JPH08319415A - Thermoplastic polymer composition - Google Patents

Abstract

(57) [Summary] (Modified) [Structure] (i) Thermoplastic polyurethane (A), styrene elastomer (B), and thermoplastic graft polymer obtained by graft-polymerizing an aromatic vinyl compound and a cyan compound on the elastomer. A polymer composition containing (C); (ii) 40-90% by weight of thermoplastic polyurethane (A), based on the total weight of (A)-(C), styrene-based elastomer (B). 5 to 35% by weight and thermoplastic graft polymer (C) 5 to 30% by weight
And (iii) the thermoplastic polyurethane (A) is a thermoplastic polyurethane obtained by the reaction of a polyester diol, an organic diisocyanate and a chain extender; a thermoplastic polymer composition. [Effect] It is non-adhesive, has excellent blocking resistance, and has excellent mold releasability, and can be smoothly wound without using a release paper when forming a film, a sheet, or the like.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a specific thermoplastic polymer composition, a film, a sheet and other molded articles made of the thermoplastic polymer composition. Specifically, the present invention is non-adhesive, has excellent blocking resistance, and excellent releasability, and can be smoothly wound without using release paper when forming a film, a sheet, etc., and A molded product such as a thermoplastic polymer composition mainly composed of a thermoplastic polyurethane, a film or a sheet made of the thermoplastic polymer composition, in which those products wound up can be smoothly rewound without causing blocking. The above-mentioned molded article obtained from the thermoplastic polymer composition of the present invention is also excellent in elastic recovery, flexibility and mechanical properties,
In particular, the film or sheet is useful as a stretchable film or sheet.

[0002]

2. Description of the Related Art Thermoplastic polyurethane has high elasticity and high strength, and has abrasion resistance, chemical resistance, oil resistance,
It has been widely used in various fields since it has excellent properties such as bending resistance and can be applied with a usual thermoplastic resin molding method. However, since thermoplastic polyurethane has strong adhesiveness and is apt to cause blocking, it is difficult to wind it alone when a film or sheet is manufactured by extrusion molding, etc. The current situation is that rewinding of films and sheets becomes difficult or impossible, making them unusable. Therefore, for the purpose of detackification, prevention of blocking, imparting releasability, etc.,
(A) a method of adding a lubricant to the thermoplastic polyurethane,
(B) A method of blending a thermoplastic polyurethane with another polymer, and (c) a release paper formed by forming a film or sheet of a thermoplastic polyurethane on a release paper containing silicone or a release paper laminated with polyethylene or polypropylene. The method of winding it together with etc. is performed.

[0003]

However, in the case of the above method (a), it is necessary to add a large amount of a lubricant in order to exhibit the antiblocking effect and the releasing effect, and as a result, the surface of the product is In addition, there is a drawback that the lubricant bleeds out and many irregularities are generated on the surface, resulting in loss of smoothness. Further, in the case of the above method (b), since it is necessary to blend a large amount of polymer, the original properties of the thermoplastic polyurethane are likely to be lost, and particularly the elastic recovery property, the flexibility and the elongation are largely lowered, and the film There is a defect that the surface of molded products such as sheets and sheets is roughened and the appearance is deteriorated. Further, in the case of the above method (c), it is necessary to use release paper or the like, which requires time and effort for molding, and moreover, since expensive release paper or the like is used, there is a drawback that the cost becomes high.

The object of the present invention is to retain the excellent properties inherent in thermoplastic polyurethanes, in particular, mechanical properties such as elastic recovery, flexibility and strength and elongation without any loss, and to maintain a large amount. Effectively prevent adhesion and blocking without using lubricants, expensive release papers, etc., to smoothly produce thermoplastic polyurethane films, sheets and other molded products with excellent physical properties and appearance. It is to provide a thermoplastic polymer composition mainly composed of a thermoplastic polyurethane which can be obtained. And another object of the present invention is a film comprising the above-mentioned thermoplastic polymer composition,
It is to provide molded products such as sheets.

[0005]

As a result of repeated studies by the present inventors in order to achieve the above object, a styrene elastomer and an aromatic vinyl compound and a cyan compound were added to the elastomer for a specific thermoplastic polyurethane. When a thermoplastic graft polymer obtained by graft polymerization is blended in a specific ratio, the thermoplastic polymer has excellent properties inherent in the thermoplastic polyurethane, and is also excellent in non-adhesiveness, blocking resistance and releasability. A composition is obtained, and when a film, sheet, or other molded article is produced using this thermoplastic polymer composition, winding and rewinding are smoothly performed without using release paper or the like. And the molded products such as films and sheets obtained there are mechanical recoverable materials such as elastic recovery, flexibility and elongation. Have excellent sex, especially films or sheets useful as an elastic film or sheet. Furthermore, when the present inventors further blend at least one of the higher fatty acid bisamide and the inorganic filler in a specific ratio to the above-mentioned thermoplastic polymer composition, its non-adhesiveness, blocking resistance, and mold release property. The present invention has been completed based on the findings that the properties are further improved.

That is, the present invention provides (i) a thermoplastic polyurethane (A), a styrene elastomer (B) and a thermoplastic graft polymer (C) obtained by graft-polymerizing an aromatic vinyl compound and a cyan compound on the elastomer. A polymer composition containing: (ii) 40 to 90% by weight of the thermoplastic polyurethane (A) and 5 to 35 of the styrene elastomer (B) based on the total weight of (A) to (C). % By weight and 5 to 30% by weight of the thermoplastic graft polymer (C);
And (iii) the thermoplastic polyurethane (A) is a thermoplastic polyurethane obtained by the reaction of a polyester diol, an organic diisocyanate and a chain extender; and (iv) the thermoplastic polyurethane (A) used for the production of the above. The polyester diol is a polyester diol having a number average molecular weight of 1000 to 8000 and containing a branched diol component having 4 to 9 carbon atoms in the range of 30 to 100% by weight based on the total diol; It is a polymer composition.

In the present invention, the higher fatty acid bisamide (D) is further added in an amount of 0.3 to 5 based on the total weight of the thermoplastic polyurethane (A), the styrene elastomer (B) and the thermoplastic graft polymer (C). The content of the inorganic filler (E) is 2 to 20% by weight.
It includes the above-mentioned thermoplastic polymer composition containing 5% by weight. Further, the present invention includes a molded article such as a film or sheet made of the above-mentioned thermoplastic polymer composition.

The thermoplastic polyurethane (A) used in the thermoplastic polymer composition of the present invention (hereinafter, simply referred to as "polymer composition") is obtained by the reaction of a polyester diol, an organic diisocyanate and a chain extender. A thermoplastic polyurethane, wherein the polyester diol used in the production of the thermoplastic polyurethane (A) contains a branched diol component having 4 to 9 carbon atoms (hereinafter, simply referred to as “branched diol component”). Number average molecular weight 1 in the range of 30 to 100% by weight based on diol
000 to 8000 polyester diols are required.

Examples of the branched diol component forming the polyester diol include 2-methyl-1,3
-Propanediol, 3-methyl-1,5-pentanediol, neopentyl glycol, 2-methyl-1,8
-Octanediol and the like. These branched diol components may be used alone or in combination of two or more. When a thermoplastic polyurethane produced using a polyester diol obtained by reacting a diol component having a branched diol component content of less than 30% by weight with a dicarboxylic acid component is used, such thermoplastic Even if the styrene elastomer (B) and the thermoplastic graft polymer (C) are blended with polyurethane in the above proportions, a polymer composition and a molded article having excellent elastic recovery and flexibility cannot be obtained. Further, in such a case, the obtained polymer composition and molded article have poor cold resistance.

The diol component constituting the polyester diol for the thermoplastic polyurethane (A) may contain a diol component other than the above-mentioned branched diol component as long as it is 70 mol% or less. Examples of other diol components include ethylene glycol, 1,4-butanediol, 1,6-hexanediol, 1,8-octanediol, and 1,9-nonanediol, which are used alone. Alternatively, two or more kinds may be used in combination.

As the dicarboxylic acid component constituting the polyester diol for the thermoplastic polyurethane (A), either an aliphatic dicarboxylic acid, an aromatic dicarboxylic acid or an ester-forming derivative thereof can be used, for example, glutaric acid. , Adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, decanedicarboxylic acid,
Aliphatic dicarboxylic acids having 6 to 12 carbon atoms such as 2-methylsuccinic acid, 2-methyladipic acid, 3-methyladipic acid, 3-methylpentanedioic acid and 2-methyloctanedioic acid, terephthalic acid, isophthalic acid, orthophthalic acid Examples thereof include aromatic dicarboxylic acids such as acids or their ester-forming derivatives. These dicarboxylic acid components may be used alone or in combination of two or more. Among them, the aliphatic dicarboxylic acid having 6 to 10 carbon atoms such as adipic acid, azelaic acid, sebacic acid or the ester-forming derivative thereof is used for the elastic recovery and elongation of the polymer composition of the present invention. And the like are favorable, which is preferable.

Further, the above polyester diol used for producing the thermoplastic polyurethane (A) is
It is necessary that the number average molecular weight is in the range of 1000 to 8000. Number average molecular weight of polyester diol is 1
If it is less than 000, the anti-adhesion effect of the polymer composition is not sufficient, and the elastic recovery property, heat resistance, cold resistance, strength and elongation, etc. are likely to decrease. On the other hand, when the number average molecular weight of the polyester diol exceeds 8000, not only the productivity of the thermoplastic polyurethane is lowered but also the melt viscosity of the thermoplastic polyurethane is high, so that the production and molding of a polymer composition using the same are carried out. Sexual stability is reduced. The number average molecular weight of the polyester diol is preferably in the range of 1000 to 6000 from the viewpoint that a non-adhesive molded article can be stably obtained. The number average molecular weight of the polyester diols referred to in the present specification is a number average molecular weight calculated on the basis of the hydroxyl value measured according to JIS K-1557.

The method for producing the above-mentioned polyester diol used for producing the thermoplastic polyurethane (A) is not particularly limited, and the conventionally known transesterification reaction and direct esterification reaction are performed using the above-mentioned diol component and dicarboxylic acid component. It can be produced by polycondensation, etc. In that case, the polycondensation reaction may be carried out in the presence of a titanium-based or tin-based polycondensation catalyst which is generally known to be usable in the production of ester-based polymers such as polyester and polycarbonate. Good. When the titanium-based polycondensation catalyst is used, it is preferable to deactivate the titanium-based polycondensation catalyst contained in the polyester diol after the completion of the polycondensation reaction. By producing the thermoplastic polyurethane (A) by using the polyester diol in which the titanium-based polycondensation catalyst has been deactivated, even if the thermoplastic polyurethane (A) is kept in a molten state at high temperature, the thermoplastic polyurethane (A) is The deterioration of the blockability between the hard segment and the soft segment constituting the composition is suppressed, and the thermoplastic polyurethane (A) has various properties such as heat resistance and elastic recovery that the thermoplastic polyurethane (A) originally had. The polymer composition contained therein can be excellently exhibited as it is in a molded article or the like.

As a method of deactivating the titanium-based esterification catalyst contained in the polyester diol produced by using the titanium-based polycondensation catalyst, for example, the polyester diol obtained by the polycondensation reaction is mixed with water under heating conditions. Examples thereof include a method of contacting and a method of treating a polyester diol with a phosphorus compound such as phosphoric acid, phosphoric acid ester, phosphorous acid, and phosphorous acid ester. Among them, the former method of contacting with water under heating conditions can be mentioned. The method is preferred. When the titanium-based esterification catalyst is deactivated by contacting with water, water is added to the polyester diol obtained by the polycondensation reaction.
It is carried out by bringing them into contact with each other in an amount of not less than wt% and heating within a range of 70 to 150 ° C, preferably within a range of 90 to 130 ° C for 1 to 3 hours. The deactivation treatment of the titanium-based esterification catalyst may be performed under normal pressure or under pressure. It is desirable to depressurize the system after deactivating the titanium-based esterification catalyst because the water used for deactivation can be removed.

As the organic diisocyanate used in the production of the thermoplastic polyurethane (A), any of the organic diisocyanates conventionally used in the production of polyurethane can be used, and the kind thereof is not particularly limited, but the aromatic diisocyanate having a molecular weight of 500 or less is used. One or more of group diisocyanates, alicyclic diisocyanates, and aliphatic diisocyanates are preferably used. Among them, p-
Phenylene diisocyanate, 4,4'-diphenylmethane diisocyanate, toluylene diisocyanate,
1,5-naphthylene diisocyanate, 4,4′-dicyclohexylmethane diisocyanate and the like are preferable,
Particularly, 4,4'-diphenylmethane diisocyanate is preferable.

As the chain extender used for producing the thermoplastic polyurethane (A), any chain extender conventionally used for producing thermoplastic polyurethane can be used, and the type thereof is not particularly limited. Among these, low molecular weight compounds having a molecular weight of 300 or less and having two or more active hydrogen atoms capable of reacting with an isocyanate group in the molecule, such as aliphatic diols, alicyclic diols and aromatic diols are preferably used. Specific examples of preferable chain extenders include ethylene glycol, diethylene glycol, propylene glycol, 1,4-butanediol and 1,5-
Pentanediol, 2-methyl-1,3-propanediol, 1,6-hexanediol, 3-methyl-1,5
-Pentanediol, neopentyl glycol, 1,9
-Nonanediol, 2-methyl-1,8-octanediol, cyclohexanediol, cyclohexanedimethanol, 1,4-bis (β-hydroxyethoxy) benzene and the like can be mentioned, and these chain extenders can be used alone. Alternatively, two or more kinds may be used in combination.

As the thermoplastic polyurethane (A), the polyester diol, the organic diisocyanate, and the chain extender described above are used, and the number of moles of the isocyanate groups of the organic diisocyanate and the total number of hydroxyl groups of the polymer diol and the chain extender are the same. The ratio (moles of isocyanate group / moles of hydroxyl group) is preferably in the range of 0.98 to 1.10. By setting the ratio of the number of moles of isocyanate group / the number of moles of hydroxyl group in the above range, various properties of the resulting thermoplastic polyurethane (A) can be maintained at a high level, and a polymer composition obtained from the thermoplastic polyurethane (A) can be maintained. The products and molded products have good flexibility, elastic recovery, and mechanical properties.

The thermoplastic polyurethane (A) preferably has a hardness (JIS-A hardness) in the range of 60 to 85. Hardness of thermoplastic polyurethane (A) is 6
When it is less than 0, the resulting polymer composition is inferior in mechanical properties and it becomes difficult to maintain non-adhesiveness, which is not preferable. On the other hand, when the hardness thereof exceeds 85, the obtained polymer composition has insufficient flexibility, which is not preferable.

The method for producing the thermoplastic polyurethane (A) used in the present invention is not particularly limited, and a known urethane can be prepared by using the above-mentioned polyester diol, organic diisocyanate, chain extender and, if necessary, other components. It may be produced by either a prepolymer method or a one-shot method by utilizing a chemical reaction technique. Among them, it is preferable to carry out the melt polymerization in the substantially absence of solvent, and the continuous melt polymerization method using a multi-screw extruder is particularly preferable.

The styrene elastomer (B) constituting the polymer composition of the present invention is a block copolymer produced from a vinyl aromatic compound and a conjugated diene compound, and is derived from the vinyl aromatic compound. Unit is 5 to 50
It is preferable that the content is in a weight percentage, and that the structure is linear. As the vinyl aromatic compound, for example, styrene, α-methylstyrene, or their alkyl-substituted or halogen-substituted compounds are used. Especially, it is preferable to use styrene. When a styrene-based elastomer (B) having a content of units derived from a vinyl aromatic compound exceeding 50% by weight is used, the compatibility with the thermoplastic polyurethane (A) is lowered, resulting in poor dispersion, which is obtained. The flexibility of the polymer composition is likely to decrease,
Not preferred. On the other hand, when a styrene elastomer (B) having a content of units derived from a vinyl aromatic compound of less than 5% by weight is used, the tackiness of a molded article such as a film provided by the obtained polymer composition is increased. Is not preferable. Examples of the conjugated diene compound include 1,3-butadiene, 2-methyl-1,3-butadiene and 2,3-
Dimethyl-1,3-butadiene, 2-neopentyl-
1,3-Butadiene, 2-chloro-1,3-butadiene and the like can be mentioned. Among them, 1,3-butadiene, 2
Preference is given to using methyl-1,3-butadiene.

The styrene elastomer (B) has a melt flow rate (MI; 200 ° C., 5 kg load) of 3
It is preferably 0 g / 10 minutes or less. When a styrene-based elastomer (B) having a melt flow rate of more than 30 g / 10 minutes is used, it tends to cause poor dispersion with the thermoplastic polyurethane (A), and a molded article such as a film provided by the resulting polymer composition. Then, the tackiness tends to increase. Further, the hardness of the styrene elastomer (B) (JI
The S-A hardness) is preferably in the range of 30 to 80 from the viewpoint of tackiness and flexibility of the polymer composition and the molded product.

As the elastomer serving as a graft base for the thermoplastic graft polymer constituting the polymer composition of the present invention, those having a second-order transition temperature lower than -30 ° C are preferable. As the aromatic vinyl compound which is one of the graft monomers, for example, styrene, α-methylstyrene, or an alkyl-substituted product or a halogen-substituted product thereof is used. Especially, it is preferable to use styrene. Further, as the vinyl cyanide compound,
For example, acrylonitrile, methacrylonitrile, etc. are used. It is particularly preferable to use acrylonitrile.

As a typical example of the thermoplastic graft polymer constituting the polymer composition of the present invention, a copolymer obtained by emulsion polymerization of a latex of a butadiene-based polymer with both graft monomers of acrylonitrile and styrene (hereinafter , Which are collectively referred to as ABS resin). As the butadiene-based polymer latex, polybutadiene latex, acrylonitrile-butadiene copolymer latex, styrene-butadiene copolymer latex and the like are used. The proportion of each of the above components in the ABS resin is preferably 5 to 50% by weight of butadiene-based polymer, 20 to 85% by weight of styrene, and 5 to 40% by weight of acrylonitrile.

As a typical example of the thermoplastic graft polymer, a resin obtained by graft-polymerizing an aromatic vinyl compound and a vinyl cyanide compound on ethylene-propylene rubber (hereinafter, abbreviated as AES resin) is mentioned. To be As the ethylene-propylene rubber, ethylene-propylene copolymer rubber, ethylene-propylene-
Diene copolymer rubber or the like is used. The use ratio (weight ratio) of ethylene and propylene is preferably in the range of 9: 1 to 2: 8. As the diene monomer, norbornenes such as alkenyl norbornene, cyclic dienes such as dicyclopentadiene, and aliphatic dienes such as hexadiene are used. The diene monomers may be used alone or in combination of two or more. The use ratio (weight ratio) of the ethylene-propylene rubber and the vinyl compound of the aromatic vinyl compound and the vinyl cyanide compound is 5: 9.
A range of 5 to 50:50 is suitable, and 10: 9.
It is preferably in the range of 0 to 40:60. The AES resin is produced by a bulk polymerization method, an emulsion polymerization method, a solution polymerization method, a bulk-suspension polymerization method, or the like.

In the polymer composition of the present invention, the thermoplastic polyurethane (A) is added in an amount of 40 based on the total weight of the thermoplastic polyurethane (A), the styrene elastomer (B) and the thermoplastic graft polymer (C). ~ 9
0% by weight, 5 to 35% by weight of styrene elastomer (B) and 5 to 30% of thermoplastic graft polymer (C)
It is necessary to contain it in a weight percentage.

In the polymer composition of the present invention, when the content of the thermoplastic polyurethane (A) is less than 40% by weight, abrasion resistance and mechanical strength of the polymer composition and molded articles such as films made of the polymer composition are obtained. And the original excellent properties of the thermoplastic polyurethane (A) are lost, while 90
When the content is more than 10% by weight, the polymer composition exhibits tackiness and blocking property, and it becomes difficult to wind and unwind a film or sheet. When the content of the styrene-based elastomer (B) is less than 5% by weight, the flexibility and elastic recovery of a molded article such as a film made of the polymer composition becomes insufficient, while when it exceeds 35% by weight. Causes blocking and poor dispersion in the polymer composition, and roughens the surface of molded articles such as films. When the content of the thermoplastic graft polymer (C) is less than 5% by weight, blocking property occurs between the films when the polymer composition is formed into a film, while when it exceeds 30% by weight, the flexibility of the polymer composition is increased. , Elastic recovery, and deterioration of physical properties occur.

Further, based on the total weight of the thermoplastic polyurethane (A), the styrene-based elastomer (B) and the thermoplastic graft polymer (C), the higher fatty acid bisamide (D) as a lubricant is contained in an amount of 0.3 to 5% by weight. It is desirable to contain it in a ratio because the non-adhesiveness is further improved and the releasability at the time of producing a molded product such as a film or a sheet is further improved. From the viewpoints of blocking resistance between molded products and deterioration of the surface of the molded product due to bleed-out, it is preferable to contain the higher fatty acid bisamide (D) in a proportion of 2 to 5% by weight. The higher fatty acid bisamide (D) has 14 carbon atoms.
Those produced from .about.35 higher saturated fatty acids and aliphatic diamines having 1 to 10 carbon atoms are preferable. The higher fatty acids include myristic acid, pentadecyl acid, palmitic acid,
Heptadecyl acid, stearic acid, nonadecanoic acid, arachidic acid, behenic acid, lignoceric acid, cetic acid, cerotic acid, heptacosanoic acid, montanic acid, melissic acid, etc. are exemplified, and as the aliphatic diamine, methylene diamine,
Examples include ethylenediamine, trimethylenediamine, tetramethylenediamine, pentamethylenediamine, hexamethylenediamine, 1,7-diaminoheptane, 1,8-diaminooctane, 1,9-diaminononane and 1,10-diaminodecane. Examples of the higher fatty acid bisamide (D) include methylenebisstearic acid amide, ethylenebisstearic acid amide, tetramethylenebisstearic acid amide, hexamethylenebisstearic acid amide, ethylenebismontanic acid amide, tetramethylenebismontanic acid amide, and hexamethylene. Bismontanic acid amide is preferable, methylenebisstearic acid amide,
More preferred is ethylenebisstearic acid amide.

Further, the polymer composition of the present invention is thermoplastic with the above-mentioned thermoplastic polyurethane (A), styrene elastomer (B), thermoplastic graft polymer (C) and optionally higher fatty acid bisamide (D). It is preferable that the inorganic filler (E) is further contained in a proportion of 2 to 5% by weight based on the total weight of the polyurethane (A), the styrene elastomer (B) and the thermoplastic graft polymer (C). By containing the inorganic filler (E) in the above proportion, the non-tackiness of the polymer composition is further improved. As the inorganic filler (E), for example, powders of calcium carbonate, mica, talc, silica, alumina, calcium silicate, calcium aluminate and the like are used, but among them, it is preferable to use calcium carbonate and mica. . These powders have a particle size of 0.5 to 2
The range of 0 μm is preferable.

The polymer composition of the present invention contains, in addition to the above-mentioned components, other lubricants, fillers, antioxidants, ultraviolet absorbers, pigments, antistatic agents, plasticizers, flame retardants, if necessary. , And one or more additives such as antifungal agents may be contained in an amount within a range that does not impair the effects of the present invention.

The thermoplastic polyurethane (A), the styrene elastomer (B) and the thermoplastic graft polymer (C) constituting the polymer composition of the present invention are simply melted to form a matrix of the thermoplastic polyurethane (A). The styrene elastomer (B) and the thermoplastic graft polymer (C) can be uniformly dispersed in the preferable particle system. Therefore, the method for producing the polymer composition of the present invention is not particularly limited, and any method conventionally used for producing a thermoplastic polyurethane or a thermoplastic polymer composition can be adopted. For example, by using a vertical or horizontal mixer that is usually used for mixing polymers, the above components are premixed at a predetermined ratio, and then a uniaxial or biaxial extruder, a mixing roll, a Banbury mixer, etc. Can be used for kneading under heating. In particular, when the mixture is heated and kneaded using an extruder, it may be extruded in a strand shape and then cut into an appropriate length to form pellets or other granular materials. In addition, when the above-mentioned components are blended at the time of polymerization of the thermoplastic polyurethane (A), the polymer composition obtained there is extruded in a strand shape and then formed into granules such as pellets having an appropriate length. The inventive polymer composition may be prepared.

The polymer composition of the present invention is thermoplastic
Capable of hot-melt molding and heat processing, and various molded products such as films and sheets can be smoothly produced by any molding method such as extrusion molding, injection molding, blow molding, calender molding, and casting. . In particular, when a film, sheet or the like is produced from the polymer composition of the present invention using a T-die type extruder or an inflation extruder, the polymer composition has non-adhesiveness, blocking resistance,
Since it is releasable and blocking does not occur between the extruded films and sheets, it can be directly extruded and wound up without using release paper, and the wound film or sheet can be easily wound. Can be returned.
Further, when a film is produced from the polymer composition of the present invention, the film forming stability is good, and the film can be made thin.

Molded products such as films and sheets obtained by using the polymer composition of the present invention have elastic recovery, flexibility,
It has excellent mechanical properties such as tensile rupture strength and tensile rupture elongation, and also has a smooth surface and a good surface condition.Making use of these properties, for sanitary use, paper diapers, sealing, Elastic film applications used for dust prevention, etc.
It can be effectively used for various applications such as general-purpose conveyor belts, various keyboard sheets, laminated products, various container and other sheet applications, sports shoes, ski shoes and other shoe sole applications.

[0033]

EXAMPLES The present invention will be specifically described below with reference to examples, but the present invention is not limited thereto. In the following examples, blocking resistance between films when producing a film using the polymer composition, tensile strength and elongation of the obtained film, surface state and residual strain were measured or evaluated by the following methods. .

(Blocking resistance between films during film formation) Using a polymer composition, a T-die type extruder (25 m
mφ) was used to rewind a film (about 38 μ) wound without using a release paper, and the degree of blocking resistance between the films was observed, and judged according to the evaluation criteria shown in Table 1 below. did.

[0035]

[Table 1]

(Tensile Strength and Elongation) A film (about 38 μ) wound with a T-die type extrusion molding machine (25 mmφ) using the polymer composition without using release paper was used.
The tensile strength at break in the MD direction was measured according to SK7311.

(Surface Condition) Using a T-die type extrusion molding machine (25 mmφ) with the polymer composition, the surface condition of the film (about 38 μ) wound up without using release paper was observed. Then, smooth ones were marked with ◯, and uneven ones were marked with x.

(Residual strain) Using a T-die type extruder (25 mmφ) using the polymer composition, a film (about 38 μ) wound without using release paper was stripped in the TD direction. Cut out sample (25 mm x 100 m
m) under the conditions of 23 ° C. and 65% RH, between chucks 5
After stretching 150% at 0 mm and a pulling speed of 300 mm / min, the film is immediately returned to its original position at a speed of 300 mm / min. After repeating this operation 3 times, the sample length L (mm) was measured and the residual strain was calculated according to the following formula.

[0039]

Residual strain (%) = [(L-50) / 50] × 100

In the following Examples and Comparative Examples, each compound is indicated by the abbreviation shown in Table 2 below.

[0041]

[Table 2]

[Reference Example 1] (Production of polyester diol A) Mixture of MOD and ND (molar ratio: 35:65) 1600
g and 1460 g of AD were charged into a reactor, and an esterification reaction was carried out at a temperature of about 220 ° C. while distilling the produced water out of the system while passing nitrogen gas through the system under normal pressure. When the acid value of the produced polyester diol became 0.3 or less, the degree of vacuum was gradually raised by a vacuum pump to complete the reaction. Obtained polyester diol (hereinafter referred to as "polyester diol A")
Had a hydroxyl value of 56 and an acid value of 0.12, and its number average molecular weight was 2,000.

Reference Example 2 (Production of Polyesterdiol B) In Reference Example 1, MP was used instead of the mixture of MOD and ND.
An esterification reaction was performed in the same manner except that D was used to obtain a polyester diol (hereinafter referred to as "polyester diol B").

Reference Example 3 (Production of Polyester Diol C) In Reference Example 1, instead of the mixture of MOD and ND, MP was used.
The esterification reaction was carried out in the same manner except that rG was used,
A polyester diol (hereinafter referred to as "polyester diol C") was obtained.

Reference Example 4 (Production of Polyesterdiol D) In Reference Example 1, BD was used instead of the mixture of MOD and ND.
A polyester diol (hereinafter, referred to as “polyester diol D”) was obtained by performing an esterification reaction in the same manner except that was used.

With respect to the polyester diols obtained in Reference Examples 1 to 4, their constituent components and number average molecular weights are shown in Table 3 together.

[0047]

[Table 3]

Example 1 A mixture of polyester diol B and BD in a molar ratio of 1: 3.1 was heated to 50 ° C., and this and MDI heated to 50 ° C. were mixed with polyester diol B: MDI: BD. Was continuously charged into a twin-screw extruder rotating in the coaxial direction by a metering pump in an amount such that the molar ratio thereof became 1: 4.1: 3.1 to carry out a continuous melt polymerization reaction. The resulting thermoplastic polyurethane melt was extruded into water in strands, then cut with a pelletizer and made into pellets. A mixture of the obtained thermoplastic polyurethane pellets and SIS and AES in the proportions shown in Table 4 was supplied to a single-screw extruder (25 mmφ, cylinder temperature: 170 to 200 ° C., die temperature: 200 ° C.). Melt kneading, extruding from a T-die, and continuously winding it through a cooling roll (surface temperature: 30 ° C.) to obtain a film (width 300 mm, thickness 4
0 μ) was prepared. The blocking resistance between the films at that time, the tensile strength and elongation of the obtained film, the surface state and the residual strain were measured or evaluated by the above-mentioned methods, and the results are shown in Table 5.

[Comparative Example 1] Only the thermoplastic polyurethane obtained in the same manner as in Example 1 was formed into a film in the same manner as in Example 1, but the films were so sticky that they could not be unwound. Further, a film was prepared by using a release paper during the film formation, and the tensile strength / elongation, surface condition and residual strain of the obtained film were measured or evaluated by the above-mentioned methods, and the results are shown in Table 5.

[Comparative Example 2] A thermoplastic polyurethane obtained in the same manner as in Example 1 was mixed with SIS at a ratio shown in Table 4 to form a film in the same manner as in Example 1. The blocking resistance between the films at that time, the tensile strength and elongation of the obtained film, the surface state and the residual strain were measured or evaluated by the above-mentioned methods, and the results are shown in Table 5.

[Comparative Example 3] A thermoplastic polyurethane obtained in the same manner as in Example 1 was mixed with AES at a ratio shown in Table 4 and formed into a film in the same manner as in Example 1. The blocking resistance between the films at that time, the tensile strength and elongation of the obtained film, the surface state and the residual strain were measured or evaluated by the above-mentioned methods, and the results are shown in Table 5.

[Examples 2 and 3] Thermoplastic polyurethanes obtained in the same manner as in Example 1 and SIS and A
A film was formed in the same manner as in Example 1 using a mixture prepared by mixing ES or ABS in the proportions shown in Table 4. The blocking resistance between the films at that time, the tensile strength and elongation of the obtained film, the surface state and the residual strain were measured or evaluated by the above-mentioned methods, and the results are shown in Table 5.

Example 4 A thermoplastic polyurethane was produced in the same manner as in Example 1 except that the polyester diol B was used in place of the polyester diol B, and the obtained thermoplastic polyurethane was mixed with SIS and AES. A film was formed in the same manner as in Example 1 using the mixture mixed in the proportions shown in Table 4. The blocking resistance between the films at that time, the tensile strength and elongation of the obtained film, the surface state and the residual strain were measured or evaluated by the above-mentioned methods, and the results are shown in Table 5.

Example 5 A thermoplastic polyurethane was produced in the same manner as in Example 1 except that polyester diol C was used instead of polyester diol B, and the obtained thermoplastic polyurethane was mixed with SIS and AES. A film was formed in the same manner as in Example 1 using the mixture mixed in the proportions shown in Table 4. The blocking resistance between the films at that time, the tensile strength and elongation of the obtained film, the surface state and the residual strain were measured or evaluated by the above-mentioned methods, and the results are shown in Table 5.

[Comparative Example 4] A thermoplastic polyurethane was produced in the same manner as in Example 1 except that the polyester diol B was used in place of the polyester diol B, and the obtained thermoplastic polyurethane was mixed with SIS and AES. A film was formed in the same manner as in Example 1 using the mixture mixed in the proportions shown in Table 4. The blocking resistance between the films at that time, the tensile strength and elongation of the obtained film, the surface state and the residual strain were measured or evaluated by the above-mentioned methods, and the results are shown in Table 5.

[Comparative Example 5] Thermoplastic polyurethane obtained in the same manner as in Example 1 and SIS and AES
A film was formed in the same manner as in Example 1 using a mixture in which and were mixed in the proportions shown in Table 4. The blocking resistance between the films at that time, the tensile strength and elongation of the obtained film, the surface state and the residual strain were measured or evaluated by the above-mentioned methods, and the results are shown in Table 5.

[0057]

[Table 4]

[0058]

[Table 5]

[0059]

The polymer composition of the present invention is non-adhesive,
It has excellent blocking resistance and releasability, and it can be smoothly wound up without using release paper when forming a film, sheet, etc., and those rolled up molded articles do not cause blocking. You can rewind smoothly. Molded articles such as films and sheets comprising the polymer composition of the present invention are also excellent in elastic recovery, flexibility and mechanical properties, and the films or sheets are particularly useful as stretchable films or sheets.

Claims (5)

[Claims] 1. A polymer containing (i) a thermoplastic polyurethane (A), a styrene elastomer (B), and a thermoplastic graft polymer (C) obtained by graft-polymerizing an aromatic vinyl compound and a cyan compound on the elastomer. 40 to 90 of the thermoplastic polyurethane (A) based on the total weight of (ii) (A) to (C).
% By weight, 5 to 35% by weight of the styrenic elastomer (B) and 5 to 30% by weight of the thermoplastic graft polymer (C); and (iii) the thermoplastic polyurethane (A) is a polyester diol. , A thermoplastic polyurethane obtained by the reaction of an organic diisocyanate and a chain extender; and (iv) the polyester diol used in the production of the thermoplastic polyurethane (A) is a branched diol component having 4 to 9 carbon atoms. Is a polyester diol having a number average molecular weight of 1000 to 8000 in the range of 30 to 100% by weight based on the total diols; 2. A higher fatty acid bisamide (D) in an amount of 0.3 to 5% by weight based on the total weight of the thermoplastic polyurethane (A), the styrene elastomer (B) and the thermoplastic graft polymer (C). 1 contained in
The thermoplastic polymer composition described. 3. An inorganic filler (E) based on the total weight of the thermoplastic polyurethane (A), the styrenic elastomer (B) and the thermoplastic graft polymer (C).
The thermoplastic polymer composition according to claim 1 or 2, which contains 2 to 5% by weight. 4. A molded article made of the thermoplastic polymer composition according to claim 1. 5. The molded article according to claim 4, which is a film or a sheet.