JPH09235461A - Resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a resin composition excellent in moldability and capable of giving moldings excellent in tensile strength and elongation, impact resistance, and abrasion resistance and to provide a molding made therefrom. SOLUTION: This composition comprises 3-90wt.%, based on the total weight of the components, thermoplastic polyurethane (A), 3-30wt.% hydroxyl-terminated polymer (B), and 5-90wt.% polyolefin resin (C) and has a number-average molecular weight of 10,000-150,000. Component B comprises hydrogenated conjugated diene compound units (I) and aromatic vinyl compound units (II) in a molar ratio (I)/(II) of 10/90 to 100/0. A molding made from this composition is also provided.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a thermoplastic polyurethane, a resin composition comprising a polymer having a hydroxyl group at a terminal and a polyolefin resin, and a molded article comprising the resin composition. The resin composition of the present invention is excellent in mechanical strength, impact resistance, wear resistance, and moldability, and is useful as a material for various molded products.

[0002]

2. Description of the Related Art Thermoplastic polyurethane has a mechanical strength,
Since it has many features such as high elasticity, abrasion resistance and oil resistance, it is attracting attention as a substitute material for rubber and plastics, and as a molding material to which ordinary plastics molding methods can be applied, it has a wide range of applications. It is used. However, the conventional thermoplastic polyurethane has very strong adhesiveness (tack property) as compared with other resins and is inferior in moldability. For example, in extrusion molding, a situation in which it is difficult to rewind a film, sheet, tube or the like is likely to occur. Also, in injection molding, the releasability from the mold is poor and the molding cycle becomes long. On the other hand, polyolefin resins such as polyethylene and polypropylene are excellent in molding processability, mechanical properties, water resistance, chemical resistance, etc., but are inferior in flexibility, adhesiveness, printability, low temperature impact resistance, etc. There is. Therefore, in order to improve the respective drawbacks of the thermoplastic polyurethane and the polyolefin resin, attempts have been made to blend these resins.

[0003]

However, since the compatibility between the thermoplastic polyurethane and the polyolefin resin is very poor, for example, even if these are simply melt-kneaded, a product excellent in mechanical strength and moldability can be obtained. Absent. further,
When this resin composition is injection-molded, surface peeling or delamination of the obtained molded product is likely to occur. Also, when extrusion molding is performed, eyelids are likely to be generated in the die. further,
When it is formed into a film, the film tends to have holes.

The object of the present invention is not only that the thermoplastic polyurethane as a constituent component and the polyolefin resin have good compatibility with each other, but also that they have excellent mechanical strength, impact resistance and abrasion resistance, as well as molding. It is to provide a resin composition having excellent processability. Further, another object of the present invention is to provide a molded article made of the above resin composition.

[0005]

As a result of repeated studies by the present inventors to achieve the above object, a specific polymer having a hydroxyl group at a terminal is added to a resin composition composed of thermoplastic polyurethane and a polyolefin resin. By blending
The compatibility of these resins is significantly improved, the mechanical strength,
It was found that a resin composition excellent in impact resistance, abrasion resistance, molding processability, etc. was obtained, and the present invention was completed based on these findings.

That is, the present invention provides a resin composition comprising (i) a thermoplastic polyurethane (A), a polymer having a hydroxyl group at the terminal (B) and a polyolefin resin (C); (ii) (A) ) To (C) based on the total weight of the thermoplastic polyurethane (A) is 3 to 90% by weight, the polymer having a hydroxyl group at the end (B) is 3 to 30% by weight, and the polyolefin resin (C) is 5%. And (iii) the polymer (B) having a hydroxyl group at the terminal is composed of a hydrogenated conjugated diene compound unit (I) and an aromatic vinyl compound unit (II). Unit (I) / Structural unit (I
The resin composition is characterized in that the molar ratio of I) is 10/90 to 100/0 and the number average molecular weight is 10,000 to 150,000.

In the present invention, higher fatty acid bisamide (D) is further added based on the total weight of thermoplastic polyurethane (A), polymer having terminal hydroxyl group (B) and polyolefin resin (C). The present invention relates to the above-mentioned resin composition containing 3 to 5% by weight. Furthermore, the present invention relates to a molded article made of the above resin composition.

[0008]

BEST MODE FOR CARRYING OUT THE INVENTION The thermoplastic polyurethane (A) used in the present invention is substantially obtained by reacting a polymeric diol, an organic diisocyanate and a chain extender.

The polymer diol is preferably an ester polymer diol such as polyester diol, polycarbonate diol or polyester polycarbonate diol; or an ether polymer diol such as polyether diol. The number average molecular weight of the high molecular diol is 9
It is preferably from 00 to 6,000, and from 1,000 to
More preferably, it is 6,000. The number average molecular weight of the high molecular weight diols referred to in this specification is JIS
It is the number average molecular weight calculated based on the hydroxyl value measured according to K 1577.

The above-mentioned polyester diol can be obtained, for example, by subjecting a dicarboxylic acid or an ester-forming derivative such as an ester or anhydride thereof and a low-molecular diol to a direct esterification reaction or transesterification reaction according to a conventional method.

Examples of the dicarboxylic acid used as a raw material for producing the polyester diol include glutaric acid,
Adipic acid, pimelic acid, suberic acid, azelaic acid,
Sebacic acid, dodecanedicarboxylic acid, 2-methylsuccinic acid, 2-methyladipic acid, 3-methyladipic acid, 3
-Methylpentanedioic acid, 2-methyloctanedioic acid, 3,
C5-C12 aliphatic dicarboxylic acids such as 8-dimethyldecanedioic acid and 3,7-dimethyldecanedioic acid; aromatic dicarboxylic acids such as terephthalic acid, isophthalic acid, orthophthalic acid, and the like. Among these, 1 type (s) or 2 or more types can be used. Among these, it is preferable to use an aliphatic dicarboxylic acid having 5 to 12 carbon atoms, and it is more preferable to use adipic acid, azelaic acid, or sebacic acid.

Examples of the low molecular weight diol component used as a raw material for producing polyester diol include ethylene glycol, 1,3-propanediol, 2-methyl-1,3-propanediol, 1,4-butanediol and neopentyl. Glycol, 1,5-pentanediol, 3-methyl-1,5-pentanediol, 1,6-
Aliphatic diols such as hexanediol, 1,8-octanediol, 2-methyl-1,8-octanediol, 1,9-nonanediol and 1,10-decanediol; cycloaliphatic rings such as cyclohexanedimethanol and cyclohexanediol Formula diol etc. can be mentioned, and 1 type (s) or 2 or more types can be used among these.
Among these, it is preferable to use an aliphatic diol having 4 to 12 carbon atoms, such as 1,4-butanediol and 3-
Methyl-1,5-pentanediol, 2-methyl-1,
It is more preferable to use 8-octanediol or 1,9-nonanediol.

The above-mentioned polycarbonate diol can be obtained, for example, by reacting a low molecular weight diol with a carbonate compound such as dialkyl carbonate, alkylene carbonate or diaryl carbonate. As the low-molecular diol which is a raw material for producing a polycarbonate diol, the low-molecular diol exemplified above as a raw material for producing a polyester diol can be used. Examples of the dialkyl carbonate include dimethyl carbonate and diethyl carbonate, examples of the alkylene carbonate include ethylene carbonate, and examples of the diaryl carbonate include diphenyl carbonate.

The above polyester polycarbonate diol can be obtained, for example, by simultaneously reacting a low molecular weight diol, a dicarboxylic acid and a carbonate compound. Alternatively, it can be obtained by previously synthesizing a polyester diol and a polycarbonate diol by the above-mentioned method and then reacting them with a carbonate compound or with a diol and a dicarboxylic acid.

As the polyether diol, for example,
Polyethylene glycol, polypropylene glycol,
Examples thereof include polytetramethylene glycol, and one or more of these can be used. Among these, it is preferable to use polytetramethylene glycol.

The type of organic diisocyanate used for producing the thermoplastic polyurethane (A) is not particularly limited,
Although any of the organic diisocyanates conventionally used for the production of ordinary thermoplastic polyurethanes can be used, one or more of aromatic diisocyanates, alicyclic diisocyanates and aliphatic diisocyanates having a molecular weight of 500 or less can be used. Preferably used. Examples of organic diisocyanates include 4,4′-diphenylmethane diisocyanate, p-phenylene diisocyanate,
Xylylene diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate, tolylene diisocyanate, 1,5-naphthylene diisocyanate,
4,4'-dicyclohexylmethane diisocyanate and the like can be mentioned, and one or more of these can be used. Among these, 4,4'-
Preference is given to using diphenylmethane diisocyanate. In addition, a tri- or more functional polyisocyanate such as triphenylmethane triisocyanate can be used in a small amount as necessary.

The type of chain extender used for producing the thermoplastic polyurethane (A) is not particularly limited, and any chain extender conventionally used for producing ordinary thermoplastic polyurethane can be used. Molecular weight 3 having two or more active hydrogen atoms capable of reacting with an isocyanate group in the molecule
It is preferable to use a low-molecular compound of not more than 00. For example, ethylene glycol, propylene glycol, 1,
4-butanediol, 1,6-hexanediol, 1,
4-bis (β-hydroxyethoxy) benzene, 1,4
Cyclohexanediol, bis- (β-hydroxyethyl) terephthalate, xylylene glycol and other diols; hydrazine, ethylenediamine, propylenediamine, xylylenediamine, isophoronediamine,
Diamines such as piperazine and its derivatives, phenylenediamine, tolylenediamine, xylenediamine, adipic acid dihydrazide, isophthalic acid dihydrazide;
Examples thereof include amino alcohols such as amino ethyl alcohol and amino propyl alcohol, and one or more of them can be used. Among these, it is preferable to use an aliphatic diol having 2 to 10 carbon atoms, and it is more preferable to use 1,4-butanediol.

The amount of the chain extender used is not particularly limited and can be appropriately selected depending on the hardness to be imparted to the polyurethane, etc. Usually, it is usually per 1 mol of the polymer diol.
It is preferably used in a proportion of 0.1 to 10 mol,
It is more preferable to use it in a ratio of 3 to 7 mol.

In producing the thermoplastic polyurethane (A), the above-mentioned polymer diol, organic diisocyanate and chain extender are added to the following formula (1); 1.00≤b / (a + c) ≤1.10 (1 (In the formula, a is the number of moles of the polymeric diol, b is the number of moles of the organic diisocyanate, and c is the number of moles of the chain extender). By using a thermoplastic polyurethane obtained by reacting a polymer diol, an organic diisocyanate and a chain extender within the above range, a resin composition having more excellent mechanical performance, impact resistance, abrasion resistance and molding processability. Is obtained.

In producing the thermoplastic polyurethane (A) using the above-mentioned polymer diol, organic diisocyanate and chain extender, it is preferable to use a tin-based urethane-forming catalyst having catalytic activity for the urethane-forming reaction. . When the tin-based urethane-forming catalyst is used, the molecular weight of polyurethane is rapidly increased, and polyurethane having various better physical properties can be obtained. Examples of the tin-based urethane-forming catalyst include dialkyltin diacetate, dialkyltin diacylate such as dibutyltin dilaurate, and dialkyltin bismercaptocarboxylic acid ester salt such as dibutyltin bis (3-mercaptopropionic acid ethoxybutyl ester) salt. be able to. The amount of these tin-based urethane-forming catalysts used is polyurethane (that is, the polymer diol used for producing polyurethane,
0.5 to 15 p in terms of tin atom, based on the total weight of the reactive raw material compounds such as organic diisocyanate and chain extender.
pm is preferred.

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

The inherent viscosity of the thermoplastic polyurethane (A) is dissolved in an N, N-dimethylformamide solution containing 0.05 mol / liter of n-butylamine so that the concentration of the thermoplastic polyurethane is 0.5 g / dl. Then 3
It is preferably 0.5 to 2.0 dl / g, and more preferably 0.8 to 1.9 dl / g, when measured at 0 ° C. When a thermoplastic polyurethane having a logarithmic viscosity in the range of 0.5 to 2.0 dl / g is used, the mechanical performance,
It is preferable because a resin composition having good abrasion resistance and non-adhesiveness can be obtained.

The polymer (B) having a hydroxyl group at the terminal used in the present invention comprises a hydrogenated conjugated diene compound unit (I) and an aromatic vinyl compound unit (II),
Structural unit (I) / structural unit (II) molar ratio is 10/90
˜100 / 0, preferably 20/80 to 95/5. By using the polymer (B) in which the content ratio of the structural unit (I) and the structural unit (II) is within the above range, a resin composition having good compatibility and excellent mechanical performance, abrasion resistance and the like can be obtained. can get.

As the conjugated diene compound unit (I) constituting the polymer (B), for example, isoprene, 1,3-butadiene, 2,3-dimethyl-1,3-butadiene,
Examples thereof include units derived from 1,3-pentadiene, 1,3-hexadiene and the like, and one or more of these may be contained. Among these, units derived from isoprene and 1,3-butadiene are preferable. Specific examples of the unit derived from isoprene include a 2-methyl-2-butene-1,4-diyl group [—CH ₂ —C (CH ₃ ) ═CH—CH ₂ —; 1,4-bond Isoprene unit], an isopropenylethylene group [-
_{CH {C (CH 3) =} CH 2} -CH 2 -; 3,4- bond of isoprene units], 1-methyl-1-vinyl ethylene group _{[-C (CH 3) (CH =} CH 2) -CH _2- ; 1,2
-Bonding isoprene unit]. 1,
Specific examples of the unit derived from 3-butadiene include a vinylethylene group [—CH (CH═CH ₂ ) —CH ₂
-; 1,2-bond butadiene unit], 2-butene 1,
4-diyl group _{[-CH 2 -CH = CH-CH 2} -; 1,4
-Bonded butadiene unit].

The aromatic vinyl compound unit (II) constituting the polymer (B) is, for example, styrene, α-methylstyrene, o-methylstyrene, m-methylstyrene,
Examples thereof include units derived from p-methylstyrene, 2,4-dimethylstyrene, vinylnaphthalene, vinylanthracene, and the like, and one or more of these may be included. Of these, units derived from styrene are preferred.

The polymer (B) is composed of only a hydrogenated conjugated diene compound unit (I) or a hydrogenated conjugated diene compound unit (I) and an aromatic vinyl compound unit (II). It is a composed polymer. Polymer (B) is hydrogenated conjugated diene compound unit (I)
And the aromatic vinyl compound unit (II), the constitutional unit (I) and the constitutional unit (II) may be arranged in any of a random shape, a block shape, and a tapered block shape. However, from the viewpoint that the obtained resin composition is more excellent in compatibility, molding processability, etc., it is preferable that the respective structural units are arranged in blocks. That is, a block copolymer containing at least one polymer block composed of the hydrogenated conjugated diene compound unit (I) and at least one polymer block composed of the aromatic vinyl compound unit (II) is preferable.

Hydrogenated conjugated diene compound unit (I)
As the polymer block consisting of, it is preferable to use at least one selected from a hydrogenated polyisoprene block, a hydrogenated polybutadiene block and a hydrogenated isoprene / butadiene copolymer block.

The hydrogenated polyisoprene block is
It is a polymer block in which some or all of the unsaturated bonds of polyisoprene mainly composed of units derived from isoprene are hydrogenated to be saturated bonds. In the hydrogenated polyisoprene block, before the hydrogenation, the 1,4-bonded isoprene unit, 3,4-
It is composed of at least one selected from a bonded isoprene unit and a 1,2-bonded isoprene unit, and the ratio of each unit is not particularly limited, but the ratio of the 1,4-bonded isoprene unit is 40 mol% or more. It is preferable that the resin composition obtained has excellent mechanical performance, impact resistance, and abrasion resistance. The hydrogenated polyisoprene block has a number average molecular weight of 8,000 to 10
It is preferably 50,000 because the resulting resin composition is excellent in mechanical performance, moldability and the like.
More preferably, it is 000 to 80,000.

The hydrogenated polybutadiene block is
It is a polymer block in which some or all of the unsaturated bonds of polybutadiene mainly composed of units derived from butadiene are saturated by hydrogenation. In the hydrogenated polybutadiene block, before the hydrogenation, it is preferably 30 to 80 mol%, more preferably 35%.
-60 mol% is the 1,2-bond butadiene unit described above, preferably 70-20 mol%, more preferably 65-40 mol% is the 1,4-bond butadiene unit described above. The proportion of 1,2-bond butadiene units in the hydrogenated polybutadiene block is 30-80.
When the amount is out of the range of mol%, the resulting resin composition has poor impact resistance. The hydrogenated polybutadiene block has a number average molecular weight of 8,000 to 10
It is preferably 50,000 because the resulting resin composition is excellent in mechanical performance, moldability and the like.
More preferably, it is 000 to 80,000.

In the hydrogenated isoprene / butadiene copolymer block, some or all of unsaturated bonds in the isoprene / butadiene copolymer mainly composed of isoprene-derived units and butadiene-derived units are saturated by hydrogenation. It is a polymer block that is a bond. In the hydrogenated isoprene / butadiene copolymer block, before the hydrogenation, the units derived from isoprene are 1,4-bonded isoprene units described above,
It is at least one unit selected from 3,4-bond isoprene units and 1,2-bond isoprene units, and the unit derived from butadiene is the above-mentioned 1,2-bond butadiene unit and / or 1, It is a 4-bond butadiene unit. The ratio of these units in the isoprene / butadiene copolymer block before hydrogenation is not particularly limited, and further, random, block,
It may be in the form of a tapered block. The hydrogenated isoprene / butadiene copolymer block has a number average molecular weight of 8,000 to 10
From the viewpoint of excellent mechanical performance, impact resistance, abrasion resistance and the like of the obtained resin composition, it is preferably 10,000 and more preferably 10,000 to 80,000.

In the present invention, the polymer block comprising the hydrogenated conjugated diene compound unit (I) constituting the polymer (B) is hydrogenated from the viewpoint of the effect of improving the impact resistance of the resin composition. It is preferably composed of at least one of a polyisoprene block and a hydrogenated isoprene / butadiene copolymer block, more preferably an isoprene / butadiene copolymer block. In the case of an isoprene / butadiene copolymer block, the molar ratio of (units derived from isoprene) :( units derived from butadiene) is within the range of 1: 9 to 9: 1 in order to improve impact resistance. Is preferred from 3: 7 to 7:
The range of 3 is more preferable.

The polymer block composed of the aromatic vinyl compound unit (II) constituting the polymer (B) has a number average molecular weight of 2,000 to 50,000. Of the number average molecular weight of 2,500 to 40,000, which is preferable because of its excellent performance and molding processability.
It is more preferably 0.

Preferred polymer (B) used in the present invention
Examples of the block copolymer include the block copolymers represented by the following formulas.

(AB) k-OH ... (BA) l-OH ... A- (BA ') m-OH ... B- (AB') n-OH ... [ In the formula, A and A ′ each independently represent a polymer block composed of an aromatic vinyl compound unit, and B and B ′ each independently represent a polymer block composed of a hydrogenated conjugated diene compound unit, k, l , M and n each independently represent an integer of 1 or more, and —OH represents a hydroxyl group. ]

In the block copolymers represented by the above formulas, k, l, m and n are preferably integers within the range of 1 to 5, and two polymer blocks composed of aromatic vinyl compound units are used. The block copolymer having the above,
It is further preferable in that the impact resistance of the obtained resin composition is further improved. In particular, the triblock copolymer represented by the following formula is preferable.

ABA-A'-OH (wherein A and A'independently represent a polymer block composed of an aromatic vinyl compound unit, and B represents a polymer block composed of a hydrogenated conjugated diene compound unit). It represents a united block, and -OH represents a hydroxyl group. ]

The polymer (B) must contain a hydroxyl group at the terminal. The hydroxyl group content of the polymer (B) is preferably 0.5 or more per molecule, and is 0.7 to
It is more preferable that the number is 2.0. Those having no hydroxyl group at the end cannot sufficiently improve the compatibility between the thermoplastic polyurethane (A) and the polyolefin resin (C), and have mechanical strength, impact resistance, abrasion resistance, etc. A resin composition excellent in heat resistance cannot be obtained.

The number average molecular weight of the polymer (B) is 10,0.
00 to 150,000, 12,500 to 120,
It is preferably 000. By using the polymer (B) having a number average molecular weight in this range, the compatibility between the thermoplastic polyurethane (A) and the polyolefin resin (C) is further improved, and the mechanical properties and abrasion resistance are more excellent. A resin composition is obtained.

The polymer (B) is obtained by, for example, anionic living polymerization using an organic alkali metal catalyst such as butyllithium, to obtain a living polymer composed of the above-mentioned monomer units, and the polymerization active terminal thereof is ethylene oxide or propylene. It is obtained by treating with oxide or the like to introduce a hydroxyl group at the terminal, and then hydrogenating the conjugated diene compound unit using a known method.

The hydrogenation state of the carbon-carbon double bond in the conjugated diene compound unit (I) constituting the polymer (B) may be partially hydrogenated or completely hydrogenated. In view of obtaining a resin composition having more excellent heat deterioration resistance and weather resistance, a carbon-carbon double bond of 50 is obtained.
% Or more is hydrogenated (that is, the degree of unsaturation is 5
It is preferably 0% or less), and 80% or more is hydrogenated (that is, the degree of unsaturation is 20% or less).
Is more preferable.

In the hydrogenation reaction of the conjugated diene compound unit, a homogeneous catalyst or a heterogeneous catalyst can be used as a catalyst. As the homogeneous catalyst, for example, an organic transition metal catalyst (nickel acetylacetonate, cobalt acetylacetonate, nickel naphthenate, cobalt naphthenate, etc.) and an alkyl compound of a metal such as aluminum, an alkali metal or an alkaline earth metal is used. Ziegler catalysts in combination can be mentioned. These catalysts are preferably used in a proportion of 0.01 to 0.1 mol% with respect to the carbon-carbon double bond contained in the conjugated diene compound unit. The hydrogenation reaction is usually at room temperature to
It is carried out at 160 ° C. under a hydrogen pressure of atmospheric pressure to 50 kg / cm ² and is completed in about 1 to 50 hours.

Examples of the polyolefin resin (C) used in the present invention include low density polyethylene, medium density polyethylene, high density polyethylene, polypropylene,
Examples thereof include polybutylene and ethylene / α-olefin copolymer. Examples of the α-olefin include propylene, 1-butene, 2-methyl-1-butene, 3-methyl-1-butene, 1-pentene, 4-methyl-1-pentene, 1-hexene, 1-octene, 1-decane, 1
-Octadecane and the like can be mentioned, and these may be used alone or in combination of two or more kinds. The melt flow rate (MI; 190 ° C., 2.16 kg load) of these polyolefin resins (C) is 0.02 to
It is preferably 30 g / 10 minutes.

The resin composition of the present invention contains 3 parts of the thermoplastic polyurethane (A) based on the total weight of the thermoplastic polyurethane (A), the hydroxyl group-terminated polymer (B) and the polyolefin resin (C). To 90% by weight, a polymer (B) having a hydroxyl group at the terminal in an amount of 3 to 30% by weight, and a polyolefin resin (C) in an amount of 5 to 90% by weight. It is preferable to contain 15 to 90% by weight of (A), 5 to 25% by weight of polymer (B) having a hydroxyl group at the terminal, and 5 to 80% by weight of polyolefin resin (C). .

The content of thermoplastic polyurethane (A) is 3
If less than wt%, the flexibility of the resulting resin composition,
Performances such as mechanical strength, impact resistance, and abrasion resistance deteriorate. 90% by weight of thermoplastic polyurethane (A)
If it exceeds, the resulting resin composition will have tackiness and blocking properties, and therefore winding and unwinding will become difficult when forming into a film. Also,
When injection molding, the molding cycle tends to be long. When the content of the polymer (B) is less than 3% by weight,
Since the compatibility between the thermoplastic polyurethane (A) and the polyolefin resin (C) is poor, the resin peeling phenomenon easily occurs on the surface of the molded product during injection molding. Further, when extrusion molding is performed, the eyelids are likely to be generated on the die. When the content of the polymer (B) exceeds 30% by weight, the compatibility between the thermoplastic polyurethane (A) and the polymer (B) may decrease, and the resulting resin composition may have tackiness. Become. When the content of the polyolefin resin (C) is less than 5% by weight, the non-tackiness of the obtained resin composition is not sufficiently improved. When the content of the polyolefin-based resin (C) exceeds 90% by weight, the compatibility between the thermoplastic polyurethane (A) and the polyolefin-based resin (C) decreases, and various physical properties tend to decrease.

Further, the resin composition of the present invention comprises a thermoplastic polyurethane (A) and a polymer having a terminal hydroxyl group (B).
Further, based on the total weight of the polyolefin resin (C), it is preferable to further contain the higher fatty acid bisamide (D) in a proportion of 0.3 to 5% by weight. By containing the higher fatty acid bisamide (D) in the above proportion, the non-tackiness, compatibility, etc. of the obtained resin composition are further improved, and the one having more excellent mechanical properties can be obtained.

As the higher fatty acid bisamide (D) which can be used in the present invention, those produced from a higher fatty acid having 14 to 35 carbon atoms and an aliphatic diamine having 1 to 10 carbon atoms are preferable. As the higher fatty acid, for example, 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. Can be mentioned. Examples of the aliphatic diamine include methylenediamine, ethylenediamine, trimethylenediamine, tetramethylenediamine, pentamethylenediamine, hexamethylenediamine, 1,7-diaminoheptane, 1,8-diaminooctane, 1,9-diaminononane, 1 , 10-diaminodecane and the like. Among the higher fatty acid bisamides produced from the higher fatty acids and aliphatic diamines, ethylenebisstearic acid amide, tetramethylenebisstearic acid amide, hexanemethylenebisstearic acid amide, ethylenebismontanic acid amide, tetramethylenebismontanic acid amide, Hexamethylenebismontanic acid amide and the like are preferable. These higher fatty acid bisamides may be used alone or in combination of two or more kinds.

Further, if desired, additives such as an ultraviolet absorber, an antioxidant, a plasticizer, an antistatic agent, an antihydrolysis agent, etc. may be used together in an amount within a range that does not adversely affect the effects of the present invention. You can

The resin composition of the present invention comprises the above-mentioned thermoplastic polyurethane (A), a polymer having a hydroxyl group at the terminal (B), a polyolefin resin (C), and optionally a higher fatty acid bisamide (D). It can be manufactured by mixing the additive of 1) by a desired method. For example, using a vertical or horizontal mixer that is usually used for mixing resin materials, after premixing the above components in a predetermined ratio, a uniaxial or biaxial extruder, a mixing roll, a Banbury mixer. It can be produced by melt-kneading under heating in a batch system or a continuous system by using the above.

The resin composition of the present invention can be melt-molded and heat-processed, and extrusion molding, injection molding, blow molding,
By any molding method such as calendar molding, casting,
Various molded products can be smoothly molded.

The resin composition of the present invention is useful as a material for a wide variety of applications such as automobile parts, machine parts, shoe soles, watch bands, packing materials, films, sheets, belts, hoses and tubes.

[0051]

EXAMPLES The present invention will be described below in more detail with reference to examples, but the present invention is not limited to these examples. In Examples and Comparative Examples, the hardness and the logarithmic viscosity of the thermoplastic polyurethane; the tensile strength and elongation of the resin composition, the impact resistance, the abrasion resistance, the surface peeling of the molded product, the non-adhesiveness and the compatibility are as follows. It was measured or evaluated by the method.

[Hardness] Injection molding of thermoplastic polyurethane (cylinder temperature: 180 to 200 ° C., mold temperature: 30)
℃) obtained a diameter of 120mm, thickness 2m
Using two layers of m-shaped discs, JIS
Shore hardness A was determined according to K6301.

[Logarithmic viscosity] 0.05% of n-butylamine
A thermoplastic polyurethane was dissolved in an N, N-dimethylformamide solution containing mol / liter so as to have a concentration of 0.5 g / dl, and the flowing time of the thermoplastic polyurethane solution at 30 ° C. was measured using an Ubbelohde viscometer. Was measured, and the logarithmic viscosity was measured by the following formula. Inherent viscosity _{= {ln (t / t 0} )} / c wherein, t is flow time of the thermoplastic polyurethane solution (in seconds), t _o is flow time of the solvent (sec), c is a thermoplastic polyurethane solution Represents the concentration (g / dl) of. ]

[Tensile Strength and Elongation] Injection molding of a resin composition (cylinder temperature: 180 to 200 ° C., mold temperature: 30 ° C.)
A punching test piece was prepared with a dumbbell No. 3 from a disc-shaped object having a diameter of 120 mm and a thickness of 2 mm obtained by
The tensile strength and tensile elongation were measured according to JIS K 7311.

[Impact resistance] A sheet having a thickness of 120 μ obtained by hot pressing the resin composition at 200 ° C. was measured for impact resistance using a film impact tester.

[Abrasion resistance] A disc-shaped object having a diameter of 120 mm and a thickness of 2 mm obtained by injection molding (cylinder temperature: 180 to 200 ° C., mold temperature: 30 ° C.) of a resin composition is used. , JIS K 7311 (load 1 kg,
The amount of wear was measured 1000 times based on the wear wheel H-22).

[Surface Peeling of Molded Product] Injection molding of a resin composition (cylinder temperature: 180 to 200 ° C., mold temperature: 3)
0 ° C) diameter 120 mm, thickness 2
The surface of the disc-shaped object having a size of mm was observed with the naked eye to examine whether or not peeling had occurred on the surface.

[Non-adhesive] T-die type extruder (25 m
mφ, cylinder temperature: 190 to 200 ° C., die temperature: 200 ° C.) When a film having a thickness of about 38 μ is formed, the film wound without using release paper is rewound to form a film. The degree of blocking resistance during the period was observed and judged according to the following evaluation criteria. (Symbol) (Evaluation Criteria) A: Easy rewinding. ○: Rewinding is possible, but a little tensile force is required for rewinding. X: Rewinding is possible, but rewinding requires a considerable tensile force.

[Compatibility] T-die type extrusion molding machine (25 mm
φ, cylinder temperature: 190-200 ° C, die temperature:
The stretched film having a thickness of 35 μm extruded at 200 ° C.) was observed with the naked eye, and those having a whitening phenomenon were marked with “x” and those not having a whitening phenomenon were marked with “◯”.

The abbreviations for the compounds and polymers used in Examples and Comparative Examples are shown below.

BD : 1,4-butanediol

MDI : 4,4′-diphenylmethane diisocyanate

PNOA : 1,9- nonanediol (N
D), 2-methyl-1,8-octanediol (MO
D) (ND: MOD molar ratio of 65:35) and adipic acid polyester having a number average molecular weight of 2,000

PMPA : number average molecular weight 3,5 consisting of 3-methyl-1,5-pentanediol and adipic acid
00 polyester diol

PBA : Polyester diol having a number average molecular weight of 2,000 and composed of 1,4-butanediol and adipic acid

PTG : Polytetramethylene glycol having a number average molecular weight of 1,000

IP-OH : Hydrogenated product of polyisoprene having a hydroxyl group at the terminal; [number average molecular weight: 20,000, hydroxyl group content: 0.93 per molecule, hydrogenation rate: 9
8%, 1,4-bond in the polyisoprene block before hydrogenation: 91 mol%, 3,4-bond: 9 mol%]

SEP-OH : polystyrene block having a hydroxyl group at the terminal (number average molecular weight: 10,000) /
Polyisoprene block (number average molecular weight: 20,000)
Hydrogenated product of diblock copolymer consisting of 0); [number average molecular weight: 30,000, styrene unit / isoprene unit molar ratio 25/75, hydroxyl group content: 0.8 per molecule
Nine, hydrogenation rate: 97%, 1,4-bond in polyisoprene block before hydrogenation: 90 mol%, 3,4
-Binding: 10 mol%]

SEPS-OH : A polystyrene block having a hydroxyl group at the terminal group (number average molecular weight: 6,000
0) / polyisoprene block (number average molecular weight: 28,
000) / polystyrene block (number average molecular weight: 6,
000) hydrogenated triblock copolymer; [number average molecular weight: 40,000, styrene unit / isoprene unit molar ratio 22/78, hydroxyl group content: 0.89 per molecule, hydrogenation rate : 98%, 1,4-bond amount in the polyisoprene block before hydrogenation: 92 mol%, 3,4-bond amount: 8 mol%]

SEEPS-OH : A polystyrene block having a hydroxyl group at the end (number average molecular weight: 6,000
0) / 1,3-Butadiene and polyisoprene copolymer block (number average molecular weight: 30,000) / polystyrene block (number average molecular weight: 6,000) hydrogenated product of triblock copolymer; [Number average molecular weight: 42,
000, styrene unit / 1,3-butadiene unit and isoprene unit molar ratio 19/81, 1,3-butadiene unit / isoprene unit molar ratio 50/50, hydroxyl group content: 0.80 per molecule, hydrogen Addition rate: 98%,
1,4-in 1,3-butadiene unit before hydrogenation
Bond: 55 mol%, 1,2-bond: 45 mol%, 1,4-bond in isoprene unit before hydrogenation: 95 mol%, 3,4-bond: 5 mol%]

SIS-OH : Polystyrene block (number average molecular weight: 6,000) / polyisoprene block (number average molecular weight: 40,000) having a hydroxyl group at the terminal
/ Polystyrene block (number average molecular weight: 6,000)
Hydrogenated triblock copolymer consisting of [number average molecular weight: 52,000, styrene unit / isoprene unit molar ratio 17/83, hydroxyl group content: 0.89 per molecule
Individual, hydrogenation rate: 85%, 1,4-bond amount in the polyisoprene block before hydrogenation: 55 mol%, 3,4
-Amount of binding: 45 mol%]

SEP : Hydrogenated product of diblock copolymer having no hydroxyl group at the terminal and comprising polystyrene block (number average molecular weight: 11,000) -polyisoprene block (number average molecular weight: 20,000); Average molecular weight:
31,000, styrene unit / isoprene unit molar ratio 27/73, hydrogenation rate: 98%, 1,4-bond in polyisoprene block: 93 mol%, 3,4-bond: 7 mol%]

PP : Polypropylene (MI: 5 g / 1
0 minutes)

PE : High density polyethylene (MI: 0.
05g / 10 minutes)

EPR : ethylene-propylene copolymer (propylene content: 22% by weight, MI: 0.9 g / 10
Minutes)

EBSA : Ethylenebisstearic acid amide

Example 1 PMPA, BD and MDI heated and melted at 50 ° C.
The molar ratio of PMPA: BD: MDI is 1: 4.17: 5.
32 and the total amount of these is 300 g / mi
n was continuously supplied to a twin-screw extruder (30 mmφ, L / D = 36, cylinder temperature: 75 to 260 ° C.) rotating coaxially by a metering pump to carry out continuous melt polymerization. The resulting polyurethane melt was continuously extruded in water in the form of strands, then cut into pellets with a pelletizer, and the pellets were dehumidified and dried at 80 ° C. for 20 hours to obtain the hardness and logarithmic viscosity shown in Table 1 below. A thermoplastic polyurethane having was obtained. 20 parts by weight of the obtained thermoplastic polyurethane, polypropylene (M
I: 5 g / 10 minutes) 60 parts by weight, and SEP-OH2
0 parts by weight was melt-kneaded with a single-screw extruder (25 mmφ, cylinder temperature: 170 to 200 ° C., die temperature: 190 ° C.), and then pelletized.
Dehumidified and dried for more than an hour. Table 2 below shows the results obtained by measuring or evaluating various physical properties of the dried pellets according to the methods described above.

Examples 2 to 9 and Comparative Examples 1 to 3 The continuous melt polymerization reaction was carried out in the same manner as in Example 1 except that the polyurethane raw materials shown in Table 1 below were used in a predetermined ratio, and shown in Table 1. A thermoplastic polyurethane having a hardness and an inherent viscosity was obtained. Further, the resin composition was produced in the blending ratio shown in Table 1, and various physical property values were measured or evaluated by the above-mentioned methods. The results are shown in Table 2 below.

[0079]

[Table 1]

[0080]

[Table 2]

Examples 10 to 20 and Comparative Examples 4 and 5 The continuous melt polymerization reaction was carried out in the same manner as in Example 1 except that the polyurethane raw materials shown in Table 3 below were used in a predetermined ratio, and shown in Table 3. A thermoplastic polyurethane having a hardness and an inherent viscosity was obtained. Further, the resin composition was produced in the blending ratio shown in Table 3, and various physical property values were measured or evaluated by the above-mentioned methods. The results are shown in Table 4 below.

[0082]

[Table 3]

[0083]

[Table 4]

[0084]

The resin composition of the present invention is excellent in tensile strength and elongation, impact resistance, abrasion resistance and molding processability because the thermoplastic polyurethane as a constituent and the polyolefin resin have good compatibility. Therefore, it is useful as a material for various molded products.

Front page continuation (72) Inventor Yoshifumi Murata 41 Miyukigaoka, Tsukuba, Ibaraki Prefecture Kuraray Co., Ltd.

Claims (6)

[Claims] 1. A resin composition comprising (i) a thermoplastic polyurethane (A), a polymer having a hydroxyl group at a terminal (B) and a polyolefin resin (C); (ii) (A) to (C) 3) to 90% by weight of the thermoplastic polyurethane (A), 3 to 30% by weight of the polymer having a hydroxyl group at the terminal and 5 to 90% by weight of the polyolefin resin (C), based on the total weight of And (iii) the polymer (B) having a hydroxyl group at the terminal comprises a hydrogenated conjugated diene compound unit (I) and an aromatic vinyl compound unit (II), and a structural unit (I) / Structural unit (I
The resin composition is characterized in that the molar ratio of I) is 10/90 to 100/0 and the number average molecular weight is 10,000 to 150,000. 2. A polymer (B) having a hydroxyl group at the terminal,
A block copolymer comprising a polymer block composed of a hydrogenated conjugated diene compound unit (I) and a polymer block composed of an aromatic vinyl compound unit (II), and having a structural unit (I) / structural unit ( The molar ratio of II) is 10/9
0 to 100/0 and number average molecular weight of 10,000 to 15
The resin composition according to claim 1, which is 10,000. 3. The resin composition according to claim 1, wherein the polymer (B) having a hydroxyl group at the terminal has a hydroxyl group content of 0.5 or more per molecule. 4. The thermoplastic polyurethane (A) comprises a polymer diol having a number average molecular weight of 900 to 6,000, an organic diisocyanate and a chain extender, represented by the following formula (1); 1.00 ≦ b / (a + c). ≦ 1.10 (1) (wherein, a is the number of moles of the polymeric diol, b is the number of moles of the organic diisocyanate, and c is the number of moles of the chain extender). The resin composition according to any one of claims 1 to 3, which is a thermoplastic polyurethane. 5. The higher fatty acid bisamide (D) is added in an amount of 0.3 to 5 parts by weight based on the total weight of the thermoplastic polyurethane (A), the polymer having a hydroxyl group at the end (B) and the polyolefin resin (C). % Content of claim 1
The resin composition according to any one of items 1 to 4. 6. A molded article made of the resin composition according to claim 1.