively as a container, stationery part, etc.

Claims (11)

A thermoplastic resin composition comprising 1 to 60% by weight of an acrylic block copolymer (A) and 99 to 40% by weight of a thermoplastic polyurethane resin (B),
A thermoplastic resin composition, wherein the thermoplastic polyurethane resin (B) is either a polyether thermoplastic polyurethane resin or a polyester thermoplastic polyurethane resin.   The acrylic block copolymer (A) is at least one selected from the group represented by the general formula: (ab) n, (ab) na (n is an integer of 1 or more). The thermoplastic resin composition according to claim 1.   The thermoplastic resin composition according to claim 1 or 2, wherein the acrylic block copolymer (A) is a triblock copolymer represented by a general formula: a-b-a.   The acrylic block copolymer (A) comprises 0.1 to 50% by weight of a methacrylic polymer block (a) and 99.9 to 50% by weight of an acrylic polymer block (b). The thermoplastic resin composition according to any one of claims 1 to 3.   The acrylic block copolymer (A) is composed of 0.1 to 40% by weight of a methacrylic polymer block (a) and 99.9 to 60% by weight of an acrylic polymer block (b). The thermoplastic resin composition according to any one of claims 1 to 4.   The acrylic block copolymer (A) is composed of 10 to 40% by weight of a methacrylic polymer block (a) and 90 to 60% by weight of an acrylic polymer block (b). To 5. The thermoplastic resin composition according to any one of 5 to 5.   Acrylic ester block (b) is 50-100% by weight of acrylic ester containing at least one monomer selected from the group consisting of n-butyl acrylate, ethyl acrylate, 2-methoxyethyl acrylate, and The thermoplastic resin composition according to claim 1, comprising 50 to 0% by weight of a vinyl monomer.   The acrylic block copolymer (A) is converted from an acid anhydride group, a carboxyl group, a hydroxyl group, and an epoxy group to at least one of the methacrylic polymer block (a) and the acrylic polymer block (b). It has at least 1 sort (s) of functional group selected from the group which consists of a thermoplastic resin composition in any one of Claim 1 to 7 characterized by the above-mentioned.   The thermoplastic resin composition according to any one of claims 1 to 8, wherein the acrylic block copolymer (A) comprises a block copolymer produced by an atom transfer radical polymerization method.   The thermoplastic resin composition according to any one of claims 1 to 9, wherein the thermoplastic polyurethane resin (B) comprises a polyether thermoplastic polyurethane resin.   A molded article comprising the thermoplastic resin composition according to any one of claims 1 to 10.