JP2000143934A - Thermoplastic elastomer composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a thermoplastic elastomer excellent in adhesion to polar resins and in mechanical properties. SOLUTION: This thermoplastic elastomer composition is composed of (I) 100 pts.wt. of a block copolymer composed of an aromatic vinyl block and conjugated diene block, and/or hydrogenated product thereof, (II) 2 to 100 pts.wt. of a modified polyolefin-based resin, (III) 10 to 250 pts.wt. of a polyurethane elastomer, and (IV) 10 to 250 pts.wt. of a paraffin-based oil.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a plastic elastomer composition comprising an addition polymerization block copolymer, a modified polyolefin resin, a polyurethane elastomer and a paraffin oil. Since the thermoplastic elastomer composition of the present invention has excellent adhesiveness to a polar resin and has good rubber-like properties, oil resistance, and moldability, it can be molded alone or co-molded. By molding and processing by extrusion and multi-layer molding,
It can be widely used for various uses including automobile interior parts, home electric parts, sports goods, miscellaneous goods, and stationery.

[0002]

2. Description of the Related Art Conventionally, products such as films, sheets, and molded products have been widely manufactured using high-molecular polymers, but depending on the type of the polymer, the use of the product, the purpose of use, and the like. In many cases, the use of a single polymer is inferior in molding processability or cannot provide physical properties suitable for the intended use or purpose of use. Therefore, using a polymer composition blended two or more polymers, or in the form of a laminate,
Improvements in molding workability, mechanical properties, chemical properties, and the like of the obtained product have been made.

[0003] In particular, recently, attempts have been made to laminate a thermoplastic elastomer on a plastic in order to improve the poor stability and tactile sensation of the plastic. By laminating thermoplastic elastomers, the touch becomes soft and the feel is good, and it gives a sense of quality, and the soundproofing and vibration-proofing properties are improved. It is being used for applications. Examples of the plastic on which the thermoplastic elastomer is laminated include polyethylene, polypropylene, ethylene-vinyl acetate copolymer, ethylene-vinyl alcohol copolymer, polyvinyl chloride, polyester, nylon, polycarbonate, polystyrene, high-impact polystyrene, and polyvinylidene chloride. , ABS resin and the like,
The laminate is used as a sheet, a film, or a molded article having a complicated shape.

[0004] As a method for producing these laminates, a method of bonding the same or different materials with an adhesive or a method of bonding by co-extrusion or multi-layer molding without using an adhesive is generally used. Can be mentioned. However, depending on the type of material to be laminated or a combination thereof,
In some cases, sufficient adhesive strength cannot be obtained. In order to bond non-adhesive materials by co-extrusion without using an adhesive, it has been practiced to use an adhesive material for both materials as an intermediate adhesive layer. There is a problem that strength may not be obtained, or durability of adhesive strength and water resistance may be poor. Various techniques aimed at solving these problems have been proposed in the prior art, and a resin composition in which a polyurethane elastomer is blended with an addition-polymerized block copolymer is known (Japanese Patent Application Laid-Open No. Hei 6 (1994) -106).
-107898, JP-A-8-72204, etc.). However, this resin composition has low mechanical strength due to poor compatibility between the addition-polymerized block copolymer and the urethane elastomer, and particularly in the case of a laminate obtained by multi-layer injection molding, surface peeling and adhesive strength. The problem such as the variation is easily caused.

[0005]

SUMMARY OF THE INVENTION An object of the present invention is to provide a thermoplastic elastomer composition having excellent adhesiveness to a synthetic resin having polarity and having good rubber-like properties, oil resistance, and moldability. In particular, it is an object of the present invention to provide a thermoplastic elastomer composition suitable for molding such as coextrusion and multilayer molding.

[0006]

Means for Solving the Problems The present inventors have made intensive studies to solve the above-mentioned problems, and as a result, the present invention has been made up of an addition-polymerized block copolymer, a modified polyolefin-based resin, a polyurethane elastomer and a paraffin-based oil. The thermoplastic elastomer composition is strongly adhered to a polar resin, and has good rubber-like properties, oil resistance, and moldability, and the thermoplastic elastomer composition is co-extruded. The present inventors have found that the present invention is suitable for forming processing such as multi-layer forming, and have completed the present invention.

That is, the present invention is selected from a block copolymer having a polymer block (A) mainly composed of an aromatic vinyl compound and a polymer block (B) mainly composed of a conjugated diene compound, and a hydrogenated product thereof. At least one type of addition-polymerized block copolymer (I) 10
2 to 100 parts by weight of the modified polyolefin resin (II) to 0 parts by weight of the polyurethane elastomer (III)
10 to 250 parts by weight, and a paraffinic oil (I
A thermoplastic elastomer composition comprising V) in an amount of 10 to 250 parts by weight.

[0008]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The present invention will be described below in detail. The addition-polymerized block copolymer (I) used in the thermoplastic elastomer composition of the present invention comprises a polymer block (A) mainly composed of an aromatic vinyl compound and a polymer block (B) mainly composed of a conjugated diene compound. And at least one selected from hydrogenated block copolymers. Polymer block (A)
Examples of the aromatic vinyl compound constituting styrene include α-methylstyrene, β-methylstyrene, o
-, M-, p-methylstyrene, t-butylstyrene,
2,4-dimethylstyrene, 2,4,6-trimethylstyrene, monofluorostyrene, difluorostyrene,
Monochlorostyrene, dichlorostyrene, methoxystyrene, vinylnaphthalene, vinylanthracene, indene, acetonaphthylene and the like can be mentioned.

The polymer block (A) mainly comprising an aromatic vinyl compound is one of the above-mentioned aromatic vinyl compounds.
It may have a structural unit consisting of only a kind or a structural unit consisting of two or more kinds, and among them, it is preferable that the structural unit mainly consists of a structural unit derived from styrene. The polymer block (A) mainly composed of an aromatic vinyl compound may have a small amount of a structural unit composed of another copolymerizable monomer together with a structural unit composed of an aromatic vinyl compound, if necessary. In this case, the proportion of the structural unit composed of another copolymerizable monomer is preferably 30% by weight or less based on the weight of the polymer block (A) mainly composed of an aromatic vinyl compound, and is preferably 10% by weight or less.
It is more preferable that the content be not more than weight%. In this case, examples of other copolymerizable monomers include ionic polymerizable monomers such as 1-butene, pentene, hexene, butadiene, isoprene, and methyl vinyl ether.

The conjugated diene compounds constituting the polymer block (B) include isoprene, butadiene, hexadiene, 2,3-dimethyl-1,3-butadiene, 1,3
-Pentadiene and the like. The polymer block (B) mainly composed of a conjugated diene compound may be composed of one kind of these conjugated diene compounds or may be composed of two or more kinds. When the polymer block (B) has structural units derived from two or more types of conjugated diene compounds, their bonding forms are random,
It may be tapered, partially blocky, or a combination of two or more thereof.

Among them, the polymer block (B) mainly composed of a conjugated diene compound is a polyisoprene block composed mainly of a monomer unit mainly composed of an isoprene unit or a part of an unsaturated bond thereof, from the viewpoint of an effect of improving rubber properties. Or a hydrogenated polyisoprene block entirely hydrogenated, a polybutadiene block composed of monomer units mainly composed of butadiene units or a hydrogenated polybutadiene block partially or wholly hydrogenated with unsaturated bonds, or an isoprene unit and butadiene It is preferable that the isoprene / butadiene copolymer block composed of monomer units mainly composed of units or a hydrogenated isoprene / butadiene block copolymer block in which a part or all of the unsaturated bonds are hydrogenated. In particular, the polymer block (B) mainly composed of a conjugated diene compound is more preferably the above-described polyisoprene block, isoprene / butadiene copolymer block, or a hydrogenated block thereof.

In the above-mentioned polyisoprene block which can be a block constituting the polymer block (B) mainly composed of a conjugated diene compound, before hydrogenation, the unit derived from isoprene is 2-methyl-2-butene-
1,4-diyl group _{[-CH 2 -C (CH 3)} = CH-C
H ₂ —; 1,4-bonded isoprene unit], isopropenylethylene group [—CH ｛—C (CH ₃ ) ＝ CH ₂ } —
CH ₂ —; a 3,4-bonded isoprene unit] and 1-
A methyl-1-vinylethylene group [—C (CH ₃ ) (CH
ＣＨCH ₂ ) —CH ₂ —; 1,2-bonded isoprene unit], and the ratio of each unit is not particularly limited.

In the above-mentioned polybutadiene block, which can be a block constituting the polymer block (B) mainly composed of a conjugated diene compound, before the hydrogenation, 70 to 20 mol%, particularly 65 to 40 mol% of the butadiene unit.
Mol% is a 2-butene-1,4-diyl group (—CH ₂ —C
H = CH—CH ₂ —; 1,4-bonded butadiene unit), and 30 to 80 mol%, particularly 35 to 60 mol% of the vinyl ethylene group [—CH (CH ＝ CH ₂ ) —CH ₂ —;
1,2-bonded butadiene unit]. If the amount of 1,4-bonds in the polybutadiene block is out of the above range of 70 to 20 mol%, the physical properties of the rubber may be poor.

In the above-mentioned isoprene / butadiene copolymer block which can be a block constituting the polymer block (B) mainly composed of a conjugated diene compound, the unit derived from isoprene is 2-methyl-butane before hydrogenation.
It comprises at least one group selected from the group consisting of a 2-butene-1,4-diyl group, an isopropenylethylene group and a 1-methyl-1-vinylethylene group, and the unit derived from butadiene is 2- It comprises a butene-1,4-diyl group and / or a vinylethylene group, and the arrangement of each unit is not particularly limited. In the isoprene / butadiene copolymer block, the arrangement of the isoprene unit and the butadiene unit may be any of a random shape, a block shape, and a tapered block shape.

The addition-polymerized block copolymer (I) is characterized in that the thermoplastic elastomer composition has good heat resistance and weather resistance. It is preferred that some or all of the bonds are hydrogenated. At that time, the hydrogenation rate of the polymer block mainly composed of a conjugated diene is preferably 50 mol% or more, more preferably 60 mol% or more, and further preferably 80 mol% or more. The bonding form between the polymer block (A) mainly composed of an aromatic vinyl compound and the polymer block (B) mainly composed of a conjugated diene compound in the addition polymerization type block copolymer (I) is not particularly limited, and is not particularly limited. Shape,
Any of branched, radial, or a combination of two or more of them may be used, and a linear connection is preferable.

The polymer block (A) in which the addition-polymerized block copolymer (I) mainly comprises an aromatic vinyl compound
And a polymer block (B) mainly composed of a conjugated diene compound having a linearly bonded structure, a diblock structure represented by AB, ABA or BA A triblock structure represented by -B, AB-
A tetrablock structure represented by AB or BABA, or a polyblock structure in which five or more A and B are linearly bonded can be employed. Among them, the diblock structure represented by AB or ABA
Is preferred from the viewpoints of elasticity, mechanical properties, melt adhesion, handleability, and the like.

In the addition polymerization type block copolymer (I), the weight ratio of [polymer block mainly composed of aromatic vinyl compound (A)]: [polymer block mainly composed of conjugated diene compound (B)] is 1 : 9 to 9: 1 is preferred from the viewpoint that the heat resistance and the mechanical properties of the thermoplastic elastomer composition and the molded article obtained therefrom are improved. Further, regarding the addition-polymerized block copolymer (I), the molecular weight of the polymer block (A) mainly composed of an aromatic vinyl compound and the polymer block (B) mainly composed of a conjugated diene compound is not particularly limited. In the previous state, the polymer block (A) mainly composed of an aromatic vinyl compound has a number average molecular weight of 2,500 to 10
And the number average molecular weight of the polymer block (B) mainly composed of a conjugated diene compound is 10,000.
It is preferable that it is in the range of 00 to 200,000 from the viewpoint that the thermoplastic elastomer composition has excellent tensile elongation at break and tensile strength at break.

The total number average molecular weight of the addition polymerization type block copolymer (I) is from 15,000 to 15,000 before hydrogenation.
A range of 300,000 is preferred from the viewpoint of mechanical properties, moldability and the like. In addition, the number average molecular weight referred to in this specification refers to a value determined from a standard polystyrene test line by a gel permeation chromatography (GPC) method. The addition-polymerized block copolymer (I) used in the thermoplastic elastomer composition of the present invention is a block copolymer having the above-mentioned block structure and generally having no functional group such as a hydroxyl group at a molecular terminal.

In the present invention, as the modified polyolefin resin (II), a modified polyolefin resin obtained by introducing at least one polar functional group into a normal polyolefin resin is used. The polar functional group is preferably at least one selected from a carboxylic anhydride, an epoxy group, and a hydroxyl group from the viewpoint that the thermoplastic elastomer composition has excellent adhesion to a polar resin. Examples of the polyolefin resin that can be subjected to such modification include homopolymers such as ethylene, propylene, 1-butene, 1-hexene, and 4-methyl-1-pentene, and structural units composed of these monomers. A copolymer as a main component is exemplified. Examples of the compound used for forming the copolymer include, for example, carbons such as propylene, 1-butene, 1-pentene, 4-methyl-1-pentene, 1-hexene, 1-octene, 1-decene, and 1-dodecene. Non-conjugated diene compounds such as α-olefins of formulas 3 to 20, 1,4-hexadiene, dicyclopentadiene, 5-ethylidene-2-norbornene and 2,5-norbornadiene, conjugated diene compounds such as butadiene, isoprene and piperylene Is mentioned. In addition, polar vinyl compounds such as vinyl acetate, acrylic acid, methacrylic acid, acrylic acid esters, methacrylic acid esters, metal salts of acrylic acid, and metal salts of methacrylic acid can be used for the constitution of the copolymer. These compounds can be used alone or in combination of two or more.

Among the above-mentioned polyolefin resins,
Polyethylene, polypropylene, ethylene / propylene copolymers, ethylene / 1-butene copolymers, ethylene / 1-octene copolymers, and the like, from the viewpoint that the resulting thermoplastic elastomer composition has excellent adhesion to polar resins. Ethylene / α-olefin copolymers are preferred. As the polyolefin resin, only one of the above-described polymers or copolymers may be used, or two or more may be used in combination.

As a method for introducing a polar functional group into a polyolefin resin, for example, when an olefin resin is produced, α, β-unsaturated carboxylic acid and / or a derivative thereof may be copolymerized or subjected to radical addition. Can be mentioned. α, β-unsaturated carboxylic acids and / or derivatives thereof include α, β-unsaturated monocarboxylic acids such as acrylic acid and methacrylic acid; and α, β-unsaturated monocarboxylic acids such as maleic acid, succinic acid, itaconic acid and phthalic acid. Unsaturated dicarboxylic acids; α, β-unsaturated monocarboxylic esters such as glycidyl acrylate, glycidyl methacrylate, hydroxyethyl acrylate and hydroxyethyl methacrylate; α, β such as maleic anhydride, succinic anhydride, itaconic anhydride and phthalic anhydride; β-unsaturated dicarboxylic anhydrides and the like can be mentioned, and among these, maleic anhydride, succinic anhydride, itaconic anhydride,
Α, β-unsaturated dicarboxylic anhydrides such as phthalic anhydride;
Glycidyl acrylate, glycidyl methacrylate,
Α, β-unsaturated monocarboxylic esters such as hydroxyethyl acrylate and hydroxyethyl methacrylate are preferred. The polar functional group is preferably introduced at a rate of 0.01 to 10 mol% based on the polyolefin resin.

The polyurethane elastomer (III) used in the thermoplastic elastomer composition of the present invention is a thermoplastic polyurethane elastomer obtained by reacting a polymer diol, an organic diisocyanate and a chain extender. The polymer diol constituting the polyurethane elastomer (III) has a number average molecular weight of 1,000 to 6,000.
Is preferable because the mechanical properties, heat resistance, cold resistance, elastic recovery and the like of the thermoplastic elastomer composition containing the polyurethane elastomer (III) are improved. Here, the number average molecular weight of the polymer diol referred to in the present specification is a number average molecular weight calculated based on the hydroxyl value measured by SITE according to JIS K-1557.

Examples of the polymer diol which can be used for the production of the polyurethane elastomer (III) include polyester diol, polyether diol, polyester ether diol, polycarbonate diol, polyester carbonate diol and the like. These can be used alone. Or two or more of them may be used in combination.
Examples of the polyester diol include ring-opening polymerization of polyester diol and lactone obtained by reacting at least one dicarboxylic acid component selected from aliphatic dicarboxylic acids, aromatic dicarboxylic acids, and ester-forming derivatives thereof with a low molecular weight diol. And the like.

More specifically, examples of the 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 dodecane diacid. One of aromatic dicarboxylic acids such as terephthalic acid, isophthalic acid and orthophthalic acid and their ester-forming derivatives
Species or two or more, for example, ethylene glycol, propylene glycol, 1,4-butanediol, 1,5-
One of aliphatic diols having 2 to 10 carbon atoms such as pentanediol, 3-methyl-1,5-pentanediol, 1,6-hexanediol, 1,9-nonanediol, and 2-methyl-1,8-octanediol Examples thereof include a polyester diol, a polycaprolactone diol, and a polyvalerolactone diol obtained by subjecting a species or two or more species to a polycondensation reaction.

Examples of the polyether diol include polyethylene glycol, polypropylene glycol, polytetramethylene glycol and the like. Examples of the above-mentioned polycarbonate diol include, for example, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,8-
One or two aliphatic diols such as octanediol
Examples thereof include polycarbonate diols obtained by reacting a seed with a carbonate such as diphenyl carbonate or alkyl carbonate or phosgene.

Also, a polyurethane elastomer (III)
The type of organic diisocyanate used for the production of is not particularly limited, but one or more of aromatic diisocyanate, alicyclic diisocyanate and aliphatic diisocyanate having a molecular weight of 500 or less are preferably used. Specific examples of the organic diisocyanate include 4,
4'-diphenylmethane diisocyanate, toluene diisocyanate, p-phenylene diisocyanate, naphthalene diisocyanate, hydrogenated 4,4'-diphenylmethane diisocyanate, isophorodiisocyanate, etc., among these organic diisocyanates, 4,4'-diphenylmethane Diisocyanates are preferably used.

Also, a polyurethane elastomer (III)
As the chain extender used in the production of the polyurethane elastomer, any chain extender conventionally used in the production of a polyurethane elastomer can be used, and the type thereof is not particularly limited. Among them, as the chain extender, one or two of aliphatic diols, alicyclic diols and aromatic diols are used.
More than one type of chain extender is preferably used. Specific examples of the chain extender preferably used include ethylene glycol, diethylene glycol, 1,4-butanediol,
1,5-pentanediol, 2-methyl-1,3-propanediol, 1,6-hexanediol, neopentyl glycol, 1,9-nonanediol, cyclohexanediol, 1,4-bis (β-hydroxyethoxy)
Diols such as benzene can be mentioned. Among the above, aliphatic diols having 2 to 6 carbon atoms are more preferably used as a chain extender, and 1,4-butanediol is particularly preferably used.

In the thermoplastic elastomer composition of the present invention, as the polyurethane elastomer (III), a polymer diol, a chain extender and an organic diisocyanate are used in the form of a polymer diol: chain extender = 1: 0.2 to 8.0 ( Molar ratio) and [the total number of moles of the polymer diol and the chain extender]: [the number of moles of the organic diisocyanate] =
1: A polyurethane elastomer obtained by reacting so as to be in the range of 0.98 to 1.04 is preferably used. The thermoplastic elastomer composition of the present invention containing such a polyurethane elastomer (III) does not cause a sharp rise in melt viscosity at the time of melt molding such as extrusion molding and injection molding, and smoothly produces a desired molded article. And the heat resistance of the obtained molded article is good.

Also, a polyurethane elastomer (III)
Has a hardness (JIS A hardness: measured at 25 ° C.) of 55 to 9
It is preferable that it is in the range of 0 because the mechanical properties of the thermoplastic elastomer composition become good and the adhesiveness and flexibility become good. When the hardness of the polyurethane elastomer (III) is less than 55, the mechanical properties of the obtained thermoplastic elastomer composition are reduced. On the other hand, when the hardness is more than 90, the adhesiveness of the obtained thermoplastic elastomer composition to polar resin and Flexibility tends to decrease.

In the plastic elastomer composition of the present invention, as the polyurethane elastomer (III), a polyurethane elastomer having a soft segment of poly (3-methyl-1,5-pentaneadipate) diol having a number average molecular weight of 2,000 or more, that is, adipine Acid and 3-
When a polyurethane diol obtained by reacting a polyester diol having a number average molecular weight of 2,000 or more obtained by polycondensation with methyl-1,5-pentanediol and the above-mentioned chain extender and organic diisocyanate is used, thermoplasticity obtained is obtained. It is preferable because the adhesiveness of the elastomer composition to the polar resin becomes excellent.

In the present invention, the method for producing the polyurethane elastomer (III) is not particularly limited, and the above-mentioned polymer diol, organic diisocyanate and chain extender are used to carry out a prepolymer method by utilizing a known urethane reaction. Or 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 production by continuous melt polymerization using a multi-screw extruder.

In the present invention, the paraffinic oil (IV) is a paraffin having a kinematic viscosity at 40 ° C. of 20 to 800 centistokes (CST), a fluidity of −40 to 0 ° C. and a flash point of 200 to 400 ° C. System oil is preferably used, and the kinematic viscosity at 40 ° C.
Flowability is -30 to 0 ° C and flash point is 250 to 350 ° C
Is more preferably used. Generally, an oil used as a process oil is a mixture of a component having an aromatic ring such as a benzene ring and a naphthene ring, a paraffin component (chain hydrocarbon), and the like. Occupying 50% by weight or more of the total carbon number of "paraffin oil"
It is called.

As the paraffinic oil (IV) used in the thermoplastic elastomer composition of the present invention, any of so-called paraffinic oils can be used. Those having an amount of 5% by weight or less are preferably used.

The thermoplastic elastomer composition of the present invention comprises:
2 to 100 parts by weight of the modified polyolefin-based resin (II) and 100 parts by weight of the above-mentioned addition-polymerized block copolymer (I), polyurethane elastomer (III)
10 to 250 parts by weight, and a paraffinic oil (I
V) in an amount of 10 to 250 parts by weight. When the content of the modified olefin-based resin (II) is less than 2 parts by weight based on 100 parts by weight of the addition-polymerized block copolymer (I), the adhesiveness of the obtained thermoplastic elastomer composition to the polar resin decreases. On the other hand, when it exceeds 100 parts by weight, the fluidity is reduced.

Further, the addition polymerization type block copolymer (I)
100 parts by weight of polyurethane elastomer (II
If the content of I) is less than 10 parts by weight, the resulting thermoplastic elastomer composition will have poor adhesion to polar resins, while if it exceeds 250 parts by weight, moldability will be reduced. When the content of the paraffinic oil (IV) is less than 10 parts by weight based on 100 parts by weight of the addition-polymerized block copolymer, the moldability of the thermoplastic elastomer composition is reduced, and 250 parts by weight is reduced. If the amount exceeds the above range, the adhesiveness of the thermoplastic elastomer composition to the polar resin and the mechanical properties are reduced. In particular, when the content of the paraffinic oil (IV) is in the range of 50 to 230 parts by weight based on 100 parts by weight of the addition-polymerized block copolymer, the moldability and the polarity of the thermoplastic elastomer composition of the present invention are determined. It is more preferable from the viewpoint of excellent adhesiveness to resin and excellent mechanical properties.

The thermoplastic elastomer composition of the present invention comprises:
If necessary, other thermoplastic resins such as an olefin resin, a styrene resin, a polyphenylene ether resin, and polyethylene glycol may be contained together with the above components. In particular, it is preferable to include an olefin-based resin in the thermoplastic elastomer composition of the present invention because the moldability and mechanical strength of the thermoplastic elastomer composition can be improved. As the polyolefin-based resin, for example, one or more kinds of polyethylene, polypropylene, polybutene resins, block copolymers and random copolymers of propylene with other α-olefins such as ethylene and 1-butene are used. can do. The amount of the olefin resin to be added to the thermoplastic elastomer composition of the present invention is 100 parts by weight based on the addition-polymerized block copolymer (I) so as not to impair the flexibility of the thermoplastic elastomer composition. Is preferably not more than 200 parts by weight.

Further, the thermoplastic elastomer composition of the present invention may contain an inorganic filler, if necessary. The inorganic filler is useful for increasing the hardness of the thermoplastic elastomer composition of the present invention and improving the economic efficiency as a bulking agent. As the inorganic filler, for example, one or more of calcium carbonate, talc, clay, synthetic silicon, titanium oxide, carbon black, barium sulfate, and the like can be used.
The compounding amount of the inorganic filler is preferably within a range where the flexibility of the thermoplastic elastomer is not impaired, and is generally 1 to 100 parts by weight of the addition polymerization type block copolymer (I).
It is preferably at most 00 parts by weight.

The thermoplastic elastomer composition of the present invention may further comprise a lubricant, a light stabilizer, a pigment, a flame retardant, an antistatic agent, a silicone oil, an antiblocking agent, an ultraviolet absorber, if necessary, in addition to the above-mentioned components. , An antioxidant or the like. The method for producing the thermoplastic elastomer composition of the present invention is not particularly limited, and any method may be used as long as it can uniformly mix the above-mentioned components used in the thermoplastic elastomer composition of the present invention. Often, a melt-kneading method is used. Melt kneading can be performed using, for example, a melt kneading apparatus such as a single screw extruder, a twin screw extruder, a kneader, and a Banbury mixer. Usually, melt kneading is performed at about 180 ° C. to 270 ° C. for about 3 to 15 minutes. Thereby, the thermoplastic elastomer composition of the present invention can be obtained.

The thermoplastic elastomer composition of the present invention comprises:
Polar resin, for example, polyurethane resin, polyamide resin, polycarbonate resin, polyester resin,
Polyphenylene sulfide resin, polyacrylate resin, polymethacrylate resin, polyether resin, acrylonitrile / styrene resin, acrylonitrile / styrene / butadiene resin, vinyl chloride resin, vinylidene chloride resin, phenol resin, epoxy resin, etc. In addition to being excellent in adhesiveness to, it has good moldability, oil resistance, mechanical properties, heat resistance, etc., so it has a layer composed of the thermoplastic elastomer composition and a layer composed of other materials by melt bonding. A laminated structure or a composite can be easily and smoothly manufactured.

The method for producing a laminated structure or composite having a layer composed of the thermoplastic elastomer composition and a layer composed of another material is not particularly limited, and any method may be employed as long as it is produced by fusion bonding. May go. Examples of the method include melting such as T-die laminate molding, coextrusion molding, blow molding, insert injection molding, two-color injection molding, core back injection molding, sandwich injection molding, injection press molding, and the like. Can be employed. In the case of the insert injection molding method among the above-mentioned molding methods, a core material (polar resin) is injection-molded in advance, and a shaped molded product is inserted into a mold. A method of injection molding a surface layer material (thermoplastic elastomer composition) into the voids is generally adopted.

In the case of the two-color injection molding method, after the core material is injection-molded using two or more injection molding machines,
By rotating or moving the mold, the mold cavity is replaced, and a gap is formed between the molded product and the mold,
There, a method of injection molding a surface material is generally adopted.
Further, in the case of the core-back injection molding method, the core material is injection-molded by using one injection molding machine and one mold, and then the volume of the mold cavity is increased. In general, a method of injection-molding a surface material in a gap between the two is adopted. In these molding methods, as the core material, one molded by a normal injection molding method or one molded by a gas injection molding method may be used.

The laminated structure (composite) obtained by such a molding method can be used as various industrial products and parts. Specific examples thereof include instrument panels, center panels, center console boxes, door trims, pillars, assist grips, handles, airbag covers and other automobile interior parts, malls and other automobile exterior parts, vacuum cleaner bumpers, remote control switches, Home appliances parts such as various key tops of OA equipment, underwater products such as underwater glasses and underwater camera covers, various cover parts, airtightness,
Industrial parts with various packings for the purpose of waterproofing, soundproofing and vibration proofing, automotive functional parts such as rack & pinion boots, suspension boots, constant velocity joint boots, curl cord electric wire coating, belts, hoses, tubes, and noise reduction gears And the like, electric and electronic parts, sporting goods, miscellaneous goods, stationery and the like.

[0043]

EXAMPLES The present invention will be specifically described below with reference to Examples and Comparative Examples, but the present invention is not limited thereto.
In the following Examples and Comparative Examples, thermoplastic elastomer compositions (pellets) used for manufacturing molded articles and laminated structures were manufactured as follows. Further, using the thermoplastic elastomer composition obtained thereby, a molded article (test piece) and a laminated structure are formed as follows,
The hardness, 100% modulus, tensile breaking strength, tensile breaking elongation, tensile permanent elongation, compression set, and peel strength of the laminated structure were measured as follows.

(1) Production of thermoplastic elastomer composition (pellet): Of the materials used in the following Examples and Comparative Examples, polymer materials other than paraffinic oil were dry-blended, and paraffinic oil was added thereto. To make a mixture by adding and impregnating the mixture, or to make a mixture without adding a paraffinic oil, and then feeding the mixture to a twin-screw extruder ("BT-30" manufactured by Plastics Industrial Research Institute) to obtain a cylinder temperature. 220 degrees, screw rotation speed 1
After melt-kneading at 50 rpm, extruding into strands,
This was cut to produce a thermoplastic elastomer composition.

(2) Measurement of hardness of molded article: Using the pellets of the thermoplastic elastomer composition produced in (1) above, an injection molding machine (“IS
-80 "; 80-ton injection molding machine), and subjected to injection molding under the conditions of a cylinder temperature of 220 ° C and a mold temperature of 40 ° C.
mm × 200 mm × 2 mm), and a molded product (test piece) obtained therefrom is used in accordance with JIS-K6301.
The hardness was measured according to (A method).

(3) Measurement of 100% modulus, tensile strength at break, and tensile elongation at break: Using pellets of the thermoplastic elastomer composition produced in the above (1), an injection molding machine ("IS" manufactured by Nissei Plastic Industry Co., Ltd.) -80 "; an 80-ton injection molding machine) to perform injection molding under the conditions of a cylinder temperature of 220 ° C. and a mold temperature of 40 ° C. to form a No. 3 dumbbell test piece, and use the dumbbell test piece. , Using Autograph (manufactured by Shimadzu Corporation)
According to K6301, 100 mm / min.
The% modulus, tensile strength at break and tensile elongation at break were measured.

(4) Measurement of tensile permanent elongation: (1)
Injection molding machine (“IS-80” manufactured by Nissei Plastics Industries, Ltd.) using pellets of the thermoplastic elastomer composition produced in
80 ton injection molding machine), cylinder temperature 22
Injection molding was performed under the conditions of 0 ° C. and a mold temperature of 40 ° C. to form a No. 3 dumbbell test piece, and the dumbbell test piece was used to form an autograph (manufactured by Shimadzu Corporation) at 100 mm / mm. Stretched for minutes. Tensile elongation is 1
Stop stretching when it reaches 00%.
Hold for 0 minutes. After that, the test piece is released and another 10
After standing for minutes, the tensile elongation was measured.

(5) Measurement of compression set: (1) above
Injection molding machine (“IS-80” manufactured by Nissei Plastics Industries, Ltd.) using pellets of the thermoplastic elastomer composition produced in
80 ton injection molding machine), cylinder temperature 22
Injection molding was performed under the conditions of 0 ° C. and a mold temperature of 40 ° C. to produce a right cylindrical molded product having a diameter of 29.0 mm and a thickness of 12.7 mm, and a temperature of 7 ° C. according to JIS-K6301.
The compression set was measured after being left for 22 hours under the condition of 0 ° C. and a compression deformation of 25%.

(6) Measurement of peel strength: acrylonitrile / styrene / butadiene-based resin ("Psycolac T"; ABS, manufactured by Ube Saikon Co., Ltd.); polycarbonate-based resin ("L-1250", manufactured by Teijin Chemicals Limited; PC) ,
Alternatively, a polyamide 66-based resin (“Leona 1300S” manufactured by Asahi Kasei Kogyo Co., Ltd .; PA66) is supplied to an injection molding machine (“IS-80” manufactured by Nissei Resin Kogyo Co., Ltd .; Injection molding was carried out at a temperature of 40 ° C. and a mold temperature of 40 ° C. to form a flat plate.
This is a flat plate mold (dimensions: length x width x thickness = 200m)
m × 200 mm × 4 mm), and using the pellets of the thermoplastic elastomer composition produced in (1) above, an injection molding machine (“IS-80” manufactured by Nissei Plastics Industries, Ltd .; 80) Injection molding machine) is used to perform injection molding under the conditions of a cylinder temperature of 220 ° C. and a mold temperature of 40 ° C., and a layer of a thermoplastic elastomer composition is laminated on one surface of a resin plate. (Dimensions: vertical x horizontal x
(Thickness = 200 mm × 200 mm × 4 mm).
From the laminated structure thus obtained, a test piece for measuring the peel strength (dimensions: length × width × thickness = 150 mm × 25 mm)
× 4 mm) and cut it out using JIS-K685.
The peel strength was measured according to the “180 ° peel test” described in No. 4.

The contents of the addition-polymerized block copolymer (I), modified polyolefin-based resin (II), polyurethane elastomer (III) and paraffin-based oil (IV) used in the following Examples and Comparative Examples are as follows. It is.

○ Addition polymerization block copolymer (I) Addition polymerization block copolymer (I-1): "Septon 4055" manufactured by Kuraray Co., Ltd. Addition polymerization block copolymer (I-2): Inc. Kuraray “Septon 4044” ○ Modified polyolefin resin (II) Modified polyolefin resin (II-1): “T7761P” (Maleic anhydride-modified EP manufactured by Nippon Synthetic Rubber Co., Ltd.)
R) Modified polyolefin-based resin (II-2): "ADMER QF500" (maleic anhydride-modified PP) manufactured by Mitsui Chemicals, Inc. Modified polyolefin-based resin (II-3): "ADMER NF500" (maleic anhydride) manufactured by Mitsui Chemicals, Inc. Acid-modified LLDPE) ○ Polyurethane elastomer (III): Kuraray Co., Ltd. “Kuramilon U 8165” [Poly (3-methyl-
Polyester polyurethane elastomer having 1,5-pentane adipate) as a soft segment] Paraffin oil (IV): "P" manufactured by Idemitsu Kosan Co., Ltd.
W-380 "

Examples 1 to 8 The addition-polymerized block copolymer (I), modified polyolefin-based resin (II), polyurethane elastomer (III) and paraffin-based oil (IV) were used in the proportions shown in Table 1 below. And pellets of the thermoplastic elastomer composition were produced in the above-described manner. Using each of the pellets thus obtained, a molded product (test piece) and a laminated structure were manufactured by the above-described method. The hardness of the resulting molded product, 10
The 0% modulus, tensile strength at break, tensile elongation at break, permanent tensile elongation, permanent compression set, and peel strength of the laminated structure were measured by the methods described above, and were as shown in Table 1 below.

<Comparative Examples 1 to 3> The addition method block copolymer (I), the polyurethane elastomer (III), and the paraffin oil (IV) were used at the ratios shown in Table 1 below, and the above method was used. A molded article (test piece) and a laminated structure were manufactured, and the hardness of the molded article obtained thereby was 100%.
The% modulus, tensile strength at break, tensile elongation at break, permanent tensile elongation, compression set, and peel strength of the laminated structure were measured by the above-described methods, and were as shown in Table 1 below.

[0054]

[Table 1]

[0055]

[Table 2]

From the results shown in Table 1, 2 to 100 parts by weight of the modified polyolefin resin (II) and 2 to 100 parts by weight of the polyurethane elastomer (III) were added to 100 parts by weight of the above addition-polymerized block copolymer (I). 10 to 250 parts by weight,
The thermoplastic elastomer compositions of Examples 1 to 8 containing paraffin oil (IV) in an amount within the range of 10 to 250 parts by weight have excellent adhesiveness to a polar resin and have a compression set and the like. It can be seen that the excellent mechanical properties of.

[0057]

The thermoplastic elastomer composition of the present invention has excellent adhesiveness to polar resins and has good rubber-like properties, oil resistance, and moldability. Or, by being formed by co-extrusion or multi-layer molding, it can be used very effectively for various molded products including automobile interior parts, home appliance parts, sports goods, miscellaneous goods, stationery, and other wide-ranging applications. Can be.

 ──────────────────────────────────────────────────続 き Continued on the front page (72) Inventor Shigeru Kawahara 41 Miyukigaoka, Tsukuba, Ibaraki Prefecture Inside Kuraray Co., Ltd. Reference) 4J002 AE05Z BB20X BB21X BP01W CK03Y GC00 GN00 GQ00 GT00

Claims (4)

[Claims] 1. A block copolymer having a polymer block (A) mainly composed of an aromatic vinyl compound and a polymer block (B) mainly composed of a conjugated diene compound, and at least one hydrogenated product thereof. With respect to 100 parts by weight of the addition-polymerized block copolymer (I),
2-100 parts by weight of the modified polyolefin resin (II),
A thermoplastic elastomer composition comprising 10 to 250 parts by weight of a polyurethane elastomer (III) and 10 to 250 parts by weight of a paraffinic oil (IV). 2. The modified polyolefin resin (II) wherein the olefin unit comprises ethylene, propylene and α.
-The thermoplastic elastomer composition according to claim 1, which is at least one compound selected from olefins. 3. The modified polyolefin resin (II) is modified with at least one functional group selected from a carboxylic anhydride, an epoxy group, and a hydroxyl group.
Or the thermoplastic elastomer composition according to 2. 4. The polyurethane elastomer (III) comprises:
The thermoplastic elastomer according to any one of claims 1 to 3, which comprises a poly (3-methyl-1,5-pentane adipate) diol having a molecular weight of 2,000 or more as a constituent and has a JIS hardness of 55 to 90. Composition.