JP3449877B2 - Thermoplastic polyurethane composition - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION [0001] TECHNICAL FIELD The present invention relates to a thermoplastic polyurethane.
From tan, olefin-based copolymers and polyethylene.
Thermoplastic polyurethane composition, said thermoplastic polyurethane
Film, sheet and other molded products
Related. The thermoplastic polyurethane composition of the present invention has
Because it has excellent lockability, it can be used for films and sheets.
When forming, take up smoothly without using release paper.
And the products rolled up may stick
Can be rewound smoothly. In addition, the heat
Films and sheets obtained from plastic polyurethane compositions
Molded products such as have excellent extensibility at low stress
Recovery stress after stretching and small residual strain after elongation
Specially as a stretchable material
It is for. [0002] 2. Description of the Related Art Thermoplastic polyurethane has mechanical performance,
Excellent properties such as abrasion resistance, elastic recovery, oil resistance, and flexibility
As a substitute for rubber and plastic
Eyed. For example, extruding thermoplastic polyurethane
Shaped film attracts attention as elastic material for disposable diapers
Have been. This elastic film for disposable diapers is
When the diaper is worn, the disposable diaper adheres to the body with moderate force
And to prevent it from falling off the body.
Thin and not only can stretch with small force, but also after stretching
High stress (recovery stress) to return to the original shape
Excellent qualitative properties (small residual strain)
Required to have. However, in elasticity
Excellent flexible thermoplastic polyurethane has a particularly strong adhesive property.
For example, a thin film is manufactured by extrusion molding
For example, use expensive release paper, etc.
It is necessary to prevent the urethane film from sticking, which is very troublesome
And costly. [0003] Therefore, the characteristics of thermoplastic polyurethane are maintained.
Polyolefin for the purpose of improving adhesiveness while maintaining
It is proposed to blend resin with thermoplastic polyurethane
Have been. For example, JP-A-2-160869 discloses
Is derived from an olefin monomer having 2 to 6 carbon atoms
The manufactured melt index is about 1 to 50 g / 10
Of polyolefin in thermoplastic polyurethane elastomer
JP-A-3-18562
High density polyethylene in thermoplastic polyurethane
Japanese Patent Application Laid-Open No. 5-156152 discloses that
Polyethylene resin and ethylene-propylene copolymer
It is stated that the base rubber is blended with thermoplastic polyurethane.
Have been. [0004] SUMMARY OF THE INVENTION
And the thermoplastic polyurethane compositions described in
Has improved adhesion, but is thinner
If you are trying to extrude a film,
May occur, and there is a problem with film formation.
Was. Also, the composition described above comprises ethylene
-By using propylene copolymer rubber in combination,
Although thin films can be extruded,
Performance in terms of recovery stress and residual strain after stretching of stretched film
However, it was not enough, and there was room for further improvement. An object of the present invention is to provide an excellent blocking resistance.
As well as excellent elongation at low stress,
Films with high recovery stress and low residual strain after elongation
Heatable for smooth production of molded products such as sheets
It is to provide a plastic polyurethane composition. Further
A film comprising the thermoplastic polyurethane composition
And molded articles such as sheets. [0006] [MEANS FOR SOLVING THE PROBLEMS] The above object should be achieved.
As a result of repeated studies by the present inventors, ethylene units and carbon
An olefin comprising an α-olefin unit having a number of 7 or more
-Based copolymers and polymers having a specific melt index
By blending ethylene with thermoplastic polyurethane
Not only has excellent blocking resistance but also elasticity
Polyurethane with very suitable mechanical properties as material
And found that polyurethane films and polyurethane sheets can be obtained.
The present invention has been completed based on these findings. That is, the present invention relates to a thermoplastic polyurethane.
(A), ethylene units (I) and carbon atoms of 7 or more
consisting of α-olefin unit (II) and structural unit
The molar ratio of (I) / structural unit (II) is 75/25 to 95 /
5, the olefin copolymer (b)
Index (190 ° C, 2.16kg load) is 0.01
Composed of polyethylene (c), which is .about.0.3 g / 10 min.
A thermoplastic polyurethane composition comprising (a) to (c)
Based on the total weight of the thermoplastic polyurethane (a)
35 to 75% by weight, 20 parts of the olefin copolymer (b)
-60% by weight and 5-12% by weight of polyethylene (c)
% Thermoplastic polyurethane characterized by containing
A composition. The present invention relates to the thermoplastic polyurethane.
Products such as films and sheets made of
You. [0008] DETAILED DESCRIPTION OF THE INVENTION Thermoplastic poly used in the present invention
Urethane (a) is a polymer polyol component,
It is composed of a cyanate component and a chain extender component. [0009] The high content of the thermoplastic polyurethane (a)
As the molecular polyol component, for example, polyester polyester
Riol, polyether polyol, polycarbonate
Polyol, polyester polycarbonate polyol
And the like. These polymer polyols alone
They may be used, or two or more kinds may be used in combination. these
Among them, polyester polyol, polyether poly
It is preferred to use oars. The above polyester polyol is, for example,
For example, dicarboxylic acid or its ester,
Ester-forming derivatives such as hydrates and low molecular polyols
For direct esterification or transesterification
Or produced by ring-opening polymerization of lactone
be able to. Dical constituting polyester polyol
Bonic acid is commonly used in the production of polyester.
What is used can be used, as a specific example
Succinic acid, glutaric acid, adipic acid, pimerine
Acid, suberic acid, azelaic acid, sebacic acid, dodecane
Diacid, methylsuccinic acid, 2-methylglutaric acid,
Tilt glutaric acid, trimethyl adipic acid, 2-methyl
Butanedioic acid, 3,8-dimethyldecandioic acid, 3,7-di
C4-12 aliphatic dicals such as methyldecandioic acid
Bonic acid; cycloaliphatic dica such as cyclohexanedicarboxylic acid
Rubonic acid; terephthalic acid, isophthalic acid, orthophthalic
Aromatic dicarboxylic acids such as acids and naphthalenedicarboxylic acids
And the like. These dicarboxylic acids are used alone
Or two or more of them may be used in combination. Among these
However, an aliphatic dicarboxylic acid having 6 to 12 carbon atoms is used.
Preferably adipic acid, azelaic acid, sebacine
More preferably, an acid is used. Low molecular weight constituting polyester polyol
Polyols are commonly used in the production of polyesters.
Can be used, and specific examples
As ethylene glycol, diethylene glycol
, Triethylene glycol, propylene glycol,
1,3-propanediol, 2-methyl-1,3-pro
Pandiol, 1,3-butylene glycol, 1,4-
Butanediol, 2-methyl-1,4-butanediol
, Neopentyl glycol, 1,5-pentanedio
, 3-methyl-1,5-pentanediol, 1,6-
Hexanediol, 1,8-octanediol, 2-meth
Tyl-1,8-octanediol, 2,7-dimethyl-
1,8-octanediol, 1,9-nonanediol,
2-methyl-1,9-nonanediol, 2,8-dimethyl
1,9-nonanediol, 1,10-decandio
, 2,2-diethyl-1,3-propanediol, etc.
An aliphatic diol having 2 to 15 carbon atoms;
Xanediol, cyclohexane dimethanol, cyclo
Octanedimethanol, dimethylcyclooctanedimeta
Alicyclic diols such as phenol; 1,4-bis (β-hydr
Aromatic dihydric alcohols such as (roxyethoxy) benzene
And the like. These low molecular weight polyols alone
They may be used, or two or more kinds may be used in combination. these
Among them, 3-methyl-1,5-pentanediol, 2
-Methyl-1,8-octanediol, 2,7-dimethyl
1,8-octanediol, 1,9-nonandio
, 2-methyl-1,9-nonanediol, 2,8-di
Methyl group on the side chain such as methyl-1,9-nonanediol
Using an aliphatic diol having 5 to 12 carbon atoms having
Preferably, more preferably 50 to the total amount of the low molecular polyol.
More preferably, it is used in an amount of at least mol%. further,
Along with the above low molecular polyol, a small amount of trifunctional or more
A low molecular polyol can be used in combination. 3 or more functional
Examples of low molecular polyols include, for example, trimethylol
Propane, trimethylolethane, glycerin, 1,
2,6-hexanetriol and the like. Examples of the lactone include ε-capro
Lactone, β-methyl-δ-valerolactone and the like.
Can be As the polyether polyol, for example,
For example, polyethylene glycol, polypropylene glycol
, Polytetramethylene glycol, poly (methyl tet
Ramethylene glycol) and the like. These ports
The reether polyols may be used alone or in combination.
The above may be used in combination. Among these, polytetrame
Preferably, tylene glycol is used. Examples of polycarbonate polyols include
For example, low molecular polyols and dialkyl carbonates,
Such as alkylene carbonate and diaryl carbonate
Use those obtained by reaction with carbonate compounds
it can. Low molecular weight polycarbonate
Riol is a component of polyester polyol
The low molecular polyol exemplified above can be used as
Wear. Dialkyl carbonate is dimethyl
Carbonate, diethyl carbonate and the like.
You. Further, as alkylene carbonate, ethylene carbonate is used.
Carbonate and the like, and diaryl carbonate and
Examples thereof include diphenyl carbonate. Polyester polycarbonate polyol
Are, for example, low molecular polyols, dicarboxylic acids and
Obtained by reacting carbonate compounds simultaneously.
You. Alternatively, the polyester po
Riol and polycarbonate polyol respectively
Synthesis and then reacting them with carbonate compounds
Or with low molecular weight polyols and dicarboxylic acids
To be obtained. The high molecular polyol has a number average molecular weight of 50.
Preferably in the range of 0 to 8,000,
More preferably, it is in the range of 5,000 to 5,000. this
Use a high molecular polyol having a number average molecular weight in the range
Thermoplastic with better mechanical performance and moldability
A polyurethane composition is obtained. In this specification,
The number average molecular weight of the polymer polyol is JIS
Calculated based on the hydroxyl value measured according to K 1577
It is the number average molecular weight given. Used for the production of thermoplastic polyurethane (a)
There is no particular limitation on the organic diisocyanate obtained,
Traditionally used in the production of normal thermoplastic polyurethane
Any of the organic diisocyanates available
For example, for example, 4,4'-diphenylmethane diisocitane
Sheet, tolylene diisocyanate, phenylene diisocyanate
Anate, xylylene diisocyanate, 1,5-naph
Tylene diisocyanate, 3,3'-dichloro-4,
4'-diphenylmethane diisocyanate, toluylene
Aromatic diisocyanates such as diisocyanates;
Samethylene diisocyanate, isophorone diisocyanate
4,4'-dicyclohexylmethane diisocyanate
Aliphatic, such as hydrogenated xylylene diisocyanate
Or an alicyclic diisocyanate.
You. These organic diisocyanates can be used alone
Or two or more of them may be used in combination. Among these,
Uses 4,4'-diphenylmethane diisocyanate
Is preferred. Used for the production of thermoplastic polyurethane (a)
There is no particular limitation on the chain extender to be used.
Chain extension traditionally used in the production of conductive polyurethane
Any of the agents may be used and react with isocyanate groups.
Molecular weight 3 having at least two active hydrogen atoms in the molecule
It is preferable to use a low-molecular compound of not more than 00. example
For example, ethylene glycol, propylene glycol, 1,
4-butanediol, 1,6-hexanediol, 1,
4-bis (β-hydroxyethoxy) benzene, 1,4
-Cyclohexanediol, bis (β-hydroxyethyl
Le) Geo such as terephthalate and xylylene glycol
Hydrazine, ethylenediamine, propylenedi
Amine, xylylenediamine, isophoronediamine,
Perazine and its derivatives, phenylenediamine, tri
Diamine, xylene diamine, dihydradipic acid
Diamines such as zide and isophthalic dihydrazide;
Minoethyl alcohol, aminopropyl alcohol, etc.
Amino alcohols and the like. These low minutes
The secondary compounds may be used alone or in combination of two or more.
You may. Among them, aliphatic di-carbons having 2 to 10 carbon atoms
All is preferably used, and 1,4-butanediol
It is more preferable to use The above-mentioned polymer polyol, organic diisocyanate
Reaction of a thermoplastic polyurethane
In producing the component (a), the mixing ratio of each component is
Hardness to be given to the target thermoplastic polyurethane
It is determined appropriately in consideration of the polymer polyol and chain.
1 mole of active hydrogen atoms contained in the extender
Isocyanate group contained in the isocyanate is 0.9 to
It is possible to use each component at a ratio of 1.2 mol.
preferable. The method for producing the thermoplastic polyurethane (a) is as follows.
There is no particular limitation, and the above-mentioned polymer polyols and organic diisomers are used.
Known urethanization using cyanates and chain extenders
The prepolymer method and one-shot method
It may be manufactured by any of the above methods. Among them, substantial
It is preferable to perform melt polymerization in the absence of a solvent, especially
Continuous melt polymerization using a multi-screw extruder is preferred
No. JIS A for thermoplastic polyurethane (a)
The hardness is preferably in the range of 55 to 85, and 6
More preferably, it is in the range of 5-82. JIS
Thermoplastic polyurethane (a) having A hardness in this range is
Mixing of olefin copolymer (b) and polyethylene (c)
It is more compatible with
When using urethane, thermoplastic polyurethane
Good flexibility and good mechanical properties for molded products obtained from composites
Properties are given. In addition, the thermoplastic poly-
Urethane (a) has a JIS A hardness of JIS K-73.
This is a value measured in accordance with No. 11. Logarithmic viscosity of thermoplastic polyurethane (a)
Is added to the N, N-dimethylformamide solution with thermoplastic resin.
Dissolve the urethane (a) to a concentration of 0.5 g / dl.
When measured at 30 ° C, 0.85 dl / g or lessAbove
Preferably, it is 1.0 dl / g or more
More preferably, it is 1.1 dl / g or more.
preferable. Thermoplastic polyurethane having the above logarithmic viscosity
When heat is applied, heat that gives molded products with less residual strain
It is preferable because a plastic polyurethane composition can be obtained. The olefin copolymer (b) is ethylene
Unit (I) and α-olefin unit having 7 or more carbon atoms
(II) and structural unit (I) / structural unit (II)
Is in the range of 75/25 to 95/5, and 85
It is preferably in the range of / 15 to 95/5. Echile
If the unit content is less than 75 mol%,
The softening temperature of the thermoplastic copolymer decreases and the thermoplastic polyurethane
It is difficult to mix uniformly with tan (a) and polyethylene (c)
Therefore, thermoplastic polyurethane obtained by blending
The film obtained from the coating composition tends to stick. one
On the other hand, polio having a content of ethylene units exceeding 95 mol%
When a olefin-based copolymer is used,
It is difficult to obtain a film having excellent shrinkability. The carbon constituting the olefin copolymer (b)
Examples of α-olefin units (II) having a prime number of 7 or more include:
For example, 1-hexene, 1-octene, 1-decene, 1-
And units derived from octadecene and the like. This
These α-olefin units (II) may be contained alone.
Or two or more of them may be contained. Among these
Is also derived from an α-olefin having 7 to 12 carbon atoms.
Unit is preferred, and is an α-olefin having 7 to 10 carbon atoms
Units derived from the above are more preferred, 1-hexene or
Units derived from 1-octene are particularly preferred. α-
When the olefin has less than 7 carbon atoms, the polyolefin
Thermoplastic polyurethane composition blended with vinyl copolymer
The film obtained from
Poor recovery performance such as residual strain. The olefin copolymer (b) has a content of 190
Melt index measured under 2.16 kg load at ℃
Is preferably in the range of 0.2 to 7 g / 10 min.
And within 0.3 to 5.5 g / 10 min.
Is more preferable. Melt index is less than 0.2g / 10min
When full, the polyolefin copolymer was blended.
The film obtained from the thermoplastic polyurethane composition is hard
And it becomes difficult to obtain a thin film.
You. On the other hand, the melt index exceeds 7 g / 10 minutes
In some cases, thermoplastic polyurethane obtained by blending this
The film obtained from the composition becomes easy to stick,
Performance also tends to decrease. Note that, in this specification,
The melt index of the olefin copolymer is ASTM
  It is a value measured according to D-1238. Shore A of olefin copolymer (b)
The hardness is preferably in the range of 40 to 90,
More preferably, it is within the range of -85. Shore A
If the hardness is less than 40, the polyolefin copolymer
Obtained from thermoplastic polyurethane composition containing body
The mechanical performance of the film tends to decrease,
When the A hardness exceeds 90, the polyolefin
Of thermoplastic polyurethane composition blended with terpolymer
Softness tends to decrease. It should be noted that, in this specification,
The Shore A hardness of the fin-based copolymer is ASTM D-
It is a value measured according to 2240. The olefin copolymer (b) is an L-type raw material.
Mooney viscosity measured at 100 ° C using a
38ML_{1 + 4}(100 ° C)
, 10-38ML_{1 + 4}(100 ° C)
Is more preferable. Oleph having the above Mooney viscosity
When the vinyl copolymer (b) is used, blocking resistance,
Flexibility and recovery performance such as recovery stress after stretching and residual strain
A better one is obtained. Note that the mu
Knee viscosity is measured according to ASTM D-1646.
Value. The method for producing the olefin copolymer (b) is as follows.
Not particularly limited, the above monomers, for example, solution polymerization
Method, bulk polymerization method, known methods such as gas phase polymerization method, usually
At a temperature of 0 to 250 ° C, normal pressure to 1000 atm (100M
It is obtained by polymerization in pa). Upon polymerization
Uses a single-site catalyst with a uniform polymerization active site
Polymer with narrow molecular weight distribution and narrow copolymer composition distribution
It is preferable because it can be easily obtained. Single site catalyst
In particular, metallocene compounds containing a tetravalent transition metal
Are preferred, for example, cyclopentadienyl titanium
Mutris (dimethylamide), methylcyclopentadie
Nil titanium tris (dimethyl amide), bis (cyclo
Lopentadienyl) titanium dichloride, dimethyl
Ryltetramethylcyclopentadienyl-t-butyla
Midozirconium dichloride, dimethylsilyltetrame
Tylcyclopentadienyl-t-butylamidohafnium
Mudichloride, dimethylsilyltetramethylcyclopen
Tadienyl-pn-butylphenylamido zirconium
Mudichloride, methylphenylsilyltetramethylcycl
Lopentadienyl-t-butylamidohafnium dichloro
Lido, (t-butylamide) (tetramethyl-cyclope
Antadienyl) -1,2-ethanediyl titanium dichloride
Do, indenyl titanium tris (dimethylamide),
Indenyl titanium tris (diethylamide), ind
Denyl titanium bis (di-n-butylamide) (di-
n-propylamide) and the like. Metallocene
When the compound is used as a polymerization catalyst,
Methyl aluminoxane, non-coordinating
Metallocene compound 1
2 to 1,000,000 mole, preferably 1 mole to 1 mole
It is used in a proportion of 50 to 5,000 mol. Polyethylene (c) was used at 190 ° C. and 2.1
Melt index measured under a load of 6 kg is 0.01
０．３0.3 g / 10 min, more preferably
It is in the range of 0.03 to 0.2 g / 10 minutes. Polyethy
Melt index of less than 0.01 g / 10 min
In some cases, thermoplastic polyurethane (a) or olefin-based
Uniform mixing with the copolymer (b) becomes difficult,
Obtained from a thermoplastic polyurethane composition obtained by
This is a factor that causes cracks in the film. Meanwhile, polyethylene
The melt index of the len exceeds 0.3 g / 10 min
In this case, a thermoplastic polyurethane containing the polyolefin is used.
Blocking resistance of film obtained from urethane composition
Is inferior. As the polyethylene (c), for example,
High density polyethylene, low density polyethylene, etc.
You. These polyethylenes may be used alone,
Two or more kinds may be used in combination. Among these, polyethylene
The density of the ren is 0.93-0.97 g / cm^ThreeWithin the range of
Certain high density polyethylenes are particularly preferred. This specification
The density of polyethylene referred to in the book is ASTM D-150.
It is a value measured according to 5. The thermoplastic polyurethane composition of the present invention comprises:
The above-mentioned thermoplastic polyurethane (a), olefin copolymer
Based on the total weight of coalesced (b) and polyethylene (c)
35 to 75 weight of the thermoplastic polyurethane (a)
%, 20 to 60% by weight of the olefin copolymer (b),
5 to 12% by weight of polyethylene (c)
Is required, and the thermoplastic polyurethane (a) is used in an amount of 45 to 7
0% by weight, 25-45 weights of olefin copolymer (b)
% Of polyethylene (c) in a proportion of 5 to 10% by weight.
It is preferred to have. Thermoplastic polyurethane (a)
If the content of is less than 35% by weight,
Mechanical performance and elongation of film obtained from urethane composition
Recovery performance such as post-recovery stress and residual strain is impaired,
On the other hand, if the content exceeds 75% by weight,
Inferiority. In addition, the olefin copolymer (b) contains
When the content is less than 20% by weight, the film is stable.
When the content exceeds 60% by weight
In addition, the filler obtained from the thermoplastic polyurethane composition
Recovery performance such as recovery stress or residual strain after elongation of the
Will be Furthermore, the content of polyethylene (c) is 5% by weight.
If less than, the blocking resistance is poor, while the content
If the amount exceeds 12% by weight, the film is stable.
In addition to impairing the properties, elongation of the resulting film
Recovery performance such as subsequent recovery stress and residual strain is also impaired. The thermoplastic polyurethane composition of the present invention comprises:
Internal release agent, reinforcement as long as the effects of the present invention are not impaired
Agents, colorants, flame retardants, UV absorbers, antioxidants,
Various additives such as a water-decomposability improver, a fungicide, and a stabilizer;
Various fibers such as glass fiber and polyester fiber;
Inorganic substances such as silica and silica;
Desired components can be blended as needed. The thermoplastic polyurethane composition of the present invention comprises:
The above components (a) to (c) and, if necessary, other components
And mixing by a desired method.
Can be. For example, commonly used for mixing resin materials
Use a vertical or horizontal mixer such as
Urethane (a), olefin-based copolymer (b) and
The polyethylene (c) was premixed at a predetermined ratio.
1, single or twin screw extruder, mixing roll, van
Batch or continuous using a Barry mixer, etc.
It can be produced by melt-kneading under heat.
As another method, a thermoplastic polyurethane (a) is used.
Olefin copolymer (b) in late stage of polymerization during production
Or polyethylene (c). The thermoplastic polyurethane composition of the present invention comprises:
Extrusion molding and injection molding are possible.
Shape, blow molding, calendar molding, casting, etc.
Various moldings can be produced smoothly by the molding method.
Wear. In particular, T-die type extruder and inflation film forming
Thermoplastic polyurethane composition of the present invention using a machine
When manufacturing films and sheets from
Because it has excellent hooking properties, use release paper or the like.
It can be extruded and wound as it is
The film or sheet taken can be easily rewound
is there. In particular, use of the thermoplastic polyurethane composition of the present invention
Molded products such as films and sheets obtained after
Recovery performance such as recovery stress and residual strain, tensile breaking strength and
Excellent mechanical performance represented by tensile elongation at break
It has a smooth surface and good surface condition.
You. In particular, recovery performance such as recovery stress and residual strain after elongation
It has excellent characteristics,
Used for kin, disposable diapers, seals, dust proof, etc.
It is particularly preferable to use it for stretch film applications. Ma
General conveyor belts, various keyboard sheets,
It can also be used for various applications such as mined products and various containers.
Can be. Further, the thermoplastic polyurethane set of the present invention
The product is a fibrous base made of non-woven fabric or other fiber cloth,
Lamination with other polymer film or sheet substrate
It is also suitable for the production of
Apply the urethane composition onto a fibrous or other substrate.
Laminate or sheet melt extrusion to produce laminate
be able to. [0036] The present invention will be described below in more detail with reference to examples.
However, the present invention is not limited by these examples.
Not something. In Examples and Comparative Examples,
Blocking properties, 100% modulus, 50% recovery stress
And residual strain are measured or evaluated by the following methods.
Was. [Blocking resistance] T-die extrusion molding machine
Extruded onto a 30 ° C chill roll and cooled
At a take-up speed of about 3 m / min without using release paper.
I wiped it. The 30-μm-thick film rolled into the chamber
After standing at warm for 24 hours, rewind by hand, then resistance
Was evaluated according to the following criteria. ：: Smooth rewinding is possible. Δ: A considerable tensile force was required, but rewinding was possible. X: The adhesive property is large and rewinding is impossible. [100% modulus, 50% recovery stress and
And residual strain] Thickness formed using a T-die extruder
Test piece (20cm × 5cm) from 30μm film
It was created. This test piece was subjected to an autograph measuring device IS
-500D (manufactured by Shimadzu Corporation) at room temperature and tensile
100% elongation at 300mm / min.
The lath (M100) was measured. Next, at a speed of 300 mm / min
Return to the position before extension (degree 1 cycle)
After stretching 100% at the same speed, return to the position before stretching
Two cycles of the hysteresis curve were measured. 2 cycles
The stress at the time of returning to 50% by eyes (50% recovery stress) and
And the residual strain when returning to the position before extension
Was. Resins used in the following Examples and Comparative Examples
Abbreviations for are shown in Table 1 below. [0040] [Table 1]Embodiment 1 60% by weight of TPU-A, 30% by weight of POE-A and P
A mixture consisting of 10% by weight of EA was mixed with a single screw extruder (2).
5mmφ, cylinder temperature: 180-200 ° C, die
(Temperature: 200 ° C) and melt-kneaded, and the T-die of an extruder
After extruding onto a cooling roll at a temperature of 30 ° C., about 3 m
/ Min winding speed and 30μm thick film
I got it. The above test method was performed using the obtained film.
It has better blocking resistance and 100% modulus (M10
0), 50% recovery stress and residual strain were evaluated. result
Are shown in Table 2 below. Examples 2 to 6 Thermoplastic polyurethane, olefin copolymer, polyether
The amount of styrene used was changed to the ratio shown in Table 2 below.
Except that the thickness was 30 μm in the same manner as in Example 1.
A film was obtained. The above test using the obtained film
Depending on the method, blocking resistance, 100% modulus
(M100), 50% recovery stress and residual strain were evaluated.
Was. The results are shown in Table 2 below. [0043] [Table 2]Comparative Examples 1 to 6 Thermoplastic polyurethane, olefin copolymer, polyether
The amount of styrene used was changed to the ratio shown in Table 3 below.
Except that the thickness was 30 μm in the same manner as in Example 1.
A film was obtained. The above test using the obtained film
Depending on the method, blocking resistance, 100% modulus
(M100), 50% recovery stress and residual strain were evaluated.
Was. The results are shown in Table 3 below. [0045] [Table 3] From the results of Tables 2 and 3 above, the following
It is clear that. The blocking resistance of the film obtained in the Examples
It is superior to the films obtained in Comparative Examples 2 to 5. The 50% recovery stress of the films obtained in the examples
Larger than the films obtained in Examples 1, 5 and 6,
It can be seen that the force to contract from the extended state is large. After 100% elongation of the film obtained in the Examples (2
The residual strains of the (a) are obtained in Comparative Examples 1, 5 and 6.
Smaller than film that has excellent recovery performance after elongation
You can see that there is. The 100% modulus (M
100) is smaller than the films obtained in Comparative Examples 1 to 6.
Small value comparable to that, excellent in extensibility at low stress
You can see that there is. [0047] The thermoplastic polyurethane composition of the present invention
Films and sheets with excellent blocking resistance
For smooth molding without using release paper
Those products that can be taken and rolled up will stick
It can be rewound smoothly without any trouble. Furthermore, the present invention
Films obtained from thermoplastic polyurethane compositions of
Molded products such as sheets have excellent extensibility at low stress.
Recovery stress after elongation, and residual strain after elongation
Is especially small
Useful as

Continuation of the front page (58) Field surveyed (Int. Cl. ⁷ , DB name) C08L 75/04-75/16 C08L 23/02-23/24

Claims (1)

(57) Claims 1. A thermoplastic polyurethane (a), comprising an ethylene unit (I) and an α-olefin unit (II) having 7 or more carbon atoms, and a structural unit (I) / Structural unit (II)
The olefin-based copolymer (b) having a molar ratio of 75/25 to 95/5, and a melt index (190 ° C,
A thermoplastic polyurethane composition comprising polyethylene (c) having a weight of 2.16 kg / min. Of 0.01 to 0.3 g / 10 min, based on the total weight of (a) to (c).
A thermoplastic polyurethane containing 35 to 75% by weight of a thermoplastic polyurethane (a), 20 to 60% by weight of an olefin-based copolymer (b), and 5 to 12% by weight of a polyethylene (c). Composition.