JPH11302495A - Thermoplastic polymer composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain thermoplastic polymer compositions excellent in clarity, softness, elasticity, mechanical properties, oil resistance and molding processability and excellent in melt adhesion to various types of materials, and laminated structures of these compositions with other materials. SOLUTION: Desired thermoplastic polymer compositions comprise a diblock copolymer of formula I: A1-B1 (wherein A1 is an aromatic vinyl compound based polymer block; and B1 is a conjugated diene compound based polymer block) and/or a hydrogenated product thereof; a triblock copolymer of formula II: A2-B2-A3 (wherein A2 and A3 are each an aromatic vinyl. compound based polymer block; and B2 is a conjugated diene compound based polymer block) and/or a hydrogenated product; a polyurethane type block copolymer having an addition polymerization block composed of a block copolymer having an aromatic vinyl compound based polymer block and a conjugated diene compound based polymer block and/or a hydrogenated product thereof and a polyurethane elastomer block; a polyurethane elastomer; and a paraffinic oil.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a thermoplastic polymer composition having excellent melt adhesion and transparency, a laminated structure having a layer of the thermoplastic polymer composition and a layer made of another material, and a laminate having the same. It relates to a manufacturing method. More specifically, the present invention is excellent in transparency, flexibility, elasticity, mechanical properties, oil resistance and moldability, and furthermore, it is strongly melt-bonded in common to various materials to form the thermoplastic polymer. A thermoplastic polymer composition capable of easily and smoothly producing various laminated structures and composites having a layer of the composition and a layer composed of the material by fusion bonding, and a thermoplastic polymer composition. The present invention relates to a laminated structure having a layer and a layer of another material, and a method for producing the same.

[0002]

2. Description of the Related Art A block copolymer having a styrene-based polymer block and a diene-based polymer block (hereinafter sometimes referred to as a "styrene-diene block copolymer") and a hydrogenated product thereof have rubber elasticity at ordinary temperature. One of the so-called thermoplastic elastomers (thermoplastic elastomers), because it has plasticity and melting by heating and can be easily molded and molded and has an excellent balance between flexibility and mechanical properties In recent years, it has been widely used in various fields.

One of the typical applications is a laminated structure (composite) having a layer of a styrene-diene block copolymer and / or a hydrogenated product thereof and a layer of a plastic and / or metal. be able to. And the plastic layer in the laminated structure described above, polyethylene, polypropylene, ethylene-vinyl acetate copolymer, ethylene-vinyl alcohol copolymer, polyvinyl chloride, polyvinylidene chloride, polystyrene, impact-resistant polystyrene, ABS resin, Synthetic resins such as polyethylene terephthalate, nylon, and polycarbonate are used. In addition, various metals such as stainless steel, iron, aluminum, copper, tinplate, and tin have been used as metal layers in the above-described laminated structure.

[0004] The above-mentioned laminated structure has a soft styrene-diene block copolymer and / or a hydrogenated layer thereof, and has good touch, elasticity, vibration-proofing, sound-proofing, and cushioning (cushioning). In addition, it has characteristics such as a damage prevention function, and the above-mentioned synthetic resin or metal layer has a shape maintaining function, a reinforcing function, a fixing function, and the like. For this reason, the laminated structure has recently been attracting attention as a high-value-added product, and is in the form of a sheet, a film, various molded products having a complicated shape, for example, an instrument panel for a car or a vehicle, a center console box. , Door trims, pillars, assist grips, and other members, construction materials such as doors and window frames, various switches and knobs for electric products, and various products such as medical casts.

However, the styrene-diene block copolymer and its hydrogenated product are low-polarity materials, and therefore can be melt-bonded to the same kind of low-polarity plastic or the like, and can be integrally formed by melting. Adhesion to plastics and metals with high melting is difficult. for that reason,
When a composite is formed by laminating with a highly polar material, the engaging portion (fitting portion) such as unevenness is made of a member (layer) made of a styrene-diene block copolymer or a hydrogenated product thereof, and made of plastic or metal. A method of providing the members (layers) and engaging (fitting) them together to join them together, a mechanical joining method such as using another joining means, or a joining method using an adhesive is adopted. However, the method of providing the engaging portion such as the unevenness requires a complicated structure of a mold for forming each member, so that it takes time and labor to manufacture the mold and increases the cost. A complicated operation of engaging (fitting) the above members is required. In addition, the method using an adhesive requires a complicated process in that both members are bonded together using an adhesive at the time of manufacturing or after manufacturing both members. In addition, the adhesive used does not always have a high adhesive strength to both materials, and therefore there are problems in terms of poor adhesion, durability of adhesive strength, water resistance and the like. In addition, there is a problem that the working environment and the global environment are deteriorated by the organic solvent used for the adhesive.

In view of the above, various techniques for improving the heat sealability of a thermoplastic elastomer such as a styrene / diene block copolymer or a hydrogenated product thereof have been proposed in the past.
As such a prior art, a heat-fusible composition in which a thermoplastic polyurethane elastomer is blended with a styrene-diene block copolymer or a hydrogenated product thereof is known (JP-A-6-167898, JP-A-8-17898). -7220
No. 4). However, when this heat-fusible composition is used, there are problems that sufficient adhesive strength may not be obtained depending on the kind of material to be laminated thereon and the adhesive strength is not maintained. Moreover, in this heat-fusible composition, it cannot be said that the compatibility (melt dispersibility) between the styrene-diene block copolymer or its hydrogenated product and the polyurethane thermoplastic elastic material is sufficiently good. However, in the case of a multilayer molded product obtained by, for example, multi-layer injection molding, problems such as delamination and variations in adhesive strength tend to occur.

Further, in a thermoplastic polymer composition containing a thermoplastic elastomer such as a styrene / diene block copolymer or a hydrogenated product thereof, the color tone and appearance of a molded article or a laminate obtained by using the same. In order to obtain good properties, it is often required to have excellent transparency.However, conventional heat-resistant materials mainly composed of thermoplastic elastomers such as styrene-diene block copolymers and hydrogenated products thereof are used. Many of the thermoplastic polymer compositions have low transparency, so that the desire to obtain a transparent thermoplastic polymer composition cannot be sufficiently satisfied.

[0008]

An object of the present invention is to provide a polymer block mainly composed of an aromatic vinyl compound, such as a styrene-diene block copolymer or a hydrogenated product thereof, and a polymer block mainly composed of a conjugated diene compound. A thermoplastic polymer composition based on a block copolymer having a coalesced block and / or a hydrogenated product thereof, which has good elasticity and flexibility originally possessed by the block copolymer,
Provides a thermoplastic polymer composition that can be firmly and easily melt-bonded to various materials without impairing various properties such as mechanical properties, oil resistance, moldability, and the like, and has excellent transparency. It is to be. An object of the present invention is to provide a laminated structure (composite) in which a layer of the above-mentioned thermoplastic polymer composition and a layer of another material are melt-bonded, and a method for producing the same.

[0009]

The present inventors have made various studies in order to achieve the above object. As a result, a block copolymer having an aromatic vinyl compound-based polymer block and a conjugated diene compound-based polymer block and / or a hydrogenated product thereof, an aromatic vinyl compound-based polymer block and a conjugated diene compound-based polymer block are formed. Polyurethane-based block copolymer having a block copolymer or an addition-polymerized block comprising a hydrogenated product thereof and a polyurethane elastomer block, a polyurethane elastomer, and a thermoplastic polymer composition containing a paraffinic oil have elasticity, It has been found that it has excellent properties such as flexibility, mechanical properties, oil resistance, and moldability, and that it can be melted and adhered to various materials firmly and easily (Japanese Patent Application No. 10-80315). issue). The present inventors continued further research based on the present invention, and found that (i) one polymer block mainly composed of an aromatic vinyl compound and one polymer block mainly composed of a conjugated diene compound were obtained. At least one diblock copolymer selected from a linked diblock copolymer and a hydrogenated product thereof; (ii) a polymer mainly composed of an aromatic vinyl compound on both sides of one polymer block mainly composed of a conjugated diene compound (Iii) at least one triblock copolymer selected from a triblock copolymer in which one united block is bonded to each unit and a hydrogenated product thereof;
From a block copolymer having a polymer block mainly composed of an aromatic vinyl compound and a polymer block mainly composed of a conjugated diene compound or a polyurethane block copolymer having an addition polymerization block composed of a hydrogenated product thereof and a polyurethane elastomer block The thermoplastic polymer composition containing at least one selected block copolymer; (iv) a polyurethane elastomer; and (v) a paraffinic oil has excellent elasticity, flexibility, mechanical properties, and oil resistance as described above. In addition to the properties of moldability, moldability and good melt adhesion to various materials,
Furthermore, they have found that they have excellent transparency, and have completed the present invention.

That is, the present invention provides (i) a compound represented by the following general formula (i):

[0011]

Embedded image A1-B1 (i) (wherein, A1 represents a polymer block mainly composed of an aromatic vinyl compound, and B1 represents a polymer block mainly composed of a conjugated diene compound.) At least one diblock copolymer (I) selected from copolymers and hydrogenated products thereof; (ii) the following general formula (ii);

[0012]

A2-B2-A3 (ii) (where A2 and A3 each independently represent a polymer block mainly composed of an aromatic vinyl compound;
Represents a polymer block mainly composed of a conjugated diene compound. At least one triblock copolymer (II) selected from the triblock copolymers represented by the following formulas and hydrogenated products thereof: (iii) a polymer block (A4) mainly composed of an aromatic vinyl compound and a conjugated diene A block copolymer having a polymer block (B3) mainly composed of a compound or an addition polymerization block (C) composed of a hydrogenated product thereof
And a polyurethane block copolymer (III) having a polyurethane elastomer block (D); (iv) a polyurethane elastomer (IV); and (v) a paraffinic oil (V). It is a plastic polymer composition.

[0013] The present invention is a laminated structure comprising a layer made of the above-mentioned thermoplastic polymer composition and a layer made of another material. And the present invention
This is a method for producing the above-mentioned laminated structure by melt-laminating a thermoplastic polymer composition with another material.

[0014]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The present invention will be described below in detail. The thermoplastic polymer composition of the present invention comprises the above-described diblock copolymer (I), triblock copolymer (II),
Polyurethane block copolymer (III), polyurethane elastomer (IV) and paraffinic oil (V)
It is necessary to contain the following five components. For example, if one of the diblock copolymer (I) and the triblock copolymer (II) is missing, a thermoplastic polymer composition having excellent transparency cannot be obtained, and the polyurethane block copolymer ( III), one or more of the polyurethane elastomer (IV) and the paraffinic oil (V), the appearance, mechanical properties and / or
Or it becomes inferior in melt adhesion.

The diblock copolymer (I) represented by the above general formula (i) used in the thermoplastic polymer composition of the present invention
Is a polymer block mainly composed of an aromatic vinyl compound A1 [hereinafter referred to as “aromatic vinyl polymer block (A
1)] and a diblock copolymer in which B1 which is a polymer block mainly composed of a conjugated diene compound [hereinafter referred to as “conjugated diene polymer block (B1)”] is bonded one by one and a hydrogenated product thereof. It consists of at least one selected. Further, the triblock copolymer (II) represented by the above general formula (ii) used in the thermoplastic polymer composition of the present invention is a polymer block mainly composed of a conjugated diene compound, B2 [hereinafter referred to as “conjugated”. A diene polymer block (B2) "], A2 and A2, which are polymer blocks mainly composed of an aromatic vinyl compound.
3 [hereinafter referred to as “aromatic vinyl polymer block (A2)” and “aromatic vinyl polymer block (A3)”] and at least one selected from a triblock copolymer and a hydrogenated product thereof. ing. Further, the polyurethane-based block copolymer (III) used in the present invention comprises a polymer block (A4) mainly composed of an aromatic vinyl compound (hereinafter referred to as “aromatic vinyl polymer block (A4)”) and a conjugated diene compound. A block copolymer having a main polymer block (B3) [hereinafter referred to as “conjugated diene polymer block (B3)”] or an addition polymerization block (C) made of a hydrogenated product thereof; and a polyurethane elastomer block (D) Is a polyurethane block copolymer having the following formula:

The aromatic vinyl polymer block (A1) in the diblock copolymer (I), the aromatic vinyl polymer block (A2) and the aromatic vinyl polymer block (A3) in the triblock copolymer (II) Examples of the aromatic vinyl compound constituting the aromatic vinyl polymer block (A4) in the addition polymerization block (C) of the polyurethane block copolymer (III) include styrene, α-methylstyrene, β- Methylstyrene, o-,
m-, p-methylstyrene, t-butylstyrene, 2,
Examples thereof include vinyl aromatic compounds such as 4-dimethylstyrene, 2,4,6-trimethylstyrene, monofluorostyrene, difluorostyrene, monochlorostyrene, dichlorostyrene, methoxystyrene, vinylnaphthalene, vinylanthracene, indene, and acetonaphthylene. . Aromatic vinyl polymer block (A
1), (A2), (A3) and (A4) may have a structural unit composed of only one kind of the above-mentioned aromatic vinyl compound, or have a structural unit composed of two or more kinds. Is also good. Among them, the aromatic vinyl polymer blocks (A1), (A2), (A3) and (A4) are preferably mainly composed of structural units derived from styrene.

An aromatic vinyl polymer block (A1),
(A2), (A3) and (A4) 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. The ratio of the structural unit composed of another copolymerizable monomer is
Aromatic vinyl polymer blocks (A1), (A2), (A
It is preferably at most 30% by weight, more preferably at most 10% by weight, based on the weight of 3) or (A4). In this case, examples of other copolymerizable monomers include ionic polymerizable monomers such as 1-butene, pentene, hexene, butadiene, isoprene, and methyl vinyl ether.

Further, the conjugated diene polymer block (B1) in the diblock copolymer (I) and the conjugated diene polymer block (B1) in the triblock copolymer (II)
2) and polyurethane block copolymer (III)
Examples of the conjugated diene compound constituting the conjugated diene polymer block (B3) in the addition polymerization block (C) are isoprene, butadiene, hexadiene, 2,3-
Examples thereof include dimethyl-1,3-butadiene and 1,3-pentadiene. The conjugated diene polymer blocks (B1), (B2) and (B3) may be composed of one or more of these conjugated diene compounds. When the conjugated diene polymer blocks (B1), (B2) and / or (B3) have structural units derived from two or more conjugated diene compounds, their bonding forms are random, tapered, and partially It may be in the form of a block or a combination of two or more of them.

Among them, the conjugated diene polymer block (B1), (B2) and / or (B3) is preferably a polyisoprene block composed of a monomer unit mainly composed of an isoprene unit, or Hydrogenated polyisoprene block in which some or all of its unsaturated bonds are hydrogenated; polybutadiene block composed of monomer units mainly composed of butadiene units or hydrogenated polybutadiene in which some or all of its unsaturated bonds are hydrogenated Block; or an isoprene / butadiene copolymer block composed of monomer units mainly composed of isoprene units and butadiene units, or a hydrogenated isoprene / butadiene copolymer block in which some or all of the unsaturated bonds are hydrogenated. . In particular, the conjugated diene polymer block (B1), (B2) and / or (B3) is more preferably the above-mentioned polyisoprene block, isoprene / butadiene copolymer block or a hydrogenated block thereof.

The conjugated diene polymer blocks (B1), (B
In the above polyisoprene block which can be a constituent block of 2) and / or (B3), before hydrogenation, the unit derived from isoprene has a 2-methyl-2-butene-1,4-diyl group [− CH ₂ -C (CH ₃ ) = CH
—CH 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 at least one group selected from the group consisting of: and the ratio of each unit is not particularly limited.

Conjugated diene polymer blocks (B1), (B
In the above-mentioned polybutadiene block which can be a building block of 2) and / or (B3), before the hydrogenation, 70 to 20 mol% of the butadiene unit, particularly 6
5 to 40 mol% is a 2-butene-1,4-diyl group (-C
H ₂ —CH ＝ CH—CH ₂ —; 1,4-linked butadiene unit), and 30 to 80 mol%, particularly 35 to 60 mol%.
Is a vinylethylene group [-CH (CH = CH) -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.

The conjugated diene polymer blocks (B1), (B
In the above isoprene / butadiene copolymer block which can be a constituent block of 2) and / or (B3),
Before the hydrogenation, the units derived from isoprene are 2-
It comprises at least one group selected from the group consisting of a methyl-2-butene-1,4-diyl group, an isopropenylethylene group and a 1-methyl-1-vinylethylene group, and a unit derived from butadiene is 2-butene
It comprises a 1,4-diyl group and / or a vinylethylene group, and the ratio of each unit is not particularly limited. In the isoprene / butadiene copolymer block, the arrangement of isoprene units and butadiene units is random, block,
It may be in any form of a tapered block. In the isoprene / butadiene copolymer block, the molar ratio of isoprene unit: butadiene unit is preferably from 1: 9 to 9: 1, and preferably from 3: 7 to 7: 3, from the viewpoint of the effect of improving the physical properties of rubber. Is more preferable.

The diblock copolymer (I), triblock copolymer (II) and polyurethane block copolymer (III) provide a thermoplastic polymer composition having good heat resistance and weather resistance. From the viewpoint, some or all of the unsaturated double bonds in the conjugated diene polymer blocks (B1), (B2) and (B3) are hydrogenated (hereinafter referred to as “hydrogenated”).
It is preferable). At that time, the hydrogenation ratio of the conjugated diene polymer blocks (B1), (B2) and (B3) is preferably 50 mol% or more, more preferably 60 mol% or more, and more preferably 80 mol% or more. It is more preferred that there be.

In the triblock copolymer (II),
The aromatic vinyl polymer block (A2) and the aromatic vinyl polymer block (A3) may be the same or different polymer blocks.

In the addition polymerization block (C) of the diblock copolymer (I), triblock copolymer (II) and polyurethane block copolymer (III), aromatic vinyl polymer block (A1), (A2), (A3) and (A4) molecular weights and conjugated diene polymer blocks (B
The molecular weights of 1), (B2) and (B3) are not particularly limited, but the number average molecular weights of the aromatic vinyl polymer blocks (A1), (A2), (A3) and (A4) before hydrogenation. Is in the range of 2,500 to 75,000, and the number average molecular weight of the conjugated diene polymer blocks (B1), (B2) and (B3) is 10,000 to 150,0.
It is preferable that it is in the range of 00 from the viewpoint that the rubber properties and the like of the thermoplastic polymer composition become excellent. The total number average molecular weight of the diblock copolymer (I) is in the range of 12,500 to 225,000 before hydrogenation, and the total number average molecular weight of the triblock copolymer (II) is Is 15,000 to 300,000 before hydrogenation
And the number average molecular weight of the addition-polymerized block (C) in the polyurethane-based block copolymer (III) is 15,000 to 300,000 before hydrogenation.
It is preferable from the viewpoint of the mechanical properties, moldability and the like of the thermoplastic polymer composition. In addition, the number average molecular weight referred to in the present specification refers to a value determined from a standard polystyrene calibration curve by gel permeation chromatography (GPC).

The diblock copolymer (I) and the triblock copolymer (II) used in the thermoplastic polymer composition of the present invention may optionally have a functional group such as a hydroxyl group at the molecular terminal. .

The polyurethane elastomer block (D) in the polyurethane block copolymer (III) may be any block as long as it is a block made of a polyurethane elastomer, but a polyurethane elastomer of the same type or similar to the polyurethane elastomer (IV) described later. What is formed is that the compatibility between the polymers in the thermoplastic polymer composition is good, and the mechanical properties of the thermoplastic polymer composition and the molded article and the laminated structure obtained therefrom are excellent. It is preferable from the point that it becomes.

The polyurethane elastomer block (D) in the polyurethane block copolymer (III) has a number average molecular weight of 200 to 15 from the viewpoint that the rubber properties of the thermoplastic polymer composition become better.
It is preferably in the range of 5,000,
More preferably, it is in the range of 0.000.

Polyurethane block copolymer (III)
Is a diblock copolymer having one addition-polymerized block (C) and one polyurethane elastomer block (D), or the addition-polymerized block (C) and the polyurethane elastomer block (D) A polyblock copolymer in which three or four or more polyblocks are combined in total may be used, but from the viewpoint of compatibility, mechanical properties, and moldability of the obtained thermoplastic polymer composition, one addition polymerization system may be used. It is preferably a diblock copolymer in which the block (C) and one polyurethane elastomer block (D) are bonded.

The method for producing the diblock copolymer (I), the triblock copolymer (II) and the polyurethane block copolymer (III) is not particularly limited, and each of the block copolymers having the above-mentioned structures is used. May be produced by any method as long as it can be produced, or a commercially available product may be used.

Although not particularly limited, diblock copolymer (I) and triblock copolymer (II)
Can be produced by, for example, an ionic polymerization method such as anionic polymerization or cationic polymerization, a single-site polymerization method, or a radical polymerization method. In the case of the anionic polymerization method, for example, using an alkyllithium compound or the like as a polymerization initiator, in an inert organic solvent such as n-hexane or cyclohexane, successively polymerize an aromatic vinyl compound and a conjugated diene compound to obtain a desired compound. It can be produced by producing a diblock copolymer or a triblock copolymer having a molecular structure and a molecular weight, and then terminating the polymerization by adding an active hydrogen compound such as alcohols, carboxylic acids and water. Then, the diblock copolymer or triblock copolymer produced as described above is preferably hydrogenated in the presence of a hydrogenation catalyst in an inert organic solvent according to a known method, to thereby obtain a hydrogenated diblock copolymer. The copolymer (I) or the triblock copolymer (II) can be obtained.

The diblock copolymer (I) or the triblock copolymer (II) whose terminal is modified with a functional group such as a hydroxyl group can be produced, for example, by the following anionic polymerization method. That is, using an alkyl lithium compound or the like as an initiator, n-hexane, in an inert organic solvent such as cyclohexane, an aromatic vinyl compound, a conjugated diene compound is sequentially polymerized, and when a desired molecular structure and a molecular weight are reached, A compound having an oxirane skeleton such as ethylene oxide, propylene oxide, or styrene oxide, or a lactone-based compound such as ε-caprolactone, β-propiolactone, dimethylpropiolactone (pivalolactone), and the like, and then an alcohol, a carboxylic acid And by adding an active hydrogen-containing compound such as water to terminate the polymerization. Then, the obtained block copolymer is preferably reacted in an inert organic solvent such as n-hexane or cyclohexane in the presence of a hydrogenation catalyst such as a Ziegler catalyst comprising an alkyl aluminum compound and cobalt or nickel. Temperature 20-150 ° C, hydrogen pressure 1
Hydrogenation under a condition of １５０150 kg / cm 2 can give a hydrogenated terminal-modified diblock copolymer (II) or triblock copolymer (II).

Further, without any limitation,
The polyurethane-based block copolymer (III) is, for example,
A polyurethane elastomer, an addition-polymerized block copolymer having an aromatic vinyl polymer block (A4) and a conjugated diene polymer block (B3) and having a functional group, preferably a hydroxyl group at a terminal, and / or a hydrogenated product thereof Can be obtained by kneading and reacting under a melting condition, and extracting and recovering the polyurethane-based block copolymer (III) from the resulting polyurethane-based reaction product. At that time, the melt-kneading of the polyurethane elastomer and the addition-polymerized block copolymer having a functional group at a terminal and / or a hydrogenated product thereof is carried out by a single screw extruder,
It can be performed using a melt kneading device such as a twin screw extruder, a kneader, and a Banbury mixer. Melt kneading conditions are
The type can be selected according to the type of the polyurethane elastomer or the addition-polymerized block copolymer and / or the hydrogenated product thereof, the type of the apparatus, and the like.
The heat treatment may be performed at a temperature of 80 to 250 ° C. for about 1 to 15 minutes.

The polyurethane-based block copolymer (III) may be prepared, for example, by reacting a polymer diol, an organic diisocyanate, and a chain extender in an extruder to produce a polyurethane elastomer. At the beginning of or during the reaction (a), addition polymerization having an aromatic vinyl polymer block (A4) and a conjugated diene polymer block (B3) in the reaction system and a functional group (preferably a hydroxyl group) at a terminal. A polyurethane-based reaction product containing a polyurethane-based block copolymer (III) is formed by adding a system-based block copolymer and / or a hydrogenated product thereof, and a polyurethane-based block copolymer is formed from the polyurethane-based reaction product. It can also be obtained by extracting and recovering the combined (III).

In the above, extraction and recovery of the polyurethane-based block copolymer (III) from the polyurethane-based reaction product can be performed, for example, by pulverizing the polyurethane-based reaction product to an appropriate size, if necessary. Unreacted polyurethane elastomer is extracted and removed by treating with a good polyurethane solvent such as dimethylformamide, and then treated with a good solvent of an addition-polymerized block copolymer such as cyclohexane and / or a hydrogenated product thereof. Of the addition-polymerized block copolymer and / or a hydrogenated product thereof is extracted and the remaining solid is dried.

The polyurethane-based reaction product obtained by reacting a polyurethane elastomer with an addition-polymerized block copolymer having a functional group and / or a hydrogenated product thereof is a polyurethane elastomer, a polyurethane-based block copolymer. It is a mixture mainly composed of a combination (III) and an addition polymerization type block copolymer. The addition-polymerized block copolymer contained in the polyurethane-based reaction product is an addition-polymerized block copolymer having an aromatic vinyl polymer block (A3) and a conjugated diene polymer block (B3), or a hydrogenated copolymer thereof. It is an additive and optionally has an unreacted hydroxyl group at its molecular terminal. And whether the addition-polymerized block copolymer contained in the polyurethane-based reaction product is a diblock copolymer in which one aromatic vinyl polymer block and one conjugated diene polymer block are bonded. Or a hydrogenated product thereof, or a triblock copolymer in which an aromatic vinyl polymer block is bonded to both sides of one conjugated diene polymer block or a hydrogenated product thereof, The diblock copolymer and triblock copolymer correspond to the diblock copolymer (I) and the triblock copolymer (II) used in the thermoplastic polymer composition of the present invention, respectively.

Therefore, the polyurethane-based reaction product obtained above is converted to a polyurethane-based block copolymer (II
When the diblock copolymer (I) or the triblock copolymer (II) is contained together with the polyurethane elastomer (IV) and the polyurethane block copolymer contained in the polyurethane reaction product, The amount of the union (III), the amount of the unreacted polyurethane elastomer, and the amount of the diblock copolymer (I) or the triblock copolymer (II) are calculated, and the amount of each component in the thermoplastic polymer composition is calculated. This polyurethane-based reaction product is left as it is while the content is adjusted to a preferable range [ie, without recovering the polyurethane-based block copolymer (III) from the polyurethane-based reaction product, As it is], it may be used for the production of the thermoplastic polymer composition of the present invention.

The polyurethane elastomer (IV) used in the thermoplastic polymer composition of the present invention is a polyurethane obtained by reacting a polymer diol, an organic diisocyanate and a chain extender. The high molecular weight diol used for the formation of the polyurethane elastomer (IV) has a number average molecular weight of 1,000 to 6,000, which indicates that the thermoplastic polymer composition of the present invention containing the polyurethane elastomer (IV) has a number average molecular weight of 1,000 to 6,000. It is preferable because the mechanical properties, heat resistance, cold resistance, elastic recovery and the like are improved. Here, the number average molecular weight of the high molecular weight diol referred to in this specification is JIS
It is a number average molecular weight calculated based on the hydroxyl value measured by SITE according to K1557.

Examples of the polymer diol which can be used for producing the polyurethane elastomer (IV) include polyester diol, polyether diol, polyester ether diol, polycarbonate diol and polyester polycarbonate diol. Can be formed using one or more of these polymer diols.

The polyester diol usable in the production of the polyurethane elastomer (IV) includes at least one dicarboxylic acid component selected from aliphatic dicarboxylic acids, aromatic dicarboxylic acids and their ester-forming derivatives, and a low molecular diol. And polyester diols obtained by ring-opening polymerization of lactone. 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, and terephthalic acid. , One or more aromatic dicarboxylic acids such as isophthalic acid and orthophthalic acid, and their ester-forming derivatives, for example, ethylene glycol, propylene glycol, 1,4-butanediol, 1,5-pentanediol, Aliphatic diols having 2 to 10 carbon atoms, such as aliphatic diols such as 2,6-hexanediol, 1,9-nonanediol, 3-methyl-1,5-pentanediol and 2-methyl-1,8-octanediol. Polyester diol, polycaprola obtained by polycondensation reaction with one or more kinds Ton diol, mention may be made of a poly-valerolactone diol.

Examples of the polyether diol usable for producing the polyurethane elastomer (IV) include, for example,
Polyethylene glycol, polypropylene glycol,
Examples thereof include polytetramethylene glycol. Examples of the polycarbonate diol that can be used for producing the polyurethane elastomer (IV) include, for example, 1,4-butanediol, 1,5-pentanediol,
Polycarbonate diols obtained by reacting one or more aliphatic diols such as 1,6-hexanediol and 1,8-octanediol with carbonates such as diphenyl carbonate and alkyl carbonate or phosgene. Can be.

The type of organic diisocyanate used for producing the polyurethane elastomer (IV) 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 preferable. Used. Specific examples of such organic diisocyanates include 4,
4'-diphenylmethane diisocyanate, toluene diisocyanate, p-phenylene diisocyanate, xylylene diisocyanate, naphthalene diisocyanate, hydrogenated 4,4'-diphenylmethane diisocyanate (4,4'-dicyclohexylmethane diisocyanate), isophorone diisocyanate, hexamethylene diisocyanate and the like. Among these organic diisocyanates, 4,4′-diphenylmethane diisocyanate is preferably used.

As the chain extender that can be used for producing the polyurethane elastomer (IV), any chain extender conventionally used for producing a polyurethane elastomer can be used, and the type thereof is not particularly limited. Among them, as the chain extender, one or more of aliphatic diols, alicyclic diols and aromatic diols are preferably used. Specific examples of preferably used chain extenders 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,
Examples thereof include diols such as 1,4-bis (β-hydroxyethoxy) benzene. Even before,
Aliphatic diols having 2 to 6 carbon atoms are more preferably used as chain extenders, and 1,4-butanediol is more preferably used.

In the thermoplastic polymer composition of the present invention, as the polyurethane elastomer (IV), a polymer diol,
When the chain extender and the organic diisocyanate are in the range of 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]:
[Mole number of organic diisocyanate] = 1: 0.98-
A polyurethane elastomer obtained by reacting in the range of 1.04 is preferably used. The thermoplastic polymer composition of the present invention containing such a polyurethane elastomer (IV) does not show a sharp rise in melt viscosity during melt molding such as extrusion molding and injection molding, and can be used to produce a desired molded article or laminated structure. Such a product can be manufactured smoothly, and the resulting product has good heat resistance.

Further, polyurethane elastomer (IV)
Has a hardness (JIS A hardness; measured at 25 ° C.) of 55 to 9
A value of 0 is preferred from the viewpoint that the mechanical properties of a product such as a molded product or a laminated structure obtained from the thermoplastic polymer composition are improved and the product has an appropriate hardness. When the hardness of the polyurethane elastomer (IV) is less than 55, the mechanical properties of products such as molded articles and laminated structures obtained from the thermoplastic polymer composition are likely to be low, while the hardness of the polyurethane elastomer (IV) is low. If it exceeds 90, the flexibility of products such as molded articles and laminated structures obtained from the thermoplastic polymer composition tends to be low.

In the thermoplastic polymer composition of the present invention,
When a polyurethane having a soft segment of poly (3-methyl-1,5-pentaneadipate) diol having a number average molecular weight of 2000 or more is used as the polyurethane elastomer (IV), that is, adipic acid and 3-methyl-
A polyester diol having a number average molecular weight of 2,000 or more obtained by polycondensation with 1,5-pentanediol,
When the above-mentioned organic diisocyanate and the polyurethane elastomer obtained by reacting the organic diisocyanate are used, the above-mentioned properties such as flexibility, elasticity, mechanical properties, oil resistance, molding workability, and melt adhesion are excellent, and particularly, compression set resistance. This makes it possible to obtain a thermoplastic polymer composition having more excellent properties and moldability.

The method for producing the polyurethane elastomer (IV) is not particularly limited, and a prepolymer method, a one-shot method, and a known urethanation reaction using the above-mentioned polymer diol, organic diisocyanate and chain extender. It may be manufactured by any of the methods. 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 thermoplastic polymer composition of the present invention, the paraffinic oil (V) has a kinematic viscosity at 40.degree. C. of 20 to 800 centistokes (cst), a fluidity of 0 to -40.degree. A paraffinic oil having a point of 200 to 400C is preferably used, and a paraffinic oil having a kinematic viscosity at 40C of 50 to 600 cst, a fluidity of 0 to -30C and a flash point of 250 to 350C is more preferably used. Can be

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. Those whose number accounts for 50% by weight or more of the total carbon number of the oil are called "paraffin oil". As the paraffinic oil (V) used in the thermoplastic polymer composition of the present invention, any of so-called paraffin oils can be used, but the content of the component having an aromatic ring is 5%. What is not more than weight% is preferably used.

The thermoplastic polymer composition of the present invention is prepared by adding the polyurethane-based block copolymer (III) to 100 parts by weight of the above-mentioned diblock copolymer (I) and triblock copolymer (II) in total. ), 10 to 250 parts by weight of the polyurethane elastomer (IV), and 2 to 150 parts by weight of the paraffinic oil (V), and the polyurethane block copolymer (III) ), 50 to 230 parts by weight of the polyurethane elastomer (IV), and 3 to 100 parts by weight of the paraffinic oil (V).

When the content of the polyurethane block copolymer (III) is less than 5 parts by weight based on 100 parts by weight of the total of the diblock copolymer (I) and the triblock copolymer (II), Diblock copolymer (I) and triblock copolymer (II) and polyurethane elastomer (IV)
, And the surface of the product such as a molded product or a laminated structure obtained by using the thermoplastic polymer composition is roughened and the adhesion between layers is apt to be reduced. On the other hand, if the content of the polyurethane-based block copolymer (III) exceeds 250 parts by weight with respect to the total of 100 parts by weight of the diblock copolymer (I) and the triblock copolymer (II), the thermoplastic polymer will The melt fluidity of the coalesced composition is reduced, and products such as molded articles and laminated structures obtained using the thermoplastic polymer composition are liable to have surface roughness and reduced adhesion between layers.

If the ratio of the polyurethane elastomer (IV) to the total of 100 parts by weight of the diblock copolymer (I) and the triblock copolymer (II) is less than 10 parts by weight, the thermoplastic polymer composition The compression set of a molded product or a laminated structure obtained from the above becomes large, the melt adhesion to other materials is reduced, the surface of the molded product is roughened, and the moldability tends to be unstable. On the other hand, when the ratio of the polyurethane elastomer (IV) to the total of 100 parts by weight of the diblock copolymer (I) and the triblock copolymer (II) exceeds 250 parts by weight, the melt adhesion to other materials decreases. In addition, the surface of the molded article tends to be rough, and the hardness of the molded article tends to increase.

When the ratio of the paraffinic oil (V) to the total of 100 parts by weight of the diblock copolymer (I) and the triblock copolymer (II) is less than 2 parts by weight,
The surface of the molded product is roughened, and it is difficult to obtain a molded product having a suitable hardness. On the other hand, when the ratio of the paraffinic oil (V) to the total of 100 parts by weight of the diblock copolymer (I) and the triblock copolymer (II) exceeds 150 parts by weight, the melt adhesion to other materials is reduced. Problems such as reduction in mechanical properties such as reduction in tensile strength and tensile elongation at break, roughening of the surface of the molded product, and breakage of spray during molding are likely to occur.

In the thermoplastic polymer composition of the present invention, the content ratio of the diblock copolymer (I): triblock copolymer (II) is 90:10 to 10:90 by weight. The weight ratio is more preferably 80:20 to 20:80. When the proportion of diblock copolymer (I) is less than 10% by weight based on the total weight of diblock copolymer (I) and triblock copolymer (II) [triblock copolymer (II) ) Is 9
0% by weight] and when the proportion of the diblock copolymer (I) exceeds 90% by weight [when the proportion of the triblock copolymer (II) is less than 10% by weight]
In any case, it becomes difficult to obtain a thermoplastic polymer composition having excellent transparency.

The thermoplastic polymer composition of the present invention contains, if necessary, other thermoplastic polymers such as an olefin polymer, a styrene resin, a polyphenylene ether resin, and polyethylene glycol together with the above-mentioned components. Is also good. In particular, it is preferable to include an olefin polymer in the thermoplastic polymer composition of the present invention, because the processability and mechanical strength of the thermoplastic polymer composition can be further improved. As the olefin-based polymer, for example, one or two or more of a block copolymer or a random copolymer of polyethylene, polypropylene, polybutene resin, propylene and another α-olefin such as ethylene or 1-butene, and the like. Can be used. The amount of the olefin-based polymer to be added to the thermoplastic polymer composition of the present invention is generally in the range of the diblock copolymer (I) and the triblock copolymer so as not to impair the flexibility of the thermoplastic polymer composition. The amount is preferably 200 parts by weight or less based on 100 parts by weight of the total of the copolymer (II).

Further, the thermoplastic polymer composition of the present invention may contain an inorganic filler, a dye and a pigment, if necessary, for the purpose of reinforcing, increasing the amount, coloring and the like. Since the thermoplastic polymer composition of the present invention itself has excellent transparency, when the inorganic filler and the dye / pigment are blended, the color tone of the inorganic filler or the dye / pigment can be clearly expressed. Thus, a product colored to a desired color tone can be obtained. As the inorganic filler or dye / pigment at that time, for example, calcium carbonate, talc, clay, synthetic silicon, titanium oxide, carbon black, barium sulfate and the like can be used. The blending amount of the inorganic filler and the dye / pigment is preferably within a range where the flexibility of the thermoplastic polymer composition is not impaired. In general, the diblock copolymer (I) and the triblock copolymer (I
100 parts by weight or less is preferable for 100 parts by weight in total of I).

Further, the thermoplastic polymer composition of the present invention comprises:
In addition to the above components, other lubricants, light stabilizers, flame retardants, antistatic agents, silicone oils, antiblocking agents, ultraviolet absorbers, antioxidants, release agents, foaming agents, fragrances, etc. One or more of the components may be contained.

The method for producing the thermoplastic polymer composition of the present invention is not particularly limited, and any method can be used as long as the above-mentioned components used in the thermoplastic polymer composition of the present invention can be uniformly mixed. It may be manufactured, and usually a melt-kneading method is used. Melt kneading can be performed using, for example, a melt kneading device such as a single screw extruder, a twin screw extruder, a kneader, a roller, and a Banbury mixer.
The thermoplastic polymer composition of the present invention can be obtained by melt-kneading at a temperature of 250 ° C. for about 30 seconds to 5 minutes.

Since the thermoplastic polymer composition of the present invention is heat-meltable and excellent in moldability, various molded articles can be produced by using the composition alone. Various molded products having excellent flexibility, elasticity, mechanical properties and oil resistance can be obtained. As a molding method at that time, various molding methods generally used for thermoplastic polymers can be used, for example, injection molding,
Extrusion molding, press molding, blow molding, calendar molding,
Any molding method such as cast molding can be adopted.

Further, the thermoplastic polymer composition of the present invention is extremely excellent in melt adhesion, and can be melted with various other materials (for example, synthetic resin, rubber, metal, wood, ceramic, paper, cloth, etc.). Since it can be firmly bonded below,
It can be used particularly effectively in the production of laminated structures (composite structures) with other materials, and therefore the present invention provides a laminate comprising a layer of the thermoplastic polymer composition of the invention and a layer of another material. Structures (complexes) are included within the scope of the present invention. The type of the other material to which the thermoplastic polymer composition of the present invention is melt-bonded is not particularly limited, and may be any. However, the thermoplastic polymer composition of the present invention is particularly suitable for melt bonding to a polar material. Excellent in nature. Therefore, the present invention
A preferred embodiment thereof includes a laminated structure of the thermoplastic polymer composition and another material having polarity.

Specific examples of other polar materials used for the laminated structure of the present invention include polyurethane, polyamide, polyester, polycarbonate, polyphenylene sulfide, polyacrylate, polymethacrylate, and the like.
Polyether, polysulfone, acrylonitrile / styrene copolymer (AS resin), rubber-reinforced polystyrene (HIPS resin), acrylonitrile-butadiene-styrene copolymer (ABS resin), methyl methacrylate /
Styrene copolymer (MS resin), methyl methacrylate /
Butadiene / styrene copolymer (MBS resin), acrylonitrile / styrene / butadiene copolymer, vinyl chloride polymer, vinylidene chloride polymer, vinyl chloride /
Various synthetic resins such as vinyl acetate copolymer, polyvinylidene fluoride phenol resin and epoxy resin; isoprene rubber, butadiene rubber, butadiene-styrene rubber, butadiene-acrylonitrile rubber, chloroprene rubber,
Various synthetic rubbers such as butyl rubber, urethane rubber, silicone rubber, fluorine rubber, acrylonitrile rubber; iron,
Examples thereof include metals such as aluminum and copper, and various alloys such as stainless steel, tinplate, and tin. However, other materials constituting the laminated structure of the present invention are, of course, not limited to those described above.

In the laminated structure of the present invention, the number of layers, the thickness, the shape, and the structure of each layer are not particularly limited, and can be determined according to the use of the laminated structure. Although not limited in any way, as the laminated structure of the present invention, for example, a laminated structure having one layer of a thermoplastic polymer composition and one layer of another material, A laminated structure having a layer of the thermoplastic polymer composition on both sides thereof, a laminated structure having a layer of the thermoplastic polymer composition between two other material layers, a layer of the thermoplastic polymer composition At least one
A laminated structure having layers and having two or more layers of the same or different other materials can be given. When the laminated structure has two or more layers made of other materials, the other materials constituting each layer may be the same or different. When the laminated structure has two or more layers made of the thermoplastic polymer composition of the present invention, the thermoplastic polymer compositions constituting each layer may be the same or different. Good.

The method for producing the laminated structure of the present invention having the layer composed of the thermoplastic polymer composition of the present invention and the layer composed of other materials is not particularly limited, and any method for producing the laminated structure by melt bonding can be used. Any method may be adopted. Among them, in the production of the laminated structure of the present invention, for example, insert injection molding method, two-color injection molding method,
Injection molding methods such as core back injection molding method, sandwich injection molding method and injection breath molding method; extrusion molding methods such as T-die laminate molding method, co-extrusion molding method and extrusion coating method; blow molding method; calendar molding method; press A molding method involving melting, such as a molding method and a melt casting method, can be employed.

In the case of the insert injection molding method among the above-mentioned molding methods, another material previously formed into a predetermined shape and dimensions is inserted into a mold, and the thermoplastic material of the present invention is inserted therein. A method of injection-molding a polymer composition to produce a laminated structure having a layer composed of the thermoplastic polymer composition of the present invention and a layer composed of another material is generally employed. In this case, the method of forming the other material to be inserted into the mold is not particularly limited. When the other material to be inserted is a synthetic resin or a rubber product, it is manufactured by any method such as injection molding, extrusion molding and cutting to a predetermined size, press molding, and casting. You may. When the other material to be inserted is a metal material, for example, it is previously formed into a predetermined shape and size by a conventional general-purpose method of manufacturing a metal product (casting, rolling, cutting, machining, grinding, etc.). What is necessary is just to form.

In the case of manufacturing a laminated structure by the two-color injection molding method described above, two or more injection molding machines are used to injection-mold other materials into the mold, and then the rotation of the mold is performed. The mold cavity of the present invention is replaced with a mold formed of another material formed by the first injection molding and the second mold wall is formed by exchanging the mold cavity by moving the mold. A method of manufacturing a laminated structure by injection molding the composition is generally employed. In the case of the core-back injection molding method described above, another injection molding machine and one mold are used to first injection-mold another material in the mold to form a molded product, and then the mold is formed. In general, a method is employed in which the cavity of the mold is enlarged, and the thermoplastic polymer composition of the present invention is injection-molded therein to produce a laminated structure.

In the above-described injection molding method, the thermoplastic polymer composition of the present invention is first injected into a mold to produce a first molded article, with the order of injection of the materials reversed, and then the other molded articles are produced. The laminated structure may be manufactured by injection molding a material (such as a thermoplastic resin).

In the case where a laminated structure having a layer of the thermoplastic polymer composition of the present invention and a layer of another thermoplastic material is produced by the above-mentioned extrusion, the inside and outside, the upper and lower sides,
The thermoplastic polymer composition of the present invention and another material (such as a thermoplastic resin) are simultaneously melt-extruded into two or more layers through a mold (e.g., an extrusion die) divided into two or more layers on the left and right sides. A joining method or the like can be adopted. When the other material is not thermoplastic, a laminated structure can be produced by extrusion-coating the thermoplastic polymer composition of the present invention on or around the other material while melting. Furthermore, for example, in the case of performing calendering, the thermoplastic polymer composition of the present invention is calendered under melting and coated and laminated on another material in a melt plasticized state or a solid state. Thus, the intended laminated structure can be manufactured. Further, for example, in the case of press molding, a laminated structure can be manufactured by performing a melt press using the thermoplastic polymer composition of the present invention under arrangement of other materials.

The type, shape and structure of the laminated structure of the present invention
The use and the like are not particularly limited, and any laminated structure having a layer made of the above-described thermoplastic polymer composition of the present invention and a layer made of another material is included in the scope of the present invention. Although not limited, the laminated structure of the present invention can be used as various industrial products and components. Specific examples include instrument panels,
Various interior parts for automobiles and vehicles such as center panels, center console boxes, door trims, pillars, and assist grips; exterior parts for automobiles such as malls; home appliances such as bumpers for vacuum cleaners, remote control switches and knobs, and various key tops for OA equipment Parts; Underwater products such as underwater glasses and underwater camera covers; Various cover parts; Industrial parts with various packings for sealing, waterproof, soundproofing, and vibration-proofing; Rack & pinion boots, suspension boots, constant velocity joints Automotive functional parts such as boots; Electric and electronic parts such as curled cord electric wire covering, belts, hoses, tubes, and sound deadening gears; Sports goods; Building materials such as doors and window frames; Various fittings; Valve parts; And various other products. And, in a product in which a layer made of the thermoplastic polymer composition of the present invention appears on at least one surface of the laminated structure, the thermoplastic polymer composition has elasticity and flexibility, It shows a soft and good feel when contacted, and has shock absorption (cushioning properties) and excellent impact resistance, so that it is also excellent in safety. Also,
By taking advantage of the high transparency, the color tone of another material to be laminated with the thermoplastic polymer composition of the present invention can be exhibited in the product. Further, even when the thermoplastic polymer composition of the present invention is in the form of a colored material, a clear color tone can be exhibited as described above.

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EXAMPLES The present invention will be described below in more detail with reference to examples and the like, but the present invention is not limited thereto. Further, using the pellets of the thermoplastic polymer composition obtained in the following Examples, Comparative Examples or Reference Examples, molded articles (test pieces) and laminated structures were prepared as follows, and their physical properties, that is, The transparency (haze value), hardness, tensile strength at break, tensile elongation at break, 100% modulus, permanent elongation and compression set of the molded product, and peel strength of the laminated structure were measured as follows.

(1) Measurement of Transparency (Haze Value): Using a pellet of the thermoplastic polymer composition produced in the following Examples, Comparative Examples or Reference Examples, an 80-ton injection molding machine (Nissei Plastic Industrial Co., Ltd.) Injection molding was performed using a company-made “IS-80” under the conditions of a cylinder temperature of 220 ° C. and a mold temperature of 40 ° C. to obtain a flat molded product (test piece) (dimensions: length × width × thickness = 200 mm) × 200 mm × 2 mm). A haze meter (“Reflectance Transmitter HR1 manufactured by Murakami Color Research Laboratory Co., Ltd.
00 ”) was used to measure the haze value. In the transparency test, the smaller the haze value, the better the transparency.

(2) Measurement of Hardness: Using a pellet of the thermoplastic polymer composition produced in the following Examples, Comparative Examples or Reference Examples, an 80-ton injection molding machine (“IS- 80 ") using cylinder temperature 22
Injection molding is performed under the conditions of 0 ° C. and a mold temperature of 40 ° C. to obtain a flat molded product (test piece) (dimensions: length × width × thickness = 200 mm)
× 200 mm × 2 mm). Using the flat molded product obtained in this way, A according to JIS-K6301
The hardness was measured.

(3) Measurement of tensile breaking strength, tensile elongation at break and 100% modulus: 80 ton injection molding machine using pellets of thermoplastic polymer composition produced in the following Examples, Comparative Examples or Reference Examples (“IS-80” manufactured by Nissei Plastic Industrial Co., Ltd.)
Injection molding was performed under the conditions of a temperature of 40 ° C. and a mold temperature of 40 ° C. to produce a No. 3 dumbbell test piece, and the dumbbell test piece was used in accordance with JIS-JIS by using an autograph (manufactured by Shimadzu Corporation). According to K6301, the tensile strength at break, tensile elongation at break and 100% modulus were measured under the condition of 500 mm / min.

(4) Measurement of Tensile Permanent Elongation: Using a pellet of the thermoplastic polymer composition produced in the following Examples, Comparative Examples or Reference Examples, an 80-ton injection molding machine (manufactured by Nissei Plastic Industry Co., Ltd.) Using IS-80 ”), injection molding was performed under the conditions of a cylinder temperature of 220 ° C. and a mold temperature of 40 ° C. to produce a No. 3 dumbbell test piece. Using the dumbbell test piece, using an autograph (manufactured by Shimadzu Corporation), stretch under the condition of 100 mm / min. When the tensile elongation reaches 100%, the stretching is stopped and the state is maintained. Hold for 10 minutes. Then release the specimen,
After further standing for 10 minutes, the tensile elongation was measured.

(5) Measurement of compression set: An 80-ton injection molding machine (manufactured by Nissei Plastic Industries Co., Ltd.) using pellets of the thermoplastic polymer composition produced in the following Examples, Comparative Examples or Reference Examples IS-80 ") and injection molding under the conditions of a cylinder temperature of 220 ° C. and a mold temperature of 40 ° C. to obtain a right cylindrical molded product (test piece having a diameter of 29.0 cm and a thickness of 12.7 mm). ) Was prepared, and the compressive deformation strain of the test piece when left for 22 hours under the conditions of a temperature of 70 ° C. and an amount of compressive deformation of 25% according to JIS-K6301 was measured, and the result was defined as a permanent compression set. .

(6) Measurement of Peel Strength in Laminated Structure: (i) Peel Strength in Laminated Structure with Synthetic Resin Plate: (a) ABS resin (“Psycholac T” by Ube Sycon Co., Ltd.), polycarbonate resin ( "L-1250" manufactured by Teijin Chemicals Limited, or polyamide resin (nylon 66, "Leona 1300S" manufactured by Asahi Kasei Corporation)
, And a flat molded product (dimensions: length x width x thickness = 200 mm x 200 mm x 1 mm) was manufactured using an 80-ton injection molding machine ("IS-80" manufactured by Nissei Plastic Industry Co., Ltd.). (B) Each of the flat molded products obtained in the above (a) is placed in a flat mold cavity (dimensions: 200 mm × 20 mm).
(0 mm × 2 mm) and placed in advance, and using the pellets of the thermoplastic polymer composition produced in the following Examples, Comparative Examples or Reference Examples, an 80-ton injection molding machine (Nissei Plastic Industrial Co., Ltd.) Injection molding was performed under the conditions of a cylinder temperature of 220 ° C. and a mold temperature of 40 ° C. using a company “IS-80”), and a layer of a thermoplastic polymer composition was laminated on one surface of the resin plate. Laminated structure (dimensions: vertical × horizontal ×
(Thickness = 200 mm × 200 mm × 2 mm). (C) A test piece for measuring the peel strength from the laminated structure obtained in (b) above (dimensions: length x width x thickness = 150 mm x 2)
5mm x 2mm) and cut it out using JIS-K
The peel strength was measured according to the “180 ° peel test” described in 6854. (Ii) Peel strength in a laminated structure with a metal plate (aluminum plate): Using an aluminum plate (dimensions: 200 mm × 200 mm × 0.2 mm) instead of a synthetic resin plate,
Performed in the same manner as in the above (b), a laminated structure in which a layer of the thermoplastic polymer composition is laminated on one surface of an aluminum plate (dimensions: length × width × thickness = 200 mm × 200 mm × 2 m)
m) was prepared. A test piece for measuring the peel strength (dimensions: length × width × thickness = 150 m) was obtained from the obtained laminated structure.
mx 25 mm x 2 mm), and using it,
The peel strength was measured according to the “180 ° peel test” described in S-K6854.

The diblock copolymer (I), triblock copolymer (II-1), triblock copolymer (II-2) and polyurethane used in the following Examples, Comparative Examples and Reference Examples Abbreviations and contents of the elastomer (IV) and the paraffinic oil (V) are as follows.

[Diblock copolymer (I)] A diblock copolymer consisting of a polystyrene block and a hydrogenated polyisoprene block (number-average molecular weight 100,000, styrene content = 50% by weight, hydrogenation rate in polyisoprene block) = 98%).

[Triblock copolymer (II)] Triblock copolymer (II-1) : Triblock copolymer composed of polystyrene block-hydrogenated polyisoprene block-polystyrene block (number average molecular weight 10
000, styrene content = 30% by weight, hydrogenation rate in polyisoprene block = 98%). Triblock copolymer (II-2) : Triblock copolymer composed of polystyrene block-hydrogenated polyisoprene block-polystyrene block (number average molecular weight 15
000, styrene content = 30% by weight, hydrogenation rate in polyisoprene block = 98%).

[Polyurethane Elastomer (IV)] Polyurethane Elastomer (IV-1) : "Kuramilon U 8165" manufactured by Kuraray Co., Ltd. [Poly (3-methyl-
Polyester-based polyurethane elastomer having 1,5-pentane adipate) as a soft segment] Polyurethane elastomer (IV-2) : "Kuramilon U 8765" manufactured by Kuraray Co., Ltd. [Poly (3-methyl-
Polyester polyurethane elastomer having 1,5-pentane adipate) as a soft segment]

[Paraffinic oil (V)] “PW-380” manufactured by Idemitsu Kosan Co., Ltd.

<< Production Example 1 >> [Production of Polyurethane Block Copolymer (III)] (1) 100 parts by weight of a preliminarily dried polyurethane elastomer ("Kuramilon U8165" manufactured by Co., Ltd.) and a hydroxyl-terminated polystyrene block / 1, Terminal-modified triblock copolymer comprising 3-butadiene / isoprene hydrogenated copolymer block / polystyrene block (number average molecular weight 40,000, styrene content in block copolymer before hydrogenation = 30% by weight, 1 , 3-butadiene unit /
The molar ratio of isoprene units = 1/1, the degree of unsaturation of 1,3-butadiene units and isoprene units = 5%, and the content of hydroxyl groups per molecule = 0.8.
After pre-mixing 100 parts by weight of "PS-OH", a twin-screw extruder ("B" manufactured by Plastics Industrial Research Institute)
T-30 ”), melt-kneaded under the conditions of a cylinder temperature of 220 ° C. and a screw rotation speed of 150 rpm, extruded and cut to produce pellets of a polyurethane reaction product. (2) Unreacted polyurethane was extracted and removed from the pellets of the polyurethane reaction product obtained in the above (1) using dimethylformamide, and then unreacted SEEPS-OH was extracted and removed using cyclohexane and remained. The solid was dried to obtain a polyurethane-based block copolymer (III) which was a diblock copolymer composed of a polyurethane block and a block derived from SEEPS-OH.

Examples 1 to 8 (1) The above-mentioned diblock copolymer (I), triblock copolymer (II) [triblock copolymer (II-1)
Or triblock copolymer (II-2)] and the polyurethane-based block copolymer (II
I), polyurethane elastomer (IV) [polyurethane elastomer (IV-1) or polyurethane elastomer (IV-2)] and paraffinic oil (V) are premixed at the ratio shown in Table 1 below, and then subjected to twin screw extrusion. Machine ("BT-30" manufactured by Plastics Industrial Research Institute)
Cylinder temperature 220 ° C and screw speed 150
The mixture was melt-kneaded under the conditions of rpm, extruded, and cut to produce pellets of the thermoplastic polymer composition. (2) Using the pellets of the thermoplastic polymer composition obtained in the above (1), a molded article (test piece) and a laminated structure are produced by the above-described method, and the transparency (haze value) and hardness thereof are obtained. The tensile strength at break, tensile elongation at break, 100% modulus, permanent elongation and 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 and 2 >> (1) The above triblock copolymer (II) [triblock copolymer (II-1) or triblock copolymer (II-2)], polyurethane elastomer ( IV-1) and the paraffinic oil (V) were premixed in the proportions shown in Table 2 below, and then supplied to a twin-screw extruder ("BT-30" manufactured by Plastics Research Institute) to obtain a cylinder temperature of 2
The mixture was melt-kneaded under conditions of 20 ° C. and a screw rotation number of 150 rpm, extruded, and cut to produce pellets of the thermoplastic polymer composition. (2) Using the pellets of the thermoplastic polymer composition obtained in the above (1), a molded article (test piece) and a laminated structure are produced by the above-described method, and the transparency (haze value) and hardness thereof are obtained. The tensile strength at break, tensile elongation at break, 100% modulus, permanent elongation and permanent compression set, and peel strength of the laminated structure were measured by the methods described above, and were as shown in Table 2 below.

Reference Example 1 (1) The above triblock copolymer (II-1), the polyurethane block copolymer (III) produced in Production Example 1 above, and the above polyurethane elastomer (IV-
1) and the paraffinic oil (V) were premixed in the proportions shown in Table 2 below, and then supplied to a twin-screw extruder ("BT-30" manufactured by Plastics Industrial Research Institute) to obtain a cylinder temperature of 220 ° C and The mixture was melt-kneaded under conditions of a screw rotation speed of 150 rpm, extruded, and cut to produce pellets of a thermoplastic polymer composition. (2) Using the pellets of the thermoplastic polymer composition obtained in the above (1), a molded article (test piece) and a laminated structure are produced by the above-described method, and the transparency (haze value) and hardness thereof are obtained. The tensile strength at break, tensile elongation at break, 100% modulus, permanent elongation and permanent compression set, and peel strength of the laminated structure were measured by the methods described above, and were as shown in Table 2 below. Reference Example 1 corresponds to a part of the above-mentioned prior application by the present inventors (Japanese Patent Application No. 10-80315).

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[Table 1]

[0086]

[Table 2]

From the results in Tables 1 and 2, the diblock copolymer (I), the triblock copolymer (II), the polyurethane block copolymer (III), the polyurethane elastomer (IV) and the paraffin-based When the thermoplastic polymer compositions of Examples 1 to 8 containing oil (V) are used, the haze value is low, and the hardness, tensile strength at break, tensile elongation at break, 100% modulus, permanent elongation, permanent compression resistance are low. Transparency, with a good balance of characteristics such as distortion,
It can be seen that a high-quality molded product excellent in various physical properties such as appearance, mechanical properties, flexibility and elasticity can be smoothly obtained.

Further, from the results in Tables 1 and 2, it is clear that the thermoplastic polymer compositions of Examples 1 to 8 have a high melt adhesion to various materials such as synthetic resins and metals. It has a layer structure made of various materials and a laminated structure made of the thermoplastic polymer composition of the present invention simply by melt molding such as insert injection molding without using an adhesive or the like, easily and That it can be manufactured smoothly,
Moreover, it can be seen that the laminated structure obtained thereby has a high peel strength and does not cause delamination or the like.

On the other hand, from the results of Tables 1 and 2,
Does not contain diblock copolymer (I) and polyurethane block copolymer (III), only three of triblock copolymer (II), polyurethane elastomer (IV) and paraffin oil (V) In the thermoplastic polymer compositions of Comparative Example 1 and Comparative Example 2 containing the same, a molded article obtained therefrom has a high haze value, a large tensile elongation, poor transparency, and poor mechanical properties. Comparative Examples 1 and 2
It can be seen that the thermoplastic polymer composition of the above shows only low melt adhesion to both synthetic resins and metals.
The results in Tables 1 and 2 above indicate that the triblock copolymer (II) and the polyurethane block copolymer (II
Molded articles obtained from the thermoplastic polymer composition of Reference Example 1 containing I), the polyurethane elastomer (IV) and the paraffinic oil (V) are obtained from the thermoplastic polymer compositions of Examples 1 to 8. Although the haze value is high and the transparency is low as compared with the molded product, the other physical properties of Examples 1 to
It is almost the same as No. 8 and also shows that it is excellent in melt adhesion to synthetic resins and metals.

[0090]

Industrial Applicability The thermoplastic polymer composition of the present invention has good elasticity, flexibility, mechanical properties, oil resistance, and moldability, and is excellent in melt adhesion and suitable for various materials. In general, they are firmly adhered to each other under melting, so that a laminated structure or a composite having a layer of the thermoplastic polymer composition of the present invention and a layer made of another material can be easily formed by melt molding or other melt bonding techniques. And can be manufactured smoothly. And
Since the thermoplastic polymer composition of the present invention is excellent in elasticity and flexibility, a laminated structure (composite) having a layer made of the thermoplastic polymer composition of the present invention on at least a part of its surface
Has a soft and resilient good feel, and is also excellent in safety due to its shock absorbing ability and cushioning effect. Further, the thermoplastic polymer composition of the present invention, by utilizing its properties such as excellent elasticity, flexibility, mechanical properties, oil resistance, and good moldability, various thermoplastic polymer compositions alone can be used. It can also be used effectively for the production of molded articles. Moreover, the thermoplastic polymer composition of the present invention has a low haze value and is excellent in transparency. Therefore, by taking advantage of its high transparency, it is possible to produce molded articles and laminates having excellent transparency, and to exhibit the color tone of other materials laminated with the thermoplastic polymer composition of the present invention in the product. When the thermoplastic polymer composition of the present invention is colored using a coloring agent such as a pigment or a dye, a product having a clear color tone and excellent appearance can be obtained.

The molded article made of the thermoplastic polymer composition of the present invention, and the laminated structure of the present invention having the layer of the thermoplastic polymer composition of the present invention and the layer of another material have the above-mentioned excellent properties. Taking advantage of, for example, instrument panel,
Various interior parts for automobiles and vehicles such as center panels, center console boxes, door trims, pillars, and assist grips; exterior parts for automobiles such as malls; home appliances such as bumpers for vacuum cleaners, remote control switches and knobs, and various key tops for OA equipment Parts; Underwater products such as underwater glasses and underwater camera covers; Various cover parts; Industrial parts with various packings for sealing, waterproof, soundproof, and vibration-proof; Rack & pinion boots, suspension boots, constant velocity joints Automobile functional parts such as boots; Electric and electronic parts such as curled cord electric wire covering, belts, hoses, tubes, and silencing gears; Sporting goods; Building materials such as doors and window frames; Various fittings; Valve parts; It can be used very effectively for a wide variety of applications.

 ──────────────────────────────────────────────────続 き Continuing on the front page (72) Inventor Shigeru Kawahara 41 Miyukigaoka, Tsukuba, Ibaraki Pref. Kuraray Co., Ltd.

Claims (6)

[Claims] (I) A1-B1 (i) wherein A1 is a polymer block mainly composed of an aromatic vinyl compound, and B1 is a conjugated diene compound At least one diblock copolymer (I) selected from a diblock copolymer represented by the following general formula (ii): and a hydrogenated product thereof. (Ii) A2-B2-A3 (ii) wherein A2 and A3 each independently represent a polymer block mainly composed of an aromatic vinyl compound;
Represents a polymer block mainly composed of a conjugated diene compound. At least one triblock copolymer (II) selected from the triblock copolymers represented by the following formulas and hydrogenated products thereof: (iii) a polymer block (A4) mainly composed of an aromatic vinyl compound and a conjugated diene A block copolymer having a polymer block (B3) mainly composed of a compound or an addition polymerization block (C) composed of a hydrogenated product thereof
And a polyurethane block copolymer (III) having a polyurethane elastomer block (D); (iv) a polyurethane elastomer (IV); and (v) a paraffinic oil (V). Plastic polymer composition. 2. A polyurethane elastomer comprising 5 to 100 parts by weight of a polyurethane block copolymer (III) based on a total of 100 parts by weight of a diblock copolymer (I) and a triblock copolymer (II). 4. The thermoplastic polymer composition according to claim 1, which contains 10 to 250 parts by weight of (IV) and 2 to 150 parts by weight of paraffinic oil (V). 3. The content ratio of diblock copolymer (I): triblock copolymer (II) is 90:10 to 10:90.
The thermoplastic polymer composition according to claim 1 or 2, wherein the weight ratio is 4. A laminated structure comprising a layer made of the thermoplastic polymer composition according to claim 1 and a layer made of another material. 5. The laminated structure according to claim 5, wherein the other material is at least one selected from a synthetic resin and a metal. 6. A method for producing a laminated structure according to claim 4, wherein the thermoplastic polymer composition according to claim 1 is melt-laminated with another material.