JPH11256029A - Thermoplastic resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a thermoplastic resin composition which can give in high productivity a molding being excellent in elongation at low stress and recovery after elongation and having a small residual strain after elongation and to provide a molding. SOLUTION: There is provided a thermoplastic resin composition comprising a thermoplastic polyurethane (a) comprising units of a polymer polyol having 2.01-2.10 hydroxyl groups per molecule and having an Mn of 500-8,000, units of an organic diisocyanate, and units of a chain extender and having a nitrogen content of 2.5 wt.% or below, a thermoplastic polyurethane (b) comprising units of a polyester diol having an Mn of 1,500-5,000, units of an organic diisocyanate, and units of a chain extender and having a nitrogen content of 2.6 wt.% or above, an endothermic peak at 200-220 deg.C as measured by differential scanning calorimetry, and having a crystallization enthalpy of 2-15 J/g, and an aromatic vinyl compound/conjugated diene block copolymer (c) and containing 40-90 wt.% component (a), 60-10 wt.% component (b), and 5-150 wt.% component (c), [each amount is based on the total weight of components (a) and (b)].

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to two kinds of thermoplastic polyurethanes, a block copolymer composed of an aromatic vinyl compound polymer block and a conjugated diene polymer block, and a hydrogenated product of the block copolymer. The present invention also relates to a thermoplastic resin composition comprising at least one of the following, and a film, sheet, or other molded article comprising the thermoplastic resin composition. The thermoplastic resin composition of the present invention is excellent in melt moldability and blocking resistance, and is particularly excellent in elongation at low stress and recovery performance after elongation by melt extrusion molding,
Molded articles such as films and sheets having a small residual strain after elongation can be manufactured with high productivity.

[0002]

2. Description of the Related Art Thermoplastic polyurethane has mechanical performance,
Because of its excellent properties such as abrasion resistance, elastic recovery, oil resistance, and flexibility, it is attracting attention as a substitute for rubber and plastic. For example, films and sheets formed by extrusion of thermoplastic polyurethane have attracted attention as stretchable materials for disposable diapers. This elastic film for disposable diapers is intended to prevent the disposable diaper from coming off the body with a moderate force when the disposable diaper is attached, and to be thin and can be stretched with a small force. Rather, the ability to return to the original shape after elongation (recovery performance) is high,
It is required to have the property of being excellent in dimensional stability (small residual strain).

[0003] In order to satisfy such demands,
Attempts have been made to reduce the hardness of thermoplastic polyurethane. In such a method, when a molded article such as a film or sheet is melt-extruded using a T-die extruder or the like, a T-die is used. A phenomenon in which the width of the extruded molded product becomes significantly narrower than the effective width of the T-die (hereinafter referred to as “neck-in phenomenon”) occurs, and only a molded product having uneven thickness at both ends can be obtained. . Therefore, in order to obtain a uniform molded article without uneven thickness, it is necessary to trim portions having uneven thickness at both ends of the molded article, and the productivity of the molded article is very poor. Furthermore, since the obtained molded article has poor blocking resistance, when producing molded articles such as films and sheets, it is necessary to produce the molded articles using expensive release paper, for example, which is extremely troublesome and costly. There is a problem that it takes.

In recent years, it has been proposed to blend a styrene-based elastomer for the purpose of improving the adhesive property and performance of the thermoplastic polyurethane while maintaining the properties of the thermoplastic polyurethane. For example, JP-A-9-25407 discloses that a nitrogen atom content obtained by reacting a polyester diol containing a 3-methyl-1,5-pentanediol unit, an organic diisocyanate and a chain extender is 2.5% by weight. % Of a thermoplastic polyurethane (A), a polyester diol, an organic diisocyanate and a chain extender, the nitrogen content is 3.5% by weight or more, and the logarithmic viscosity is 0.9 dl / g or less. A thermoplastic polyurethane composition obtained by blending an aromatic vinyl compound-conjugated diene block copolymer with a composition comprising a thermoplastic polyurethane (B) having a crystallization enthalpy of (1).

[0005]

However, according to the study of the present inventors, according to the study of the present inventors, a thermoplastic polyurethane containing only a polyester diol unit having 2.00 hydroxyl groups per molecule as described above was used. In this case, simply blending the aromatic vinyl compound-conjugated diene block copolymer may cause a neck-in phenomenon that occurs when a molded article such as a film or sheet is melt-extruded using a T-die type extruder or the like. It was found that the recovery performance of the resulting film or sheet was not sufficiently improved.

An object of the present invention is to improve a neck-in phenomenon that occurs when melt-extrusion molding is performed using a T-die extruder or the like,
To provide a thermoplastic resin composition that is excellent in stretchability at low stress and recovery performance after stretch, and has low residual strain after stretching, such as a film or sheet, which can be manufactured with high productivity. is there. It is still another object of the present invention to provide a molded article such as a film or sheet made of the thermoplastic resin composition.

[0007]

As a result of repeated studies by the present inventors to achieve the above object, the number of hydroxyl groups per molecule of thermoplastic polyurethane is from 2.01 to 2.10.
It has been found that it is important to use a thermoplastic polyurethane having specific crystallinity in combination with a low-hardness thermoplastic polyurethane containing a high molecular weight polyol unit. Furthermore, as a result of repeated studies based on these findings, the number of hydroxyl groups per molecule is from 2.01 to 2.10.
5% by weight or less of a thermoplastic polyurethane (a), and a nitrogen atom content of 2.6% by weight or more of a thermoplastic polyurethane (b) having a specific enthalpy of crystallization,
By blending at least one of a block copolymer composed of an aromatic vinyl compound polymer block and a conjugated diene polymer block and a hydrogenated product of the block copolymer in a specific amount, a T-die extruder or the like is used. In addition to improving the neck-in phenomenon during melt extrusion molding, it also has excellent recovery performance after elongation, and produces molded products such as films and sheets with excellent mechanical properties as stretchable materials with high productivity. The inventors have found that the present invention can be performed and completed the present invention.

That is, the present invention provides (i) a thermoplastic polyurethane (a), a thermoplastic polyurethane (b), a block copolymer composed of an aromatic vinyl compound polymer block and a conjugated diene polymer block, and At least one kind of hydrogenated block copolymer (c) (hereinafter sometimes referred to as “block copolymer (c)”)
(Ii) the thermoplastic polyurethane (a) has a number of hydroxyl groups per molecule of 2.01 to 2.10 and a number average molecular weight of 500 to 8,000. Consisting of a polymer diol unit, an organic diisocyanate unit and a chain extender unit,
(Iii) the thermoplastic polyurethane (b) has a polyester diol unit having a number average molecular weight of 1,500 to 5,000, an organic diisocyanate unit, and (iii) a thermoplastic polyurethane having a nitrogen atom content of 2.5% by weight or less. It consists of a chain extender unit, has a nitrogen atom content of 2.6% by weight or more, shows an endothermic peak in the range of 200 to 220 ° C. by differential scanning calorimetry (DSC), and crystallizes from the endothermic peak. A thermoplastic polyurethane having an enthalpy (ΔH) of from 2 to 15 J / g; and (iv) 40 thermoplastic polyurethanes (a) based on the total weight of the thermoplastic polyurethanes (a) and (b). To 90% by weight, 60 to 10% by weight of the thermoplastic polyurethane (b), and an aromatic vinyl compound polymer block and a conjugated diene. A thermoplastic resin composition comprising a block copolymer composed of united blocks and at least one kind (c) of a hydrogenated product of the block copolymer in a proportion of 5 to 150% by weight. It is. Further, the present invention is a molded article such as a film or a sheet made of the thermoplastic resin composition.

[0009]

BEST MODE FOR CARRYING OUT THE INVENTION The thermoplastic polyurethane (a) used in the present invention is composed of a polymer polyol unit, an organic diisocyanate unit and a chain extender unit. Further, the thermoplastic polyurethane (b) used in the present invention
Is composed of a polyesterdiol unit, an organic diisocyanate unit and a chain extender unit.

Examples of the polymer polyol unit constituting the thermoplastic polyurethane (a) include polyester polyol, polyether polyol, polycarbonate polyol, polyester polycarbonate polyol and the like. These polymer polyols may be used alone or in combination of two or more. Among these, it is preferable to use a polyester polyol or a polyether polyol, and it is more preferable to use a polyester polyol.

The above polyester polyol is subjected to, for example, a direct esterification reaction or a transesterification reaction between the polyol and an ester-forming derivative such as a polycarboxylic acid or an ester or an anhydride thereof according to a conventional method,
Alternatively, it can be produced by ring-opening polymerization of a lactone using a polyol or the like as an initiator.

As the polyol constituting the polyester polyol, those generally used in the production of polyester can be used. Examples thereof include ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol and 1,3-propanediol. , 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, 1,8-octanediol, 2-methyl-1,8-octanediol, 2,7-dimethyl-1 , 8-octanediol,
Aliphatic diols having 2 to 15 carbon atoms such as 1,9-nonanediol, 2-methyl-1,9-nonanediol, 2,8-dimethyl-1,9-nonanediol, and 1,10-decanediol; 1 Alicyclic diols such as 1,4-cyclohexanediol, cyclohexanedimethanol, cyclooctanedimethanol and dimethylcyclooctanedimethanol; one molecule such as aromatic dihydric alcohols such as 1,4-bis (β-hydroxyethoxy) benzene Diols having two hydroxyl groups per molecule; and trimethylolpropane, trimethylolethane, glycerin, 1,2,2
Examples thereof include polyols having three or more hydroxyl groups per molecule, such as 6-hexanetriol, pentaerythritol, diglycerin, and methylglycoxide. These polyols may be used alone or in combination of two or more. Among them, 2-methyl-1,4
-Butanediol, 3-methyl-1,5-pentanediol, 2-methyl-1,8-octanediol, 2-methyl-1,9-nonanediol, 2,7-dimethyl-
1,8-octanediol, 2,8-dimethyl-1,9
It is preferable to use an aliphatic diol having 5 to 12 carbon atoms having a methyl group as a side chain, such as nonanediol, and the aliphatic diol is used in an amount of 30 mol% or more based on the total amount of the polyol. Is more preferable,
More preferably, it is used in a proportion of 50 mol% or more. It is preferable to use a small amount of trimethylolpropane from the viewpoint that a thermoplastic resin composition having excellent performance such as flexibility can be obtained.

As the polycarboxylic acid constituting the polyester polyol, those generally used in the production of polyester can be used. For example, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid can be used. Acid, sebacic acid, dodecandioic acid, methyl succinic acid, 2-methylglutaric acid, 3-methylglutaric acid, trimethyladipic acid, 2-methyloctanedioic acid, 3,8-dimethyldecandioic acid, 3,7-dimethyldecane An aliphatic dicarboxylic acid having 4 to 12 carbon atoms such as a diacid;
Alicyclic dicarboxylic acids such as cyclohexanedicarboxylic acid; aromatic dicarboxylic acids such as terephthalic acid, isophthalic acid, orthophthalic acid, and naphthalenedicarboxylic acid; trifunctional or higher polycarboxylic acids such as trimellitic acid and pyromellitic acid; . These polycarboxylic acids may be used alone or in combination of two or more.
Among these, it is preferable to use a fatty acid dicarboxylic acid having 6 to 12 carbon atoms, and it is more preferable to use adipic acid, azelaic acid, and sebacic acid.

Examples of the lactone include ε-caprolactone and β-methyl-δ-valerolactone.

Examples of polyether polyols include polyethylene glycol, polypropylene glycol, polytetramethylene glycol, and poly (methyltetrafluoroethylene) obtained by ring-opening polymerization of a cyclic ether, preferably in the presence of a small amount of a trifunctional or higher polyol. Methylene glycol)
And the like, and one or more of these can be used. Among these, it is preferable to use polytetramethylene glycol.

As the polycarbonate polyol, for example, those obtained by reacting a polyol with a carbonate compound such as dialkyl carbonate, alkylene carbonate, diaryl carbonate and the like can be used. As the polyol constituting the polycarbonate polyol, the polyol exemplified above as the constituent component of the polyester polyol can be used. Also, as the dialkyl carbonate, dimethyl carbonate,
Diethyl carbonate and the like. Further, the alkylene carbonate includes ethylene carbonate, and the diaryl carbonate includes diphenyl carbonate.

The polyester polycarbonate polyol is obtained, for example, by simultaneously reacting a polyol, a polycarboxylic acid and a carbonate compound.
Alternatively, it can be obtained by previously synthesizing a polyester polyol and a polycarbonate polyol by the above-mentioned method, and then reacting them with a carbonate compound or with a polyol and a polycarboxylic acid.

The high molecular weight polyol constituting the thermoplastic polyurethane (a) has a hydroxyl group number of 2.01 per molecule.
２．１2.10 and 2.01
More preferably within a range of 2.07 to 2.07.
More preferably, it is in the range of 1-2.05. By using a polymer polyol having the number of hydroxyl groups per molecule within the above range, a neck-in phenomenon that occurs when a molded article such as a film or a sheet is melt-extruded by a T-die type extruder or the like is improved, Not only is the productivity of the molded product further improved, but even if the molded product such as a film or sheet extruded from the T-die is taken up at a high speed, defective phenomena such as necking and cracking hardly occur. further,
A molded article such as a film or sheet having a small thickness, a good surface condition, a high recovery performance after elongation, and a small residual strain after elongation can be obtained.

Examples of the high molecular polyol constituting the thermoplastic polyurethane (a) include, among the above-mentioned raw material components of the high molecular polyol, a component having two functional groups in one molecule and a functional group in one molecule. And a component having three or more hydroxyl groups per molecule of the high molecular polyol.
The polymer polyol produced by using the compound in such a ratio as to be 01 to 2.10 may be used alone, or a polymer diol having 2 hydroxyl groups per molecule and a hydroxyl group per molecule may be used. May be used as a mixture of a polymer polyol having a value of greater than 2 and a ratio of the number of hydroxyl groups per molecule of the polymer polyol being 2.01 to 2.10.

The number average molecular weight of the high molecular polyol is 500
8,000, preferably 600-5,000, and more preferably 800-5,000. By using a polymer polyol having a number average molecular weight in this range, a thermoplastic resin composition having more excellent mechanical performance and melt moldability can be obtained. The number average molecular weight of the high molecular polyol referred to in the present specification is J
It is a number average molecular weight calculated based on a hydroxyl value measured according to IS K-1577.

As the polyester diol constituting the thermoplastic polyurethane (b), for example, a diol and an ester-forming derivative such as a dicarboxylic acid or an ester or an anhydride thereof can be directly esterified or transesterified according to a conventional method. Or by subjecting a lactone to ring-opening polymerization using a diol or the like as an initiator.

As the diol constituting the polyester diol, those generally used in the production of polyester can be used. Examples thereof include ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol and 1,3-propanediol. , 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, 1,8-octanediol, 2-methyl-1,8-octanediol,
2,7-dimethyl-1,8-octanediol, 1,9
-Nonanediol, 2-methyl-1,9-nonanediol, 2,8-dimethyl-1,9-nonanediol, 1,
Aliphatic diols having 2 to 15 carbon atoms such as 10-decanediol; alicyclic diols such as 1,4-cyclohexanediol, cyclohexanedimethanol, cyclooctanedimethanol, dimethylcyclooctanedimethanol; 1,4-bis ( Examples thereof include diols having two hydroxyl groups per molecule such as aromatic dihydric alcohols such as β-hydroxyethoxy) benzene. These diols may be used alone or in combination of two or more. Among these, 2-methyl-1,4-butanediol, 3-methyl-1,5-pentanediol, 2-methyl-1,4-butanediol,
Methyl-1,8-octanediol, 2-methyl-1,
Use is made of an aliphatic diol having 5 to 12 carbon atoms having a methyl group as a side chain, such as 9-nonanediol, 2,7-dimethyl-1,8-octanediol and 2,8-dimethyl-1,9-nonanediol. Preferably, these aliphatic diols are added in an amount of 30 mol% based on the total amount of
It is more preferably used in the above ratio, and further preferably used in a ratio of 50 mol% or more.

As the dicarboxylic acid constituting the polyester diol, those generally used in the production of polyester can be used. For example, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid , Sebacic acid, dodecanedioic acid, methylsuccinic acid, 2-methylglutaric acid, 3-methylglutaric acid, trimethyladipic acid, 2-methyloctanedioic acid,
Aliphatic dicarboxylic acids having 4 to 12 carbon atoms such as 3,8-dimethyldecandioic acid and 3,7-dimethyldecandioic acid; alicyclic dicarboxylic acids such as cyclohexanedicarboxylic acid; terephthalic acid, isophthalic acid, orthophthalic acid; And aromatic dicarboxylic acids such as naphthalenedicarboxylic acid. These dicarboxylic acids may be used alone or in combination of two or more. Among these, it is preferable to use a fatty acid dicarboxylic acid having 6 to 12 carbon atoms, and it is more preferable to use adipic acid, azelaic acid, and sebacic acid.

Examples of the lactone include ε-caprolactone and β-methyl-δ-valerolactone.

The polyester diol constituting the thermoplastic polyurethane (b) has a number average molecular weight of 1,500 to 5,
000, preferably from 1,800 to 4,000. By using a polyester diol having a number average molecular weight within this range, a thermoplastic resin composition having more excellent mechanical performance and melt moldability can be obtained.

Thermoplastic polyurethanes (a) and (b)
There is no particular limitation on the organic diisocyanate used in the production of the thermoplastic polyurethane, and any organic diisocyanate conventionally used in the production of ordinary thermoplastic polyurethanes may be used. For example, 4,4′-diphenylmethane diisocyanate, tri Range isocyanate, phenylene diisocyanate, xylylene diisocyanate,
1,5-naphthylene diisocyanate, 3,3′-dichloro-4,4′-diphenylmethane diisocyanate,
Aromatic diisocyanates such as tolylene diisocyanate; aliphatic or alicyclic diisocyanates such as hexamethylene diisocyanate, isophorone diisocyanate, 4,4'-dicyclohexylmethane diisocyanate, and hydrogenated xylylene diisocyanate. These organic diisocyanates may be used alone or in combination of two or more. Among these, it is preferable to use 4,4'-diphenylmethane diisocyanate.

Thermoplastic polyurethanes (a) and (b)
There is no particular limitation on the chain extender used in the production of
Any of the chain extenders conventionally used in the production of ordinary thermoplastic polyurethanes may be used, and low molecular weight compounds having a molecular weight of 300 or less and having two or more active hydrogen atoms capable of reacting with isocyanate groups in the molecule. It is preferable to use For example, ethylene glycol, propylene glycol, 1,4-butanediol, 1,6-hexanediol, 1,4-bis (β-hydroxyethoxy) benzene, 1,4-cyclohexanediol, bis (β-hydroxyethyl) terephthalate And diols such as xylylene glycol; diamines such as hydrazine, ethylenediamine, propylenediamine, xylylenediamine, isophoronediamine, piperazine and derivatives thereof, phenylenediamine, tolylenediamine, xylenediamine, adipic dihydrazide, and isophthalic dihydrazide; Examples include amino alcohols such as aminoethyl alcohol and aminopropyl alcohol. These low molecular compounds may be used alone or in combination of two or more. Among them, those having 2 to 10 carbon atoms
It is preferable to use an aliphatic diol, and more preferable to use 1,4-butanediol.

The above-mentioned polymer polyol or polyester diol is reacted with an organic diisocyanate and a chain extender to form a thermoplastic polyurethane (a) or (b).
In producing, the mixing ratio of each component is appropriately determined in consideration of the hardness to be imparted to the intended thermoplastic polyurethane and the like, but the polymer polyol or polyester diol and the chain extender have It is preferable to use each component in such a ratio that the isocyanate group contained in the organic diisocyanate is 0.9 to 1.2 mol per 1 mol of active hydrogen atoms. The use of the above components in the above proportions is preferable because a thermoplastic resin composition excellent in melt extrusion moldability, recovery performance, blocking resistance, flexibility, elastic recovery and the like can be obtained.

Thermoplastic polyurethanes (a) and (b)
The production method is not particularly limited, using the above-mentioned polymer polyol or polyester diol, an organic diisocyanate and a chain extender, utilizing a known urethanation reaction technique, a prepolymer method and a one-shot method. Any of them may be manufactured. Among these, it is preferable to carry out melt polymerization substantially in the absence of a solvent, and it is more preferable to employ a continuous melt polymerization method using a multi-screw extruder.

The nitrogen content of the thermoplastic polyurethane (a) is 2.5% by weight or less, preferably 1.0 to 2.5% by weight, and more preferably 1.5 to 2.5% by weight. More preferably, it is 1.7 to 2.5% by weight. When the nitrogen content of the thermoplastic polyurethane (a) exceeds 2.5% by weight, the hardness of the obtained thermoplastic resin composition becomes high, and a stretchable film having excellent flexibility and elastic recovery properties is obtained. Molded articles such as sheets cannot be obtained.

The nitrogen content of the thermoplastic polyurethane (b) is at least 2.6% by weight, preferably from 2.6 to 6.0% by weight, and more preferably from 2.8 to 5.0% by weight. More preferably, the content is 3.0 to 4.0% by weight. When the nitrogen content of the thermoplastic polyurethane (b) is less than 2.6% by weight, the resulting thermoplastic resin composition has poor melt moldability and blocking resistance.

The logarithmic viscosity of the thermoplastic polyurethane (a) is determined by dissolving the thermoplastic polyurethane (a) in an N, N-dimethylformamide solution to a concentration of 0.5 g / dl and measuring at 30 ° C. It is preferably at least 0.8 dl / g, more preferably at least 0.9 dl / g, even more preferably at least 1.0 dl / g. When the thermoplastic polyurethane (a) having the logarithmic viscosity in the above range is used, a thermoplastic resin composition that gives a molded article with less residual strain can be obtained.

The logarithmic viscosity of the thermoplastic polyurethane (b) is determined by dissolving the thermoplastic polyurethane (b) in an N, N-dimethylformamide solution to a concentration of 0.5 g / dl and measuring at 30 ° C. 0.2 to 1.2 dl / g
Is preferably 0.3 to 1.1 dl / g, and more preferably 0.5 to 1.1 dl / g. When the thermoplastic polyurethane (b) having the logarithmic viscosity in the above range is used, a thermoplastic resin composition having more excellent melt moldability and blocking resistance can be obtained.

The thermoplastic polyurethane (b) has an endothermic peak in the range of 200 to 220 ° C. by differential scanning calorimetry (DSC), and has a crystallization enthalpy (ΔH) determined from the endothermic peak of 2 to 15 J / g. And preferably 3 to 10 J / g. When the temperature of the endothermic peak is less than 200 ° C., or when the crystallization enthalpy (ΔH) is less than 2 J / g, the resulting thermoplastic resin composition has poor extrusion moldability and blocking resistance.
On the other hand, when the endothermic peak temperature exceeds 220 ° C., or when the crystallization enthalpy (ΔH) exceeds 15 J / g, an unmelted substance is liable to be generated in the obtained thermoplastic resin composition, and a film, a sheet, etc. When molding into a molded article of the above, bumps are likely to occur. Also, the blocking resistance is poor.

Aromatic vinyl compound in block copolymer (c) Examples of the aromatic vinyl compound constituting the polymer block include styrene, α-methylstyrene,
3-methylstyrene, 4-propylstyrene, 4-cyclohexylstyrene, 4-dodecylstyrene, 2-ethyl-4-benzylstyrene, 4- (phenylbutyl) styrene, 1-vinylnaphthalene, and the like. Species or two or more can be used. Of these, styrene and α-methylstyrene are preferably used.

The conjugated diene constituting the conjugated diene polymer block in the block copolymer (c) includes, for example, 1,3-butadiene, 2-methyl-1,3-butadiene, 2,3-dimethyl-1,2 Examples thereof include 3-butadiene, 2-neopentyl-1,3-butadiene, 1,3-pentadiene, and 1,3-hexadiene, and one or more of these can be used. Among these, 1,3-butadiene and 2-methyl-1,3-butadiene are preferably used.

The bonding form between the aromatic vinyl compound polymer block and the conjugated diene polymer block in the block copolymer (c) is not particularly limited, and may be linear, branched, radial, or two or more of them. Any combination of bonding forms may be used, and a linear bonding form is preferable. As examples of the block copolymer (c), when an aromatic vinyl compound polymer block is represented by X and a conjugated diene polymer block is represented by Y, (XY) nX,
(XY) m, Y- (XY) p [n, m and p each represent an integer of 1 or more. ] And the like. Among them, X-
It is preferable to use a diblock copolymer represented by Y and a triblock copolymer represented by XYX.

As the block copolymer (c), a copolymer in which part or all of the unsaturated double bond in the conjugated diene polymer block is hydrogenated can be used. Such a hydrogenated block copolymer (c)
When a is used, a thermoplastic resin composition having better heat resistance, light resistance and the like can be obtained.

In the block copolymer (c), the content of the structural unit derived from the aromatic vinyl compound is preferably from 5 to 75% by weight based on all the structural units, and is preferably from 10 to 65% by weight.
More preferably, it is% by weight. When a block copolymer (c) containing a structural unit derived from an aromatic vinyl compound within the above range is used, excellent melt moldability when producing a film or sheet, thinning can be achieved, and blocking resistance is achieved. It is possible to obtain a resin having better recovery properties such as flexibility, flexibility, recovery stress after elongation and residual strain.

230 ° C. of the block copolymer (c);
The melt index measured under a load of 16 kg is 10
It is preferably at most 0 g / 10 min, more preferably at most 80 g / 10 min. When a block copolymer (c) having a melt index in the above range is used,
It is excellent in melt moldability when producing a film or sheet, can achieve a thin film, and has more excellent blocking resistance, flexibility, and recovery performance such as recovery stress after stretching and residual strain. In addition, the melt index of the block copolymer (c) referred to in this specification is ASTM D-123.
It is a value measured according to 8.

The JIS A hardness of the block copolymer (c) is preferably from 30 to 98. The block copolymer (c) having a JIS A hardness within this range has more excellent compatibility with the thermoplastic polyurethane, and when such a block copolymer is used, the block copolymer (c) may have a high degree of compatibility with the thermoplastic resin composition. The resulting molded article is given sufficient flexibility and good mechanical performance. The JIS A hardness of the block copolymer (c) referred to in the present specification is a value measured according to JIS K-6301.

The thermoplastic resin composition of the present invention comprises a thermoplastic polyurethane (a) and a thermoplastic polyurethane (b)
40 to 90% by weight of the thermoplastic polyurethane (a) and 60% by weight of the thermoplastic polyurethane (b) based on the total weight of
Must be contained at a rate of 10 to 10% by weight,
It is preferable that the thermoplastic polyurethane (a) is contained in a proportion of 45 to 85% by weight and the thermoplastic polyurethane (b) is contained in a proportion of 55 to 15% by weight. Thermoplastic polyurethane (a)
Is less than 40% by weight (when the content of the thermoplastic polyurethane (b) is more than 60% by weight), the hardness of the thermoplastic resin composition is high, so that the thickness is small and the surface state is low. It is difficult to obtain a good film or sheet, and the resulting film or sheet has poor flexibility and elastic recovery. On the other hand, when the content of the thermoplastic polyurethane (a) exceeds 90% by weight (when the content of the thermoplastic polyurethane (b) is less than 10% by weight), the film or sheet is extruded by a T-die extruder or the like. The neck-in phenomenon that occurs when melt extrusion molding etc. is not sufficiently improved, the range of thickness unevenness occurring at both ends of molded products such as films and sheets is widened, and this thickness unevenness part is trimmed The productivity of the resulting homogeneous product is reduced. Furthermore, blocking resistance is also inferior.

The content of the block copolymer (c) is determined by the difference between the thermoplastic polyurethane (a) and the thermoplastic polyurethane (b).
Is in the range of 5 to 150% by weight, preferably in the range of 20 to 120% by weight, based on the total weight of When the content of the block copolymer (c) is less than 5% by weight, the blocking resistance, the flexibility of the obtained molded product, and the like are inferior. On the other hand, when the content of the block copolymer (c) exceeds 150% by weight, the flexibility of the obtained molded article is impaired.

The thermoplastic resin composition of the present invention is obtained by adding a bisamide compound (d) to the thermoplastic resin composition comprising the thermoplastic polyurethane (a), the thermoplastic polyurethane (b) and the block copolymer (c). ) Is preferably from 0.05 to 1 based on the total weight of the thermoplastic polyurethane (a) and the thermoplastic polyurethane (b).
0% by weight, more preferably 0.05 to 8% by weight
, More preferably 0.1 to 6% by weight. By containing the bisamide compound (d) at the above ratio, a thermoplastic resin composition having further improved blocking resistance and releasability can be obtained.

As the bisamide compound (d), for example, bisamide compounds represented by the following general formulas (1) and (2) are preferable. R ¹ -CONH-R ² -NHCO-R ³ (1) (wherein, R ¹ and R ³ each represent an alkyl group or an alkenyl group, and R ² represents an alkylene group or an arylene group.) R ⁴ -NHCO —R ⁵ —CONH—R ⁶ (2) (wherein, R ⁴ and R ⁶ each represent an alkyl group or an alkenyl group, and R ⁵ represents an alkylene group or an arylene group.) In the above general formula (1), , R ¹ and R ³ have 6 to ³ carbon atoms
More preferably, R 5 is an alkyl or alkenyl group having 5 and R ² is an alkylene group or an arylene group having 2 to 12 carbon atoms. In the above general formula (2), R ⁴ and R ⁶
Is an alkyl or alkenyl group having 6 to 35 carbon atoms,
More preferably, R ⁵ is an alkylene group or an arylene group having 2 to 12 carbon atoms.

The bisamide compound represented by the general formula (1) is a compound obtained from an aliphatic monocarboxylic acid and a diamine, and among them, an aliphatic monocarboxylic acid having 6 to 35 carbon atoms and a C2 to C2 compound. Compounds derived from a diamine of 12 are more preferable, and specific examples thereof include methylene bisstearic acid amide, ethylenebiscaprylic amide, ethylenebiscapric amide, ethylenebislauric amide, ethylenebismyristic amide, Bispalmitic acid amide, ethylenebisstearic acid amide, ethylenebisisostearic acid amide, ethylenebisbehenic acid amide, ethylenebismontanamide, tetramethylenebisstearic acid amide,
Tetramethylenebisisostearic acid amide, tetramethylenebismontanamide, hexamethylenebiscaprylic amide, hexamethylenebiscapric amide,
Hexamethylene bislaurate amide, hexamethylene bismyristate amide, hexamethylene bispalmitate amide, hexamethylene bis stearamide,
Hexamethylenebisisostearamide, Hexamethylenebisbehenamide, Hexamethylenebismontanamide, Ethylenebisoleamide, Ethylenebiserucamide, Tetramethylenebisoleamide, Tetramethylenebiserucamide, Hexamethylenebis Oleic acid amide, m-xylylenebisstearic acid amide, m-xylenebismontanamide and the like can be mentioned.

The bisamide compound represented by the general formula (2) is a compound obtained from an aliphatic monoamine and a dicarboxylic acid, and among them, an aliphatic monoamine having 6 to 35 carbon atoms and a dicarboxylic acid having 2 to 12 carbon atoms. Compounds derived from acids are more preferable, and specific examples thereof include:
N, N'-distearyl adipamide, N, N'-
Distearyl sebacamide, N, N'-distearyl azelaic amide, N, N'-dioleyl adipamide, N, N'-dioleyl sebacamide,
N, N'-dioleyl azelaic acid amide, N, N'-
Distearyl isophthalamide, N, N'-dioleyl isophthalamide and the like can be mentioned.

The bisamide compounds represented by the above general formulas (1) and (2) may be used alone or in combination of two or more.

The thermoplastic resin composition of the present invention may contain a polyolefin resin such as high-density polyethylene, medium-density polyethylene, low-density polyethylene, polypropylene and polybutylene, and a paraffinic oil for the purpose of further improving blocking resistance. Can be blended.

The thermoplastic resin composition of the present invention contains a reinforcing agent, a coloring agent, a lubricant, and the like as long as the effects of the present invention are not impaired.
Various additives such as a flame retardant, an ultraviolet absorber, an antioxidant, a hydrolysis resistance improver, a fungicide, an antibacterial agent, and a stabilizer; various fibers such as a glass fiber and a polyester fiber; an inorganic substance such as talc and silica; Arbitrary components such as various coupling agents can be blended as needed.

The thermoplastic resin composition of the present invention comprises the above-mentioned thermoplastic polyurethane (a), thermoplastic polyurethane (b), block copolymer (c) and, if necessary, other components in a desired manner. It can be manufactured by mixing. For example, a thermoplastic polyurethane (a), a thermoplastic polyurethane (b), a block copolymer (c) and, if necessary, a thermoplastic polyurethane (a), a thermoplastic polyurethane (b), and a After pre-mixing the other components in a predetermined ratio, it can be manufactured by melt-kneading under heating in a batch or continuous manner using a single-screw or twin-screw extruder, mixing roll, Banbury mixer, or the like. it can.

The thermoplastic resin composition of the present invention can be melt-molded, and various molded articles can be smoothly molded by any molding method such as extrusion molding, inflation molding, injection molding, blow molding, calendar molding, and casting. Can be manufactured. In particular, since the thermoplastic resin composition of the present invention is excellent in melt extrusion moldability, for example, in molding of a film or a sheet by a T-die type extruder, a film extruded from the effective width of the T-die. The neck-in phenomenon, in which the width of molded articles such as sheets and sheets, is considerably reduced, has been significantly improved, and the range of thickness unevenness at both ends of molded articles such as films and sheets caused by the neck-in phenomenon is narrowed. The productivity of the product obtained by trimming the thickness unevenness portion is improved. Also, when a molded product such as a film or a sheet extruded from a T-die is taken at a high speed, the entire molded product such as a film or a sheet is not uniformly stretched and necking or cracking which causes constriction. As a result, high quality products can be obtained with high productivity. Furthermore, molded articles such as films and sheets obtained by using the thermoplastic resin composition of the present invention are excellent in stretchability at low stress, recovery performance such as recovery stress or residual strain after elongation, tensile fracture. It has excellent mechanical properties such as strength and tensile elongation at break, and has a smooth surface and good surface condition. In particular, it excels in elasticity at low stress and recovery performance such as recovery stress after elongation and residual strain.Employing these characteristics, it is used for disposable diapers, sanitary napkins, sealing, and dustproofing. It is particularly preferred to use it for stretch film applications. Further, it can be used for various uses such as sheet use for general-purpose conveyor belts, various keyboard sheets, laminated products, various containers, and the like. Furthermore, the film or sheet made of the thermoplastic resin composition of the present invention has excellent adhesiveness with a fibrous base material made of a nonwoven fabric or another fiber cloth, or a base material made of another polymer film or sheet. Therefore, it is suitable for manufacturing a laminate. For example, the thermoplastic resin composition of the present invention can be melt-extruded on a fibrous base material or another base material into a film or a sheet to produce a laminate.

[0053]

EXAMPLES Hereinafter, the present invention will be described specifically with reference to Examples, but the present invention is not limited to these Examples. In Examples and Comparative Examples, the nitrogen atom content, logarithmic viscosity, and differential scanning calorimetry (DS
C), melt moldability, film production state, surface state, blocking resistance, 100% modulus (M100), recovery rate and residual strain were measured or evaluated by the following methods.

[Nitrogen atom content] The nitrogen content was determined by elemental analysis of thermoplastic polyurethane using an elemental analyzer (Model 240-2 manufactured by PerkinElmer).

[Logarithmic viscosity] A thermoplastic polyurethane was added to an N, N-dimethylformamide solution at a concentration of 0.5 g / dl.
The polyurethane solution was dissolved using an Ubbelohde viscometer and the flow time at 30 ° C. was measured.
The logarithmic viscosity was determined by the following equation. Logarithmic viscosity = [ln (t / t ₀ )] / c [where t is the flow time (seconds) of the polyurethane solution, t ₀
Represents the flow time (second) of the solvent, and c represents the concentration (g / dl) of the polyurethane solution. ]

[Differential Scanning Calorimetry (DSC)] The enthalpy of fusion of the thermoplastic polyurethane was measured using a differential scanning calorimeter (DSC30 manufactured by Mettler). 10 mg of thermoplastic polyurethane was used for the measurement, and the temperature was measured at a rate of 10 ° C./min in a nitrogen gas atmosphere. The crystallization enthalpy (ΔH) was determined from the endothermic peak temperature and the endothermic peak area in the range of 200 to 220 ° C. I asked.

[Melt Formability] While discharging the film extruded from the T-die type extruder, the film width 10 cm below the T-die exit was measured, and the neck-in rate (%) was determined according to the following formula. It was used as an index of melt moldability. The smaller this value is, the more the neck-in phenomenon is improved, indicating that the melt-moldability is excellent. Neck-in rate (%) = (W ₂ −W ₁ ) / W ₂ × 100 (where W ₁ represents a film width 10 cm below the T-die exit, and W ₂ represents an effective width of the T-die. )

[Production state and surface state of film] A film extruded from a T-die type extruder onto a cooling roll at 30 ° C and cooled is taken up at a winding speed of about 2.5 m / min without using release paper. Rolled up. During the winding,
The production state of the film was observed and evaluated according to the following criteria. ：: Without causing a defect phenomenon such as cracking in the film,
Can be wound up normally. Δ: The film could be wound up although some defects such as cracks occurred in the film. X: A defective phenomenon such as a crack occurred in the film, and the film could not be wound. Furthermore, observe the surface condition of the wound film,
平滑 indicates a smooth surface, and X indicates an uneven surface due to poor dispersion.

[Blocking Resistance] A film extruded from a T-die extruder onto a cooling roll at 30 ° C. and cooled was wound up at a winding speed of about 2.5 m / min without using release paper. . The wound film is allowed to stand at room temperature for 24 hours.
After being left for a while, it was rewound by hand and the resistance at that time was evaluated according to the following criteria. ◎: Rewinding is extremely easy without requiring any tensile force. ：: Can be smoothly rewound. Δ: A considerable tensile force was required, but rewinding was possible. X: The adhesive property is large and rewinding is impossible.

[100% Modulus (M100), Recovery Ratio and Residual Strain] A test piece (20 cm × 5) was prepared from a 50 μm thick film formed using a T-die extruder.
cm). This test piece was stretched to 100% at room temperature at a tensile speed of 300 mm / min by using an autograph measuring device IS-500D (manufactured by Shimadzu Corporation).
The 0% modulus (M50) and 100% modulus (M100) were measured. Next, it returned to the position before extension at a speed of 300 mm / min (first cycle). The stress (A) at the time of returning to the 50% elongation position was measured, and the recovery rate (%) was determined according to the following formula, and used as an index of the recovery performance. Recovery rate (%) = (A / M50) × 100 Further, after continuous elongation at the same speed for 100%, the residual strain at the time when it returned to the position before the elongation (second cycle) was determined. The smaller the value of the 100% modulus (M100), the better the extensibility at low stress. Also, the larger the value of the recovery rate, the stronger the force to return to the original state after elongation, indicating that the recovery performance is excellent. Furthermore, it shows that the smaller the value of the residual strain, the better the recovery performance that returns to the original state after elongation.

Abbreviations relating to the resins and compounds used in the following Examples and Comparative Examples are shown below.

TPU-a1 : 1 prepared by reacting 3-methyl-1,5-pentanediol with adipic acid
A polyester diol having a number of hydroxyl groups per molecule of 2.00 and a number average molecular weight of 3500 (hereinafter referred to as “polyester diol (1)”);
The number of hydroxyl groups per molecule produced by reacting -methyl-1,5-pentanediol, trimethylolpropane and adipic acid is 3.00, and the number average molecular weight is 2
A mixture of polyester polyol (hereinafter, referred to as "polyester polyol (2)") having a molar ratio of 98/2 polyester diol (1) / polyester polyol (2) of 2 and a hydroxyl number per molecule of 2 .02] / 4,4'-diphenylmethane diisocyanate / 1,4-butanediol-based thermoplastic polyurethane [nitrogen atom content: 2.4% by weight, logarithmic viscosity: 1.2
5 dl / g]

TPU-a2 : a mixture of polyester diol (1) and polyester polyol (2) [polyester diol (1) / polyester polyol (2) molar ratio is 95/5, and the number of hydroxyl groups per molecule is 2.05 ] / 4,4'-diphenylmethane diisocyanate / 1,4-butanediol-based thermoplastic polyurethane [nitrogen atom content is 1.9% by weight, logarithmic viscosity is 1.20]
dl / g]

TPU-a3 : 2,7-dimethyl-1,8
A mixture of octanediol and 2,8-dimethyl-1,9-nonanediol (at a molar ratio of 35/65) and adipic acid, the number of hydroxyl groups per molecule being 2.00, Polyester diol having an average molecular weight of 2000 (hereinafter referred to as "polyester diol (3)") and polyester polyol (2)
[Polyester diol (3) / polyester polyol (2) molar ratio of 97/3, number of hydroxyl groups per molecule is 2.03] / 4,4'-diphenylmethane diisocyanate / 1,4-butanediol Thermoplastic polyurethane [nitrogen atom content: 2.2% by weight, logarithmic viscosity: 1.31 dl / g]

TPU-a4 : a mixture of polyester diol (1) and polyester polyol (2) [polyester diol (1) / polyester polyol (2) molar ratio is 88/12, and the number of hydroxyl groups per molecule is 2.12 ] / 4,4'-diphenylmethane diisocyanate / 1,4-butanediol-based thermoplastic polyurethane [nitrogen atom content: 2.4% by weight, insoluble in DMF solvent]

TPU-a5 : Polyester diol (1) / 4,4′-diphenylmethane diisocyanate / 1,4-butanediol-based thermoplastic polyurethane [nitrogen atom content: 2.4% by weight, logarithmic viscosity: 0.75 dl
/ G]

TPU-b1 : polyester diol (1) / 4,4′-diphenylmethane diisocyanate / 1,4-butanediol thermoplastic polyurethane [nitrogen atom content: 3.2% by weight, differential scanning calorimetry (DS)
Endothermic peak temperature of 204 ° C., crystallization enthalpy (ΔH) 3.5 J / g, logarithmic viscosity 0.74 dl / g]

TPU-b2: a mixture of 1,4-butanediol and 1,6-hexanediol (molar ratio: 60/4
0) and adipic acid, polyester diol (number average molecular weight: 2000) / 4,4'-diphenylmethane diisocyanate / 1,4-butanediol thermoplastic polyurethane [nitrogen atom content: 3.1% by weight, differential scanning calorimetry (DSC) endothermic peak temperature 206 ° C., crystallization enthalpy (ΔH) 5.3 J / g, logarithmic viscosity 1.01 d
l / g]

TPU-b3: Polyester diol composed of 1,4-butanediol and adipic acid (number average molecular weight 1000) / 4,4′-diphenylmethane diisocyanate / 1,4-butanediol-based thermoplastic polyurethane [nitrogen atom content 4.4% by weight, differential scanning calorimetry (DSC) endothermic peak temperature of 175 ° C., crystallization enthalpy (ΔH) 0 J / g, logarithmic viscosity 0.90 dl / g]

TPU-b4: Polyester diol (number average molecular weight 2000) / 4 comprising a mixture of 1,9-nonanediol and 2-methyl-1,8-octanediol (molar ratio 65:35) and adipic acid 4'-diphenylmethane diisocyanate / 1,4-butanediol-based thermoplastic polyurethane [nitrogen atom content 4.3% by weight,
Endothermic peak temperature 228 of differential scanning calorimetry (DSC)
° C, crystallization enthalpy (ΔH) 20.5 J / g, logarithmic viscosity 0.70 dl / g]

TPS-1 : Hydrogenated product of triblock copolymer consisting of polystyrene block-polyisoprene block-polystyrene block [styrene content is 30
% By weight, the content of 1,2-bonds and 3,4-bonds in the polyisoprene block is 7%, the hydrogenation ratio in the polyisoprene block is 98% or more, and the melt index (230 ° C., 2.16 kg load) is 2.4g / 10
Min, JIS A hardness is 80]

TPS-2 : hydrogenated triblock copolymer consisting of polystyrene block-polyisoprene block-polystyrene block [styrene content is 20
% By weight, the content of 1,2-bonds and 3,4-bonds in the polyisoprene block is 55%, the hydrogenation rate in the polyisoprene block is 92%, and the melt index (230 ° C., 2.16 kg load) is 6 g. / 10 minutes, JI
SA hardness is 52]

TPS-3 : Triblock copolymer composed of polystyrene block-polyisoprene block-polystyrene block [styrene content: 15% by weight, content of 1,2-bond and 3,4-bond in polyisoprene block Is 5%, melt index (190 ° C,
2.16 kg load) is 2 g / 10 min, JIS A hardness is 37]

TPS-4 : hydrogenated triblock copolymer consisting of polystyrene block-polyisoprene block-polystyrene block [styrene content is 30
Weight%, content of 1,2-bond and 3,4-bond in polyisoprene block is 5%, hydrogenation rate in polyisoprene block is 98% or more, melt index (230 ° C., 2.16 kg load) flow Without)

AM : Ethylene bisstearic acid amide

PP : polypropylene [Melt index (230 ° C., 2.16 kg load) is 240 g / 10
Minutes)

Oil : paraffinic oil [containing 70% by weight of paraffin and 30% by weight of naphthene, and having a kinematic viscosity of 4 × 10 ⁻⁴ m ⁻² / sec (40 ° C.)]

Examples 1 to 3 A mixture of a thermoplastic polyurethane (TPU) and a block copolymer (TPS) in the proportions shown in Table 1 below was mixed with a single screw extruder (25 mmφ, cylinder temperature:
The thermoplastic resin composition was manufactured by melt-kneading at 180 to 200 ° C and a die temperature of 200 ° C). Table 1 below shows the results of the evaluation of the thermoplastic resin composition by the above evaluation method.

Example 4 The same procedures as in Examples 1 to 3 were carried out except that the thermoplastic polyurethane (TPU), block copolymer (TPS) and bisamide compound (AM) were used in the proportions shown in Table 1 below. A thermoplastic resin composition was produced by the method. Table 1 below shows the results of the evaluation of the thermoplastic resin composition by the above evaluation method.

Example 5 Examples 1 to 3 except that thermoplastic polyurethane (TPU), block copolymer (TPS), polyolefin (PP) and paraffinic oil were used in the proportions shown in Table 1 below. A thermoplastic resin composition was produced in the same manner as in the above. Table 1 below shows the results of the evaluation of the thermoplastic resin composition by the above evaluation method.

[0081]

[Table 1]

Comparative Examples 1, 2, 6 The same procedures as in Examples 1 to 3 were carried out except that the thermoplastic polyurethane (TPU) and the block copolymer (TPS) were used in the proportions shown in Table 2 below. A thermoplastic resin composition was manufactured. About this thermoplastic resin composition,
The results evaluated by the above evaluation method are shown in Table 2 below.

Comparative Example 3 A thermoplastic resin composition was prepared in the same manner as in Examples 1 to 3, except that the thermoplastic polyurethane (TPU) and the block copolymer (TPS) were used in the proportions shown in Table 2 below. Was manufactured. From this thermoplastic resin composition, a thickness of 5
A film of 0 μm was produced, but the blocking resistance was poor and it was difficult to rewind the film.
Modulus (M100), recovery and residual strain could not be evaluated. The obtained evaluation results are shown in Table 2 below.

Comparative Examples 4 and 5 The thermoplastic polyurethane (TPU) and the block copolymer (TPS) were used in the same manner as in Examples 1 to 3, except that they were used in the proportions shown in Table 2 below. A resin composition was manufactured. From this thermoplastic resin composition, a thickness of 5
Although a film having a thickness of 0 μm was produced, the film was cracked, and the blocking resistance and the 100% modulus (M1
00), a film capable of evaluating the recovery rate and residual strain could not be obtained. Table 2 below shows the obtained evaluation results.
Shown in

[0085]

[Table 2]

[0086]

As described above, the thermoplastic resin composition of the present invention has a remarkably improved neck-in phenomenon which is generated when a melt-extrusion molding is performed by a T-die type extruder or the like, and is excellent in blocking resistance. By using the thermoplastic resin composition of the present invention, it is possible to produce a molded product such as a film or a sheet having excellent extensibility at low stress and recovery performance after elongation and small residual strain after elongation, with high productivity. Can be.

Claims (3)

[Claims] 1. A block copolymer comprising (i) a thermoplastic polyurethane (a), a thermoplastic polyurethane (b), an aromatic vinyl compound polymer block and a conjugated diene polymer block, and the block copolymer. (Ii) the thermoplastic polyurethane (a) has a number of hydroxyl groups per molecule of from 2.01 to 2.10. Consisting of a polymer diol unit having a number average molecular weight of 500 to 8,000, an organic diisocyanate unit and a chain extender unit,
(Iii) the thermoplastic polyurethane (b) has a polyester diol unit having a number average molecular weight of 1,500 to 5,000, an organic diisocyanate unit, and (iii) a thermoplastic polyurethane having a nitrogen atom content of 2.5% by weight or less. It consists of a chain extender unit, has a nitrogen atom content of 2.6% by weight or more, shows an endothermic peak in the range of 200 to 220 ° C. by differential scanning calorimetry (DSC), and crystallizes from the endothermic peak. A thermoplastic polyurethane having an enthalpy (ΔH) of from 2 to 15 J / g; and (iv) 40 thermoplastic polyurethanes (a) based on the total weight of the thermoplastic polyurethanes (a) and (b). To 90% by weight, 60 to 10% by weight of the thermoplastic polyurethane (b), and an aromatic vinyl compound polymer block and a conjugated diene. A thermoplastic resin composition comprising a block copolymer composed of united blocks and at least one kind (c) of a hydrogenated product of the block copolymer in a proportion of 5 to 150% by weight. . 2. A molded article comprising the thermoplastic resin composition according to claim 1. 3. The molded article according to claim 2, which is a film or a sheet.