JPH0853615A - Thermoplastic polyurethane composition - Google Patents

Abstract

PURPOSE:To impart nonadhesiveness to thereby improve antiblocking properties, releasability, etc., by incorporating a styrene elastomer, an olefin elastomer, and a polyolefin resin into a thermoplastic polyurethane in respective specific amounts. CONSTITUTION:40-90wt.% thermoplastic polyurethane is mixed with 5-35wt.% styrene elastomer (e.g. a styrene/1,3-butadiene block copolymer), 5-25wt.% olefin elastomer (e.g. an ethylene/propylene copolymer rubber), and 5-15wt.% polyolefin resin (e.g. high-density polyethylene), the total amount being 100wt.%, to produce the objective composition. According to need, a higher fatty acid bisamide (e.g. methylenebisstearamide) can be further incorporated in an amount of 0.3-4wt.%. The resulting composition is suited for use in producing a film, a laminated sheet, etc.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a thermoplastic polyurethane composition, a film, a sheet and other molded articles made of the thermoplastic polyurethane composition, a film-like or sheet-like laminate having the thermoplastic polyurethane composition as a surface layer. Regarding the body Specifically, the present invention is non-adhesive, has excellent blocking resistance, and excellent releasability, and does not require release paper when producing a film or sheet, a film-like or sheet-like laminate, and the like. It can be rolled up smoothly, and those rolled up products can be rewound smoothly without causing blocking, and when molded using a mold, take out the molded product from the mold. The present invention relates to a thermoplastic polyurethane composition capable of smoothly performing the above, a film, a sheet, a molded article such as a molded article made of the composition, and a film-like or sheet-like laminate having the composition as a surface layer.

[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 produced by extrusion molding or the like. The current situation is that the rewinding of films and sheets becomes difficult or impossible, making them unusable. Also, when a thermoplastic polyurethane is introduced into a mold to produce a molded article,
Due to the adhesiveness, the molded product adheres to the wall surface of the mold and cannot be easily taken out from the mold. Therefore, for the purpose of detackification, prevention of blocking, imparting releasability, etc., (i) a method of adding a lubricant to the thermoplastic polyurethane, (ii) a method of blending the thermoplastic polyurethane with another polymer, ( iii) A method of forming a film of a thermoplastic polyurethane film or sheet on a release paper containing silicone or a release paper laminated with polyethylene or polypropylene and winding the film together with the release paper, and (iv) releasing on the inner surface of the mold during molding. A method of applying a mold agent has been conventionally performed.

However, in the case of the above method (i), it is necessary to add a large amount of a lubricant in order to exert an antiblocking effect and a releasing effect, and as a result, the lubricant bleeds out on the surface of the product and the surface is However, there is a drawback in that many irregularities occur and the smoothness is lost. Further, in the case of the above-mentioned method (ii), since it is necessary to blend an extremely large amount of polymer, the original characteristics of the thermoplastic polyurethane are easily lost, and moreover, the molded article such as a film or a sheet is easily lost. There is a drawback that the surface becomes rough and the appearance becomes poor. Furthermore, the above (iii) and (iv)
In the case of the above method, it is necessary to separately prepare a release paper and a release agent for molding, which requires a lot of time for molding, and the cost is high because an expensive release paper or release agent is used. There is a drawback that

[0004]

SUMMARY OF THE INVENTION An object of the present invention is to retain the excellent properties inherently possessed by thermoplastic polyurethane without impairing them, and to use a large amount of lubricant,
Thermoplastic polyurethane films, sheets, and other molded products that have excellent physical properties and appearance by effectively preventing adhesion and blocking without using expensive release papers and release agents.
It is intended to provide a thermoplastic polyurethane composition capable of smoothly producing a laminate or the like. The object of the present invention is to provide a film, a sheet, a molded article such as a molded article, which is made of the above-mentioned thermoplastic polyurethane composition, and a film-like or sheet-like laminate having a surface layer of the thermoplastic polyurethane composition. It is to be.

[0005]

As a result of repeated studies by the present inventors to achieve the above object, a styrene elastomer, an olefin elastomer and a polyolefin resin are blended in a specific ratio with a thermoplastic polyurethane. Then, a thermoplastic polyurethane composition having the original excellent properties of the thermoplastic polyurethane and excellent in non-adhesiveness, anti-blocking property and releasability is obtained, and the thermoplastic polyurethane composition is used to produce a film. When producing molded products such as sheets, sheets, molded products, and laminates, winding, rewinding, and release from the mold are smooth and easy without the use of release paper or release agent. It has been found that a product excellent in physical properties and appearance can be manufactured. Furthermore, the present inventors further confirmed that when a specific amount of higher fatty acid bisamide was added as a lubricant to the above-mentioned thermoplastic polyurethane composition, its non-adhesiveness, blocking resistance and releasability were further improved. The present invention has been completed based on the findings and those findings.

That is, the present invention contains a thermoplastic polyurethane (A), a styrene-based elastomer (B), an olefin-based elastomer (C) and a polyolefin resin (D), and the total of (A) to (D) described above. Based on the weight, the thermoplastic polyurethane (A) is 40 to 90% by weight, the styrene elastomer (B) is 5 to 35% by weight, the olefin elastomer (C) is 5 to 25% by weight, and the polyolefin resin (D) is It is a thermoplastic polyurethane composition characterized by being contained in a proportion of 5 to 15% by weight. Then, in the present invention, based on the total weight of the thermoplastic polyurethane (A), the styrene elastomer (B), the olefin elastomer (C) and the polyolefin resin (D), the (E) higher fatty acid bisamide is further added to 0.3. ~ 4
The above-mentioned thermoplastic polyurethane composition, which is contained in a weight percentage, is included as a preferred embodiment.

Further, the present invention provides a molded article such as a film, a sheet or a molded article, which comprises the above thermoplastic polyurethane composition, and a film-like or sheet-like laminate having the thermoplastic polyurethane composition as a surface layer. Including the body.

The thermoplastic polyurethane (A) used in the thermoplastic polyurethane composition of the present invention (hereinafter simply referred to as "polyurethane composition") is a thermoplastic polyurethane obtained by the reaction of a polymeric diol, an organic diisocyanate and a chain extender. is there. Examples of the polymer diol that constitutes the thermoplastic polyurethane include polyester diol, polyether diol, polyester ether diol, polycarbonate diol, polyester polycarbonate diol, etc. These may be used alone or in combination of two or more. You may use together.

As the polyester diol in this case, a polyester diol obtained by reacting an aliphatic dicarboxylic acid, an aromatic dicarboxylic acid or an ester-forming derivative thereof with a low molecular weight diol, and a polyester diol obtained by ring-opening polymerization of a lactone. Any of these can be used. More specifically, examples of the above-mentioned polyester diol include aliphatic dicarboxylic acids having 6 to 10 carbon atoms such as glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, and dodecanedioic acid, and terephthalic acid. One or more of aromatic dicarboxylic acids such as acid, isophthalic acid, orthophthalic acid or their ester-forming derivatives, and an aliphatic diol having 2 to 10 carbon atoms (for example, ethylene glycol, propylene glycol, 1,4 -Butanediol, 1,5-pentanediol, 3-methyl-1,5-pentanediol,
1,6-hexanediol, 1,9-nonanediol,
2-methyl-1,8-octanediol and the like), and a polyester diol obtained by polycondensation reaction with one or more of them, and further polycaprolactone diol, polyvalerolactone diol and the like.

As the polyether diol, for example, polyethylene glycol, polypropylene glycol, polytetramethylene ether glycol or the like can be used. Furthermore, examples of the above-mentioned polycarbonate diol include 1,4-butane diol and 1,5-butane diol.
Pentanediol, 1,6-hexanediol, 1,8
There may be mentioned polycarbonate diols obtained by reacting one or two kinds of aliphatic diols such as octane diol with a carbonic acid ester such as diphenyl carbonate or alkyl carbonate or phosgene.

Further, the above-mentioned polymer diol constituting the thermoplastic polyurethane (A) has a number average molecular weight of 100.
It is preferable that the polyurethane composition has a mechanical property, heat resistance, cold resistance, elastic recovery, etc. of 0 to 6000. Here, the number average molecular weight of the polymeric diol as referred to herein is the number average molecular weight calculated based on the hydroxyl value measured by SITE according to JIS K-1557.

The type of organic diisocyanate used for producing the thermoplastic polyurethane (A) is not particularly limited, and any of the organic diisocyanates conventionally used for producing ordinary thermoplastic polyurethane can be used.
One or more of aromatic diisocyanates, alicyclic diisocyanates and aliphatic diisocyanates having a molecular weight of 500 or less are preferably used. Examples of organic diisocyanates include 4,4′-diphenylmethane diisocyanate, toluene diisocyanate, p-phenylene diisocyanate, naphthalene diisocyanate,
Examples thereof include hydrogenated 4,4'-diphenylmethane diisocyanate and isophorone diisocyanate, and among them, 4,4'-diphenylmethane diisocyanate is preferable.

As the chain extender used in the production of the thermoplastic polyurethane (A), any chain extender conventionally used in the production of ordinary thermoplastic polyurethanes can be used, and the type thereof is particularly Not limited. Among them, it is preferable to use one kind or two or more kinds of the aliphatic diol, the alicyclic diol and the aromatic diol as the chain extender, and specific examples thereof include ethylene glycol, diethylene glycol and 1,4-butanediol. , 1,5-pentanediol, 2-methyl-1,3-
Propanediol, 1,6-hexanediol, neopentyl glycol, 1,9-nonanediol, cyclohexanediol, cyclohexanedimethanol, 1,4
There may be mentioned diols such as -bis (β-hydroxyethoxy) benzene. Among the above, an aliphatic diol having 2 to 6 carbon atoms is preferably used as the chain extender, and 1,4-butanediol is more preferable.

The thermoplastic polyurethane (A) used in the polyurethane composition of the present invention is the above-mentioned polymer diol:
Chain extender = 1: 0.2 to 8.0, and [total mole number of polymer diol and chain extender]: [mol number of organic diisocyanate] = 1: 0.98 to 1: 1 It is preferably a polyurethane obtained by reacting a polymer diol, an organic diisocyanate and a chain extender in a range of 10.10. When such a thermoplastic polyurethane (A) is used, when a molding such as extrusion molding is carried out using the polyurethane composition of the present invention, a rapid increase in melt viscosity is eliminated, and a molded article having good moldability can be produced. In addition, the heat resistance of the obtained molded product becomes good.

The thermoplastic polyurethane (A) preferably has a hardness (JIS A hardness) of 55 to 85. When the hardness of the thermoplastic polyurethane (A) is less than 55, the mechanical properties of the molded product obtained from the polyurethane composition are likely to deteriorate, while when it exceeds 85, the flexibility of the molded product obtained from the polyurethane composition is increased. It tends to decrease.

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

As the styrene elastomer (B) used in the polyurethane composition of the present invention, any of the styrene elastomers known before the present application can be used. As a preferable example of the styrene elastomer (B), a styrene elastomer comprising a block copolymer of a vinyl aromatic compound and a conjugated diene and / or a non-aromatic nuclear double bond thereof is partially or completely hydrogenated. Those are preferably used. In that case, the molecular structure of the block copolymer may be linear, branched or radial. The block copolymer preferably contains 5 to 50% by weight of a vinyl aromatic compound unit and has a linear structure, and the distribution state of the vinyl aromatic compound in the block copolymer. May be random, tapered, partially block-shaped, or a mixed type thereof. Preferred examples of the vinyl aromatic compound in the styrene elastomer (B) composed of a block copolymer of a vinyl aromatic compound and a conjugated diene include styrene, α-methylstyrene, and benzene nucleus substituted with alkyl and / or halogen. Examples thereof include styrene, and styrene is particularly preferable. Further, examples of the conjugated diene include 1,3-butadiene, 2-methyl-1,3-butadiene (also known as isoprene), 1,3-pentadiene, and 2,3-dimethyl-.
1,3-butadiene, 2-neopentyl-1,3-butadiene, 2-chloro-1,3-butadiene and the like can be mentioned, and 1,3-butadiene and / or 2-methyl-1,3-butadiene are preferable.

The styrene elastomer (B) used in the polyurethane composition of the present invention has a melt flow rate (MI; 190 ° C., 2.16 kg load) of 1 to 1.
5 g / min and hardness (JIS A hardness) of 30 to 80
Is preferable in terms of elastic recovery and flexibility.

As the olefinic elastomer (C) used in the polyurethane composition of the present invention, any of the olefinic elastomers known before this application can be used. For example, ethylene-propylene copolymer rubber (EPM); ethylene- Propylene-diene copolymer rubber (EPD
M); an olefin elastomer comprising a hard segment of polyethylene and / or polypropylene and a soft segment of EPM and / or EPDM; a hard segment of polyethylene and a soft ethylene-vinyl acetate copolymer and / or ethylene-ethyl acrylate copolymer Elastomer consisting of segments; Butyl rubber;
An elastomer in which the cross-linking point is a metal ion bond and the soft segment is non-crystalline polyethylene can be used.

Among them, as the olefin elastomer (C), EPDM or an olefin elastomer comprising a hard segment of polyethylene and / or polypropylene and a soft segment of EPM and / or EPDM is preferable. Hard segment of polyethylene and / or polypropylene and EPM and / or
Alternatively, in the above-mentioned olefinic elastomer composed of a soft segment of EPDM, even if the hard segment and the soft segment are bonded in the form of a block copolymer,
Alternatively, it may be in a blended form. When the hard segment and the soft segment are in a blended form, both segments are simply mixed, a simple blend type, a partially crosslinked type that is partially crosslinked by a crosslinking agent such as peroxide, or a crosslinking such as peroxide. It may be a completely crosslinked type in which the agent is completely crosslinked. In the olefin elastomer composed of EPDM or the above olefin elastomer having EPDM as the soft segment, the diene compound constituting EPDM is ethylidene norbornene, 1,
One or more of 4-hexadiene and dicyclopentadiene are preferably used.

The olefin elastomer (C) used in the polyurethane composition of the present invention has a melt flow rate (MI; 230 ° C., 10 kg load) of 10 to 6.
0 g / min and hardness (JIS A hardness) of 50 to 80
Is preferable from the viewpoints of blocking resistance and flexibility.

Further, as the polyolefin resin (D) used in the polyurethane composition of the present invention, low density polyethylene, high density polyethylene, polypropylene and the like are preferably used, and among them, high density polyethylene is more preferable. The polyolefin resin (D) used in the polyurethane composition of the present invention has a melt flow rate (MI; 190 ° C., 2.16 kg load) of 0.02-1.
5 g / min and hardness (JIS A hardness) of 40 to 85
Is preferable from the viewpoints of blocking resistance and flexibility.

In the polyurethane composition of the present invention, the thermoplastic polyurethane (A), the styrene elastomer (B), the olefin elastomer (C) and the polyolefin resin (D) are added based on the total weight of the thermoplastic polyurethane (A). 40 to 90% by weight of A), 5 to 35% by weight of styrene elastomer (B), 5 to 25% by weight of olefin elastomer (C) and 5 to 15% by weight of polyolefin resin (D). It is necessary that the thermoplastic polyurethane (A) is
90% by weight, 5-25 styrene elastomer (B)
% By weight, 5 to 15% by weight of olefin elastomer (C) and 5 to 10% by weight of polyolefin resin (D).
It is preferable to contain it in a ratio of.

In the polyurethane composition of the present invention, when the content of the thermoplastic polyurethane (A) is less than 40% by weight, the polyurethane composition has various excellent properties inherent to the thermoplastic polyurethane (especially abrasion resistance, strength, Flexibility etc.)
On the other hand, when it exceeds 90% by weight, the polyurethane composition exhibits tackiness and blocking properties, making it difficult to wind or rewind the film or sheet, and to separate the molded product from the mold or the like. Mold becomes difficult. Also,
When the content of the styrene-based elastomer (B) is less than 5% by weight or more than 35% by weight, the polyurethane composition becomes tacky and blocking,
This makes it difficult to wind or rewind the film or sheet, it becomes difficult to release the molded product from the mold, the surface is roughened, and the mechanical properties are deteriorated.

Further, if the content of the olefinic elastomer (C) in the polyurethane composition is less than 5% by weight, the polyurethane composition will have tackiness and blocking property, and the film or sheet will be wound or unwound. ,
It becomes difficult to release the molded product from the mold, etc. On the other hand, if it exceeds 25% by weight, the surface of the molded product such as the film may be roughened, or the molded product loses its flexibility, and the physical properties (particularly strength) deteriorate Occurs. Further, when the content of the polyolefin resin (D) in the polyurethane composition is less than 5% by weight, tackiness and blocking property occur, so that film, sheet or the like can be wound, unwound, or molded from a mold. On the other hand, if it exceeds 15% by weight, the surface of the molded product such as a film is roughened, and the mechanical properties such as tensile breaking strength and tensile breaking elongation of the molded product are deteriorated.

Further, the polyurethane composition of the present invention has a higher grade based on the total weight of the above-mentioned thermoplastic polyurethane (A), styrene elastomer (B), olefin elastomer (C) and polyolefin resin (D). The fatty acid bisamide (E) is preferably contained in a proportion of 4% by weight or less, more preferably the higher fatty acid bisamide (E) is contained in a proportion of 0.3 to 4% by weight,
More preferably, the content is 1 to 3% by weight. By containing the higher fatty acid bisamide (B) in the above proportion, the non-adhesiveness, blocking resistance and releasability of the polyurethane composition are further improved. When the content of the higher fatty acid bisamide (E) exceeds 4% by weight, the blocking resistance and the releasing property are improved, but the higher fatty acid bisamide bleeds out on the surface of the film, sheet or other molded product to deteriorate the surface condition. To do.

The higher fatty acid bisamide (E) used in the polyurethane composition of the present invention is a higher fatty acid obtained by the reaction of a saturated higher fatty acid having 14 to 35 carbon atoms and an aliphatic diamine having 1 to 10 carbon atoms. Bisamide is preferred. Examples of saturated higher fatty acids in that case 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, and the like, and examples of aliphatic diamines include methylenediamine, ethylenediamine, trimethylenediamine,
Tetramethylenediamine, pentamethylenediamine, hexamethylenediamine, 1,7-diaminoheptane,
1,8-diaminooctane, 1,9-diaminononane,
1,10-diaminodecane and the like can be mentioned.
Among the higher fatty acid bisamides obtained by the reaction of the above saturated higher fatty acids and aliphatic diamines, methylenebisstearic acid amide, ethylenebisstearic acid amide, tetramethylenebisstellaric acid amide, hexamethylenebisstearic acid amide, ethylene Bismontanic acid amide, tetramethylenebismontanic acid amide, and hexamethylenebismontanic acid amide are preferable, and methylenebisstearic acid amide and / or ethylenebisstearic acid amide are more preferably used.

The polyurethane composition of the present invention contains, in addition to the above-mentioned components, an antioxidant, an ultraviolet absorber, and
One or more additives such as pigments, fillers, antistatic agents, plasticizers, flame retardants, and antifungal agents may be contained in an amount within the range that does not impair the effects of the present invention.

The method for producing the polyurethane 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, thermoplastic polyurethane (A), styrene-based elastomer (B), olefin-based elastomer (C), polyolefin resin (D), and, if necessary, higher fatty acid bisamide (E) and other additives for mixing the polymer. After premixing with the above-mentioned predetermined ratio using a vertical type or horizontal type mixer which is usually used, a single-screw extruder, a twin-screw extruder, a mixing roll, a Banbury mixer or the like is used in a batch type or a continuous type. It is manufactured by kneading under heating. When heat kneading is performed using an extruder, the polyurethane composition of the present invention may be manufactured by melt-kneading, extruding into a strand shape, and then cutting into a suitable length to form granules such as pellets. In addition to the above method, thermoplastic polyurethane (A)
A styrene-based elastomer (B), an olefin-based elastomer (C), a polyolefin resin (D), and, if necessary, a higher fatty acid bisamide (E) and other additives are added during the polymerization of The polyurethane composition of the present invention may be produced by a method of extruding a product into a strand shape and then cutting it into an appropriate length to form a pellet or other granular material. Further, the thermoplastic polyurethane (A), the styrene elastomer (B), the olefin elastomer (C), the polyolefin resin (D), and, if necessary, the higher fatty acid bisamide (E) without producing pellets of the polyurethane composition. ) And other additives are preliminarily dry-blended, and then the blended product is directly supplied to a molding machine such as an extrusion molding machine, melt-kneaded, and extrusion-molded to directly produce a molded product.

The polyurethane composition of the present invention is thermoplastic and can be melt-molded and heat-processed, extruded,
Various molded products can be smoothly manufactured by any molding method such as injection molding, blow molding, calendar molding, and casting. In particular, when a film, sheet or the like is produced from the polyurethane composition of the present invention using a T-die type extrusion molding machine or an inflation extrusion molding machine, the polyurethane composition has non-adhesiveness, blocking resistance, and releasability. However, since blocking does not occur between the extruded film and sheet, without using release paper,
It can be directly extruded and wound up, and the wound film or sheet can be easily rewound. Even when a molded article is manufactured by injection molding or other molding, the polyurethane composition of the present invention is non-adhesive and has excellent mold release property, so that molding can be performed without applying a mold release agent to the inner surface of the mold. The product can be easily demolded, and the amount of release agent used and the number of times it is applied to the inner surface of the mold are reduced compared to conventional thermoplastic polyurethane molding even if a release agent is used. be able to.

Furthermore, the polyurethane composition of the present invention is also suitable for producing a laminate with a substrate made of a non-woven fabric or other fiber cloth, or a substrate made of another polymer film or sheet. Even when the polyurethane composition of the invention is melt-extruded in the form of a film or a sheet onto a fiber cloth or other substrate to produce a laminate, the surface layer made of the polyurethane composition has non-adhesiveness and releasability. Since it is excellent and does not cause blocking, such a film-shaped or sheet-shaped laminated body can be smoothly wound, and the wound laminated body can be easily rewound. A laminate obtained by laminating the polyurethane composition of the present invention on a fiber cloth can be effectively used for applications such as synthetic leather.

Films, sheets, molded articles such as molded articles obtained by using the polyurethane composition of the present invention, and the above-mentioned laminates are excellent in mechanical properties represented by tensile breaking strength and tensile breaking elongation. In addition, since it has a smooth surface and the surface condition is also good, it is used as a stretchable film for sanitary use, paper diapers, sealing, dustproof, general-purpose conveyor belts, various keyboard sheets, It can be effectively used for various applications such as laminated products, seats for various containers, and shoe soles for sports shoes and ski shoes.

[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, as the thermoplastic polyurethane (A), styrene elastomer (B), olefin elastomer (C), polyolefin resin (D) and (E) higher fatty acid bisamide, the following ones were used.

<Thermoplastic Polyurethane (A)> ○ PU-1 (abbreviation): Polyester thermoplastic polyurethane [Kuraray Co., Ltd. "Kuramiron U 2175"; hardness (JIS A hardness) 75] (number average molecular weight 2000 Polybutylene adipate diol, 4,4′-diphenylmethane diisocyanate and 1,4-butane diol are thermoplastic polyurethanes obtained by reacting them in a molar ratio of 1.0: 2.3: 1.3) PU-2 ( PU-2 ) Abbreviation): Polyether thermoplastic polyurethane [Kuraray Co., Ltd. "Kuramiron U 9185"; hardness (JIS A hardness) 85] (polytetramethylene ether glycol having a number average molecular weight of 1000, 4,4'-diphenylmethane diisocyanate and 1 , 4-butanediol at a molar ratio of 1.0: 2.2: 1.2 Thermoplastic polyurethane) PU-3 (abbreviation): polyester-based thermoplastic polyurethane [as described in Example 5 below, polycaprolactone diol having a number average molecular weight of 2000, 4,4'-
Thermoplastic polyurethane obtained by reacting diphenylmethane diisocyanate and 1,4-butanediol in a molar ratio of 1: 2.5: 1.5 (hardness (JIS A hardness 75)]

<< Styrene-based elastomer (B) >> SIS (abbreviation): Styrene-butadiene block copolymer elastomer [JSR-SIS manufactured by Japan Synthetic Rubber Co., Ltd.
5000 ", styrene content 15% by weight, MI = 2 g /
10 minutes (190 ° C, 2.16kg load), hardness (JIS
A hardness) 38] << Olefin Elastomer (C) >> ○ TPO (abbreviation): Partially cross-linked olefin elastomer consisting of EPDM and polypropylene [Mitsui Petrochemical Co., Ltd. "Miralastomer 7030N", MI = 40 g / 10
Minute (230 ° C., 10 kg load), hardness (JIS A hardness) 65] << Polyolefin resin (D) >> ○ HDPE (abbreviation): high density polyethylene [Mitsui Petrochemical's "high density polyethylene 7000F", MI =
0.05 g / 10 minutes (190 ° C, 2.16 kg load),
Hardness (JIS A hardness)] << Higher fatty acid bisamide (E) >> HABA (abbreviation): Ethylenebisstearic acid amide (NOF Corporation “Alflo 50S”, melting point 140-1)
45 ° C)

In the following Examples and Comparative Examples, the blocking resistance, tensile breaking strength and tensile breaking elongation, and surface condition of the film were measured or evaluated as follows.

<Blocking resistance of film> In the following Examples and Comparative Examples, a film (length: 5 m) extruded from a T-die and wound into a roll was wound, left standing for 24 hours, and then manually. The film was rewound and the degree of blocking between films at that time was evaluated according to the evaluation criteria shown in Table 1 below.

[0038]

[Table 1]  Evaluation of film blocking resistance ○: No blocking occurred between the wound films.
It can be easily and smoothly rewound. Δ: Blocking occurred between the wound films
However, it is possible to rewind by applying force.
It X: The blocking between the wound films is large and the force is high.
It is impossible to rewind even if adding.

<< Tensile Breaking Strength and Tensile Breaking Elongation >> A tensile test was conducted according to JIS K 7311 using the films produced by extrusion molding from a T-die in the following Examples and Comparative Examples, and before the test. The elongation from the marked distance was taken as the tensile breaking elongation, and the stress at break was taken as the breaking strength.

<Surface Condition> In the following Examples and Comparative Examples, the surface condition of the film produced by extrusion molding from a T-die was observed with the naked eye, and a film having no unevenness and having a smooth surface was marked with a circle. Those having irregularities and not smooth were evaluated as x.

Examples 1 to 4 and Comparative Examples 1 to 8 (1) Thermoplastic polyurethane (A) (PU-1 or PU-2), styrene elastomer (B) (SI)
S), olefinic elastomer (C) (TPO), polyolefin resin (D) (HDPE) and higher fatty acid bisamide (E) (HABA) are dry blended at the weight ratios shown in Table 2 below, and then the extruder [ Single screw extruder "GT-25" (φ25mm, manufactured by Plastic Engineering Laboratory)
L / D = 25) (cylinder temperature; supply part 175 ° C., compression part 190 ° C., metering part 200 ° C .; die temperature 200 ° C.), melt kneading, and then cooling roll from the T die (surface temperature 30 ° C. ) It is extruded on top and cooled down to 2.6 m /
The film was wound at a winding speed of a minute and a constant winding tension (using a powder brake) to produce a film having a thickness shown in Table 2 below. (2) The blocking resistance, the tensile breaking strength and the tensile breaking elongation, and the surface state of the film obtained in (1) above were measured or evaluated by the methods described above, and the results shown in Table 2 below were obtained. there were.

Example 5 and Comparative Example 9 (1) Polybutylene adipate diol having a number average molecular weight of 2000 (hereinafter referred to as POH) and 1,4-
Butanediol (hereinafter referred to as BD) 1: 1.3
And a mixture heated to 30 ° C at a molar ratio of 50 ° C
4,4′-diphenylmethane diisocyanate (hereinafter referred to as MDI) heated and melted in POH: BD:
The MDI molar ratio was set to a ratio of 1: 2.3: 1.3, and the mixture was continuously charged into a twin-screw type extruder rotating in the same direction with a metering pump to carry out a continuous melt polymerization reaction. Thermoplastic polyurethane (PU-3) [Hardness (JIS
A hardness) 75] was manufactured. At that time, the temperature of the intermediate portion (polymerization portion), which was the highest temperature when the inside of the twin-screw extruder was divided into three zones of a front portion, an intermediate portion and a rear portion, was 240 ° C. In addition, a styrene-based elastomer (B) (SIS), an olefin-based elastomer (C) (TPO), a polyolefin resin (D) (HD) are supplied from a supply port provided in the rear portion of the twin screw type extruder.
PE) and higher fatty acid bisamide (E) (HABA)
Was supplied at a weight ratio shown in Table 2 below, melt-kneaded, and then continuously extruded into water in a strand form, and then pelletized using a pelletizer. (2) Using the pellets of the polyurethane composition obtained in (1) above, using the same extruder as used in Examples 1 to 4 above, in the same manner as in Examples 1 to 4. T
The film was extruded from a die onto a cooling roll and then wound to manufacture a film having a thickness shown in Table 2 below. (3) When the blocking resistance, the tensile breaking strength and the tensile breaking elongation, and the surface state of the film obtained in (2) above were measured or evaluated by the above-mentioned methods, the results shown in Table 2 below were obtained. there were.

[0043]

[Table 2]

From the results shown in Table 2 above, the thermoplastic polyurethane (A), styrene elastomer (B), olefin elastomer (C), polyolefin resin (D) and higher fatty acid bisamide (E) are specified in the present invention. When the polyurethane compositions of the present invention of Examples 1 to 5 contained in the above specific proportions are used, the film is non-adhesive and has no blocking, and winding and rewinding are easy and smooth. It can be seen that the film obtained from the polyurethane composition is excellent in mechanical properties such as tensile strength at break and tensile elongation at break, and the surface condition is smooth and good. On the other hand, in the case of the polyurethane compositions of Comparative Examples 1 to 9 lacking one or more of the styrene elastomer (B), the olefin elastomer (C) and the polyolefin resin (D), the film is Is tacky, causes blocking, and is difficult or impossible to rewind (Comparative Examples 1 to 3, Comparative Examples 5 to 6 and Comparative Examples 8 to 9),
Even if the film has no tackiness and can be rewound, the tensile strength at break of the film is extremely small and mechanical properties are remarkably inferior (Comparative Example 4 and Comparative Example 7). It can be seen that they are defective (Comparative Examples 3 to 5, Comparative Example 7 and Comparative Example 9).

[0045]

EFFECT OF THE INVENTION Since the polyurethane composition of the present invention is non-adhesive, and has excellent blocking resistance and release property, release paper is used when producing a film or sheet, a film-like or sheet-like laminate, and the like. You can wind it up without using
The wound film, sheet, laminate or the like can be easily rewound without causing blocking. Further, when the polyurethane composition of the present invention is used for molding or the like, since it is non-adhesive and has excellent mold releasability, it does not adhere to a mold or the like and a mold release agent is formed on the inner surface of the mold. The molded product can be easily taken out from the mold without performing the above, and even when the mold releasing agent is used, the amount of the mold releasing agent used can be greatly reduced as compared with the conventional case. Furthermore, in the polyurethane composition of the present invention, thermoplastic polyurethane (A), styrene elastomer (B), olefin elastomer (C), polyolefin resin (D).
Since the higher fatty acid bisamide (E) used in some cases is well compatible with each other, phase separation and bleed-out of these components do not occur, and mechanical strength represented by tensile strength at break and tensile elongation at break It is possible to obtain a molded product having good characteristics and having a smooth surface state without unevenness and having a high commercial value.

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Claims (6)

[Claims] 1. A thermoplastic polyurethane (A), a styrene elastomer (B), an olefin elastomer (C).
And a polyolefin resin (D), and based on the total weight of (A) to (D) described above, the thermoplastic polyurethane (A) is 40 to 90% by weight, and the styrene elastomer (B) is 5 to 35% by weight. %, 5 to 25% by weight of the olefinic elastomer (C) and 5 to 15% by weight of the polyolefin resin (D), a thermoplastic polyurethane composition. 2. Based on the total weight of the thermoplastic polyurethane (A), the styrene elastomer (B), the olefin elastomer (C) and the polyolefin resin (D), the (E) higher fatty acid bisamide is added in an amount of 0.3 to 0.3. Four
The thermoplastic polyurethane composition according to claim 1, which is contained in a weight percentage. 3. A molded article comprising the thermoplastic polyurethane composition according to claim 1. 4. The molded product according to claim 3, which is a film or a sheet. 5. The molded article is a molded article.
Molded product. 6. A film-shaped or sheet-shaped laminated body having the thermoplastic polyurethane composition according to claim 1 or 2 as a surface layer.