JP3419593B2 - Thermoplastic polyurethane composition - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION [0001] The present invention relates to a low-hardness thermoplastic resin.
Compounding urethane and high hardness thermoplastic polyurethane
Thermoplastic polyurethane compositionThingFilm
CToRelated. The present inventionUse withThermoplastic polyurethane
Non-adhesive, anti-blocking and release properties
Excellent when releasing into films, sheets, etc.
Winding can be performed smoothly without using paper pattern
These moldings are circular without blocking.
It can be rewound smoothly. The thermoplastic polyurethane of the present invention
Film, sheet obtained from the tongue compositionIs, Elastic recovery
Excellent in flexibility, flexibility and mechanical properties, ExtensionShrink fill
Useful as a system or sheet. [0002] 2. Description of the Related Art Thermoplastic polyurethane has elasticity and abrasion resistance.
Has many features such as excellent oil resistance and oil resistance.
Is attracting attention as an alternative to rubber and plastic.
Molding materials that can be used with ordinary plastic molding methods
Used in a wide range of applications as a material. However, low
Hard thermoplastic polyurethane has strong adhesiveness,
It is easy to cause foaming, so extrusion
When film or sheet is manufactured, take it up by itself
Is difficult. That is, when wound alone,
Difficult or impossible to rewind film or sheet
At present, it becomes impossible to use it. this
Detackification, blocking prevention, imparting release properties, etc.
For adding lubricant to thermoplastic polyurethane for the purpose of
Method, blending other polymers with thermoplastic polyurethane
Method, thermoplastic polyurethane film or sheet
Release sheet or release paper containing silicone or polyethylene
Film formation on release paper laminated with polypropylene
And roll it up with release paper etc.
You. [0003] SUMMARY OF THE INVENTION
In the case of the method described above, the blocking prevention effect and the release effect
In order to achieve the effect, it is necessary to use a large amount of lubricant.
As a result, lubricant bleeds out on the product surface.
Fogging on the film or sheet surface,
There is a disadvantage that lubricity is poor. Also adhered during secondary processing
When it is necessary to use
It may not be good. In the case of the above method,
Incorporate large amounts of polymer to obtain anti-blocking
Need to lose the inherent properties of thermoplastic polyurethane.
Easily, and the surface of the film or sheet is rough.
There is a disadvantage that the appearance is poor. Above
Method, release paper must be used.
It takes a lot of time and effort to form, and expensive release paper
There is a drawback that the cost is high because of use. It is an object of the present invention to provide a thermoplastic polyurethane
Excellent inherent properties: flexibility, elastic recovery
Large amounts of lubricants and porosities without losing their properties and mechanical properties.
Even without using rimmers, expensive release paper, etc.
Heat that effectively prevents locking and has excellent appearance and physical properties
Plastic polyurethane film or sheetToProduce smoothly
To provide a thermoplastic polyurethane compositionAnd
AndTakeA thermoplastic polyurethane composition
Film or seaToTo provide. [0005] According to the present invention, the above-mentioned object is achieved.
The purpose is to have a number average molecular weight of 2000-8000,
30 mol% or more of all units is 3-methyl-1,5-pe
Polyester diol consisting of pentanediol units
Obtained by reacting an organic diisocyanate and a chain extender.
Thermoplastic polymer having a nitrogen atom content of 2.5% by weight or less
Urethane (A) and number average molecular weight of 1500 to 40
00 polyester diols, organic diisocyanates and
Nitrogen chain content obtained by reacting
3.5% by weight or more and logarithmic viscosity of 0.9 dl / g or less
200-220 ° C. by differential scanning calorimetry (DSC).
The endothermic peak is shown in the range, and the result obtained from this endothermic peak is
Heatable with crystallization enthalpy (ΔH) of 2 to 15 J / g
Made of plastic polyurethane (B), thermoplastic polyurethane
(A) and thermoplastic polyurethane (B) in a weight ratio of 5
Thermoplastic having a ratio of 0:50 to 90:10
Polyurethane compositionThingFilm or sheetToOffer
It is achieved by offering. Used for the production of thermoplastic polyurethane (A)
Polyester diol [hereinafter referred to as polyester geo
(A) and a thermoplastic polyurethane
Polyester diol used in the production of (B)
Below, referred to as polyester diol (B)]
Consists of a diol unit and a dicarboxylic acid unit.
You. The diol constituting the polyester diol (A)
3-methyl-1,5-pentanedio in all units
The content rate of the metal unit must be 30 mol% or more.
And preferably at least 50 mol%. 3-me
When the content of tyl-1,5-pentanediol unit is 30
% Of polyester diol (A)
Thermoplastic polyurethane obtained due to high crystallinity
(A) Poor flexibility, cold resistance, elastic recovery, etc.
I don't. The di-constituting polyester diol (A)
If the total unit is less than 70 mol%, 3-
Diols other than methyl-1,5-pentanediol unit
Units can be included. For example, ethylene glyco
, Propylene glycol, 1,3-propanediol
1,4-butanediol, 1,5-pentanedio
, Neopentyl glycol, 1,6-hexanediol
1,1,7-heptanediol, 1,8-octanediol
, 1,9-nonanediol, 1,10-decandio
Oils such as alcohol, 2-methyl-1,8-octanediol
Aliphatic diols: cyclohexanedimethanol, cyclohexane
A simple substance derived from an alicyclic diol such as xandiol
And one or more of these may be included.
I can do it. The di-constituent of the polyester diol (A)
Examples of the carboxylic acid unit include glutaric acid and adipate.
Acid, pimelic acid, suberic acid, azelaic acid, sebashi
Saturated aliphatic dicarboxylic acids such as acid; cyclohexanedi
Saturated alicyclic dicarboxylic acids such as carboxylic acids; phthalic acid,
Aromatic dicarboxylic acids such as terephthalic acid and isophthalic acid
Acids; unsaturated fats such as maleic acid, fumaric acid, itaconic acid
List of units derived from aliphatic dicarboxylic acid, etc.
And one or more of these can be included.
Wear. The di-constituting polyester diol (B)
All units include, for example, ethylene glycol,
Propylene glycol, 1,3-propanediol, 1,
4-butanediol, 1,5-pentanediol, neo
Pentyl glycol, 1,6-hexanediol, 1,
7-heptanediol, 1,8-octanediol,
1,9-nonanediol, 1,10-decanediol,
3-methyl-1,5-pentanediol, 2-methyl-
Aliphatic diols such as 1,8-octanediol;
Rohexanedimethanol, cyclohexanediol, etc.
The unit derived from the alicyclic diol of
One or more of these can be included
You. The di-constituting polyester diol (B)
Examples of the carboxylic acid unit include glutaric acid and adipate.
Acid, pimelic acid, suberic acid, azelaic acid, sebashi
Saturated aliphatic dicarboxylic acids such as acid; cyclohexanedi
Saturated alicyclic dicarboxylic acids such as carboxylic acids; phthalic acid,
Aromatic dicarboxylic acids such as terephthalic acid and isophthalic acid
Acids; unsaturated fats such as maleic acid, fumaric acid, itaconic acid
List of units derived from aliphatic dicarboxylic acid, etc.
And one or more of these can be included.
Wear. Among these, from saturated aliphatic dicarboxylic acids
Including the derived units for flexibility and elastic recovery
Preferred from the point. Number average molecule of polyester diol (A)
The amount is 2000-8000, 3000-6000
It is preferred that When the number average molecular weight is less than 2000
Low hardness with excellent performance such as elastic recovery and flexibility
Cannot be obtained.
If the number average molecular weight exceeds 8000, the thermoplastic resin will
Not only does the productivity of the urethane (A) decrease,
The extrusion moldability of the thermoplastic polyurethane composition
It is not preferable because it becomes good. Number average molecule of polyester diol (B)
The amount is 1500-4000, 2000-3500
It is preferred that When the number average molecular weight is less than 1500
In the case, the resulting thermoplastic polyurethane composition
The locking property decreases. In addition, the number average molecular weight is 4000
If it exceeds 100, the fluidity of the thermoplastic polyurethane (B) is low.
Lower dispersibility in thermoplastic polyurethane (A)
Extrusion of the resulting thermoplastic polyurethane composition
The shape and the like become poor. In addition, the polystyrene referred to in this specification
The number average molecular weight of terdiol is JIS K
Calculated based on the hydroxyl value measured according to 1577
Is the number average molecular weight. Polyester diols (A) and (B)
Uses the aforementioned dicarboxylic acid component and diol component
Known transesterification and direct esterification reactions
It is produced by polycondensation by, for example. That
In some cases, the polycondensation reaction is a titanium- or tin-based polycondensation catalyst.
The reaction can be carried out in the presence of a medium, but a titanium-based polycondensation catalyst
When is used, after the end of the polycondensation reaction, the polyester
Deactivate the titanium-based polycondensation catalyst contained in the diol
Is preferred. Polyester diols (A) and (B)
The use of titanium-based polycondensation catalysts in the production of
Has traditionally been used in the manufacture of polyester diols.
Any titanium-based polycondensation catalyst can be used, especially
Although not limited, examples of preferred titanium-based polycondensation catalyst
Is titanic acid, tetraalkoxy titanium compound, titanium
Includes acylate compounds, titanium chelate compounds, etc.
be able to. More specifically, tetraisopropylthio
Tanate, tetra-n-butyl titanate, tetra-2
-Ethylhexyl titanate, tetrastearyl titane
Tetraalkoxytitanium compounds such as
Xytitanium stearate, polyisopropoxytitanium
Titanium acylate compounds such as tearate, titanium acetate
Cyl acetate, triethanolamine titanate,
Tantalum lactate, titanium ethyl lactate
Titanium clean such as titanium octylene glycolate
Compounds. The amount of the titanium-based polycondensation catalyst used is not particularly limited.
Not generally, but generally form polyester diols
About 0.1 to 50 ppm based on the total weight of the reaction components
And more preferably about 1 to 30 ppm.
preferable. Titanium contained in polyester diol
As a method for deactivating the polycondensation catalyst, for example, esterification reaction
After heating the polyester diol obtained
To deactivate the polyester by contacting it with water,
Phosphoric acid, phosphoric acid ester, phosphorous acid, phosphorous acid S
Methods of treating with phosphorus compounds such as ter
Can be. Deactivates titanium-based polycondensation catalyst by contact with water
The polyester obtained by the esterification reaction.
Water is added to terdiol in an amount of 1% by weight or more,
° C, preferably at a temperature of 90 to 130 ° C for 1 to 3 hours
Good to do. Deactivation treatment of titanium-based polycondensation catalysts under normal pressure
It may be performed or under pressure. Titanium-based heavy shrinkage
If the system is depressurized after deactivating the combined catalyst, it is used for deactivation.
It is desirable to be able to remove the water that has been removed. Thermoplastic polyurethanes (A) and (B)
The type of organic diisosonate used in the production of
Unlimited, traditionally used in normal polyurethane production
Any of the used organic diisocyanates can be used
And those having a molecular weight of 500 or less are preferred. Organic
Examples of soocyanates include, for example, 4,4'-dife
Nylmethane diisocyanate, p-phenylene diisocyanate
Anate, toluylene diisocyanate, 1,5-naph
Tylene diisocyanate, 3,3'-dichloro-4,
4'-diphenylmethane diisocyanate, xylylene
Aromatic diisocyanates such as diisocyanates,
Hexamethylene diisocyanate, isophorone diisocyanate
Anate, 4,4'-dicyclohexylmethanediisocyanate
Fats such as anate and hydrogenated xylylene diisocyanate
Aliphatic or alicyclic diisocyanates
Can be. One of these organic diisocyanates
Alternatively, two or more are used. Of these,
The use of 4'-diphenylmethane diisocyanate
Is preferred. Also, triphenylmethane triisocyanate
Need tri- or more functional polyisocyanates such as
Small amounts can be used accordingly. Thermoplastic polyurethanes (A) and (B)
As chain extenders used in the production of
Anything conventionally used in the manufacture of tongues can be used
Is not particularly limited, but can react with isocyanate groups.
Having two or more active hydrogen atoms in the molecule, having a molecular weight of 30
It is preferred to use 0 or less low molecular weight compounds. example
For example, ethylene glycol, 1,4-butanediol,
1,6-hexanediol, 1,4-bis (β-hydro
(Xyethoxy) benzene, 1,4-cyclohexanedioxide
, Bis (β-hydroxyethyl) terephthalate,
Diols such as xylylene glycol;
, Ethylenediamine, propylenediamine, xylene
Diamine, isophorone diamine, piperazine, piperazine
Derivatives, phenylenediamine, tolylenediamine,
Silylenediamine, adipic dihydrazide, isophthal
Diamines such as diacid dihydrazide, aminoethyl alcohol
Amino alcohols such as coal and aminopropyl alcohol
And one or more of these.
The top is used. Of these, 1,4-butanedi
The use of oars provides flexibility, elastic recovery,
It is preferable in terms of properties. Thermoplastic polyurethanes (A) and (B)
In the production of polyester diol and polyester chain
Isocyanate per equivalent of active hydrogen atom in the long agent
The amount is such that the nate group equivalent is 0.98 to 1.10.
It is preferred to use mechanical diisocyanates. above
Polyester diol, chain extender and organic die
Softness and elastic recovery by using socyanate
Thermoplastic polyurethane with excellent properties, mechanical properties and moldability
It is preferable because a product is obtained. The above-mentioned polyester diol, organic diiso
Thermoplastic polyurethane using cyanate and chain extender
Catalytic activity for urethanization reaction during production
Can be used as a tin-based urethane-forming catalyst
You. The use of a tin-based urethanization catalyst allows the
The molecular weight of urethane increases rapidly, and even after molding
The molecular weight of the plastic polyurethane is maintained at a sufficiently high level.
Thermoplastic polyurethane with better physical properties
Is obtained. Examples of the tin-based urethanization catalyst include, for example,
Dibutyltin diacetate, dibutyltin dilaurate
Dialkyltin diacylate, dibutyltin bis
(Ethoxybutyl 3-ester 3-mercaptopropionate
B) dialkyltin bismercaptocarboxylic acid such as salt
Ester salts and the like can be mentioned. These tin-based
The amount of urethanization catalyst used is equivalent to polyurethane
Tan (ie polyester diol, organic diisocyanate)
(Total weight of reactive raw material compounds such as heatsinks and chain extenders)
It is preferably 0.5 to 15 ppm. Thermoplastic polyurethanes (A) and (B)
The production method of the polyester
(A) or (B), an organic diisocyanate and
Prepolymer method, one-shot method using chain extender
Known urethanation reaction techniques such as can be adopted
You. When producing the thermoplastic polyurethane (A),
Among them, melt polymerization in the absence of solvent
It is preferable to adopt a method, in particular, a multi-screw
It is preferable to adopt a continuous melt polymerization method using a mold extruder.
No. Also, when producing a thermoplastic polyurethane (B)
If the belt method is adopted by the prepolymer method,
Thermoplastic polyurethane composition has increased blocking resistance
Excellent thingsNextIt is preferable because it is easy. The thermoplastic polyurethanes (A) and (B)
Of the polymerization process or after the polymerization, if necessary, a coloring agent,
Lubricants, crystal nucleating agents, flame retardants, UV absorbers, antioxidants,
Weather resistance improver, hydrolysis inhibitor, tackifier, fungicide
One or two or more additives such as
No. The thermoplastic polyurethane (A) contains nitrogen atoms.
The prevalence must be 2.5% by weight or less. Nitrification
If the atomic atom content exceeds 2.5% by weight,
The hardness of the thermoplastic polyurethane composition increases,
Films and sheets with excellent elasticity and elastic recovery
Cannot be obtained. On the other hand, nitrogen of thermoplastic polyurethane (B)
The atomic content must be at least 3.5% by weight.
You. When the nitrogen content is less than 3.5% by weight,
Low blocking resistance of thermoplastic polyurethane composition
Down. The logarithmic viscosity of the thermoplastic polyurethane (A)
There are no particular restrictions on the thermoplastic polyurethane obtained.
Uniformity, mechanical performance, elastic recovery, anti-blowing
The logarithmic viscosity is 0.7 from the point of more excellent
It is preferably in the range of 1.5 dl / g. Logarithmic viscosity of thermoplastic polyurethane (B)
Needs to be 0.9 dl / g or less. Logarithm
If the viscosity is greater than 0.9 dl / g,
Low, poor mixing with the thermoplastic polyurethane (A)
Thermoplastic polyurethane with excellent blocking resistance
It is difficult to obtain a composition. Furthermore, films, sheets, etc.
When molding into a molded product of
Likely to happen. In addition, a pair of thermoplastic polyurethane (B)
Although there is no particular lower limit for the number viscosity, thermoplastic polyurethane
If the difference in logarithmic viscosity with (A) becomes too large,
Thermoplastic polyurethane composition tends to be non-uniform,
When molded, a uniform film or sheet is obtained.
Logarithmic viscosity is preferably 0.4 dl / g or more.
Good. In addition, the logarithmic viscosity referred to in this specification is n-butyl
N, N-dimethyl containing 0.05 mol / l
Polyurethane is added to the formamide solution at a concentration of 0.5 g / d
1 and dissolved at 30 ° C.
You. The thermoplastic polyurethane (B) is subjected to differential scanning.
In the calorimetric measurement (DSC), the endothermic
Crystallization energy determined from this endothermic peak.
Talpy (ΔH) is in the range of 2 to 15 J / g
is necessary. If the endothermic peak temperature is less than 220 ° C,
Or when the crystallization enthalpy (ΔH) is less than 2 J / g
The block resistance of the resulting thermoplastic polyurethane composition
Poor kingness. On the other hand, the endothermic peak temperature exceeds 220 ° C.
Enthalpy (ΔH) is 15 J
/ G, the obtained thermoplastic polyurethane
Unmelted material is likely to be generated in the composition, and films and sheets
Bubbles occur when molded into such a shape. Also, anti-blocky
Also tends to be poor. The present inventionConstruct film and sheetHeatable
The plastic polyurethane composition is a thermoplastic polyurethane resin as described above.
Specific thermoplastic polyurethane (B)
It is necessary to mix them in proportions. That is, in the present invention,
Plastic polyurethane (A) and thermoplastic polyurethane (B)
Is 50:50 to 90:10, and 55: 4
It is preferably from 5 to 80:20. Thermoplastic polyurethane
When the mixing ratio of the tan (B) exceeds 50% by weight,
The hardness of the obtained thermoplastic polyurethane composition is high.
And the flexibility and elastic recovery are reduced. On the other hand, thermoplastic
When the mixing ratio of the urethane (B) is less than 10% by weight
Is the block-resistant thermoplastic polyurethane composition obtained.
Insufficiency. The present inventionUse withThermoplastic polyurethane group
The composition comprises the thermoplastic polyurethane (A) described above and a thermoplastic
Using plastic polyurethane (B), ordinary polymer block
It can be manufactured by the rendering method. For example, heat
Thermoplastic polyurethane (A) and thermoplastic polyurethane
(B) and a vertical as commonly used for mixing resin materials.
Pre-mix at a predetermined ratio using a horizontal or horizontal mixer.
After mixing, single or twin screw extruder, Mixin glow
Batch or continuous using a mixer, Banbury mixer, etc.
It is produced by melt-kneading under heating according to the formula. What
When mixing, if necessary, montanic acid wax
Lubricants, fillers, UV absorption
Agent, antioxidant, plasticizer, antistatic agent, hydrolysis prevention
Additives such as agents and pigments within a range that does not impair the effects of the present invention.
It may be added within the box. [0031]the aboveThe thermoplastic polyurethane composition of
Extrusion molding and injection molding are possible.
Shape, blow molding, calendar molding, casting, etc.
Various molded products, such as films and sheets, depending on the forming method
Can be manufactured smoothly. In particular, T-die extrusion
Using a forming machine or an inflation extruder,heat
Films, sheets, etc. from plastic polyurethane compositions
When manufacturing, between extruded films and sheets
Since blocking does not occur, use release paper or the like.
And can be directly extruded and wound.
Films and sheets can be easily rewound.
You. Also,heatFilm from plastic polyurethane composition
When manufacturing, thin film is possible due to good film formation stability.
Noh. From the thermoplastic polyurethane composition of the present invention
The resulting film, seaIs, Flexibility, elastic recovery, force
Because of its excellent mechanical strength, it can be used for disposable diapers,
Stretchable filler used for kin, filling, dustproof, etc.
System; general-purpose conveyor belts, various keyboard sheets
For various uses such as sheet use for
It can be used for effect. [0033] The present invention will now be described in more detail with reference to examples.
As will be appreciated, the invention is not limited thereby. Less than
In the following Examples and Comparative Examples, thermoplastic polyurethane
Atom content, logarithmic viscosity, differential scanning calorimetry (D
SC); of a molded article comprising the thermoplastic polyurethane composition
Hardness, blocking resistance, breaking strength, surface condition, residual strain
み was measured or evaluated by the following method. [Nitrogen atom content] Elemental analyzer (Perky
Nelmer; 240-2 type)
Determined by elemental analysis of polyurethane. [Logarithmic viscosity] N, N-dimethylformamid
0.5 g / dl of thermoplastic polyurethane in the solution
And dissolve it using an Ubbelohde viscometer.
The falling time of polyurethane solution at 30 ℃
The logarithmic viscosity was determined by the following equation. Logarithmic viscosity = ｛ln (t / t)₀)｝ / C [In the formula, t is the flow time (second) of the polyurethane solution, t is
₀Is the solvent flow time (seconds), and c is the polyurethane solution
Indicates the concentration (g / dl). ] [Differential scanning calorimetry (DSC)] Differential scanning
Thermoplastic using a calorimeter (Mettler; DSC30)
The enthalpy of fusion of the water-soluble polyurethane (B) was measured.
The amount of sample used for the measurement was about 10 mg, and the nitrogen gas atmosphere
Measured at a heating rate of 10 ° C / min.
And the peak area of the endothermic peak at 200 to 220 ° C
Further, the crystallization enthalpy (ΔH) was determined. [Hardness] Disk-shaped object obtained by injection molding
(Diameter 120mm, thickness 2mm)
Shore according to JIS K 6301
It was measured with an A hardness meter. [Blocking resistance] T-die extrusion molding machine
(25mmφ) to produce a film and release paper
About 38μm thick film wound without using
And rewind the film, the degree of blocking resistance between the films
Was observed and evaluated according to the evaluation criteria shown in Table 1 below. [0040] [Table 1] [Break strength] T-die extruder (25 m
mφ) to produce a film without using release paper
For the film with a thickness of about 38 μm,
  According to K 7311, the machine axis direction (MD direction)
The tensile strength at break was measured. [Surface condition] T-die extruder (25 m
mφ) to produce a film without using release paper
Fill the film with a thickness of about 38 μm
Observe the surface condition of the
Those having more irregularities on the surface were rated as x. [Residual strain] T-die extruder (25 m
mφ) to produce a film without using release paper
MD film about 38μm thick film
Sample piece (25 mm x 100 m
m) was prepared. Using this sample piece, 23 ° C, 65%
Under the condition of RH, the distance between the chucks is 50 mm and the pulling speed is 300
100% elongation immediately after 100% elongation at 100 mm / min
Returned to the original position in degrees. After repeating this operation twice
Is measured in accordance with the following equation.
The strain was determined. [0044] Residual strain (%) = [(L-50) / 50] × 100 Compounds used in the following Examples and Comparative Examples
The abbreviations and compound names for the products are shown in Table 2 below. [0046] [Table 2] Embodiment 1 Number average molecular weight of 3500 as polyester diol
PMPA, BD and MDI were measured at 85 ° C, 50
From the storage tank heated to 50 ° C and 50 ° C.
So that the molar ratio of ル / MDI / BD is ３/2,
Twin screw type rotating coaxially by metering pump
The mixture was continuously supplied to an extruder to perform continuous melt polymerization. This
When the heating zone of the extruder, the front, middle and
Divided into three zones at the rear, the temperature at the middle was 230 ° C,
The temperature of the part was set to 200 ° C. Polyurethane produced
Continuously extruded into a strand of water
Cut the pellet with a pelletizer at 80 ° C for 6 hours.
While drying. The thermoplastic polyurethane thus obtained is
Nitrogen of tan [corresponding to thermoplastic polyurethane (A)]
The atomic content was 1.9% by weight. Polyester in the reaction vessel
PBA having a number average molecular weight of 2,000 as sterdiol
After heating to 50 ° C, add to 50 ° C while stirring.
The heated MDI was mixed with a PBA / MDI molar ratio of 1 / 7.1.
And reacted for 5 minutes. In addition, 50
The BD heated to ℃ was converted to PBA / MDI / BD = 1/7.
It was added to 1 / 6.1 and reacted for 5 minutes. Anti
The reaction was transferred to a hot plate at 140 ° C to complete the reaction.
Then, the reaction product on the obtained plate is pulverized,
Pelletizing with thermoplastic polyurethane [Heat
Corresponding to the plastic polyurethane (B)]. This heat
The nitrogen content of the plastic polyurethane is 4.6% by weight,
Logarithmic viscosity is 0.60 dl / g, and differential scanning calorimetry
(DSC) shows an endothermic peak at 205 ° C.
The crystallization enthalpy (ΔH) determined from the peak is 9.3 J
/ G. Thermoplastic polyurethane (A) and heatable
Each dried pellet of plastic polyurethane (B) was used as (A)
Blend so that the weight ratio of (B) would be 70:30
After that, a single screw extruder (25 mmφ, cylinder temperature: 1)
80-200 ° C, die temperature: 200 ° C)
The mixture was melt-kneaded to produce a thermoplastic polyurethane composition. Sa
Further, the thermoplastic polyurethane composition was extruded by T-die extrusion.
Extruded from the molding machine, cooled roll (surface temperature: 30-4
0 ° C.) and continuously wound to a thickness of about 38 μm,
A 300 mm wide film was produced. Of the resulting molded product
The physical properties are shown in Table 4 below. Examples 2 to 6, Comparative Examples 1 to 7 The thermoplastic polyurethane (A) shown in Table 3 below and
Same as Example 1 except that (B) is used at a predetermined ratio
To produce a thermoplastic polyurethane composition. Obtained
The physical properties of the molded article are shown in Table 4 below. [0049] [Table 3] [0050] [Table 4] As is clear from Tables 3 and 4, the actual
From the thermoplastic polyurethane compositions of the present invention of Examples 1 to 6
The resulting film has flexibility, elastic recovery, and mechanical strength.
Not only excellent in degree, but also excellent in blocking resistance
You can see that In contrast, thermoplastic polyurethane
When the nitrogen atom content of (B) is less than 3.5% by weight (ratio
Comparative Example 1) The thermoplastic polyurethane (B) was not used at all.
(Comparative Example 2), the thermoplastic polyurethane (B)
When the number average molecular weight of the ester diol is less than 1500
(Comparative Example 4) and thermoplastic polyurethane (A)
MPD is used as the diol component of the ester diol
In the case of no comparison (Comparative Example 7),
It turns out that the blocking resistance of LUM is remarkably inferior.
You. Logarithmic viscosity of thermoplastic polyurethane (B) is 0.9d
In the case of greater than 1 / g (Comparative Example 3), thermoplastic polyurethane
Tan (B) at 220 ° C. by differential scanning calorimetry (DSC)
Endothermic peak at a higher temperature, or
When the energy (ΔH) is larger than 15 J / g (Comparative Example
6) shows the smoothness of the surface state of the obtained film.
Poor nature. The content ratio of the thermoplastic polyurethane (B) is 4
When the content exceeds 0% by weight (Comparative Example 5), the obtained heat
Flexible film with high hardness of plastic polyurethane composition
Cannot be obtained. [0052] EFFECT OF THE INVENTION The thermoplastic polyurethane composition of the present invention
Film, seaIs, Flexibility, elastic recovery, mechanics
CharacteristicExcellentHave been, ExtensionShrinkable film or sheet
And useful.

Claims (1)

(57) [Claim 1] A number average molecular weight is 2,000 to 8,000, and 30 mol% or more of diol unit is 3-methyl-1,
Thermoplastic polyurethane (A) having a nitrogen atom content of 2.5% by weight or less, obtained by reacting a polyester diol comprising 5-pentanediol units, an organic diisocyanate and a chain extender, and a number average molecular weight of 1500
A nitrogen atom content of not less than 3.5% by weight and a logarithmic viscosity of not more than 0.9 dl / g, obtained by reacting a polyester diol, an organic diisocyanate and a chain extender of up to 4000, with a differential scanning calorimetry (DSC) At 200-22
It comprises an endothermic peak in the range of 0 ° C., and comprises a thermoplastic polyurethane (B) having a crystallization enthalpy (ΔH) of 2 to 15 J / g determined from the endothermic peak, and comprises a thermoplastic polyurethane (A) and a thermoplastic polyurethane (A). A film or sheet comprising a thermoplastic polyurethane composition, wherein the weight ratio of B) is from 50:50 to 90:10.
G.