JPH11228809A - Thermoplastic resin composition - Google Patents

Abstract

(57) [Problem] To provide a thermoplastic resin composition capable of producing high-quality molded products such as films and sheets with high productivity, and a molded product comprising the composition. SOLUTION: The number of hydroxyl groups per molecule is 2.01 to 2.10
In, the number average molecular weight of the polymer polyol unit of 500 to 8000, a thermoplastic polyurethane comprising an organic diisocyanate unit and a chain extender unit (a), an ethylene-α-olefin copolymer (b), an aromatic vinyl compound polymer A block copolymer composed of a block and a conjugated diene polymer block and a hydrogenated product thereof (c), and a bisamide compound (d)
A thermoplastic resin composition consisting of components (a) and (b)
30-90% by weight of component (a), based on the total weight of
70 to 10% by weight of (b), 1 to 30% by weight of component (c), and component (d)
A thermoplastic resin composition containing 0.05 to 10% by weight;
And a molded article comprising the composition.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a specific thermoplastic polyurethane, an ethylene-.alpha.-olefin copolymer, a block copolymer composed of an aromatic vinyl compound polymer block and a conjugated diene polymer block, and the block copolymer. The present invention relates to a thermoplastic resin composition comprising a hydrogenated product of a copolymer and a bisamide compound, and a film, a sheet, and other molded articles comprising the thermoplastic resin composition. The thermoplastic resin composition of the present invention is excellent in melt moldability, in particular, by melt extrusion molding or inflation molding, molded products such as high-quality films and sheets,
It 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. Instead, the stress (recovery stress) that tries to return to the original shape after elongation 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.

[0004] In recent years, it has been proposed to blend an olefin or styrene 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-8-
No. 143766 discloses polyester diol units,
A thermoplastic polymer composition in which an olefin elastomer and an aromatic vinyl compound-conjugated diene block copolymer are blended with a general thermoplastic polyurethane comprising an organic diisocyanate unit and a chain extender unit is described.

[0005]

However, according to the study of the present inventors, it is impossible to obtain a T-die type extruder or the like simply by blending an olefin or styrene elastomer with a general thermoplastic polyurethane. It has been found that the neck-in phenomenon that occurs when melt-extrusion of a molded article such as a film or a sheet by using the same is not sufficiently improved. Further, it has been found that when a molded article such as a film or a sheet is melt-molded from this thermoplastic polymer composition using an inflation molding machine, unevenness in thickness and cracks are likely to occur.

An object of the present invention is to improve the neck-in phenomenon that occurs when melt-extrusion molding is performed by a T-die type extruder or the like, and the unevenness and cracks that occur when melt-molding is performed by an inflation molding machine. An object of the present invention is to provide a thermoplastic resin composition capable of producing molded articles such as films and sheets with high productivity. It is a further object of the present invention to provide a molded article such as a film or sheet made of the thermoplastic resin composition.

[0007]

Means for Solving the Problems The inventors of the present invention have conducted various studies to achieve the above object, and as a result, have found that the number of hydroxyl groups per molecule is from 2.01 to 2.10. And a specific thermoplastic polyurethane comprising a chain extender unit, an ethylene-α-olefin copolymer, a block copolymer composed of an aromatic vinyl compound polymer block and a conjugated diene polymer block, and the block copolymer. At least one of the hydrogenated
By incorporating a seed and a bisamide compound, T
-The neck-in phenomenon at the time of melt-extrusion molding with a die-type extruder or the like is sufficiently improved, and not only can a molded article free of defective phenomena such as necking and cracking be produced with good yield, but also with an inflation molding machine. It has been found that even when melt-molded, uneven thickness and cracks are less likely to occur and a high-quality molded product can be produced with high productivity, and the present invention has been completed based on these findings.

That is, the present invention relates to (i) a thermoplastic polyurethane (a), an ethylene-α-olefin copolymer (b), a block copolymer comprising an aromatic vinyl compound polymer block and a conjugated diene polymer block. Thermoplastic resin composition comprising a polymer and at least one hydrogenated product of the block copolymer (c) (hereinafter sometimes referred to as “block copolymer (c)”), and a bisamide compound (d) (Ii) 30 to 90% by weight of the thermoplastic polyurethane (a) based on the total weight of the thermoplastic polyurethane (a) and the ethylene-α-olefin copolymer (b), A block copolymer comprising 70 to 10% by weight of an olefin copolymer (b), an aromatic vinyl compound polymer block and a conjugated diene polymer block; The hydrogenated block copolymer contains at least one kind (c) of 1 to 30% by weight and the bisamide compound (d) at a rate of 0.05 to 10% by weight, and (iii) the thermoplastic resin. The number of hydroxyl groups per molecule of the polyurethane (a) is 2.01 to
2.10 and a number average molecular weight of 500 to 8,000.
A thermoplastic resin composition comprising a thermoplastic polyurethane comprising a high molecular weight polyol unit, an organic diisocyanate unit and a chain extender unit. 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.

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, 2,7
-Dimethyl-1,8-octanediol, 2-methyl-
1,9-nonanediol, 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 it is more preferable to use these aliphatic diols in a proportion of 30 mol% or more based on the total amount of the polyol. More preferably, 5
More preferably, it is used in a proportion of 0 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.
7, and more preferably 2.01 to 2.05. When the number of hydroxyl groups per molecule of the polymer polyol is less than 2.01, when a molded article such as a film or a sheet is melt-extruded from a thermoplastic resin composition obtained by a T-die extruder or the like, a neck-in phenomenon occurs. As a result, the width of a molded product such as an extruded film or sheet becomes considerably smaller than the effective width of the T-die. Furthermore, since unevenness in thickness occurs at both ends of a molded product such as a film or a sheet, the productivity of a product obtained by trimming the thickness unevenness portion is low. Further, when a molded product such as a film or a sheet extruded from a T-die is taken up at a high speed, defective phenomena such as necking and cracking are likely to occur.
Further, when a film or sheet is formed by inflation molding, defective phenomena such as uneven thickness and cracks are likely to occur. On the other hand, the number of hydroxyl groups per molecule is 2.10.
When a larger polymer polyol is used, it is difficult to obtain a film having a small thickness, a good surface state, and excellent elasticity from the obtained thermoplastic resin composition.

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.

The organic diisocyanate used for producing the thermoplastic polyurethane (a) is not particularly limited.
Any of the organic diisocyanates conventionally used in the production of ordinary thermoplastic polyurethanes may be used. For example, 4,4'-diphenylmethane diisocyanate, tolylene diisocyanate, phenylene diisocyanate, xylylene diisocyanate, 1,5- Naphthylene diisocyanate, 3,3'-dichloro-4,
Aromatic diisocyanates such as 4'-diphenylmethane diisocyanate and toluylene diisocyanate; aliphatic or alicyclic diisocyanates such as hexamethylene diisocyanate, isophorone diisocyanate, 4,4'-dicyclohexylmethane diisocyanate and hydrogenated xylylene diisocyanate; it can. These organic diisocyanates may be used alone or in combination of two or more. Among these,
It is preferred to use 4,4'-diphenylmethane diisocyanate.

The chain extender used in the production of the thermoplastic polyurethane (a) is not particularly limited, and any of the chain extenders conventionally used in the production of ordinary thermoplastic polyurethanes may be used. Molecular weight 3 having at least two active hydrogen atoms capable of reacting with isocyanate groups in the molecule
It is preferable to use a low-molecular compound of not more than 00. For example, ethylene glycol, propylene glycol, 1,
4-butanediol, 1,6-hexanediol, 1,
4-bis (β-hydroxyethoxy) benzene, 1,4
Diols such as cyclohexanediol, bis (β-hydroxyethyl) terephthalate and xylylene glycol; hydrazine, ethylenediamine, propylenediamine, xylylenediamine, isophoronediamine, piperazine and derivatives thereof, phenylenediamine, tolylenediamine, xylenediamine, Diamines such as adipic dihydrazide and isophthalic dihydrazide; and 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 these, it is preferable to use an aliphatic diol having 2 to 10 carbon atoms, and it is more preferable to use 1,4-butanediol.

In producing the thermoplastic polyurethane (a) by reacting the above-mentioned polymer polyol, organic diisocyanate and chain extender, the mixing ratio of each component depends on the hardness to be imparted to the target thermoplastic polyurethane. It is appropriately determined in consideration of the isocyanate group contained in the organic diisocyanate is 0.9 to 1 mol per active hydrogen atom contained in the polymer polyol and the chain extender.
It is preferable to use each component at a ratio of 1.2 mol.

The method for producing the thermoplastic polyurethane (a) is not particularly limited, and the prepolymer method and the urethanization reaction technique using the above-mentioned polymer polyol, organic diisocyanate and chain extender are used. It may be manufactured by any one-shot method. Among them, it is preferable to carry out melt polymerization substantially in the absence of a solvent, and particularly preferable to use continuous melt polymerization using a multi-screw extruder.

JIS A for thermoplastic polyurethane (a)
The hardness is preferably from 55 to 85, and is preferably from 60 to 80.
Is more preferable. The thermoplastic polyurethane (a) having a JIS A hardness in this range has more excellent compatibility with the ethylene-α-olefin copolymer (b) and the block copolymer (c). In the case where is used, sufficient flexibility and good mechanical properties are imparted to a molded article obtained from the thermoplastic resin composition. In addition, the thermoplastic polyurethane (a) referred to in this specification
Is a value measured according to JIS K-7311.

The logarithmic viscosity of the thermoplastic polyurethane (a) is determined by dissolving the thermoplastic polyurethane (a) in an N, N-dimethylformamide solution at 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. It is preferable to use a thermoplastic polyurethane having the above-mentioned logarithmic viscosity, since a thermoplastic resin composition that gives a molded article with less residual strain can be obtained.

Ethylene-α-olefin copolymer (b)
Is composed of an ethylene unit and an α-olefin unit. Examples of the α-olefin unit constituting the ethylene-α-olefin copolymer (b) include propylene, 1-butene, 4-methyl-1-pentene, 1-hexene, 1-octene, 1-decene, -Units derived from octadecene and the like. These α-olefin units may be contained alone or in combination of two or more. Among them, a unit derived from an α-olefin having 4 or more carbon atoms is preferable, and an α-olefin having 7 to 12 carbon atoms is preferable because recovery performance such as recovery stress or residual strain after elongation is more excellent. Units derived from olefins are more preferred, units derived from α-olefins having 7 to 10 carbon atoms are more preferred, and units derived from 1-hexene or 1-octene are particularly preferred. Further, a small amount of a non-conjugated diene unit can be used together with the above-mentioned α-olefin unit, if necessary. Examples of the non-conjugated diene unit include units derived from ethylidene norbornene, dicyclopentadiene, 1,4-hexadiene, methylene norbornene, and the like.

Ethylene-α-olefin copolymer (b)
Is a molar ratio of ethylene units / α-olefin units = 55/45 to 55/45.
99/1, preferably 75/25 to 95/5
Is more preferable. Content of ethylene unit is 5
When the amount is less than 5 mol%, the softening temperature of the ethylene-α-olefin copolymer becomes low, and it becomes difficult to uniformly mix with the thermoplastic polyurethane (a) or the block copolymer (c). When the ethylene-α-olefin copolymer is used, the film obtained from the thermoplastic resin composition tends to stick easily. On the other hand, when an ethylene-α-olefin copolymer having an ethylene unit content of more than 99 mol% is used, it tends to be difficult to obtain a film having a small thickness and excellent stretchability.

Ethylene-α-olefin copolymer (b)
The melt index measured at 190 ° C. under a load of 2.16 kg is preferably in the range of 0.1 to 12 g / 10 min, more preferably in the range of 0.2 to 7 g / 10 min. More preferably, it is in the range of 0.4 to 5 g / 10 minutes. When the ethylene-α-olefin copolymer (b) having the above melt index is used, it is excellent in melt moldability when producing a film or a sheet, can achieve a thin film, has anti-blocking properties, flexibility,
A material having more excellent recovery performance such as recovery stress and residual strain after elongation can be obtained. In addition, ethylene-α referred to in this specification
-The melt index of the olefin copolymer (b) is
It is a value measured in accordance with ASTM D-1238.

Ethylene-α-olefin copolymer (b)
Is preferably in the range of 30 to 90, more preferably in the range of 40 to 85. When the ethylene-α-olefin copolymer (b) having the above Shore A hardness is used, a thermoplastic resin composition and a molded article obtained therefrom are more excellent in elastic recovery and mechanical performance. . The Shore A hardness of the ethylene-α-olefin copolymer (b) referred to in the present specification is a value measured according to ASTM D-2240.

Ethylene-α-olefin copolymer (b)
Is preferably a Mooney viscosity measured at 100 ° C. using an L-shaped rotor is in the range of _{5~60ML 1 + 4 (100 ℃)} , within the scope of 10~38ML ₁ + 4 (100 ℃) More preferably, there is. When the ethylene-α-olefin copolymer (b) having the above Mooney viscosity is used, one having more excellent blocking resistance, flexibility, and recovery performance such as recovery stress after elongation and residual strain can be obtained.
The Mooney viscosity of the ethylene-α-olefin copolymer (b) referred to in the present specification is a value measured according to ASTM D-1646.

Ethylene-α-olefin copolymer (b)
The production method of is not particularly limited, the above monomers, for example, by a known method such as a solution polymerization method, a bulk polymerization method, and a gas phase polymerization method, usually at a temperature of 0 to 250 ° C. and a normal pressure to 1000 It is obtained by polymerization at atmospheric pressure (100 MPa). In the polymerization, it is preferable to use a single-site catalyst having a uniform polymerization active point, since a polymer having a narrow molecular weight distribution and a narrow copolymer composition distribution can be easily obtained. Among the single-site catalysts, metallocene compounds containing a tetravalent transition metal are particularly preferable. For example, cyclopentadienyltitanium tris (dimethylamide), methylcyclopentadienyltitanium tris (dimethylamide), bis (cyclopentadiene) Enyl) titanium dichloride, dimethylsilyltetramethylcyclopentadienyl-t-
Butylamidozirconium dichloride, dimethylsilyltetramethylcyclopentadienyl-t-butylamidohafnium dichloride, dimethylsilyltetramethylcyclopentadienyl-pn-butylphenylamidozirconium dichloride, methylphenylsilyltetramethylcyclopentadienyl- t-butylamide hafnium dichloride, (t-butylamide) (tetramethyl-
Cyclopentadienyl) -1,2-ethanediyltitanium dichloride, indenyl titanium tris (dimethylamide), indenyl titanium tris (diethylamide), indenyl titanium bis (di-n-butylamide) (di-n-propylamide ). When a metallocene compound is used as a polymerization catalyst, since polymerization activity is not exhibited by itself, a co-catalyst such as methylaluminoxane or a non-coordinating boron compound is used in an amount of 2 to 1,000,000 per mole of the metallocene compound. 2,000 mol, preferably 50 to 5,000 mol, in combination.

Aromatic vinyl compound in the 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), those in which part or all of the unsaturated double bonds in the conjugated diene polymer block are hydrogenated can also be used. Such a hydrogenated block copolymer (c)
When a is used, a thermoplastic polymer 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 the block copolymer (c) having the above melt index is used, it is excellent in melt moldability when producing a film or a sheet, can be formed into a thin film, has blocking resistance, flexibility, recovery stress after elongation, and the like. A material having better recovery performance such as residual strain can be obtained. In addition, the melt index of the block copolymer (c) referred to in the present specification is a value measured according to ASTM D-1238.

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 better compatibility with the thermoplastic polyurethane (a) and the ethylene-α-olefin copolymer (b). When a polymer is used, a molded article obtained from the thermoplastic resin composition 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 bisamide compound (d) is, for example, represented by the following general formulas (1) and (2): R ¹ -CONH-R ² -NHCO-R ³ (1) (wherein R ¹ and R ³ are respectively R ² represents 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 are each 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 35 carbon atoms.
And R ² is more preferably an alkylene group or an arylene group having 2 to 12 carbon atoms. In the above general formula (2), R ⁴ and R ⁶ are more preferably an alkyl group or an alkenyl group having ⁶ to 35 carbon atoms, and R ⁵ is more preferably an alkylene group or an arylene group having 2 to 12 carbon atoms.

The bisamide compound represented by the above 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, and ethylene 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 comprises the thermoplastic polyurethane (a) in an amount of 30 to 90 based on the total weight of the thermoplastic polyurethane (a) and the ethylene-α-olefin copolymer (b). % By weight, ethylene-α-
It is necessary to contain the olefin copolymer (b) at a ratio of 70 to 10% by weight, and the thermoplastic polyurethane (a) is 45 to 90% by weight, and the ethylene-α-olefin copolymer (b) is used. Is preferably contained at a ratio of 55 to 10% by weight. When the content of the thermoplastic polyurethane (a) is less than 30% by weight, the mechanical performance, recovery stress, and recovery performance such as residual strain of a film obtained from the thermoplastic resin composition are impaired. 9 content
If it exceeds 0% by weight, the blocking resistance is poor.

The content of the block copolymer (c) is in the range of 1 to 30% by weight based on the total weight of the thermoplastic polyurethane (a) and the ethylene-α-olefin copolymer (b). , Preferably in the range of 2 to 20% by weight. When the content of the block copolymer (c) is less than 1% by weight, the blocking resistance is poor. Even when the content of the block copolymer (c) exceeds 30% by weight, the blocking resistance is inferior, and the mechanical performance, recovery stress, and residual strain of a film obtained from the thermoplastic resin composition are also poor. Be impaired.

The content of the bisamide compound (d) is 0.05 to 10% by weight based on the total weight of the thermoplastic polyurethane (a) and the ethylene-α-olefin copolymer (b), and is preferably It is 0.05 to 8% by weight, and more preferably 0.1 to 6% by weight. By including the bisamide compound (d) in the above range, it is possible to produce a molded article such as a film or a sheet by inflation molding requiring high blocking resistance (opening property).

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.

Further, the thermoplastic resin composition of the present invention includes:
Various additives such as a reinforcing agent, a coloring agent, a flame retardant, an ultraviolet absorber, an antioxidant, a hydrolysis resistance improving agent, a fungicide, an antibacterial agent, and a stabilizer, as long as the effects of the present invention are not impaired; Various components such as fibers and polyester fibers; inorganic materials such as talc and silica; and optional components such as various coupling agents can be added as necessary.

The thermoplastic resin composition of the present invention comprises the thermoplastic polyurethane (a), ethylene-α-olefin copolymer (b), block copolymer (c), bisamide compound (d) and It can be produced by mixing other components according to a desired method. For example, a thermoplastic polyurethane (a), an ethylene-α-olefin copolymer (b), and a block copolymer (c) are prepared by using a vertical or horizontal mixer as generally used for mixing resin materials. , The bisamide compound (d) and, if necessary, other components are premixed at a predetermined ratio, and then batchwise or continuously using a single-screw or twin-screw extruder, mixing roll, Banbury mixer, or the like. It can be produced by melt-kneading under heating.
As another method, for example, an ethylene-α-olefin copolymer (b), a block copolymer (c), a bisamide compound (d), Other components may be added according to the requirements.

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, the thermoplastic resin composition of the present invention has excellent melt moldability. For example, in a melt extrusion 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, resulting in necking or cracking that causes constriction. Therefore, a molded product of good quality can be obtained with high productivity. Further, also in the molding of films and sheets by an inflation molding machine, defective phenomena such as uneven thickness and cracks of the obtained molded product are remarkably improved, and a high-quality molded product 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.

[0051]

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, melt extrusion moldability, film production state, surface state, blocking resistance, 100% modulus (M100), inflation moldability, and opening property were measured or evaluated by the following methods. .

[Melt Extrusion 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 ratio (%) was calculated according to the following equation. It was determined and used as an index for melt extrusion moldability. The smaller this value is, the more the neck-in phenomenon is improved, indicating that the melt extrudability 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] T
A film extruded from a die-type extruder onto a cooling roll at 30 ° C. and cooled was wound up at a winding speed of about 3 m / min without using release paper. During the winding,
The state of film production 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 type extruder onto a cooling roll at 30 ° C. and cooled was wound up at a winding speed of about 3 m / min without using release paper. After leaving the wound film at room temperature for 24 hours, the film 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)] T-
A test piece (20 cm × 5 cm) was prepared from a 30 μm thick film formed using a die-type extruder. Using an autograph measuring device IS-500D (manufactured by Shimadzu Corporation), the test piece was subjected to a tensile speed of 300 mm / at room temperature.
100% elongation at 100% in minutes (M100)
Was measured. The smaller the value of the 100% modulus (M100), the better the extensibility at low stress.

[Inflation Formability and Opening Property] A film extruded into a tube from a single screw extruder (50 mmφ, cylinder temperature: 170 to 200 ° C., die temperature: 200 ° C.) equipped with an inflation die is vertically oriented. While taking it up, it was wound continuously for 2 hours at a winding speed of about 8 m / min. The state of film production was observed and evaluated according to the following criteria. ：: The film can be wound up normally without causing defects such as uneven thickness and cracks in the film. Δ: The film was somewhat defective, such as uneven thickness and cracks, but could be wound up. ×: Inferior phenomena such as uneven thickness and cracks occurred on the film, and winding was impossible. Further, the opening properties of the wound tube-shaped film were evaluated, and those having good opening properties were evaluated as ○, and those having large adhesiveness between the films and poor opening properties were evaluated as x.

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

TPU-A : Polyester polyol produced by reacting 3-methyl-1,5-pentanediol with adipic acid, having a hydroxyl number per molecule of 2.00 and a number average molecular weight of 3,500 (Hereinafter, referred to as “polyester polyol (1)”), and 3-methyl-1,5-pentanediol, trimethylolpropane, and adipic acid, which have a hydroxyl group number of 3 per molecule. And a mixture of polyester polyols having a number average molecular weight of 2,000 (hereinafter referred to as “polyester polyol (2)”) in which the molar ratio of polyester polyol (1) / polyester polyol (2) is 98/2. The number of hydroxyl groups per molecule is 2.02], 4,4'-diphenylmethane diisocyanate and Thermoplastic polyurethane [JIS A hardness obtained is reacted with 4-butanediol 6
5, logarithmic viscosity is 1.08 dl / g]

TPU-B : a mixture of polyester polyol (1) and polyester polyol (2) [molar ratio of polyester polyol (1) / polyester polyol (2): 95/5, number of hydroxyl groups per molecule: 2.05 Is reacted with 4,4'-diphenylmethane diisocyanate and 1,4-butanediol to obtain a thermoplastic polyurethane [JIS A hardness of 7
5, logarithmic viscosity is 1.01 dl / g]

TPU-C : 2,7-dimethyl-1,8-
The number of hydroxyl groups per molecule produced by reacting a mixture of octanediol and 2,8-dimethyl-1,9-nonanediol (molar ratio 35/65) and adipic acid is 2.00, and the number average A mixture of a polyester polyol having a molecular weight of 2,000 (hereinafter referred to as “polyester polyol (3)”) and a polyester polyol (2) [polyester polyol (3) / polyester polyol (2) has a molar ratio of 97/3] A thermoplastic polyurethane obtained by reacting 2.03] of hydroxyl groups per molecule with 4,4'-diphenylmethane diisocyanate and 1,4-butanediol [JI
SA hardness is 70, logarithmic viscosity is 1.05 dl / g]

TPU-D : Polyester polyol (1) having 2.00 hydroxyl groups per molecule,
4'-diphenylmethane diisocyanate and 1,4
-Thermoplastic polyurethane obtained by reacting with butanediol [JIS A hardness is 75, logarithmic viscosity is 1.20 d
l / g]

Mixture of TPU-E polyester polyol (1) and polyester polyol (2) [Polyester polyol (1) / polyester polyol (2) has a molar ratio of 88/12,
The number of hydroxyl groups per molecule] is 2.12, which is obtained by reacting 2.12 with 4,4′-diphenylmethane diisocyanate and 1,4-butanediol.
IS A hardness is 75, DMF solvent insoluble]

POE-A : ethylene-1-octene copolymer [“ENGAG” manufactured by Dupont Dow Elastomer Co., Ltd.]
EEG8100 "; molar ratio of ethylene units / 1-octene units = 92.7 / 7.3, melt index (1
90 ° C., 2.16 kg load) = 1.0 g / 10 min, Shore A hardness 75, Mooney viscosity 35.6 ML
_{1 + 4} (100 ℃)]

POE-B : ethylene-1-octene copolymer [“ENGAG” manufactured by Dupont Dow Elastomer Co., Ltd.]
EEG8200 "; the molar ratio of ethylene units / 1-octene units is 92.2 / 7.8, and the melt index (1
90 ° C., 2.16 kg load) 4.2 g / 10 min, Shore A hardness 75, Mooney viscosity 12.1 ML _{1 + 4} (1
00 ° C)]

TPS-A : hydrogenated product of a triblock copolymer consisting of a 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 95%, and the melt index (230 ° C., 2.16 kg load) is 70 g. / 10 minutes, J
IS A hardness is 80]

TPS-B : 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-C : A mixture (weight ratio) of a hydrogenated product of a diblock copolymer composed of a polystyrene block and a polyisoprene block and a hydrogenated product of a triblock copolymer composed of a polystyrene block, a polyisoprene block and a polystyrene block. 20:80) [styrene content: 13% by weight, content of 1,2-bond and 3,4-bond in polyisoprene block: 5%, hydrogenation rate in polyisoprene block: 98%, melt index (230 ° C., 2.16 kg load) is 0.
5 g / 10 min, JIS A hardness is 52]

TPS-D : hydrogenated triblock copolymer composed of polystyrene block-polyisoprene block-polystyrene block [styrene content is 30
% By weight, content of 1,2- and 3,4-bonds in the polyisoprene block is 5%, hydrogenation rate in the polyisoprene block is 98%, melt index (230 ° C, 2.16 kg load) is flowing Measurement is not possible

TPS-E : triblock copolymer consisting 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]

AM: Ethylene bisstearic acid amide

PE : polyethylene [melt index (190 ° C., 2.16 kg load) is 0.04 g / 10
Min, density 0.956 g / cm ³ ]

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 6 Thermoplastic polyurethane (TPU), ethylene-α-olefin copolymer (POE), block copolymer (TP
S), a mixture of a bisamide compound (AM) and other components (PE, PP, oil) in the proportions shown in Table 1 below were mixed with a single screw extruder (25 mmφ, cylinder temperature: 180 to 200 ° C., die (Temperature: 200 ° C.) to produce a thermoplastic resin composition. Table 1 below shows the results of the evaluation of the thermoplastic resin composition by the above evaluation method.

[0075]

[Table 1]

Comparative Examples 1 and 2 Thermoplastic polyurethane (TPU), ethylene-α-olefin copolymer (POE), block copolymer (TP
A thermoplastic resin composition was produced in the same manner as in Examples 1 to 6, except that S) and the bisamide compound (AM) were used in the proportions shown in Table 2 below. Table 2 below shows the results of the evaluation of the thermoplastic resin composition by the above evaluation method.

Comparative Examples 3 and 4 Thermoplastic polyurethane (TPU), ethylene-α-olefin copolymer (POE), block copolymer (TP
A thermoplastic resin composition was produced in the same manner as in Examples 1 to 6, except that S) and the bisamide compound (AM) were used in the proportions shown in Table 2 below. An attempt was made to produce a film having a thickness of 30 μm from this thermoplastic resin composition by using a T-die type extruder.
A film whose% modulus (M100) could be evaluated was not obtained. Furthermore, the inflation moldability was poor, and a film whose mouth opening property could be evaluated was not obtained. The obtained evaluation results are shown in Table 2 below.

[0078]

[Table 2]

[0079]

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. Furthermore, thickness unevenness and cracks generated when melt-molding with an inflation molding machine are remarkably improved. By using the thermoplastic resin composition of the present invention, molded products such as high quality films and sheets can be manufactured with high productivity.

──────────────────────────────────────────────────の Continued on front page (51) Int.Cl. ⁶ Identification code FI (C08L 75/04 23:08 53:02)

Claims (3)

[Claims] 1. A block copolymer composed of (i) a thermoplastic polyurethane (a), an ethylene-α-olefin copolymer (b), an aromatic vinyl compound polymer block and a conjugated diene polymer block. A thermoplastic resin composition comprising at least one hydrogenated product of a block copolymer (c) and a bisamide compound (d); (ii) a thermoplastic polyurethane (a) and ethylene-α
-30 to 90% by weight of thermoplastic polyurethane (a), 70 to 10% by weight of ethylene-α-olefin copolymer (b), aromatic vinyl compound based on the total weight of olefin copolymer (b) At least one kind of a block copolymer composed of a polymer block and a conjugated diene polymer block and a hydrogenated product of the block copolymer (c):
And the bisamide compound (d) at a ratio of 0.05 to 10% by weight; and (iii) the thermoplastic polyurethane (a) has a hydroxyl group number per molecule of 2. A thermoplastic resin composition, which is a thermoplastic polyurethane comprising a high molecular polyol unit having an average molecular weight of 500 to 8,000, an organic diisocyanate unit and a chain extender unit having a number average molecular weight of 500 to 8,000. 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.