JP2003041089A - Thermoplastic elastomer composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a thermoplastic elastomer composition that shows excellent adhesion to polar resin despite of high content of inorganic filler and has excellent dynamic performance. SOLUTION: The thermoplastic elastomer composition comprises (I) 100 mass parts of a specified addition-polymerized block copolymer, (II) 10-300 mass parts of polyurethane elastomer, (III) 5-100 mass parts of polyurethane block copolymer and (IV) 50-500 mass parts of surface-treated calcium carbonate. In the elastomer composition, the polyurethane block copolymer (III) comprises (C) an addition-polymerized block derived from a specified addition- polymerized block copolymer and (D) a polyurethane block derived from polyurethane elastomer.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a thermoplastic elastomer composition comprising an addition polymerization block copolymer, a polyurethane elastomer, a polyurethane block copolymer and surface-treated calcium carbonate. The thermoplastic elastomer composition of the present invention has excellent adhesiveness to polar resins, and also has good rubber-like properties, oil resistance, and molding processability, so that it is a single molded product or a coextrusion molded product or a multi-layered product. In the field of molded articles and the like, it can be extremely effectively used for various molded articles such as automobile interior parts, home electric appliance parts, sports equipment, miscellaneous goods, and stationery, and a wide range of other applications.

[0002]

2. Description of the Related Art Conventionally, a laminate having the advantages of both materials by adhering different kinds of materials to form a laminate, or by laminating another kind of material with the same material. There are attempts to produce laminates that make up for the shortcomings of these materials. In particular, in recent years, attempts have been made to laminate a thermoplastic elastomer on a plastic in order to improve the fragile feeling and poor tactile feel of the plastic. The laminate obtained by laminating this thermoplastic elastomer has a soft touch, a good feel, a high-class feeling, and soundproofing,
It can be said that it is suitable for interior parts of automobiles, home electric appliances, etc. due to its excellent anti-vibration property. 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, impact polystyrene, polyvinylidene chloride,
Acrylic resin, ABS resin and the like are mentioned, and the laminate is
It is used as a sheet, a film, or a molded product having a complicated shape.

Generally, these laminates can be obtained by a method of adhering the same or different materials with an adhesive, or a method of adhering by coextrusion or multi-layer molding without using an adhesive. However, depending on the type of materials to be laminated or a combination thereof, a sufficient adhesive effect may not be obtained, and in particular, when a laminate is obtained by coextrusion or multi-layer molding without using an adhesive, mutual adhesiveness is not obtained. No material could be used. Therefore, in order to bond non-adhesive materials to each other by coextrusion,
A method of using an adhesive material as an intermediate adhesive layer for both materials has been carried out, but there were problems that a sufficient adhesive effect was not always obtained, and the durability of adhesive strength and water resistance were poor. . In order to solve these problems, JP-A-6-65467 and JP-A-8-72204 disclose a technique of adding a polyurethane elastomer to an addition polymerization block copolymer. However, the resin composition described in this publication has a low compatibility with the addition-polymerization block copolymer and the polyurethane elastomer, so that the mechanical strength is low. Occurs. In order to solve these problems, JP-A No. 11-323073 discloses a block having a (hydrogenated) styrene / diene copolymer block and a thermoplastic polyurethane elastomer block with respect to a styrene / diene block copolymer. A thermoplastic polymer composition in which a copolymer, a thermoplastic polyurethane elastomer and a paraffin oil are blended in specific amounts is disclosed. This thermoplastic polymer composition has excellent elasticity, flexibility, mechanical properties, oil resistance, molding processability, and also has excellent melt adhesiveness, and is excellent in firmly adhering to various materials. Have characteristics. However, when an inorganic filler is added to this thermoplastic polymer composition for cost reduction, there is a problem that the adhesive strength and mechanical properties are deteriorated.

[0004]

SUMMARY OF THE INVENTION It is an object of the present invention to provide a thermosetting resin having excellent adhesiveness to a polar synthetic resin, good rubber properties and molding processability even when a large amount of inorganic filler is contained. It is intended to provide a thermoplastic elastomer composition, and particularly to provide a thermoplastic elastomer composition suitable for molding processing such as coextrusion and multilayer molding.

[0005]

As a result of intensive studies to solve the above problems, the present inventors have found that an addition polymerization block copolymer, a polyurethane elastomer, a polyurethane block copolymer and a surface-treated carbonic acid. The thermoplastic elastomer composition composed of calcium has excellent adhesiveness to polar resins, and also has good rubber properties, oil resistance, and moldability, and further, the thermoplastic elastomer composition is coextruded or compounded. The present invention has been completed by finding that it is suitable for layer forming applications.

That is, the present invention provides (i) a block copolymer having a polymer block (A-1) composed of an aromatic vinyl compound unit and a polymer block (B-1) composed of a conjugated diene compound unit. And at least one addition polymerization block copolymer (I) selected from hydrogenated products thereof and (100) parts by mass; (ii) polyurethane elastomer (II) 10 to 300 parts by mass; (iii) aromatic vinyl compound At least one addition polymerization block selected from a block copolymer having a polymer block (A-2) composed of a unit and a polymer block (B-2) composed of a conjugated diene compound unit, and a hydrogenated product thereof It comprises an addition polymerization block (C) derived from a copolymer and a polyurethane block (D) derived from a polyurethane elastomer. A thermoplastic elastomer composition comprising a polyurethane block copolymer (III) in an amount of 5 to 200 parts by mass; and (iv) a surface-treated calcium carbonate (IV) in an amount of 50 to 500 parts by mass.

The present invention further relates to a laminated structure having a layer made of the above-mentioned thermoplastic elastomer composition and a layer made of another material, and the above-mentioned thermoplastic elastomer composition fused to a layer made of another material. It is a method for manufacturing the laminated structure by laminating.

[0008]

BEST MODE FOR CARRYING OUT THE INVENTION The present invention will be described in detail below. The addition polymerization block copolymer (I) in the present invention is a polymer block (A-1) mainly composed of an aromatic vinyl compound unit [hereinafter referred to as "aromatic vinyl polymer block (A-1)"]. Polymer block (B-1) mainly composed of at least one conjugated diene compound unit
At least one addition-polymerization block copolymer selected from at least one block copolymer [hereinafter referred to as “conjugated diene polymer block (B-1)”] and hydrogenated product thereof. However, it is not particularly limited. Examples of such an addition-polymerization block copolymer (I) include a diblock consisting of one aromatic vinyl polymer block (A-1) and one conjugated diene polymer block (B-1). Block copolymer, triblock copolymer consisting of two aromatic vinyl polymer blocks (A-1) and one conjugated diene polymer block (B-1), from four or more polymer blocks And the like. Among these, as the addition polymerization block copolymer (I), 1 is attached to each end of one conjugated diene polymer block (B-1).
The triblock copolymer having the individual aromatic vinyl polymer blocks (A-1) improves the mechanical properties such as tensile breaking elongation and tensile breaking strength of the resulting thermoplastic elastomer composition. preferable.

Examples of the aromatic vinyl compound unit constituting the aromatic vinyl polymer block (A-1) include styrene, α-methylstyrene, β-methylstyrene and o.
-, M-, p-methylstyrene, t-butylstyrene,
2,4-dimethylstyrene, 2,4,6-trimethylstyrene, monofluorostyrene, difluorostyrene,
Examples thereof include units consisting of monochlorostyrene, dichlorostyrene, methoxystyrene, vinylnaphthalene, vinylanthracene, indene, acetonaphthylene and the like. The aromatic vinyl polymer block (A-1) may be composed of only one kind of the above-mentioned aromatic vinyl compound units, or may be composed of two or more kinds.
Among them, aromatic vinyl polymer block (A-1)
Is preferably composed mainly of structural units derived from styrene.

Aromatic vinyl polymer block (A-1)
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, and a structure composed of another copolymerizable monomer in that case. The ratio of the units is such that the aromatic vinyl polymer block (A-
It is preferably 30% by mass or less, and more preferably 10% by mass or less, based on the mass of 1). Examples of the other copolymerizable monomer unit in that case include 1-butene, pentene, hexene, butadiene, isoprene,
Examples thereof include units composed of ion-polymerizable monomers such as methyl vinyl ether.

The conjugated diene compound units constituting the conjugated diene polymer block (B-1) include isoprene, butadiene, hexadiene and 2,3-dimethyl-1,3-.
Examples thereof include units made of butadiene and 1,3-pentadiene. Conjugated diene polymer block (B-
1) may be composed of only one type of these conjugated diene compound units, or may be composed of two or more types. When the conjugated diene polymer block (B-1) has a structural unit derived from two or more kinds of conjugated diene compounds, the bonding form thereof is random, tapered, partially block-shaped, or two kinds thereof. It can be a combination of the above.

Among them, the conjugated diene polymer block (B-1) is a polyisoprene block composed of a monomer unit mainly containing an isoprene unit or hydrogenated polyisoprene in which a part or all of its unsaturated bond is hydrogenated. Block; polybutadiene block consisting of monomer units mainly consisting of butadiene units or hydrogenated polybutadiene block in which a part or all of unsaturated bonds thereof are hydrogenated; or isoprene consisting of monomer units consisting mainly of isoprene units and butadiene units It is preferably a hydrogenated isoprene / butadiene copolymer block in which some or all of the / butadiene copolymer blocks or unsaturated bonds thereof are hydrogenated.

In the above polyisoprene block which can be a constituent block of the conjugated diene polymer block (B-1), the unit derived from isoprene is 2-methyl-2-butene-1,4 before hydrogenation. -Diyl group [-C
H ₂ —C (CH ₃ ) ═CH—CH ₂ —; 1,4-bond isoprene unit], isopropenylethylene group [—CH
_{(C (CH 3) = CH} 2) -CH 2 -; 3,4- bond of isoprene units] and 1-methyl-1-vinyl ethylene group _{[-C (CH 3) (CH} = CH 2) -CH 2 -; 1,2
-Bonding isoprene unit], and the ratio of each unit is not particularly limited.

In the above-mentioned polybutadiene block which can be a constituent block of the conjugated diene polymer block (B-1), 70% of the butadiene unit thereof is added before the hydrogenation.
-20 mol%, especially 65-40 mol% is 2-butene-
1,4-diyl group _{(-CH 2 -CH = CH-CH} 2 -;
1,4-bond butadiene unit), and 30 to 80 mol%, particularly 35 to 60 mol% of vinylethylene group [-CH
(CH = CH ₂ ) -CH _2- ; 1,2-bond butadiene unit] is preferable. When the 1,4-bond amount in the polybutadiene block is within the above range of 70 to 20 mol%, the rubber physical properties will be good.

In the above-mentioned isoprene / butadiene copolymer block which can be a constituent block of the conjugated diene polymer block (B-1), the unit derived from isoprene is 2-methyl-2-butene-1 before hydrogenation. , 4-diyl group, isopropenylethylene group and 1-methyl-
It is composed of at least one group selected from the group consisting of 1-vinylethylene groups, and the unit derived from butadiene is composed of 2-butene-1,4-diyl group and / or vinylethylene group, The unit ratio is not particularly limited. In the isoprene / butadiene copolymer block, the arrangement of isoprene units and butadiene units may be any of random, block, and tapered block shapes. In the isoprene / butadiene copolymer block, the molar ratio of isoprene unit: butadiene unit is 1: 9 to 9: from the viewpoint of the effect of improving rubber physical properties.
It is preferably 1, and more preferably 3: 7 to 7: 3.

The addition-polymerization block copolymer (I) is preferable because the thermoplastic elastomer composition has good heat resistance and weather resistance, and therefore, the unsaturated diene polymer block (B-1) is unsaturated. It is preferable that some or all of the heavy bonds are hydrogenated (hereinafter sometimes referred to as “hydrogenated”). The hydrogenation rate of the conjugated diene polymer block (B-1) at that time is preferably 50 mol% or more, more preferably 60 mol% or more, and 80
More preferably, it is at least mol%.

In the addition polymerization block copolymer (I), the molecular weight of the aromatic vinyl polymer block (A-1) and the molecular weight of the conjugated diene polymer block (B-1) are not particularly limited, but aromatic vinyl Polymer block (A-
The number average molecular weight of 1) is 2,000 to 100,000,
It is preferably in the range of 2,500 to 75,000,
The number average molecular weight of the conjugated diene polymer block (B-1) is 10,000 to 150,000 before hydrogenation.
It is preferable that it is within the range from the viewpoints of mechanical properties, molding processability and the like of the obtained thermoplastic elastomer composition. The molecular weight of the addition polymerization block copolymer (I) is 12,000 to 2,000,000, preferably 3
It is preferably in the range of 10,000 to 1,000,000. In addition, the molecular weight as used in this specification means the number average molecular weight calculated | required from the standard polystyrene calibration curve by the gel permeation chromatography (GPC) method.

Although not limited thereto, the addition polymerization block copolymer (I) may be produced by, for example, an ionic polymerization method such as anionic polymerization or cationic polymerization, a single site polymerization method, a radical polymerization method, or the like. You can
In the case of the anionic polymerization method, for example, an aromatic vinyl compound and a conjugated diene compound are sequentially polymerized in an inert organic solvent such as n-hexane or cyclohexane using an alkyllithium compound or the like as a polymerization initiator to obtain a desired compound. After producing a diblock copolymer or triblock copolymer having a molecular structure and a molecular weight, alcohols,
It can be produced by adding active hydrogen compounds such as carboxylic acids and water to terminate the polymerization.

The polyurethane elastomer (II) constituting the thermoplastic elastomer composition of the present invention is not particularly limited as long as it is a thermoplastic polyurethane elastomer obtained by the reaction of a polymer diol, an organic diisocyanate and a chain extender. Polyurethane elastomer (II)
The polymer diol used in the production of
It is preferably from 000 to 6,000 from the viewpoint that the thermoplastic elastomer composition containing the polyurethane elastomer (II) has good mechanical properties, heat resistance, cold resistance, elastic recovery and the like. Here, the number average molecular weight of the high molecular diol as referred to in the present specification is the number average molecular weight calculated based on the hydroxyl value measured according to JIS K-1557.

Examples of polymer diols that can be used in the production of the polyurethane elastomer (II) include polyester diols, polyether diols, polyester ether diols, polycarbonate diols and polyester carbonate diols, which are used alone. Alternatively, two or more kinds may be used in combination.
Examples of the above polyester diol include polyester diol obtained by reacting at least one dicarboxylic acid component selected from an aliphatic dicarboxylic acid, an aromatic dicarboxylic acid and their ester-forming derivatives with a low molecular weight diol, and ring opening of a lactone. Examples thereof include polyester diols obtained by polymerization.

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 dodecanedioic acid. One or more of aromatic dicarboxylic acids such as terephthalic acid, isophthalic acid, orthophthalic acid and their ester-forming derivatives, and, for example, ethylene glycol, propylene glycol, 1,4-butanediol, 1,5
Of an aliphatic diol 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. Polyester diol obtained by polycondensation reaction with one or more kinds;
Examples thereof include polycaprolactone diol and polyvalerolactone diol.

Examples of the above polyether diols include polyethylene glycol, polypropylene glycol, polytetramethylene glycol and the like. Examples of the above-mentioned polycarbonate diol include one or two kinds of aliphatic diols such as 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, and 1,8-octanediol. , A polycarbonate diol obtained by reaction with a carbonic acid ester such as diphenyl carbonate or alkyl carbonate, or phosgene.

The type of organic diisocyanate used for producing the polyurethane elastomer (II) is not particularly limited, but one or more of aromatic diisocyanates having a molecular weight of 500 or less, alicyclic diisocyanates and aliphatic diisocyanates are used. Is 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 and the like can be mentioned. Among these organic diisocyanates, 4,4'-diphenylmethane diisocyanate is It is preferably used.

As the chain extender used for producing the polyurethane elastomer (II), any chain extender conventionally used for producing a polyurethane elastomer can be used, and the kind thereof is not particularly limited. Among them, as the chain extender, one or more of aliphatic diol, alicyclic diol and aromatic diol are preferably used. Specific examples of the chain extender 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-
Mention may be made of diols such as hydroxyethoxy) benzene. Among the above, an aliphatic diol having 2 to 6 carbon atoms is more preferably used as the chain extender,
1,4-butanediol is particularly preferably used.

In the thermoplastic elastomer composition of the present invention, as the polyurethane elastomer (II), a polymer diol, a chain extender and an organic diisocyanate are added, and a polymer diol: chain extender = 1: 0.2 to 1: 8. Within the range of 0 (molar ratio), and [total number of moles of polymer diol and chain extender]: [number of moles of organic diisocyanate] =
A polyurethane elastomer obtained by reacting it in the range of 1: 0.98 to 1: 1.04 is preferably used. Such polyurethane elastomer (II)
The thermoplastic elastomer composition containing, extrusion molding,
The melt viscosity does not sharply increase during melt molding such as injection molding, the desired molded article can be smoothly produced, and the resulting molded article has good heat resistance.

In the plastic elastomer composition of the present invention, the polyurethane elastomer (II) has a soft segment of poly (3-methyl-1,5-pentaneadipate) diol having a number average molecular weight of 2000 or more, that is, Adipic acid and 3-
When a polyurethane elastomer obtained by reacting a polyester diol having a number average molecular weight of 2000 or more obtained by polycondensation with methyl-1,5-pentanediol and the above-mentioned chain extender and an organic diisocyanate is used, heat obtained is obtained. It is preferable because the adhesive property of the plastic elastomer composition to the polar resin becomes excellent.

Further, the polyurethane elastomer (II)
Is the A hardness specified in JIS-K6301 (JIS-A
Hardness: measured at 25 ° C.) so that the type and proportion of each of the above-mentioned manufacturing raw materials are selected so that it falls within the range of 55 to 90, the resulting thermoplastic elastomer composition has good mechanical properties, In addition, it is preferable because the adhesiveness and flexibility are good.

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

The polyurethane block copolymer (III) in the thermoplastic elastomer composition of the present invention comprises a polymer block (A-) mainly containing an aromatic vinyl compound unit.
At least one addition polymerization system selected from a block copolymer comprising at least one of 2) and at least one polymer block (B-2) mainly containing a conjugated diene compound unit and a hydrogenated product thereof. A polyurethane block copolymer comprising an addition polymerization block (C) derived from a block copolymer and a polyurethane block (D) derived from a polyurethane elastomer, for example, one addition polymerization block ( A diblock copolymer composed of C) and one polyurethane block (D), a triblock copolymer composed of two addition polymerization system blocks (C) and one polyurethane block (D), and the like. be able to. Among these, as the polyurethane block copolymer (III), one addition polymerization block (C) and one polyurethane block (D) are used.
A diblock copolymer consisting of And, the content ratio of the addition polymerization type block (C) and the polyurethane block (D) in the polyurethane type block copolymer (III) is preferably in the range of 1: 9 to 9: 1 by mass ratio, It is more preferably within the range of 2: 8 to 8: 2, and even more preferably within the range of 3: 7 to 7: 3. The addition-polymerization block (C) and the polyurethane block (D) may be bonded by a chemical bond such as urethane bond or ester bond.

The polymer block (A-2) constituting the addition polymerization system block (C) is the aromatic vinyl polymer block (A-) of the addition polymerization system block copolymer (I).
The polymer unit (B-2) can be composed of the same monomer units as those mentioned above as the monomer unit constituting 1), and the polymer block (B-2) is a conjugated diene polymer block (B-
Monomer units or (co) similar to those listed above as the monomer units or (co) polymer blocks constituting 1)
It can be composed of polymer blocks. Molecular weight of polymer block (A-2), polymer block (B-
The molecular weight and hydrogenation rate of 2) and the molecular weight of the addition polymerization system block (C) are also determined by the aromatic vinyl polymer block (A-
1) and the conjugated diene polymer block (B-1), and the addition polymerization block copolymer (I) preferably have the same molecular weight or hydrogenation ratio as those mentioned above.

The polyurethane block (D) constituting the polyurethane block copolymer (III) can be formed from various polyurethane elastomers similar to those mentioned above for the polyurethane elastomer (II). In particular, it is preferable that the polyurethane block is formed of a polyurethane elastomer having a composition similar to that of the polyurethane elastomer (II) from the viewpoint of excellent adhesiveness and mechanical properties of the resulting thermoplastic elastomer composition.

Polyurethane block copolymer (III)
Is not particularly limited, and, for example, an addition-polymerization block copolymer having a hydroxyl group at the terminal and composed of a polymer block (A-1) and a polymer block (B-2) and a polyurethane elastomer may be prepared under melting conditions. It can be obtained by extracting and recovering the polyurethane block copolymer (III) from the polyurethane reaction product obtained by mixing by mixing.

In the addition polymerization block copolymer having a hydroxyl group at the terminal, the hydroxyl group at the terminal is present in either the polymer block (A-2) or the polymer block (B-2). Although it may be present, it is preferably present at the terminal of the polymer block (A-2) forming a hard block in the addition-polymerization block copolymer. The content of terminal hydroxyl groups in the addition polymerization block copolymer is preferably 0.5 or more on average per molecule, and more preferably in the range of 0.7 to 2.

Polyurethane block copolymer (III)
In the production of, the melt-kneading of the addition-polymerization block copolymer having a hydroxyl group at the terminal and the polyurethane elastomer is performed using a melt-kneading device such as a single-screw extruder, a twin-screw extruder, a kneader, a Banbury mixer. be able to. The conditions for melt-kneading can be appropriately selected depending on the type of polyurethane elastomer or addition-polymerization type block copolymer to be used, type of apparatus, etc., but usually 180 to 25
It may be carried out at a temperature of 0 ° C. for about 1 to 15 minutes. In addition, the polyurethane block copolymer (III) is prepared by adding an addition polymerization block copolymer having a hydroxyl group at the end together with a polymer diol, an organic diisocyanate and a chain extender during the production of a polyurethane elastomer using an extruder. , A method of melt-kneading, or a method of adding an addition-polymerization block copolymer having a hydroxyl group at the end from the middle of the cylinder of the extruder when the molecular weight of the polyurethane elastomer has risen to some extent during the production of the polyurethane elastomer. You can

The polyurethane-based reaction product obtained by the above-mentioned method is mainly contained in the polyurethane-based block copolymer, the polyurethane elastomer and the addition-polymerized block copolymer, and is therefore included in the polyurethane-based reaction product. While analyzing the content of the polyurethane block copolymer (III), the content of the polyurethane block copolymer (III) in the thermoplastic elastomer composition is adjusted to fall within the range of the present invention. , Without extracting and recovering the polyurethane block copolymer (III) from the polyurethane reaction product,
The polyurethane-based reaction product containing the polyurethane-based block copolymer (III) may be used as it is for the preparation of the thermoplastic elastomer composition of the present invention.

In the thermoplastic elastomer composition of the present invention, the content of the polyurethane block copolymer (III) is in the range of 5 to 200 parts by mass with respect to 100 parts by mass of the addition polymerization block copolymer (I). Within, 20-18
It is preferably in the range of 0 parts by mass, more preferably in the range of 50 to 150 parts by mass. When the content of the polyurethane block copolymer (III) is less than 5 parts by mass, the compatibility between the addition polymerization block copolymer (I) and the polyurethane elastomer (II) in the thermoplastic elastomer composition is low. On the other hand, if it exceeds 200 parts by mass, the moldability decreases.

In the thermoplastic elastomer composition of the present invention, the surface-treated calcium carbonate (IV) is added in an amount of 50 to 500 with respect to 100 parts by mass of the addition polymerization block copolymer (I).
Contains by mass. If the content of the surface-treated calcium carbonate (IV) exceeds 500 parts by mass, the adhesiveness and mechanical properties of the thermoplastic elastomer composition with respect to the polar resin deteriorate. The content of the surface-treated calcium carbonate (IV) is 60 with respect to 100 parts by mass of the addition polymerization block copolymer (I).
It is preferably ˜450 parts by mass, more preferably 70 to 400 parts by mass.

Calcium carbonate includes ground calcium carbonate obtained by grinding natural limestone and precipitated calcium carbonate which is chemically synthesized. For the surface treatment of the heavy calcium carbonate, for example, fatty acid, stearic acid, beef tallow ester, surfactant, resin acid, titanate coupling agent, phosphate coupling agent and the like can be used. For the surface treatment of precipitated calcium carbonate, for example, fatty acids, resin acids, maleic acids having double bonds, organic acids such as sorbic acid, sulfonic acid-based surfactants, titanate-based coupling agents, silane-based coupling agents. And a phosphoric acid-based coupling agent or the like can be used. Among these, the surface-treated calcium carbonate (IV) used in the present invention is
Preference is given to ground calcium carbonate, which is preferably surface-treated with at least one selected from the group consisting of saturated fatty acids, unsaturated fatty acids, aliphatic carboxylic acids and resin acids, saturated or unsaturated. More preferably, it is surface-treated with the fatty acid of. When calcium carbonate is not surface-treated, mechanical properties such as tensile properties of the resulting composition and adhesion to a layer made of another material of the laminated structure are deteriorated.

The surface treatment method of calcium carbonate includes dry treatment and wet treatment, and any treatment method may be used. Among these, the dry treatment is performed by stirring calcium carbonate and the surface treatment agent while heating, and the wet treatment is performed by adding the surface treatment agent to an aqueous slurry of calcium carbonate to a temperature higher than the melting point of the treatment agent. It is performed by heating and stirring. Among these, as an example of dry treatment, calcium carbonate and a surface treatment agent are put into a super mixer or the like, and the mixture is heated at 1000 to 3000 rpm for 10 minutes while heating the calcium carbonate and the surface treatment agent.
It can be performed by mixing for 60 minutes. The amount of surface treatment with the surface treatment agent is not particularly limited, but is 0.1 with respect to 100 parts by mass of calcium carbonate.
It is preferably in the range of ˜20 parts by mass. When the amount of surface treatment is within the above range, the resulting thermoplastic elastomer composition has good tensile properties.

The average particle size of the surface-treated calcium carbonate (IV) is not particularly limited, but it is 0.5 to 5 μm, preferably 1 to 3 μm in the case of heavy calcium carbonate, and 0.05 to 0. Those having a thickness of 5 μm, preferably 0.1 to 0.3 μm are suitably used.

The paraffinic oil (V) that can be added to the thermoplastic elastomer composition of the present invention includes:
Kinematic viscosity at 40 ° C. is 2 × 10 ⁻⁵ to 8 × 10 ⁻⁴ m ² /
Seconds, preferably 5 × 10 ^{−5 to} 6 × 10 ⁻⁴ m ² / sec,
Pour point is -40 to 0 ° C, preferably -30 to 0 ° C, and flash point is 200 to 400 ° C, preferably 250 to 350.
What is ° C is preferred. Further, the aromatic ring component contained in the paraffinic oil (V) is preferably 5% by mass or less.

The content of the paraffinic oil (V) should be kept within the range where the physical properties of the thermoplastic elastomer composition are not impaired, but it is 300 with respect to 100 parts by mass of the addition polymerization type block copolymer (I). It is preferably not more than 10 parts by mass, more preferably in the range of 10 to 250 parts by mass. Paraffin oil (V) content is 30
When it is 0 part by mass or less, the mechanical properties such as the adhesiveness and flexibility of the thermoplastic elastomer composition to the polar resin will be excellent.

The thermoplastic elastomer composition of the present invention comprises
The above-mentioned addition polymerization block copolymer (I), polyurethane elastomer (II), polyurethane block copolymer (III), surface-treated calcium carbonate (IV) and / or
Alternatively, the respective components corresponding to the paraffinic oil (V) may be mixed and produced so that the content ratio of each component in the thermoplastic elastomer composition is within the above range. In that case, for example, an addition polymerization block copolymer (I), a polyurethane elastomer (I
I), polyurethane block copolymer (III), surface-treated calcium carbonate (IV) and paraffin oil (V) are usually mixed with a kneader such as a single-screw extruder, a twin-screw extruder, a kneader or a Banbury mixer. 180 ° C-270
It can be obtained by melt-kneading at a temperature of 3 to 15 minutes.

The thermoplastic elastomer composition of the present invention comprises
A hardness defined in JIS-K6301 (JIS-A hardness: measured at 25 ° C.) is 20 to 90, preferably 30 to
By selecting the types and ratios of the above-mentioned respective components so as to fall within the range of 85, the resulting thermoplastic elastomer composition will have good mechanical properties and good adhesiveness and flexibility. Is preferable.

The thermoplastic elastomer composition of the present invention may contain another type of thermoplastic resin, preferably an olefin resin, in order to improve molding processability, mechanical strength and the like. As the olefin resin, for example,
Block copolymers and random copolymers of polyethylene, polypropylene, polybutene, propylene and α-olefins such as ethylene and 1-butene can be used.
The content of the olefin resin is preferably in a range that does not impair the flexibility of the resulting thermoplastic elastomer composition, and the addition polymerization block copolymer (I) 10
It is preferably 0 to 200 parts by mass with respect to 0 parts by mass.

Further, the thermoplastic elastomer composition of the present invention may contain an inorganic filler other than the surface-treated calcium carbonate (IV). As the inorganic filler,
For example, talc, clay, synthetic silicon, titanium oxide, carbon black, barium sulfate, etc. can be used. The content of the inorganic filler is preferably within a range in which the heat fusion property of the obtained thermoplastic elastomer is not impaired, and is 0 to 50 parts by mass with respect to 100 parts by mass of the addition polymerization block copolymer (I). Preferably.

Further, in the thermoplastic elastomer composition of the present invention, in addition to the above-mentioned components, a lubricant, a light stabilizer, a pigment,
A flame retardant, an antistatic agent, a silicone oil, an antiblocking agent, an ultraviolet absorber, an antioxidant and the like may be appropriately contained.

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. At least one layer of the thermoplastic elastomer composition of the present invention and other materials are preferable, since it has adhesiveness to metal and metal, and good molding processability, oil resistance, mechanical properties, heat resistance and the like. Can be widely used for a laminated structure having at least one layer composed of at least one selected from polar resins and metals.

The method for producing a laminated structure using the heat-capable elastomer composition of the present invention includes T-die laminate molding method, co-extrusion molding method, blow molding method, insert injection molding method, two-color injection molding method, Various melt lamination molding methods such as a core back injection molding method, a sandwich injection molding method, an injection press molding method can be used. Of the above-mentioned molding methods, the insert injection molding method means that a core material (polar resin) is injection-molded in advance, a shaped molded product is inserted into a mold, and then a space between the molded product and the mold is formed. Is a molding method of injection molding a surface layer material (thermoplastic elastomer composition). In addition, the two-color injection molding method is a method in which two or more injection molding machines are used to injection-mold a core material, and then the mold is rotated or moved to replace the mold cavity. This is a molding method in which a surface layer material is injection-molded in a space formed between the product and the mold. Further, the core-back injection molding method refers to injection molding of a core material by using one injection molding machine and one mold, and thereafter, the volume of the mold cavity is expanded to obtain the molded product and the mold. It is a molding method in which a surface layer material is injection-molded in a space between and. The core material can be molded by various molding methods such as a normal injection molding method and a gas injection molding method. In the laminated structure included in the present invention, the shape of the core material is not particularly limited, and a plate shape, a sheet shape,
In addition to the tape shape, it may have various shapes such as a cylindrical shape and a rod shape, and may have a laminated structure on a part of the surface of these core materials.

The laminated structure obtained by such a melt lamination molding method can be used as various industrial parts.
Specifically, instrumental parts, center panels, center console boxes, door trims, pillars, assist grips, steering wheels, automobile interior parts such as airbag covers, automobile exterior parts such as moldings, vacuum cleaner bumpers, remote control switches, OA equipment. Home appliances such as various key tops, underwater products such as underwater glasses, underwater camera covers, various cover parts, industrial parts with various packings for the purpose of sealing, waterproofing, soundproofing and vibration isolation, racks and pinions Automotive functional parts such as boots, suspension boots, constant velocity joint boots, curl cord electric wire coatings, electric and electronic parts such as belts, hoses, tubes, and silence gears,
It can be used for sports equipment, miscellaneous goods, stationery, etc.

[0051]

[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, the production of test pieces, the measurement of adhesiveness (peel strength) and various physical properties, and the evaluation of the quality of molded articles were carried out as follows.

Measurement of Tensile Breaking Strength, Tensile Breaking Elongation, and Tensile Elastic Modulus: The thermoplastic elastomer compositions obtained in Examples or Comparative Examples were treated with a 15-ton injection molding machine [FANU].
C “ROBOSHOT-α15”],
Molding was performed under the conditions of a cylinder temperature of 220 ° C. and a mold temperature of 40 ° C. to obtain No. 2 dumbbell. Using this No. 2 dumbbell, using Autograph [Shimadzu Corporation],
According to JIS-K6301, the tensile breaking strength, the tensile breaking elongation, and the tensile elastic modulus were measured under the condition of 500 mm / min.

Measurement of hardness (JIS-A): The thermoplastic elastomer composition obtained in each of Examples and Comparative Examples was measured with 80
Ton injection molding machine ["IS-80" manufactured by Nissei Plastic Co., Ltd.]
Was used under the conditions of a cylinder temperature of 220 ° C. and a mold temperature of 40 ° C. to obtain a flat plate of 200 mm × 200 mm × 2 mm. Using this flat plate, A hardness was measured according to JIS-K6301.

Measurement of compression set: The thermoplastic elastomer compositions obtained in Examples or Comparative Examples were measured for cylinder temperature using an 80-ton injection molding machine ["IS-80" manufactured by Nissei Plastic Industry Co., Ltd.]. Molded under the conditions of 220 ° C. and mold temperature of 40 ° C. to produce a right columnar molded product having a diameter of 29.0 mm and a thickness of 12.7 mm, and according to JIS-K6301, temperature 70 ° C., compression deformation amount. The compression set after standing for 22 hours under the condition of 25% was measured.

Measurement of adhesiveness (peeling strength): Polycarbonate resin ["L-1250" manufactured by Teijin Chemicals Ltd .; hereinafter abbreviated as PC], acrylonitrile / styrene /
Butadiene-based resin [Ube Saikon Co., Ltd. "Cycolac T"; hereinafter abbreviated as ABS], polymethacrylate resin [Kuraray Co., Ltd. "Parapet GF"; hereinafter abbreviated as PMMA], and Polyamide 66 resin [Asahi Kasei Kogyo Co., Ltd. "Leona 1300S"; hereinafter abbreviated as PA66] was used with a 100 ton injection molding machine [Nissei Plastic Industry Co., Ltd. "SG-100"] 100
A flat plate of mm × 50 mm × 1 mm was formed. Obtained A
Plate each plate of BS, PC, PMMA and PA66 for 10
It was fixed in a 0 mm × 50 mm × 2 mm flat plate mold, and the thermoplastic elastomer composition obtained in Examples or Comparative Examples was molded under the conditions of a cylinder temperature of 220 ° C. and a mold temperature of 40 ° C. A flat plate molded product of layers was obtained. A test piece measuring 75 mm × 25 mm × 2 mm was cut out from the obtained flat plate molded product to obtain a test piece for measuring adhesiveness (peel strength). The adhesion test was performed according to JIS-K6854.

In the following Examples or Comparative Examples, addition polymerization type block copolymer (I), polyurethane elastomer (II), polyurethane type block copolymer (III), surface treated calcium carbonate (IV), calcium carbonate and The following was used as the paraffinic oil (V).

Addition-polymerization block copolymer (I): a triblock copolymer composed of polystyrene block / hydrogenated polybutadiene block / polystyrene block. The number average molecular weight is 200,000, the styrene content on the basis of the block copolymer before hydrogenation is 33% by mass, and the hydrogenation rate of the butadiene unit is 98 mol%.

Polyurethane elastomer (II) Polyurethane elastomer (II-1): number average molecular weight 3
500 poly (3-methyl-1,5-pentaneadipate) diol, 1,4-butanediol and 4,4 ′
Made from diphenylmethane diisocyanate. JIS-A hardness 65. Polyurethane elastomer (II-2): number average molecular weight 3
500 poly (3-methyl-1,5-pentaneadipate) diol, 1,4-butanediol and 4,4 ′
Made from diphenylmethane diisocyanate. JIS-A hardness 80.

Polyurethane block copolymer (II
I): Polyurethane-SEEPS diblock copolymer pre-dried polyurethane (poly (3-methyl-1,5-pentaneadipate) diol having a number average molecular weight of 3500, 1,4-butanediol and 4,4′- Manufactured from diphenylmethane diisocyanate; JIS
-A hardness 65) 100 parts by mass, and a terminal-modified triblock copolymer (polystyrene block having a hydroxyl group at the end / 1,3-butadiene / isoprene hydrogenated copolymer block / polystyrene block (number average molecular weight: 4)
0000, styrene content on the basis of block copolymer before hydrogenation = 30 mass%, molar ratio of 1,3-butadiene unit and isoprene unit = 1/1, hydrogenation of 1,3-butadiene unit and isoprene unit Ratio = 98 mol%, hydroxyl group content per molecule = 0.8; hereinafter referred to as "SEEPS
After premixing 100 parts by mass of "-OH", a twin-screw extruder (Plastic Industry Research Laboratory "BT-"
30 "), the mixture is melted and kneaded at a cylinder temperature of 220 degrees and a screw rotation speed of 150 rpm to form polyurethane reaction product pellets, and unreacted polyurethane is extracted and removed from the pellets using dimethylformamide. Unreacted SEEP with cyclohexane
What was obtained by extracting and removing S-OH and drying the remaining solid substance.

Surface treatment calcium carbonate (IV): “Snowlight SS” manufactured by Maruo Calcium Co., Ltd. (heavy calcium carbonate; dry surface treatment with fatty acid; average particle size 2.2 μm)

Calcium carbonate (without surface treatment): "Super # 2000" manufactured by Maruo Calcium Co., Ltd. (heavy calcium carbonate; average particle size 1.1 μm)

Paraffin oil (V): "PW-380" manufactured by Idemitsu Kosan Co., Ltd.

<Examples 1 to 9> The above-mentioned addition polymerization block copolymer (I) and polyurethane elastomer (I
I), polyurethane block copolymer (III), surface-treated calcium carbonate (IV) and paraffinic oil (V) were premixed in the proportions shown in Table 1 below, and then twin-screw extruder (Plastics Industry Laboratory) Manufactured "BT-30") and melt-kneaded at a cylinder temperature of 220 degrees and a screw rotation speed of 150 rpm to obtain pellets. Next, using the pellets, a test piece was prepared by the method described above, and the adhesiveness and mechanical properties were measured by the method described above. The results are shown in Table 1 below.

[0064]

[Table 1]

<Comparative Examples 1 to 3> The above-mentioned addition polymerization block copolymer (I) and polyurethane elastomer (I
I), polyurethane block copolymer (III), calcium carbonate and paraffin oil (V) are shown in Table 2 below.
After premixing at the ratio shown in (1), the mixture was supplied to a twin-screw extruder ("BT-30" manufactured by Plastic Industry Laboratory Co., Ltd.) and melt-kneaded at a cylinder temperature of 220 degrees and a screw rotation speed of 150 rpm to obtain pellets. Then using this pellet,
The test piece was prepared by the above-mentioned method, and the adhesiveness and mechanical properties were measured by the above-mentioned method. The results are shown in Table 2 below.

[0066]

[Table 2]

Comparison of Example 1 containing 200 parts by mass of paraffinic oil (V) with Comparative Example 1 in Examples and Comparative Examples containing 100 parts by mass of calcium carbonate in Tables 1 and 2 above. From the comparison between Example 4 containing 80 parts by mass of paraffinic oil (V) and Comparative Example 2 and the comparison between Example 7 containing no paraffinic oil (V) and Comparative Example 3, the addition polymerization system described above was compared. Block copolymer (I), polyurethane elastomer (II),
The thermoplastic elastomer composition of Example containing the polyurethane block copolymer (III), the surface-treated calcium carbonate (IV) and the paraffinic oil (V) in the proportions defined in the present invention was surface-treated. It can be seen that, as compared with the composition obtained from the comparative example containing calcium carbonate which is not added, the adhesiveness to the polar resin and the tensile properties are excellent.

[0068]

INDUSTRIAL APPLICABILITY The thermoplastic elastomer composition of the present invention has excellent adhesiveness to polar resins despite containing a large amount of filler, and has good rubber-like properties, oil resistance and molding processability. Therefore, it is extremely suitable for various molded products such as automobile interior parts, home electric appliances parts, sports equipment, miscellaneous goods, and stationery, as well as for a wide range of other applications, alone or in the fields of co-extrusion and multi-layer molding. It can be used effectively.

─────────────────────────────────────────────────── ─── Continuation of front page (51) Int.Cl. ⁷ Identification code FI theme code (reference) C08L 91/00 C08L 91/00 F term (reference) 4F100 AA02A AB01B AH02A AK01B AK51A AK73A AL02A AL09A BA02 BA07 GB33 GB48 GB71 GB87 JB07 JK07 JL01 JL11 4J002 BP01W CK03X CK04X CQ03Y DE236 FB166 FB216 FB236 FB266 FD016 GF00 GN00 GQ00

Claims (8)

[Claims] 1. A block copolymer having (i) a polymer block (A-1) composed of an aromatic vinyl compound unit and a polymer block (B-1) composed of a conjugated diene compound unit, and hydrogenation thereof. At least one selected from
(Ii) 10 to 300 parts by mass of the polyurethane elastomer (II); (iii) a polymer block consisting of an aromatic vinyl compound unit (A-2); And a polymer block (B-2) composed of a conjugated diene compound unit and an addition polymerization system derived from at least one addition polymerization block copolymer selected from hydrogenated products thereof. 5 to 200 parts by mass of a polyurethane block copolymer (III) comprising a block (C) and a polyurethane block (D) derived from a polyurethane elastomer; and (iv) 50 to 500 parts by mass of surface-treated calcium carbonate (IV). A thermoplastic elastomer composition containing; 2. The thermoplastic elastomer composition according to claim 1, wherein the polyurethane elastomer (II) contains a poly (3-methyl-1,5-pentaneadipate) diol unit having a molecular weight of 2000 or more as a constituent component. object. 3. The thermoplastic elastomer composition according to claim 1, wherein the surface-treated calcium carbonate (IV) is surface-treated with a fatty acid. 4. The thermoplastic elastomer composition according to claim 1, further comprising 300 parts by mass or less of paraffinic oil (V). 5. The thermoplastic elastomer composition according to any one of claims 1 to 4, which has a JIS-A hardness of 20 to 90. 6. A laminated structure having a layer made of the thermoplastic elastomer composition according to claim 1 and a layer made of another material. 7. The laminated structure according to claim 6, wherein the layer made of another material is a layer made of at least one selected from polar resins and metals. 8. The laminated structure according to claim 6, wherein the thermoplastic elastomer composition according to any one of claims 1 to 5 is melt-laminated with respect to a layer made of another material. Production method.