WO2006077772A1

WO2006077772A1 - Thermoplastic polymer composition

Info

Publication number: WO2006077772A1
Application number: PCT/JP2006/300335
Authority: WO
Inventors: Hidekazu Saito; Hiroyuki Ono
Original assignee: Kuraray Co., Ltd.
Priority date: 2005-01-21
Filing date: 2006-01-13
Publication date: 2006-07-27
Also published as: TW200632026A; JP5111851B2; JPWO2006077772A1

Abstract

A thermoplastic polymer composition which comprises a (hydrogenated) block copolymer having an aromatic vinyl polymer block and a conjugated diene polymer block; a block copolymer having an addition polymer block comprising a (hydrogenated) block copolymer having an aromatic vinyl polymer block and a conjugated diene polymer block and a polycarbonate block, or a melt kneading reaction mixture of a (hydrogenated) block copolymer of a polymer block based on an aromatic vinyl compound having a polycarbonate reactive group and a conjugated diene polymer block with a polycarbonate or a polycarbonate forming material; a thermoplastic polyurethane; and a paraffinic oil. The thermoplastic polymer composition is excellent in the melt formability, is improved, in particular, in the occurrence of failures, such as a gum, the uneveness of thickness, a string and a crack, during the melt extrusion forming including the inflation forming, and also is effective for producing a formed article being excellent in flexibility, mechanical performance, wear resistance, light resistance and the like and various composite formed articles being firmly melt-adhered with another material.

Description

Specification

Thermoplastic polymer composition

Technical field

[0001] The present invention relates to a thermoplastic polymer composition, a molded article comprising the thermoplastic polymer composition, and a composite molded article. The thermoplastic polymer composition of the present invention is excellent in handleability and melt moldability, and a melted product such as an extrudate adheres or adheres to a molding apparatus part, particularly a die part in melt extrusion molding, at the time of melt molding. It is possible to perform molding with good productivity, and it is possible to perform various moldings with excellent mechanical properties such as appearance, dimensional stability, flexibility, strength, wear resistance, and light resistance. Since a molded product can be produced smoothly and firmly bonded to various materials, it can be used effectively in the production of various molded products and composite molded articles by making use of these characteristics.

Background art

[0002] A block copolymer having a styrene polymer block and a conjugated gen polymer block and a hydrogenated product thereof (hereinafter collectively referred to as "(hydrogenated) styrene 'conjugated gen block copolymer") Can be easily plasticized and melted by heating, and can be molded easily. Shika also has rubber elasticity at room temperature and has a good balance between flexibility and mechanical properties. For this reason, V is widely used in various fields as a kind of so-called thermoplastic elastomer (thermoplastic elastomer) in recent years.

[0003] (Hydrogenated) Styrene conjugated gen block copolymer has low polarity! Therefore, it has low polarity! Although it can be melt-bonded or integrally formed with other polymers, it has high polarity. ! It is difficult to melt and bond with polymers and metals.

So far, a composition in which an engineering plastic having a specific crystalline melting point and viscosity is blended with a (hydrogenated) styrene 'conjugated gen block copolymer is known. As one of the engineering plastics, a thermoplastic polyurethane is known. Is used (see Patent Document 1). Patent Document 1 describes that the composition is suitable as an insulator for a conductor or a wire for soldering. However, in the case where a thermoplastic polyurethane is used as the engineering plastic, (Hydrogenated) Styrene Conjugated Gen Block Since the compatibility between the copolymer and the thermoplastic polyurethane is poor, the properties of both polymers are not sufficiently exhibited, and a useful composition cannot be obtained.

[0004] In addition, various techniques for improving the heat-fusibility of (hydrogenated) styrene conjugated gen block copolymers have been proposed in the past. As such conventional techniques, (hydrogenated) ) A heat-fusible composition in which a thermoplastic polyurethane is blended with a styrene 'conjugated gen block copolymer is known (see Patent Documents 2 to 4). However, these heat-fusible compositions have problems such that sufficient adhesive strength cannot be obtained depending on the material to be heat-sealed and the adhesive strength is not sustainable. In addition, in these heat-fusible compositions, the compatibility between the (hydrogenated) styrene 'conjugated gen block copolymer and the thermoplastic polyurethane cannot be said to be sufficiently good. The laminated molded products obtained by these methods are prone to problems such as delamination and uneven adhesion.

[0005] (Hydrogenated) styrene 'carbon for the purpose of improving the compatibility between the conjugated gen block copolymer and the thermoplastic polyurethane, and improving the melt adhesion of the composition containing both polymers. A composition in which a thermoplastic polyurethane is blended with a (hydrogenated) styrene 'conjugated gen block copolymer modified with an acid group, a hydroxyl group or other polar group is known (see Patent Documents 5 and 6). . In addition, a (hydrogenated) styrene 'conjugated gen block copolymer modified with a carboxylic acid group and a composition that also has a thermoplastic polyurethane strength are provided with a hindered phenol and a phosphate in order to improve thermal stability during molding. A composition containing a phyto compound is known (see Patent Document 7). However, these compositions are easily molded and adhered to a molding device such as a die part during melt molding, and have a predetermined dimension, and are excellent in surface smoothness and appearance. The product may not be obtained, and it is not sufficiently satisfactory in terms of handleability, melt moldability, etc. In addition, it is also excellent in terms of melt adhesion with other materials. Difficult,

[0006] (Hydrogenated) styrene conjugated gen block copolymer, which can solve the problems in the above-mentioned conventional compositions containing a styrene / conjugated gen block copolymer and a thermoplastic polyurethane, (Hydrogenated) A thermoplastic polymer composition containing an addition polymerization block composed of a styrene / conjugated gen block copolymer and a block copolymer having a polyurethane block, a thermoplastic polyurethane and a paraffinic oil is known. Have (See Patent Document 8). This thermoplastic polymer composition has good flexibility, elasticity, mechanical properties, oil resistance and molding processability, and has excellent melt adhesion and is melted into various materials. It has excellent properties such as strong adhesion. Therefore, the present inventors further studied this thermoplastic polymer composition, and as a result, an addition made of a (hydrogenated) styrene′-conjugated gen block copolymer used in this thermoplastic polymer composition. A block copolymer having a polymerization block and a polyurethane block may be dissociated at the joint between the addition polymerization block and the polyurethane block depending on the thermal conditions during molding molding. It has been found that there is room for further improvement from the standpoint of improving heat resistance at the plant. Moreover, there was room for further improvement from the viewpoint of obtaining a thermoplastic polymer composition having higher tensile breaking strength.

[0007] Patent Document 1: Japanese Patent Laid-Open No. 52-150464

Patent Document 2: JP-A-6-65467

Patent Document 3: JP-A-6-107898

Patent Document 4: JP-A-8-72204

Patent Document 5: Japanese Patent Laid-Open No. 63-99257

Patent Document 6: Japanese Patent Laid-Open No. 3-234755

Patent Document 7: JP-A-7-126474

Patent Document 8: Japanese Patent Application Laid-Open No. 11-323073

Patent Document 9: Japanese Patent Laid-Open No. 2001-220505

Patent Document 10: Japanese Patent Application Laid-Open No. 2001-220506

Patent Document 11: Japanese Patent Laid-Open No. 10-139963

Disclosure of the invention

Problems to be solved by the invention

[0008] As described above, the range of use of various thermoplastic elastomers including (hydrogenated) styrene 'conjugated gen block copolymers has been expanded, and accordingly, molding processability is further improved. There is a demand for high-performance power.

The object of the present invention is to solve the above-mentioned problems in the prior art, and is excellent in melt moldability, handling and performance without adhesion or adhesion to a molding apparatus during melt molding, and particularly in Produces molded products with excellent appearance and dimensional stability without adhesion of extrudates to the die during melt extrusion molding, including freight molding, and without thickness spots, cracks, or streaks in the molded products. Molded products that can be manufactured smoothly and with excellent mechanical properties such as flexibility, tensile breaking strength, wear resistance, light resistance, heat resistance, and melt adhesion with other materials. The object is to provide a thermoplastic polymer composition capable of producing a composite molded body.

Furthermore, an object of the present invention is to provide a molded article made of the thermoplastic polymer composition and a composite molded body of the thermoplastic polymer composition and other materials.

Means for solving the problem

In the course of studying the thermoplastic polymer composition described in Patent Document 8 described above, the present inventors included an addition polymerization block composed of a (hydrogenated) styrene 'conjugated gen block copolymer contained therein. If the thermal stability of the block copolymer having a polyurethane block can be raised to a higher level, the adhesion of the extrudate to the die portion that occurs during melt extrusion molding can be prevented or reduced, so that I came up with the idea that defective phenomena such as thick spots, streaks, and cracks could be improved, and further research. Then, in the thermoplastic polymer composition described in Patent Document 8, a (hydrogenated) styrene block having an addition polymerization system block having a conjugated gen block copolymer force and a polyurethane block used therein. A new thermoplastic polymer composition was prepared by replacing the copolymer with a block copolymer having an addition polymerization block (polyhydrogenated) styrene-conjugated gen block copolymer and a polycarbonate block. Handling, properties, melt moldability, physical properties, etc. were examined. As a result, the thermoplastic polymer composition containing an addition polymerization block composed of a (hydrogenated) styrene conjugated gen block copolymer and a block copolymer having a polycarbonate block is transferred to a molding apparatus during melt molding. Extrusion does not adhere to the die part during melt extrusion molding including inflation molding, and the thickness unevenness during extrusion molding is excellent. It has been found that there are no streaks, cracks, etc., and it is also excellent in mechanical properties such as flexibility, tensile breaking strength, wear resistance, light resistance, heat resistance, and melt adhesion with other materials. It was. [0010] Further, in the thermoplastic polymer composition described above, the present inventors provide a block copolymer having an addition polymerization block composed of a (hydrogenated) styrene 'conjugated gen block copolymer and a polycarbonate block. A block copolymer prepared by reacting polycarbonate with a reactive hydrogenated (styrene) conjugated gen block copolymer and polycarbonate, or a functional group reactive with polycarbonate. (Hydrogenated) Styrene Conjugated Genblock Copolymer, Compound Having Two Hydroxyl Groups, and Block Copolymer Prepared by Reacting Carbonate Precursor under Melting and Kneading are preferably Used, It has been found that the reaction under the melt kneading for preparing is preferably carried out in the presence of a catalyst.

Furthermore, the inventors of the present invention have a thermoplastic polymer block described in the above-mentioned Patent Document 8, wherein the (hydrogenated) styrene ′ conjugated gen block copolymer also has an attached calopolymerization block. Instead of a block copolymer having a polyurethane block, a reaction mixture prepared by reacting a polycarbonate and a (hydrogenated) styrene conjugated gen block copolymer having a functional group reactive with polycarbonate under melt kneading, Alternatively, use a reaction mixture prepared by reacting (hydrogenated) styrene conjugated gen block copolymer having a functional group reactive with polycarbonate, a compound having two hydroxyl groups, and a polycarbonate precursor under melt kneading. The present inventors have also found that a thermoplastic polymer composition having the above-described excellent properties can be obtained.

[0011] Further, the inventors of the thermoplastic polymer composition include, as polyurethane, a polymer polyol, a chain extender, and an organic diisocyanate compound, and are derived from an organic diisocyanate compound. A thermoplastic polyurethane formed by using a reaction raw material having a nitrogen atom content of 1 to 6.5% by mass based on the total mass of the polymer polyol, the chain extender and the organic diisocyanate compound is preferably used. I found out that

Furthermore, the present inventors use the polymer polyol, the chain extender, and the organic diisocyanate compound as they are in the thermoplastic polymer composition instead of using the previously prepared thermoplastic polyurethane. The present inventors have found that a thermoplastic polymer composition having the above-described excellent characteristics can be obtained even when melt kneading is used, and the present invention has been completed based on these various findings. That is, the present invention provides:

(1) A block copolymer having an aromatic vinyl compound polymer block (a-1) and a conjugated diene polymer block (b 1) or an addition polymerization block copolymer (I) having a hydrogenated product force thereof, Addition polymerization block (ii) comprising a block copolymer having an aromatic vinyl compound polymer block (a-2) and a conjugated diene polymer block (b-2) or a hydrogenated product thereof, and a polycarbonate polymer A thermoplastic polymer composition characterized by containing a block copolymer (II) having a block (mouth), a thermoplastic polyurethane (、), and a paraffinic oil (IV) [hereinafter referred to as “thermoplastic weight”. Combined composition (i)!

[0013] And the present invention provides:

(2) Block copolymer (Π) force The thermoplastic polymer composition according to (1), which is at least one of the following block copolymer (ΠΑ) and block copolymer (ΠΒ).

Block book (ΠΑ):

A block copolymer having a polymer block (a-2) and a conjugated diene polymer block (b-2), or a hydrogenated product thereof, and a polycarbonate polymer (Roh 1) A block copolymer prepared by reacting an addition polymerization block copolymer (I-1) having a functional group capable of reacting with a polycarbonate polymer (Rho 1) under melt kneading.

Block block integration (IIB):

A block copolymer having a polymer block (a-2) and a conjugated diene polymer block (b-2), or a hydrogenated product thereof, and a polycarbonate polymer (Roh 1) Block copolymer prepared by reacting an addition polymerization block copolymer (i-1) having a functional group capable of reacting with a compound having two hydroxyl groups and a carbonate precursor under melt kneading.

[0014] The present invention also provides:

(3) The thermoplastic polymer composition according to (2) above, wherein the block copolymer (ΠΑ) and the block copolymer (ΠΒ) are prepared by reacting in the presence of a catalyst under melt-kneading; and ,

(4) Addition polymerization type block copolymer (I) 5 parts of block copolymer (II) per 100 parts by mass ~ 200 parts by mass, 100 to 800 parts by mass of thermoplastic polyurethane (III) and 10 to 200 parts by mass of paraffinic oil (IV) are contained in any of the above (1) to (3) A thermoplastic polymer composition;

It is.

[0015] Furthermore, the present invention provides:

(5) A block copolymer having an aromatic vinyl compound-based polymer block (a-1) and a conjugated-gen-based polymer block (b-1) or an addition polymerization block copolymer having a hydrogenated product (1) A thermoplastic polymer composition obtained by melt-kneading at least one of the following reaction mixture (Ila) and reaction mixture (lib), thermoplastic polyurethane (III), and paraffinic oil (IV) [hereinafter referred to as It may be referred to as “thermoplastic polymer composition (ii)”. A block copolymer having a polymer block (a-2) and a conjugated diene polymer block (b-2), or a hydrogenated product thereof, and a polycarbonate polymer (Roh 1) A reaction mixture obtained by reacting an addition polymerization block copolymer (I-1) having a functional group capable of reacting with a polycarbonate polymer (Rho 1) under melt kneading. A block copolymer having a polymer block (a-2) and a conjugated diene polymer block (b-2), or a hydrogenated product thereof, and a polycarbonate polymer (Roh 1) A reaction mixture obtained by reacting an addition polymerization block copolymer having a functional group capable of reacting with (I-1), a compound having two hydroxyl groups, and a carbonate precursor under melt kneading.

[0016] And the present invention provides:

(6) A block copolymer having an aromatic vinyl compound polymer block (a-1) and a conjugated diene polymer block (b-1), or an addition polymerization block copolymer having a hydrogenated product (1) , At least one of the following reaction mixture (Ila) and reaction mixture (lib), high molecular polyol, chain extender, organic diisocyanate compound, and paraffinic oil It is a thermoplastic polymer composition obtained by melt-kneading (IV) [hereinafter, this may be referred to as “thermoplastic polymer composition (iii)”].

'' Kun 馳 a):

A block copolymer having a polymer block (a-2) and a conjugated diene polymer block (b-2), or a hydrogenated product thereof, and a polycarbonate polymer (Roh 1) A reaction mixture obtained by reacting an addition polymerization block copolymer (I-1) having a functional group capable of reacting with a polycarbonate polymer (Rho 1) under melt kneading.

'Kun 馳 b):

A block copolymer having a polymer block (a-2) and a conjugated diene polymer block (b-2), or a hydrogenated product thereof, and a polycarbonate polymer (Roh 1) A reaction mixture obtained by reacting an addition polymerization block copolymer having a functional group capable of reacting with (I-1), a compound having two hydroxyl groups, and a carbonate precursor under melt kneading.

[0017] Further, the present invention provides:

(7) The thermoplastic polymer composition according to any one of the above (2) to (6), wherein the functional group capable of reacting with the polycarbonate polymer in the addition polymerization block copolymer (I-1) is a hydroxyl group. ;

and,

(8) The thermoplastic polymer composition according to the above (7), wherein the addition polymerization block copolymer (i-1) has an average of 0.6 or more hydroxyl groups per molecule per terminal;

It is.

[0018] And the present invention provides:

(9) Thermoplastic polyurethane (III) is a reaction raw material for forming a thermoplastic polyurethane that also has a high molecular weight polyol, a chain extender, and an organic diisocyanate compound, and contains nitrogen atoms derived from the organic diisocyanate compound. The thermoplastic polyurethane formed by using a reaction raw material whose amount is 1 to 6.5% by mass based on the total mass of the polymer polyol, the chain extender and the organic diisocyanate compound ( 1) to (5), (7) and (8) V, any thermoplastic polymer composition.

Furthermore, the present invention provides

(10) The thermoplasticity according to any one of (1) to (9) above, wherein a tensile strength at break measured in accordance with JIS K-7311 is 8 MPa or more using a dumbbell-type test piece specified in JIS 3 It is a polymer composition.

And this invention,

(11) A molded article comprising any one of the thermoplastic polymer compositions of (1) to (10); and

(12) A composite molded article comprising the thermoplastic polymer composition according to any one of (1) to (10) and another material;

It is.

The invention's effect

[0019] The thermoplastic polymer composition of the present invention is excellent in melt moldability and handling properties without adhesion or adhesion to a molding apparatus during melt molding, and particularly in melt extrusion molding including inflation molding. At this time, the extrudate does not adhere to the die part, and no thick spots, streaks, cracks, etc. are produced during extrusion molding, and a high-quality molded article having excellent appearance and dimensional stability can be produced with high productivity.

Molded articles obtained from the thermoplastic polymer composition of the present invention are excellent in mechanical properties such as flexibility and tensile breaking strength, wear resistance, light resistance, heat resistance, and the like, and melted with other materials. It has excellent adhesiveness and adheres firmly to other materials.

Therefore, the thermoplastic polymer composition of the present invention makes use of such excellent properties, and is in the form of a film used for various molded products and products, for example, electrical products, synthetic leather, automobile-related devices and the like. It can be used effectively for the manufacture of various molded products bonded to other materials, such as products, sheets, hoses, tubes, other molded products, and other materials.

BEST MODE FOR CARRYING OUT THE INVENTION

[0020] The present invention is described in detail below.

The present invention

(i) addition polymerization block copolymer (I), block copolymer (共), thermoplastic polyurethane ( III) and a paraffinic oil (IV) thermoplastic polymer composition [thermoplastic polymer composition (i)];

(ii) Heat obtained by melt-kneading at least one of addition block copolymer (I), reaction mixture (Ila) and reaction mixture (lib), thermoplastic polyurethane (III) and paraffinic oil (IV) A plastic polymer composition [thermoplastic polymer composition (ii)]; and

(iii) addition polymerization block copolymer (I), at least one of reaction mixture (Ila) and reaction mixture (lib), polymer polyol, chain extender, organic diisocyanate compound, and paraffinic oil A thermoplastic polymer composition obtained by melt-kneading (IV) [thermoplastic polymer composition (iii)];

Is included.

The thermoplastic polymer composition (i) to (iii) of the present invention [Hereinafter, the thermoplastic polymer composition (i) to (iii) may be collectively referred to as “thermoplastic polymer composition”)] The addition polymerization type block copolymer (I) used has an aromatic vinyl compound type polymer block (a-1). Also used as an addition polymer block (ii) in the block copolymer (共) used in the thermoplastic polymer composition (i) and as a block copolymer (II) in the thermoplastic polymer composition (i). V, addition block copolymer (ii) used to form the obtained block copolymer (得る) and block copolymer (共) (ii), and thermoplastic polymer compositions (ii) and (m) The addition polymerization block copolymer (I-1) used to form the reaction mixture (Ila) and the reaction mixture (lib) in this case is not less than the aromatic vinyl compound polymer block (a-2). Have.

Examples of the aromatic bur compound constituting the aromatic vinyl compound-based polymer blocks (a-1) and (a-2) include styrene, α-methylstyrene, β-methylstyrene, ο-methylenostyrene, m —Methylanol styrene, p-methylol styrene, 2,4 dimethyl styrene, 2, 4, 6 trimethyl styrene, 4 propino styrene, t-butyl styrene, 4 cyclohexyl styrene, 4 dodecyl styrene, 2 ethyl 4 benzyl styrene, 4 (Fuenolebutinore) Mention may be made of aromatic vinyl compounds such as styrene, 1-vininolenaphthalene, vinylenoanthracene, indene, acetonaphthylene, monofunololeostyrene, difonoreostyrene, monochlorostyrene, methoxystyrene, etc. it can. Aromatic vinyl compound The physical polymer blocks (a-1) and (a-2) may be formed of one kind of aromatic bee complex force, and may have two or more kinds of aromatic bee lei compound strength. It may be formed. The aromatic bur compound-based polymer blocks (a-1) and (a-2) are preferably formed mainly from structural units derived from styrene and Z or a-methylstyrene.

[0022] The aromatic vinyl compound-based polymer blocks (a-1) and (a-2) are composed of structural units derived from the aromatic vinyl compound and, if necessary, other copolymerizable monomers. It may contain a small amount of structural units derived from one or more of the body. The content of structural units derived from other copolymerizable monomers is 30% by mass or less, particularly 10% based on the mass of the aromatic vinyl compound polymer block (a-1) or (a-2). More preferably, it is less than or equal to mass%. Examples of other copolymerizable monomers include 1-butene, 1-pentene, 1-hexene, butadiene, 2-methyl-1,3-butadiene (isoprene), and methyl vinyl ether.

[0023] Further, the addition polymerization block copolymer (I) used in the thermoplastic polymer compositions (i) to (iii) of the present invention is a conjugated gen polymer block (b — Has 1). Also used as an addition polymerization block (ii) in the block copolymer (i) used in the thermoplastic polymer composition (i) and as a block copolymer (ii) in the thermoplastic polymer composition (i). Block copolymer (ii) and addition copolymer block copolymer (ii) used to form block copolymer (ii), and reaction mixture in thermoplastic polymer compositions (ii) and (m) (Ila) and the addition polymerization block copolymer (I-1) used for the formation of the reaction mixture (lib) both have a conjugated gen polymer block (b-2).

Conjugated Genuine compounds constituting the Conjugated Polymer Blocks (b-1) and (b-2) are 1,3 butadiene, 2-methyl-1,3 butadiene (isoprene), 2,3 dimethyl-1 , 3 Butadiene, 1,3 pentagen, 1,3 hexagen, and the like. The conjugated gen-based polymer blocks (b-1) and (b-2) may be formed from one type of conjugated gen compound or may be formed from two or more types of conjugated genic compounds. You can do it. Conjugated polymer block (b— 1) and Z or (b— 2) In the case of containing structural units derived from conjugated genie compounds with more than one kind of force, their bonding form may be random, tapered or partially blocky, and they are mixed. Well, okay.

[0024] Conjugated polymer block (b-1) and Z or (b-2) are hydrogenated! Even if not, it may be partly hydrogenated or all hydrogenated. The hydrogenation rate of the co-gene polymer block (b-1) and Z or (b-2) is 50 mol% or more, more preferably 60 mol% or more from the viewpoint of heat resistance, weather resistance and light resistance. In particular, it is preferably 80 mol% or more. The hydrogenation rate (mol%) is a ratio with respect to the total number of moles of double bonds existing in the conjugated diene polymer block (b-1) or (b-2) before hydrogenation. .

[0025] In particular, since the thermoplastic polymer composition excellent in flexibility, mechanical performance and melt moldability can be obtained more smoothly, the conjugated gen polymer block (b-1) and the conjugated gen series The polymer block (b-2) is an isoprene polymer block that may be hydrogenated, hydrogenated, a butadiene polymer block and a hydrogenated copolymer of isoprene and butadiene. Polymer block power Preferably at least one polymer block selected.

[0026] The content of the structural unit derived from the aromatic vinyl compound in the addition polymerization block copolymer (I) is 5 to 90% by mass relative to the mass of the addition polymerization block copolymer (I). 10 to 90 mass to a further ^_0/0, and particularly preferably 20 to 80 wt%.

The content of the structural unit derived from the aromatic beryl compound in the addition copolymerization block (ii) of the block copolymer (II) is 5 to 5 to the mass of the addition polymerization block (ii). It is preferably 90% by mass, more preferably 10 to 90% by mass, and particularly preferably 20 to 80% by mass.

In addition, the addition of structural units derived from aromatic belief compounds in the addition copolymer block copolymer (ii) used to form the block copolymer (共) and block copolymer (ΠΒ) The amount of the structural unit derived from the aromatic belief compound in the addition polymerization system block copolymer (I 1) used to form the reaction mixture (Ila) and the reaction mixture (lib) 5 to 90% by mass, more preferably 10 to 90% by mass, and particularly preferably 20 to 80% by mass with respect to the mass of the polymerization block copolymer (I-1). Use of addition polymerization block copolymer (I), block copolymer (II), and addition polymerization block copolymer (I-1) in which the content of structural units derived from aromatic vinyl compounds is within the above range. By doing so, it is possible to obtain a thermoplastic polymer composition that is superior in flexibility, mechanical performance and melt moldability.

[0027] Aromatic vinyl compound polymer block (a) in addition polymerization block copolymer (I)

1) and conjugation-based polymer block (b— 1) bonding form, aromatic copolymer copolymer block (a) in the addition polymerization block (ii) of block copolymer (II) 2) and conjugated gen-based polymer block (b-2) combined form, block copolymer (ΠΑ) and block copolymer (ΠΒ) used for formation of block copolymer (ΠΒ)ー In 1) the aromatic bull compound-based polymer block (a-2) and the conjugated-gen-based polymer block (b-2) are bonded together, and the reaction mixture (Ila) and reaction mixture (lib) are formed. The bond form of the aromatic beryl compound polymer block (a 2) and the conjugated gen polymer block (b-2) in the attached caropolymer block copolymer (I-1) is It is not limited and can be linear, branched, radial, or a combined form thereof. It is flexible, the point mosquitoes ゝ et preferable to be able to obtain a thermoplastic polymer composition excellent in such mechanical properties and melt forming shape retention by a linear bonding form Among the Guso.

[0028] Used to form addition polymerization block copolymer (I), block copolymer (II), block copolymer (ΠΑ) and block copolymer (ΠΑ) in addition copolymer block copolymer (I) and block copolymer (II) Addition polymerization block copolymers (I-1), and addition polymerization block copolymers (I-1) used to form the reaction mixture (Ila) and reaction mixture (lib) include aromatic vinyl compounds. When the polymer blocks (a-1) and (a-2) are represented by X and the conjugated diene polymer blocks (b1) and (b-2) are represented by Y, for example, the following formula:

(X-Y) -X

m

(X-Y)

Y— (X-Y)

P

(In the formula, m, n and p each represent an integer of 1 or more)

Can be mentioned.

Among these, the thermoplastic polymer composition of the present invention is melt moldable, flexible, mechanical In terms of performance, etc., addition polymerization block copolymer (1), addition copolymer block (ii), block copolymer (ii) and block copolymer (II) in block copolymer (II) The addition polymerization block copolymer (I-1) used for the formation of the polymer (ΠΒ) and the addition polymerization block copolymer (I-1) used for the formation of the reaction mixture (Ila) and the reaction mixture (lib) are: The formula: X—Y—X is preferred to be in the form of a diblock copolymer represented by X—Y or a triblock copolymer represented by the formula: X—Y—X. More preferably, it is in the form of a triblock copolymer. In particular, in the form of a triblock copolymer represented by the formula: X—Y—X, the impregnation ability (oil retention ability) of paraffinic oil (IV) in the thermoplastic polymer composition is increased. It is also preferable from the viewpoint of preventing the transfer of paraffinic oil (IV) (bleed out, etc.) more effectively!

When the addition polymerization block copolymer (I) contains two or more aromatic vinyl compound polymer blocks X, the addition polymerization block (ii) of the block copolymer (Π) is an aromatic vinyl compound. When two or more polymer blocks X are contained, the addition copolymer block copolymer (I-1) used to form the block copolymer (ΠΑ) and the block copolymer (ΠΒ) Aromatic vinyl compound-based polymer when the addition of two or more polymer blocks X, and addition polymerization block copolymer (I-1) used to form Z or reaction mixture (Ila) and reaction mixture (lib) When two or more blocks X are contained, the aromatic beryl compound polymer block may be a polymer block having the same contents or a polymer block having different contents.

In addition, when the addition polymerization block copolymer (I) contains two or more conjugated gen polymer blocks Y, the addition polymerization block (ii) of the block copolymer (Π) has two or more conjugates. When the gen-based polymer block γ is contained, the addition copolymer-based block copolymer (I-1) used to form the block copolymer (ΠΑ) and the block copolymer (ΠΒ) has two or more conjugated gens. Conjugated diene containing two or more addition polymerization block copolymers (i-1) used for forming Z or reaction mixture (Ila) and reaction mixture (lib). When the polymer block Y is contained, the conjugation polymer block may be a polymer block having the same contents or a polymer block having different contents. For example, two aromatic vinyl compound-based polymer blocks X in a triblock structure represented by X—Y—X or two conjugated gen systems in a triblock structure represented by Υ—Χ—Χ The polymer block γ may be the same or different in the type of aromatic belief compound or conjugated gen compound constituting them, the type of bonding, the number average molecular weight of the polymer block, and the like. Also good.

[0030] Aromatic vinyl compound polymer block (a) in addition polymerization block copolymer (I)

The number average molecular weight of 1) and the conjugated gen polymer block (b-1) is not particularly limited, but the number of aromatic vinyl compound polymer blocks (a-1) in the state before hydrogenation. The average molecular weight force is in the range of 2,500 to 125,000, especially 10,000 to 100,000, and the number average molecular weight of the conjugated gen-based polymer block (b-1) is 10,000 to 250,000, in particular It is preferably within the range of 20,000 to 200,000. An addition polymerization block copolymer (I) composed of an aromatic bur compound polymer block (a-1) and a conjugated diene polymer block (b-1) having a number average molecular weight within the above range is prepared. By using the thermoplastic polymer composition of the present invention, the melt moldability, flexibility, mechanical performance and the like become better.

[0031] The total number average molecular weight of the addition polymerization block copolymer (I) is in the range of 15,000 to 500,000, particularly 80,000 to 400,000 in the state before hydrogenation. Powerful! / By using the addition polymerization block copolymer (I) having a strong number average molecular weight, the thermoplastic polymer composition of the present invention is more excellent in melt moldability, flexibility, mechanical performance and the like. Become.

[0032] Also, the number average of the aromatic vinyl compound polymer block ( _a -2) and the conjugated gen polymer block (b-2) in the addition polymerization block (ii) of the block copolymer (ii). Aromatic beryl polymer block in addition polymer block copolymer (I-1) used to form molecular weight, block copolymer (ΠΑ) and block copolymer (ΠΒ) ( Number average molecular weights of a—2) and conjugation polymer blocks (b—2), addition polymerization block copolymers (i—1) used to form reaction mixture (Ila) and reaction mixture (lib) The number average molecular weights of the aromatic bur compound polymer block (a-2) and the conjugated diene polymer block (b-2) in Fig. 1 are not particularly limited. The difference is that the number average molecular weight of the aromatic vinyl compound polymer block (a-2) is in the range of 2,500 to 75,000, particularly 5,000 to 50,000, and the conjugated gen polymer block ( It is preferable that the number average molecular weight force of b) is in the range of 000 to 150,000, especially 10,000 to 100,000.

When the number average molecular weights of the aromatic vinyl compound-based polymer block (a-2) and the conjugation-based polymer block (b-2) are within the above range, the melt moldability of the thermoplastic polymer composition of the present invention , Flexibility, mechanical performance, etc. will be better.

[0033] Further, the number average molecular weight of the addition polymerization block (ii) of the block copolymer (II), the addition polymerization system used for forming the block copolymer (ΠΑ) and the block copolymer (ΠΒ) Total number average molecular weight of block copolymer (I-1), total number average of addition polymerization block copolymer (I-1) used to form reaction mixture (Ila) and reaction mixture (lib) The molecular weight is preferably in the range of 15,000 to 300,000, particularly in the range of 20,000 to 100,000 before hydrogenation. By using a block copolymer (II) containing an addition polymerization block (ii) having such a number average molecular weight, or an addition polymerization block copolymer (ii) having a strong number average molecular weight. By using the block copolymer (ΠΑ), the block copolymer (ΠΒ), the reaction mixture (Ila) and Z or the reaction mixture (lib) formed by using the thermoplastic polymer composition of the present invention, Melt formability, flexibility, mechanical performance, etc. are improved.

[0034] In this specification,! / ヽぅ, the number average molecular weight of each of the aromatic vinyl compound-based polymer block (a-1) and the conjugated-gen-based polymer block (b-1), the addition polymerization block The total number average molecular weight of the copolymer (I), the number average molecular weight of each of the aromatic vinyl compound polymer block (a-2) and the conjugated diene polymer block (b-2), the addition polymerization system block ( B) The overall number average molecular weight of the addition polymer block copolymer (a-1) and conjugate polymer block (a-2) in the addition polymerization block copolymer (i-1) ( The number average molecular weight of each b-2) and the total number average molecular weight of the addition polymerization block copolymer (I-1) are both converted to standard polystyrene by gel permeation chromatography (GPC). It is the value measured by.

[0035] Addition polymerization block copolymer used in the thermoplastic polymer compositions (i) to (iii) of the present invention (I) preferably has a melt flow rate (MFR) measured at 230 ° C. under a load of 2.16 kg of not more than lOgZlO, more preferably not more than 5 gZlO, especially not more than 3 gZlO. By using the addition polymerization type block copolymer (I) having such a melt flow rate (MFR), the thermoplastic polymer composition of the present invention is more excellent in melt moldability, flexibility, mechanical performance and the like. It will be.

[0036] Further, the block copolymer (ii) constituting the block copolymer (II) used in the thermoplastic polymer composition (i) of the present invention, and a block copolymer usable as the block copolymer (II). Addition block copolymer (II) used to form polymer (II A) and block copolymer (共)

1) and the reaction mixture (Ila) in the thermoplastic polymer compositions (ii) and (m) of the present invention

) And the addition polymerization block copolymer (i-1) used to form the reaction mixture (lib) both have a melt flow rate (MFR) of 0.01 measured at 230 ° C and 2.16 kg load. It is preferable to be within the range of ~ lOOgZlO, particularly 0.05 to 80g / 10min. Accordingly, the block copolymer (11), block copolymer (共), block copolymer (ΠΒ) or reaction mixture (Ila) and Z or reaction mixture (lib) can be added to the addition polymerization block copolymer. The compatibility with the polymer (I) and the thermoplastic polyurethane (III) is improved, and a thermoplastic polymer composition excellent in mechanical performance and melt moldability can be obtained.

The melt flow rate (MFR) of the addition polymerization block copolymer (I) and the addition polymerization block copolymer (I1) in this specification are both measured in accordance with ASTM D-1238. It is the value.

In addition, the melt flow rate (MFR) of the attached polymer block (ii) in this specification is the same as that of the block copolymer (II) in which the polycarbonate polymer block (mouth) is replaced with a hydrogen atom. It is a value measured according to ASTM D-1238 using a coalescence.

[0037] Addition polymerization block copolymer used in the thermoplastic polymer compositions (i) to (iii) of the present invention

The JIS A hardness of (I) is in the range of 30 to 95, more preferably 40 to 90, and particularly 50 to 85. By using the addition polymerization block copolymer (I) having such JIS A hardness, the thermoplastic polymer composition of the present invention has improved strength, such as melt moldability, flexibility and mechanical performance.

Further, it constitutes the block copolymer (II) used in the thermoplastic polymer composition (i) of the present invention. Addition polymerization block (ii), block copolymer (II A) that can be used as block copolymer (II), and addition polymerization block copolymer (ii) used to form block copolymer (ii)

) And the addition polymerization block copolymer (i-1) used for the formation of the reaction mixture (lib), the JIS A hardness is 30 to 95, more preferably 40 to 90, especially 50 to 85. It is preferable that the thermoplastic polymer composition of the present invention has better melt moldability, flexibility, mechanical performance, and the like.

The JIS A hardness of the addition polymerization block copolymer (I) and the addition polymerization block copolymer (I-1) in this specification is a value measured in accordance with JIS K-6253. It is.

In addition, the JIS A hardness of the addition polymerization block (ii) in this specification is JIS A using a polymer in which the polycarbonate polymer block (mouth) is replaced with a hydrogen atom in the block copolymer (II). K—Measured according to 6253.

[0038] The method for producing the addition polymerization block copolymer (I) used in the thermoplastic polymer compositions (i) to (iii) is not particularly limited, and the addition polymerization block copolymer having the structure described above is not particularly limited. A polymer can be produced, or it can be produced by a deviation method.

The addition polymerization block copolymer (I) can be produced, for example, by ion polymerization methods such as anion polymerization or cationic polymerization, single site polymerization methods, radical polymerization methods, and the like. In the case of the char-on polymerization method, for example, using an alkyl lithium compound as a polymerization initiator in an inert organic solvent such as n-hexane or cyclohexane, an aromatic vinyl compound or a conjugated conjugated compound is used. Is produced by sequentially polymerizing the polymer to produce a block copolymer having a desired molecular structure and molecular weight, and then adding an active hydrogen-containing compound such as alcohols, carboxylic acids and water to stop the polymerization. can do. Then, the obtained block copolymer is preferably used in an inert organic solvent such as n-hexane or cyclohexane, as an alkylaluminum compound and a catalyst such as cobalt catalyst and nickel. A hydrogenated product may be obtained by hydrogenating in the presence of a hydrogenation reaction catalyst under conditions of a reaction temperature of 20 to 150 ° C. and a hydrogen pressure of 0.1 to 15 MPa.

[0039] In the above, before adding the active hydrogen-containing compound to stop the polymerization, for example, Add compounds having an oxysilane skeleton, such as ethylene oxide, propylene oxide, styrene oxide, etc., latonic compounds such as ε-force prolatatatone, j8-propiolatathone, dimethylpropiolatatane (pinolalataton), methylvalerolatataton, etc. As a result, an addition polymerization block copolymer (I) having a functional group such as a hydroxyl group or a carboxyl group in the molecule can be produced.

In addition, in the above, an addition polymerization block copolymer having an functional group such as an acid anhydride group in the molecule by modifying the block copolymer before or after hydrogenation with maleic anhydride or the like, if desired. The polymer (I) can also be produced.

As the addition polymerization block copolymer (I), a commercially available product may be used.

[0040] Examples of the polycarbonate polymer block (mouth) constituting the block copolymer (II) used in the thermoplastic polymer composition (i) include a compound having two hydroxyl groups and a carbonate precursor. Examples thereof include a block made of polycarbonate produced by reacting a body. In addition, the reaction mixture in the polycarbonate-based polymer (Roh 1) used for forming the block copolymer (共) that can be used as the block copolymer (II), and the thermoplastic polymer compositions (ii) and (m). Examples of the polycarbonate polymer (Rho 1) used for the formation of (Ila) include polycarbonate produced by reacting a compound having two hydroxyl groups with a carbonate precursor.

[0041] Examples of the compound having two hydroxyl groups used in the production of polycarbonate include bivalent phenol and aliphatic diol.

Typical examples of divalent phenols in this case are 2, 2 bis (4-hydroxyphenol) propane [bisphenol A], 1, 1-bis (4 hydroxyphenol) ethane, 1, 1-bis. (4 hydroxyphenol) cyclohexane, 2,2 bis (4 hydroxy-1,3,5 dimethylphenol) propane, 2,2 bis (4 hydroxy-3,5 dibromophenol) propane, 2, 2 Bis (4hydroxy-1,3,5,2-phenyl) propane, 2,2Bis (4-hydroxy-3-methylphenyl) propane, hydroquinone, 4,4'-dihydroxydiphenyl, bis (4hydroxyphenol) ) Sulfide, bis (4-hydroxyphenol) sulphone, bis (4-hydroxyphenol) sulfoxide and the like. Among these However, 2,2-bis (4-hydroxyphenol) propane (commonly known as bisphenol A) is particularly preferred as a divalent phenol.

[0042] In addition, examples of the aliphatic diol used in the production of polycarbonate include ethylene glycol, propylene glycol, hexylene glycol, and 3-methyl-1,5-pentanediol.

[0043] Polycarbonate-based polymer block (mouth) in block copolymer (II), polycarbonate-based polymer (Roh 1) used to form block copolymer (ΠΑ) that can be used as block copolymer (II), The polycarbonate polymer (Mouth 1) used for forming the reaction mixture (Ila) also has the strength of the polycarbonate polymer obtained by the reaction of one of the two hydroxyl group-containing compounds with the carbonate precursor. Alternatively, it may have a polycarbonate polymer strength obtained by reacting two or more of the above-mentioned compounds having two hydroxyl groups with a carbonate precursor.

[0044] The carbonate precursor includes carbohalide, carbonate ester, haloformate, and the like, and specific examples include phosgene, diphenol carbonate, methyl chlorocarbonate, dihaloformate of divalent phenol, and the like. Can be mentioned. Of these, phosgene is preferred as the carbonate precursor!

Polycarbonate-based polymer block (mouth) in block copolymer (II), polycarbonate-based polymer (Roh 1) used for forming block copolymer (ΠΑ) that can be used as block copolymer (II), reaction mixture ( The polycarbonate-based polymer (Mouth 1) used in the formation of (Ila) may be formed using one type of carbonate precursor, or formed using two or more types of carbonate precursors. Even so!

[0045] Polyforce used to form block copolymer (ΠΑ) that can be used as block copolymer (II)-Molecular weight of sulfonate polymer (Mouth-1), and polycarbonate used to form reaction mixture (Ila) The molecular weight of the polymer (Rho 1) is in the range of 10,000 to 100,000, especially 15,000 to 60,000, in terms of viscosity average molecular weight. The thermoplastic polymer of the present invention It is preferable from the viewpoints of melt moldability, flexibility, mechanical performance and the like of the composition.

The viscosity average molecular weight of the polycarbonate polymer (Rho 1) in this specification is a value measured by a solution viscosity method (measurement temperature = 20 ° C., solvent = methylene chloride). [0046] In the block copolymer (II) used in the thermoplastic polymer composition (i) of the present invention, the form of bonding between the attached caropolymer block (ii) and the polycarbonate polymer block (mouth) is particularly limited. However, it may be any of linear, branched, radial, or a combined form in which they are combined, but the linear combined form indicates that the thermoplastic polymer composition (i) is melt-molded. From the viewpoints of properties, flexibility, mechanical performance and the like.

When the addition polymerization block (ii) is represented by α and the polycarbonate polymer block (mouth) is represented by β, the linear block copolymer is represented by, for example, the formula: α-j8 List various block copolymers such as diblock copolymers, formula; α-j8-triblock copolymer represented by α, formula; β-a-β represented triblock copolymer Can do. Among them, the block copolymer (II) dynamic formula; α- | 8 diblock copolymer, melt moldability, flexibility and mechanical performance of the thermoplastic polymer composition (i) I like it because it becomes better.

[0047] In the block copolymer (II), the addition polymerization block (ii): the mass of the polycarbonate polymer block (port;) it force S, 20: 80 to 80: 20, and [30: 70] It is preferable that the thermoplastic polymer composition (i) has a point strength such as melt moldability, flexibility and mechanical performance within the range of ˜70: 30, particularly 35:65 to 6 5:35.

[0048] The block copolymer (II) used in the thermoplastic polymer composition (i) of the present invention is known and includes improved compatibility between polycarbonate-based resin and rubber-reinforced styrene-based resin, and polycarbonate. It has been used in the past for the purpose of improving the compatibility between monotonic and polyester-based resins (see Patent Documents 9 and 10). However, it has been conventionally known that the block copolymer (II) is used in combination with the addition polymerization block copolymer (I) and the thermoplastic polyurethane (III).

[0049] In the thermoplastic polymer composition (i) of the present invention, the conventionally known block copolymer (II) can be used as it is, but the melt moldability and flexibility of the thermoplastic polymer composition can be used. From the standpoint of mechanical performance and the like, the block copolymer (II) includes at least one block copolymer (ΠΑ) and block copolymer (ΠΒ) prepared by a specific method. Polymers are preferably used.

Block copolymer (IIA): A block copolymer having a polymer block (a-2) and a conjugated diene polymer block (b-2), or a hydrogenated product thereof, and a polycarbonate polymer (Roh 1) A block copolymer prepared by reacting an addition polymerization block copolymer (I-1) having a functional group capable of reacting with a polycarbonate polymer (Rho 1) under melt kneading.

Block copolymer (IIB):

In the block copolymer (ΠΒ), a polycarbonate polymer block (mouth) is formed by a reaction between a compound having two hydroxyl groups and a carbonate precursor.

[0050] The block copolymer (ブロック) and the addition copolymer block copolymer (ii) used for the preparation of the block copolymer (ΠΑ) and the block copolymer (ΠΒ) that can be used in the thermoplastic polymer composition (i) and the thermoplastic Of the addition polymer block copolymer (I-1) used to form the reaction mixture (Ila) and (lib) in the polymerizable polymer composition (ii) and (m). Examples of the functional group capable of reacting with) include a carboxyl group, an acid anhydride group, an alkoxy group, a phenyl group, a thiocarboxyl group, an isocyanate group, a hydroxyl group, an amino group, and a mercapto group. The addition polymerization block copolymer (I1) may have one of these functional groups, or may have two or more of these functional groups, and a hydroxyl group is preferable.

Further, it is preferable that the above addition polymerization block copolymer (I-1) has a functional group capable of reacting with the polycarbonate polymer (Rho 1) at the molecular end of the copolymer. ,

[0051] The block copolymer (ブロック) and the addition copolymer block copolymer (ii) used for the preparation of the block copolymer (ΠΑ) and the block copolymer (ΠΒ) that can be used in the thermoplastic polymer composition (i) and the thermoplastic Used to form reaction mixtures (Ila) and (lib) in functional polymer compositions (ii) and (m) The number of functional groups capable of reacting with the polycarbonate polymer (Rho 1) in the addition polymerization block copolymer (I-1) is the same per molecule of the addition polymerization block copolymer (I-1). On average, it is preferably 0.6 or more, more preferably 0.7 or more, and particularly preferably 0.7 to 1.

Depending on the production process, the addition-polymerization block copolymer (I-1) does not have a functional group capable of reacting with the polycarbonate-based polymer (Rho 1). A force-added polymerization block copolymer (a hydrogenated or non-hydrogenated block copolymer having a non-group aromatic vinyl compound polymer block and a conjugated diene polymer block) ( 1), the number of functional groups capable of reacting with the polycarbonate polymer (Mouth 1) is on average 0.6 or more, more preferably 0.7 or more, especially on a molecule basis. 0. Smooth use of block copolymer (11), block copolymer (ΠΑ), block copolymer (ΠΒ), reaction mixture (Ila) or (lib) Can be prepared.

The production method of the addition polymerization block copolymer (I-1) is not limited in any way. For example, ion polymerization methods such as cation polymerization, cation polymerization, single site polymerization, radical polymerization, etc. Can be manufactured. In the case of the char-on polymerization method, for example, using an alkyl lithium compound or the like as a polymerization initiator, an aromatic vinyl compound or a conjugated diene compound is prepared in an inert organic solvent such as n-hexane or cyclohexane. When the desired molecular structure and molecular weight are achieved by sequential polymerization, compounds having an oxysilane skeleton such as ethylene oxide, propylene oxide, and styrene oxide, ε-force prolatatatone, β-propiolataton, dimethylpropiolataton (pivalolataton), methylvalerolataton It can be produced by adding an active hydrogen-containing compound such as alcohols, carboxylic acids, and water to stop the polymerization. In addition, the block copolymer obtained thereby is preferably subjected to a hydrogenation reaction such as a Ziegler catalyst such as cobalt and nickel in an inert organic solvent such as η-hexane and cyclohexane. A hydrogenated product may be obtained by hydrogenating under the conditions of a reaction temperature of 20 to 150 ° C. and a hydrogen pressure of 0.1 to 15 MPa in the presence of a catalyst. If desired, before or after hydrogenation The copolymer may be modified with maleic anhydride or the like.

As the addition polymerization block copolymer (I-1), a commercially available product may be used.

[0053] In the thermoplastic polymer composition (i), the polycarbonate polymer (Rho 1) and the thermoplastic polymer compositions (の) and () used for the preparation of the block copolymer (ΠΑ) that can be used. The polycarbonate-based polymer (Mouth-1) used for forming the reaction mixture (Ila) can be produced by reacting a compound having two hydroxyl groups with a carbonate precursor by a solution method or a melting method. . In preparing the block copolymer (ΠΑ) and the reaction mixture (Ila), a reaction mixture containing a polycarbonate polymer (Mouth-1) obtained by reacting a compound having two hydroxyl groups with a carbonate precursor. V may be used directly as it is, and the polycarbonate polymer (Rho 1) may be separated from the reaction mixture and used. Alternatively, a block copolymer (ΠΑ) and a reaction mixture (Ila) may be prepared using a commercially available polycarbonate as a polycarbonate polymer (Rho 1).

[0054] As the polycarbonate polymer (Roh 1), a polycarbonate produced using a molecular weight regulator, a branching agent, a catalyst, or the like may be used as necessary. Further, the polycarbonate polymer (Rho 1) may contain additives, for example, heat stabilizers such as phosphites, phosphate esters, and phosphonates; triazole, acetophenone, salicylate, etc. Ultraviolet absorbers; low molecular weight polycarbonates of tetrabromobisphenol A and tetrabromobisphenol A; flame retardants such as decarburized phenol ether; colorants, fluorescent brighteners and the like.

[0055] The block copolymer (用いる) that can be used in the thermoplastic polymer composition (i) and the reaction mixture (lib) in the thermoplastic polymer compositions (ii) and (m) 2 As the compound having two hydroxyl groups and the carbonate precursor, the polycarbonate and the polycarbonate-based polymer (low 1) constituting the polycarbonate polymer block (mouth) in the block copolymer (II) are described above. Specific examples of compounds having two hydroxyl groups (for example, bisphenol A, various other divalent phenols, aliphatic diols, etc.), carbonate precursors [for example, carbohalides, carbonate esters, halides, etc. Mouth formate etc. (specific examples include phosgene, diphenol carbonate, black mouth methyl carbonate, dihaloformate of divalent phenol, etc.)].

[0056] In preparing the block copolymer (共) that can be used in the thermoplastic polymer composition (i) and the reaction mixture (Ila) used in the thermoplastic polymer compositions (ii) and (m), the block copolymer is used. Since the compatibility of the polymer (ΠΑ) or the reaction mixture (Ila) with the addition polymerization block copolymer (I) and the thermoplastic polyurethane (III) is improved, the addition polymerization block copolymer ( 1) and polycarbonate polymer (Rho 1), [mass of addition polymerization block copolymer (I-1)]: [mass of polycarbonate polymer (mouth-1)] = 20: 80 ~ It is preferable to use within the range of 80:20, further 30:70 to 70:30, especially 35:65 to 65:35! In preparing the block copolymer (ΠΒ) that can be used in the thermoplastic polymer composition (i) and the reaction mixture (lib) used in the thermoplastic polymer compositions (ii) and (m), a probe is used. Since the compatibility of the copolymer (反応) or the reaction mixture (lib) with the addition polymerization block copolymer (I) and the thermoplastic polyurethane (III) is improved, the addition polymerization block Copolymer (ii), compound having two hydroxyl groups and carbonate precursor [mass of addition-polymerized block copolymer (ii)]: [compound having two hydroxyl groups and force-bonate precursor The total mass of the body] = 20: 80-80: 20, more preferably 30: 70-70: 30, and particularly preferably within the range of 3 5: 65-65: 35! / ,.

[0057] The above reaction for preparing the block copolymer (共), the block copolymer (ΠΒ), the reaction mixture (Ila) and the reaction mixture (lib) can be carried out in the presence of a catalyst. preferable. Examples of the catalyst include organic titanium compounds, organic antimony compounds, organic germanium compounds, organic manganese compounds, organic tin compounds, organic zinc compounds, organic strength compounds, and organic lead compounds. Organic metal compounds such as organic samarium compounds, organic lanthanum compounds, organic ytterbium compounds, organic cobalt compounds, organic cadmium compounds, or organic magnesium compounds. One or more of these may be used. it can. Of these, one or more of organic titanium compounds, organic tin compounds, and organic samarium compounds are preferably used. When two or more kinds of catalysts are used in combination, the metals contained in each catalyst may be the same or different.

[0058] The type of the organic titanium compound that is preferably used as the catalyst is not particularly limited. For example, tetraisopropinoretitanate, tetrabutyl titanate, tetra-2-ethylhexyl titanate, ethylene glycol titanate, butylene glycol titanate, potassium potassium oxalate, potassium potassium tartrate, titanium acetyl cetate, dibutoxy bis (triethanolamine) Nate) titanium, potassium hexafluorotitanate, and the like, and one or more of these can be used. Among these, titanium alcoholates such as tetraisopropyl titanate and tetrabutyl titanate are particularly preferably used.

[0059] The kind of the above-described organotin compound that is preferably used as the catalyst is not particularly limited, and examples thereof include monomethyltin oxide, monoethyltin oxide, monopropyl tin oxide, monobutyltin oxide, and di-2- Ethylhexyltin oxide, dibutyltin oxide, furmethyltin oxide, monobutyltin trichloride, dibutyltin dichloride, dimethyltin dibromide, monobutyltin monoacetate, monobutyltin monopropylate, dibutyltin diacetate, dibutyltin sulfide, Diphenol tin sulfide can be used, and one or more of these can be used. Among them, monomethyl tin oxide, monoethyl tin oxide, tin oxide such as monopropyl tin oxide, dibutyl tin oxide; and monobutyl tin monoacetate, monobutinoles monobutyrate, dibutinores diacetate, etc. One or more of these tin carboxylates are preferably used.

[0060] The organic samarium compound preferably used as a catalyst is not particularly limited, and examples thereof include samarium acetate, samarium oxalate, samarium acetylacetonate, samarium oxide, samarium chloride, and samarium bromide. One or more of these can be used. Of these, samarium acetyl cetate is particularly preferably used.

[0061] The amount of the above-mentioned catalyst used is the total mass of the addition polymerization block copolymer (I-1) and the polycarbonate polymer (Rho 1) or the addition polymerization block copolymer (I-1). ), Based on the total mass of the compound having two hydroxyl groups and the carbonate precursor, from 0.5 lp pm to 0.2 mass%, more preferably from 0.5 ppm to 0.02 mass%, especially from lppm to 0.01 mass % Is preferable. [0062] When a catalyst is used in preparing the block copolymer (共), the block copolymer (ΠΒ), the reaction mixture (Ila), and the reaction mixture (lib), an addition polymerization block copolymer is used. Unless the compatibility with (I) and thermoplastic polyurethane (III) is impaired, the obtained block copolymer (ΠΑ), block copolymer (ΠΒ), reaction mixture (Ila) and reaction mixture ( It is preferable to add a catalyst deactivator to II b). Examples of the catalyst deactivator include lauryl phosphate, oleinorephosphate, stearinorephosphate, dilaurinophosphate, dioleyl phosphate, distearyl phosphate, tris (2-ethylhexyl) phosphate, bis (octadecyl) Phosphorus compounds such as pentaerythritol diphosphate, phenethyl phosphonate, 3,5-di-tert-butyl-4-ethyl benzyl phosphonate; 2, 2, -methylenebis (4-methyl-6t butylphenol), 2, 2, Methylene bis (4-ethyl 6 t butylphenol), 2 hydroxy-4-benzyloxybenzophenone, 2— (2,1 hydroxy-1,3,5,1 t-butylphenol) benzotriazole, 2— [2 hydroxy 3,5bis (α, a-dimethylbenzyl) phenol] Examples include phenolic compounds such as 2 H benzotriazole, 4, 4, 1-octyl-2, 2, 1-biphenol, etc. Among them, phosphorus compounds are preferably used.

[0063] The amount of the catalyst deactivator used is the total mass of the addition polymerization block copolymer (I-1) and the polycarbonate polymer (mouth 1), or the addition polymerization block copolymer (I-1). Based on the total mass of the compound with two hydroxyl groups and the carbonate precursor !, lppn! To 2 mass ^_0/0, more 5Ppm～0. 2 mass ^_0/0, especially 10Ppm～0. And this is preferably in the range of 1 wt%.

[0064] In preparing the block copolymer (共) that can be used in the thermoplastic polymer composition (i), for example, an addition polymerization block copolymer (I-1) and a polycarbonate polymer (Mouth 1) are used. A method of melt kneading usually at 180 to 300 ° C. for 3 to 15 minutes using a kneader such as a single screw extruder, a twin screw extruder, a kneader, or a banner mixer in the presence of a catalyst as necessary. By adopting it, a block copolymer (こと) can be obtained.

In preparing a block copolymer (ΠΒ) that can be used in the thermoplastic polymer composition (i), for example, an addition polymerization block copolymer (I-1), a compound having two hydroxyl groups is used. Products and carbonate precursors, optionally in the presence of a catalyst, single screw extruder, twin screw A block copolymer (ΠΒ) can be obtained by using a kneading machine such as an extruder, kneader, Banbury mixer, etc., usually at 180 to 300 ° C for 3 to 15 minutes. When an agent is used, the addition is preferably performed after the completion of the carbonate bond formation reaction until the end of the melt kneading.

[0065] When the block copolymer (ブロック) is prepared by reacting the addition polymerization block copolymer (I-1) with the polycarbonate polymer (Roh 1), and the addition polymerization block copolymer ( 1) When a block copolymer (ΠΒ) is prepared by reacting a compound having two hydroxyl groups and a carbonate precursor, the block copolymer (ΠΒ) is contained in the reaction product obtained by the reaction. In addition to ΠΑ) or block copolymer (ΠΒ), an unreacted addition polymerization block copolymer (ii), an unreacted polycarbonate polymer (row 1), a compound having two hydroxyl groups And carbonate precursor force The block copolymer is composed of a polycarbonate, an aromatic vinyl compound polymer block and a conjugated diene polymer block, and has no functional group reactive with the polycarbonate polymer (Rho 1). One or more of components such as polymers may be contained, and the content of these components varies depending on the reaction conditions such as the ratio of raw materials used in the reaction and reaction temperature.

In the thermoplastic polymer composition (i) of the present invention, the block copolymer (ΠΑ) or the reaction product containing the above-mentioned other components together with the block copolymer (ΠΒ) may generally be used without particular problems. Often does not occur. Therefore, the reaction product containing the block copolymer (II A) or the block copolymer (ΠΒ) without separating and recovering the block copolymer (ΠΑ) or the block copolymer (ΠΒ) from the reaction product. When the thermoplastic polymer composition (i) of the present invention is produced using the product, the production process of the thermoplastic polymer composition (i) can be simplified.

[0066] In the thermoplastic polymer composition (i), when the above-mentioned reaction product containing the block copolymer (ΠΑ) or the block copolymer (ΠΒ) and other components is used, an addition is required. Polymerization system To have good compatibility with both the block copolymer (I) and the thermoplastic polyurethane (III), the tensile strength at break is lOMPa or more, further 12 MPa or more, especially 15 MPa or more. It is preferable to use the reaction product which is The tensile strength at break in the present specification is a value measured according to JIS K-7311.

[0067] In the thermoplastic polymer composition (i), when the above-mentioned reaction product containing the block copolymer (ΠΑ) or the block copolymer (ΠΒ) and other components is used, In order to improve the melt moldability, flexibility, mechanical performance, etc. of the thermoplastic polymer composition (i) of the invention, a JIS A hardness of 40 to 99, further ί 50 to 95, especially 60 It is preferred to use a reaction product in the range of ~ 95.

The JIS hardness of the reaction product referred to in the present specification is a value measured according to JIS K-6253.

[0068] In preparing the reaction mixture (Ila) used for the thermoplastic polymer compositions (ii) and (m), for example, an addition polymerization block copolymer (I-1) and a polycarbonate-based polymer are used. Combine (Raw 1) in the presence of a catalyst, if necessary, with a kneader such as a single screw extruder, twin screw extruder, kneader, Banbury mixer, etc., usually at 180 to 300 ° C for 3 to 15 minutes. A reaction mixture (Ila) can be obtained by adopting a melt-kneading method.

Further, in preparing the reaction mixture (lib) used for the thermoplastic polymer compositions Gi) and (m), for example, an addition polymerization block copolymer (I-1), a compound having two hydroxyl groups, and A method in which a carbonate precursor is melt-kneaded usually at 180-300 ° C for 3-15 minutes using a kneader such as a single-screw extruder, twin-screw extruder, kneader, Banbury mixer, etc. in the presence of a catalyst as necessary. Can be used to obtain a reaction mixture (lib). In the case where a catalyst deactivator is used, it is preferably added after the completion of the carbonate bond formation reaction until the end of the melt kneading.

[0069] The reaction mixture (Ila) and the reaction mixture (lib) used in the thermoplastic polymer compositions (ii) and (m) are composed of an addition polymerization block copolymer (I) and a thermoplastic polyurethane (III). In order to have good compatibility with both, it is preferable to use the reaction mixture having a tensile strength at break of 1 OMPa or more, more preferably 12 MPa or more, and particularly preferably 15 MPa or more. The reaction mixture (Ila) and reaction mixture (lib) used for the products (ii) and (iii) are the melt moldability, flexibility, strength of the thermoplastic polymer compositions (ii) and (iii). It is preferable to use a reaction mixture having a JIS A hardness of 40 to 99, more preferably 50 to 95, particularly 60 to 95, in order to improve the chemical performance.

The JIS A hardness of the reaction mixture as used herein is a value measured according to JIS K-6253.

[0070] The thermoplastic polymer compositions (i) to (iii) of the present invention include the above addition polymerization block copolymer (I), block copolymer (II), reaction mixture (Ila) or reaction. The thermoplastic polyurethane (III) is contained together with the mixture (lib).

As the thermoplastic polyurethane (III), those in which a polymer polyol, a chain extender and an organic diisocyanate compound are also formed are preferable.

[0071] Examples of the polymer polyol used for forming the thermoplastic polyurethane (III) include polyester polyols, polyether polyols, polycarbonate polyols, polyester polycarbonate polyols, polyolefin polyols, conjugated polyethylene polymer polyols, and castor oils. Polyols, silicone polyols, and bull polymer polyols can be used, and one or more of these can be used. Among these, as the polymer polyol, one or more of polyester polyols, polyether polyols and polyolefin polyols are preferably used, and polyester polyols and Z or polyether polyols are more preferably used.

[0072] The polyester polyol preferably used for forming the thermoplastic polyurethane (III) is, for example, a force for directly subjecting a polyol component and a polycarboxylic acid component to an esterification reaction or a transesterification reaction, or starting a polyol component. It can be produced by ring-opening polymerization of rataton as an agent.

[0073] Examples of the polyol component used in the production of the polyester polyol include those generally used in the production of polyester, such as ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, 1, 3 propanediol, 2 —Methyl-1,3 propanediol, 2,2 Jetyl 1,3 propanediol, 1,3 butanediol, 1,4 butanediol, 2-methyl-1,4 butanediol, neopentyl glycol, 1,5 pentanediol, 3 —Methyl- 1, 5 pentane All, 1,6 hexanediol, 1,7 heptanediol, 1,8 octanediol, 2-methyl-1,8 octanediol, 2,7 dimethyl-1,8 octanediol, 1,9-nonanediol, 2-methyl-1, Aliphatic diols having 2 to 15 carbon atoms such as 9-nonanediol, 2,8 dimethyl-1,9-nonanediol, 1,10 decanediol; 1,4-cyclohexanediol, cyclohexanedimethanol, cyclooctanedimethanol, etc. Alicyclic diols; aromatic diols such as 1,4 bis (j8-hydroxyethoxy) benzene; trimethylolpropane, trimethylolethane, glycerin, 1,2,6hexanetriol, pentaerythritol, diglycerin, etc. One or more polyhydric alcohols having 3 or more hydroxyl groups per molecule can be used

[0074] Among them, in the production of the polyester polyol, propylene glycol, 2-methyl-1,4 butanediol, 3-methyl-1,5 pentanediol, 2-methyl-1,8 octanediol, 2, 7 One or two aliphatic diols having 3 to 12 carbon atoms having a methyl group as a side chain, such as dimethyl-1,8-octanediol, 2-methyl-1,9-nonanediol, and 2,8 dimethyl-1,9-nonanediol. It is preferable to use more than one species. In particular, among these polyol components, an aliphatic diol having 3 to 12 carbon atoms having a methyl group as a side chain is 10 mol% or more, more preferably 30 mol% or more of all polyol components used for the production of polyester polyol, It is preferable to use it at a ratio of 50 mol% or more.

[0075] Further, as the polycarboxylic acid component used in the production of the polyester polyol described above, polycarboxylic acid components generally used in the production of polyester, for example, succinic acid, glutaric acid, adipic acid, pimelic acid, Suberic acid, azelaic acid, sebacic acid, dodecanedioic acid, methylsuccinic acid, 2-methyldaltaric acid, 3-methyldaltaric acid, trimethyladipic acid, 2 methyloctanedioic acid, 3,8 dimethyldecanedioic acid, 3,7 dimethyldecane Aliphatic dicarboxylic acids having 4 to 12 carbon atoms such as diacids; cycloaliphatic dicarboxylic acids such as cyclohexanedicarboxylic acid, dimer acid and hydrogenated dimer acid; terephthalic acid, isophthalic acid, orthophthalic acid, naphthalenedicarboxylic acid, etc. Aromatic dicarboxylic acids: Trimellitic acid, polymellitic acid such as pyromellitic acid Bon acid; etc. can be mentioned their esters or ester forming derivatives such as their anhydrides, these one or Two or more types can be used. Among them, one or more of aliphatic dicarboxylic acids having 6 to 12 carbon atoms, adipic acid, azelaic acid and sebacic acid are preferably used as the polycarboxylic acid component.

[0076] Further, examples of the ratatones used for the production of the polyester polyol include ε-force prolatatanes, β-methyl-1-δ-valerolatatanes, and the like.

[0077] The above-described polyether polyols preferably used for forming the thermoplastic polyurethane (III) include, for example, poly (ethylene glycol), poly (propylene glycol), poly (polyethylene glycol) obtained by ring-opening polymerization of a cyclic ether. (Tetramethylene glycol), poly (methyltetramethylene glycol) and the like can be used, and one or more of these can be used. Of these, poly (tetramethylene glycol) and cocoon or poly (methyl tetramethylene glycol) are preferably used.

[0078] The polycarbonate polyol that can be used for forming the thermoplastic polyurethane (III) is obtained by, for example, reacting a polyol component with a carbonate compound such as dialkyl carbonate, alkylene carbonate, or diaryl carbonate. Can be listed.

As the polyol component constituting the polycarbonate polyol, the polyol component exemplified as the constituent component of the polyester polyol can be used. Examples of the dialkyl carbonate include dimethyl carbonate and jetyl carbonate. Examples of the alkylene carbonate include ethylene carbonate. Examples of the dialyl carbonate include , Diphenol-bonate and the like.

[0079] Examples of the above-described polyester polycarbonate polyol that can be used to form the thermoplastic polyurethane (III) include those obtained by reacting a polyol component, a polycarboxylic acid component and a carbonate compound at the same time, or a polyester synthesized in advance. Examples include those obtained by reacting polyols and polycarbonate polyols with carbonated compounds, or those obtained by reacting previously synthesized polyester polyols and polycarbonate polyols with polyol components and polycarboxylic acid components. Can do. [0080] The above-mentioned conjugated gen-based polyol or polyolefin-based polyol that can be used to form the thermoplastic polyurethane (III) includes a conjugated diene such as butadiene and isoprene, or a conjugated gen in the presence of a polymerization initiator. Polyisoprene polyol, polybutadiene polyol, poly (butadiene z isoprene) polyol, poly (butadiene Z acrylonitrile) obtained by reacting an epoxy compound with the polymerization active terminal after polymerizing other monomers by a living polymerization method or the like. Examples thereof include polyols, poly (butadiene Z styrene) polyols, hydrogenated products thereof, and the like, and one or more of these can be used.

[0081] The number average molecular weight of the high molecular polyol used for forming the thermoplastic polyurethane (III) is within the range of 500 to 10,000, more preferably 700 to 8,000, and particularly 800 to 5,000. S Preferred. By containing a thermoplastic polyurethane (III) produced using a polymer polyol having a number average molecular weight in the above range, the melt moldability, flexibility, mechanical performance, etc. of the thermoplastic polymer composition of the present invention The characteristics are excellent.

The number average molecular weight of the polymer polyol referred to in the present specification is a number average molecular weight calculated based on a hydroxyl value measured in accordance with JIS K-1557.

[0082] In addition, the polymer polyol used for forming the thermoplastic polyurethane (III) has a hydroxyl number per molecule of 2.0 to 2.1, and even ί or 2. 0 to 2.05. In particular, it is preferably within the range of 2.002 to 2.03 even. By containing the thermoplastic polyurethane (III) formed using a polymer polyol having a number of hydroxyl groups per molecule within the above range, the melt moldability, flexibility, Properties such as mechanical performance and wear resistance are excellent.

When multiple types of polymer polyols are used, the average number of hydroxyl groups per molecule calculated from the number of hydroxyl groups per molecule and the amount used (number of moles) is calculated for each molecule. The number of hydroxyl groups.

[0083] The chain extender used for forming the thermoplastic polyurethane (III) may be any chain extender conventionally used in the production of polyurethane, and any of them may be an active hydrogen atom capable of reacting with an isocyanate group. A low molecular weight compound having a molecular weight of 400 or less having 2 or more in the molecule is preferably used. [0084] Examples of chain extenders include ethylene glycol, propylene glycol, 1,4-butanediol, 1,6 hexanediol, 2-methyl-1,3 propanediol, 2,2 jetyl-1,3 propanediol, 2 Butyl-2-ethyl-1,3-propanediol, 1,3-butanediol, 2-methyl-1,4-butanediol, neopentyl glycol, 3-methyl-1,5-pentanediol, 2,4 jetyl-1,5-pentanediol, 2 ethyl-1 , 3 hexanediol, 2-methyl-1,8-octanediol, 2,7 dimethyl-1,8 octanediol, 2-methyl-1,9-nonanediol, 2,8 dimethyl-1,9-nonanediol, 1,4 bis (j8— Hydroxyethoxy) benzene, 1,4-cyclohexanediol, bis (j8-hydroxyethyl) terephthalate, xyl Rylene glycol, 1,4-cyclohexane dimethanol, 1, 4 (or 5) —octane dimethanol, 3 (or 4), 8 (or 9) —dihydroxymethyltricyclo (5, 2, 1, 0 ² ^'6) diols such as decane; hydrazine, Echirenjiamin, propylene di § Min, xylylene § Min, isophorone § Min, piperidines Rajin and its derivatives, Hue - Renjia Min, Torirenjiamin, Kishirenjiamin, adipic acid dihydrazide, isophthalic Examples include diamines such as acid dihydrazide; amino alcohols such as aminoamino alcohol and aminopropyl alcohol, and one or more of these can be used. Among them, aliphatic diols having 2 to 12 carbon atoms are preferably used, and one or two of 1,4 butanediol, 3-methyl-1,5-pentanediol, 2-methyl-1,8 octanediol and 1,9-nonanediol are used. More than species are more preferably used. In addition, when thermoplastic polyurethane (III) produced using an aliphatic diol having a number average molecular weight of 100 to 400 as a chain extender is used as a chain extender, the value of the loss coefficient is around room temperature. A thermoplastic polymer composition excellent in vibration damping performance that maintains a large loss coefficient value over a large and wide temperature range can be obtained. As the aliphatic diol having such a branch in the molecule, an aliphatic diol having 5 to 12 carbon atoms having a methyl group as a side chain is preferably used.

[0085] Further, as the organic diisocyanate compound used for forming the thermoplastic polyurethane (III), an organic diisocyanate compound, which has been conventionally used in the production of polyurethane, for example, 4, 4'—Diphenylmethane diisocyanate, tolylene diisocyanate, phenolic diene Aromatic diisocyanates such as isocyanate, xylylene diisocyanate, 1,5-naphthylene diisocyanate, 3, 3, -dichloro-4,4, -diphenylmethane diisocyanate; hexamethylene diisocyanate, isophorone Aliphatic or alicyclic diisocyanates such as diisocyanate, 4,4'-dicyclohexylmethane diisocyanate, hydrogenated xylylene diisocyanate, etc. can be mentioned, and one or more of these Can be used.

Among them, the thermoplastic polymer composition of the present invention is excellent in melt moldability, flexibility, mechanical performance, etc., so it is formed using 4,4'-diphenylmethane diisocyanate. It is preferable to contain the thermoplastic polyurethane (III). In addition, thermoplastic polyurethane (III) formed using an aliphatic or alicyclic diisocyanate is preferably used because of its excellent light resistance.

[0086] In forming the thermoplastic polyurethane (III), the organic diisocyanate compound is based on the total mass of the polymer polyol, the chain extender and the organic diisocyanate compound. It is preferable to use a polyurethane raw material having a nitrogen atom content derived from a material in the range of 1 to 6.5% by mass, more preferably 1 to 6% by mass, and particularly 1.3 to 5.5% by mass. By including the thermoplastic polyurethane (III) formed using such a polyurethane raw material, the melt moldability, flexibility, mechanical performance and the like of the thermoplastic polymer composition of the present invention are improved. The

[0087] Further, as the thermoplastic polyurethane (III), it is possible to use a thermoplastic polyurethane having a JIS A hardness of 30 to 99, more preferably 45 to 97, particularly 60 to 95. The combined composition is preferred because it has better melt moldability, flexibility, mechanical performance, and the like.

[0088] As the thermoplastic polyurethane (III), a commercially available product may be used, or the thermoplastic polyurethane (III) may be prepared by reacting the above-described polymer polyol, chain extender, and organic diisocyanate compound. You may use what you did.

In forming the thermoplastic polyurethane (III), the polymer polyol and the chain extender have! /, And the organic diisocyanate compound has 1 mole of the active hydrogen atom. It is preferable to use each component in such a ratio that the group is 0.9 to 1.3 moles. ,. By containing the thermoplastic polyurethane (III) formed by using each component in the above proportion, the melt moldability, flexibility and mechanical properties of the thermoplastic polymer compositions (i) to (iii) of the present invention are as follows. The characteristics such as Noh are better.

[0089] Further, as the thermoplastic polyurethane (III), [number of moles of polymer polyol]: [number of moles of chain extender] = 1: 0.2 to 8.0 (molar ratio) and [polymer polyol] And the total number of moles of chain extender]: [number of moles of organic diisocyanate compound] = 1: 0.9.98-1.04 (molar ratio) If the thermoplastic polymer composition of the present invention is contained, a rapid increase in melt viscosity does not occur when performing melt molding such as extrusion molding and injection molding, and the desired molded article or laminated structure Etc. can be manufactured smoothly.

[0090] In forming the thermoplastic polyurethane (III), a urethanization reaction catalyst may be used. Examples of powerful urethane reaction catalysts include organotin compounds such as dibutyltin diacetate, dibutyltin dilaurate, and dibutyltin bis (3-mercaptopropionic acid ethoxybutyl ester) salt; titanic acid; tetraisopropyl titanate, tetra-n- Organic titanium compounds such as butyrate titanate, polyhydroxytitanium stearate, titanium acetylacetonate; triethylenediamine, N-methylmorpholine, N, N, Ν ', Ν, tetramethylethylenedi And tertiary amine compounds such as ァ, Ν, Ν, Ν ', N'-tetramethylhexamethylenediamine, triethylamine, Ν, Ν-dimethylaminoethanol, etc. Or two or more can be used.

The amount of the urethanization reaction catalyst used is 0.1 ppm to 0.2% by mass, more preferably 0.5 ppm to 0.02% by mass based on the total mass of the polymer polyol, the chain extender and the organic disoocyanate compound. It is preferably in the range of lppm to 0.01 mass%.

The urethanization reaction catalyst can be contained in one or more of the polymer polyol, chain extender, and organic diisocyanate compound. The polymer polyol should be contained in the polymer polyol. Is preferred!

[0091] When the thermoplastic polyurethane (III) is produced using the urethanization reaction catalyst, it is preferable to add a urethane-type reaction catalyst deactivator to the obtained thermoplastic polyurethane (ΠΙ). Examples of the urethanization catalyst deactivator include lauryl phosphate, oleyl phosphate, stearinorephosphate, dilaurinorephosphate, diolenorephosphate, diester. Phosphorus compounds such as stearyl phosphate, tris (2-ethylhexyl) phosphate, bis (octadecyl) pentaerythritol diphosphate, jetyl phosphonate, 3,5-di-tert-butyl-4-hydroxybenzylphosphonate 2, 2, -methylenebis (4-methyl-6t-butylphenol), 2,2, -methylenebis (4-ethyl-6-t butylenophenol), 2 hydroxy-1-pentinoreoxybenzophenone, 2- (2 , Monohydroxy-1,3,5,1t-butylphenol) benzotriazole, 2- [2 hydroxy-3,5 bis (α, a-dimethylbenzyl) phenol] 2H benzotriazole, 4, 4 Examples include phenolic compounds such as'-octyl-2,2'-biphenol, among which phosphorus compounds are preferably used. It is.

The amount of the urethanization catalyst deactivator used is lppm to 2% by mass, and 5ppm based on the total mass of the polymer polyol, chain extender and organic diisocyanate compound used to form the thermoplastic polyurethane (5). It is preferable to be within the range of ˜0.2% by mass, particularly 10 ppm to 0.1% by mass.

[0092] Further, the ratio of the urethanization reaction catalyst deactivator to the urethanization reaction catalyst is such that when a phosphorus compound is used as the urethanization reaction catalyst deactivator, the metal atom 1 of the urethanization reaction catalyst is 1 The phosphorus atom of the phosphorus compound is preferably used in the range of 0.1 to 500 mol, more preferably 0.2 to 200 mol, and particularly preferably 0.5 to 100 mol with respect to mol. In addition, when a phenolic compound is used as the urethanization reaction catalyst deactivator, 1 to 5000 moles as a hydroxyl group of the phenolic compound relative to 1 mole of the metal atom of the urethanization reaction catalyst, and further 2 to 2000 It is preferred to use within the range of mol, especially 5 to: L000 mol.

The urethanization reaction catalyst deactivator comprises an addition polymerization block copolymer (I), a block copolymer (11), a reaction mixture (Ila) or a reaction mixture (lib), a thermoplastic polyurethane (III), A paraffinic oil (IV) and other components as necessary were mixed and melt-kneaded to produce a thermoplastic polymer composition, and the physical properties of the thermoplastic polymer composition reached desired values. It is preferable to add at the time from the viewpoint of melt moldability, flexibility, mechanical performance, etc. of the thermoplastic polymer composition of the present invention.

[0093] The method for forming the thermoplastic polyurethane (III) is not particularly limited, and the polymer polyol, chain elongation, A long agent and an organic diisocyanate compound may be used to produce either a prepolymer method or a one-shot method using a known urethanization reaction. Of these, it is preferable to use melt polymerization in the absence of any solvent, especially using a multi-screw extruder.

V, preferably formed by continuous melt polymerization.

[0094] In the thermoplastic polymer compositions (i) to (m) of the present invention, a thermoplastic polyurethane prepared in advance as the thermoplastic polyurethane (III) may be used, or the thermoplastic polymer of the present invention. The raw material component for the composition may be mixed with a polymer polyol, a chain extender and an organic diisocyanate compound to form a thermoplastic polyurethane in the composition simultaneously with the production of the thermoplastic polymer composition. Yo ...

[0095] As the paraffinic oil (IV) used in the thermoplastic polymer compositions (i) to (iii) of the present invention, those containing 60% by mass or more of a nophine component (chain hydrocarbon) are used. However, those containing 80% by mass or more of the paraffin component (chain hydrocarbon) are preferred. The paraffinic oil (IV) may contain a component having an aromatic ring such as a benzene ring or a naphthene ring as other components.

[0096] As the norafin oil (IV), the kinematic viscosity measured at 40 ° C is in the range of 20 to 800 centistoise (cSt (mmVs)), particularly 50 to 600 centistoise (cSt (mmVs)). It is preferable to use what is in By using the paraffinic oil (IV) having a strong kinematic viscosity, the thermoplastic polymer composition of the present invention is more excellent in properties such as melt moldability, flexibility and mechanical performance.

The kinematic viscosity of the paraffinic oil (IV) referred to in this specification is a value measured according to JIS K-2283.

[0097] In the present invention, it is preferable to use a paraffinic oil (IV) having a pour point in the range of 40 to 0 ° C, particularly 30 to 0 ° C. By using the paraffinic oil (IV) having the above pour point, the thermoplastic polymer composition of the present invention is more excellent in properties such as melt moldability, flexibility and mechanical performance.

The pour point of paraffinic oil (IV) in the present specification is a value measured in accordance with JIS K-2269.

[0098] The flash point of paraffinic oil (IV) is in the range of 200 to 400 ° C, especially 250 to 350 ° C. It is preferable that it exists in. By using the paraffinic oil (IV) having a flash point in the above range, the thermoplastic polymer composition of the present invention has more excellent characteristics such as melt moldability, flexibility and mechanical performance. Become.

The flash point of paraffinic oil (IV) in the present specification is a value measured according to JIS K-2265.

[0099] The thermoplastic polymer composition (i) of the present invention has excellent properties such as melt moldability, anti-adhesion to a molding machine, flexibility, mechanical properties, and melt adhesion to other materials. From this point, the addition copolymerization block copolymer (I) per 100 parts by mass of the block copolymer (II) is 5 to 200 parts by mass, the thermoplastic polyurethane (III) is 100 to 800 parts by mass and paraffin. It is preferable to contain 10 to 200 parts by mass of the system oil (IV).

[0100] In the thermoplastic polymer composition (i), the content of the block copolymer (II) is less than 5 parts by mass with respect to 100 parts by mass of the addition polymerization block copolymer (I). In this case, the compatibility between the addition polymerization type block copolymer (I) and the thermoplastic polyurethane (III) becomes insufficient, and the thermoplastic polymer has flexibility, mechanical performance and melt moldability. In some cases, it may be difficult to obtain the composition, and the product such as a molded product or a laminated structure obtained by using the thermoplastic polymer composition tends to easily cause surface roughness and lower adhesion between layers. is there. On the other hand, in the thermoplastic polymer composition (i), if the content of the block copolymer (Π) exceeds 200 parts by mass with respect to 100 parts by mass of the addition polymerization block copolymer (I), the thermoplastic polymer The melt flowability and melt adhesion of the polymer composition are lowered, and the molded product tends to be rough, and the adhesion between layers in the laminated structure tends to occur. The thermoplastic polymer composition (i) of the present invention contains 10 to 180 parts by mass of the block copolymer (II) with respect to 100 parts by mass of the addition polymerization block copolymer (I). More preferably, it is contained in a proportion of 20 to 150 parts by mass, which is more preferable.

[0101] In addition, in the thermoplastic polymer composition (i), the ratio of the thermoplastic polyurethane (III) is less than 100 parts by mass with respect to 100 parts by mass of the addition polymerization block copolymer (I). It is difficult to obtain a thermoplastic polymer composition having flexibility, mechanical performance, and melt moldability, and it is easy to obtain a compression set of a molded product or a laminated structure obtained from the thermoplastic polymer composition. Tends to be large, and melt adhesion with other materials is reduced, resulting in molding The surface of the product is roughened, and the moldability tends to become unstable. In particular, when melt extrusion molding including inflation molding is performed using the thermoplastic polymer composition (i), the moldability may be lowered. On the other hand, in the thermoplastic polymer composition (i), when the ratio of the thermoplastic polyurethane (III) exceeds 800 parts by mass with respect to 100 parts by mass of the addition polymerization block copolymer (I), As the plastic polymer composition is easily attached to the molding apparatus, the melt moldability tends to be unstable, and the surface of the molded product tends to be roughened.

The thermoplastic polymer composition (i) of the present invention contains 150 to 800 parts by mass of the thermoplastic polyurethane (III) with respect to 100 parts by mass of the addition polymerization block copolymer (I). It is particularly preferred to contain it in a proportion of 200 to 700 parts by mass, more preferably 350 to 700 parts by mass.

[0102] Further, in the thermoplastic polymer composition (i), the ratio of the paraffinic oil (IV) is less than 10 parts by mass with respect to 100 parts by mass of the addition polymerization type block copolymer (I). In addition, there is a tendency that a compression set of a molded product or a laminated structure obtained from the thermoplastic polymer composition is increased, or the surface of the molded product is liable to be roughened. On the other hand, in the thermoplastic polymer composition (i), when the ratio of the paraffinic oil (IV) exceeds 200 parts by mass with respect to 100 parts by mass of the addition polymerization block copolymer (I), the thermoplastic polymer composition It becomes difficult to melt-mold products, and melt adhesion with other materials decreases, resulting in decreased mechanical performance such as tensile breaking strength and tensile breaking elongation of molded products obtained from thermoplastic polymer compositions. There is a tendency that problems such as rough surface of the molded product and running out of the spool during molding tend to occur.

The thermoplastic polymer composition (i) of the present invention contains 50 to 150 parts by mass of the nophine oil (IV) with respect to 100 parts by mass of the addition polymerization block copolymer (I). It is more preferable that it is contained in a proportion of 75 to 125 parts by mass.

[0103] In the production of the thermoplastic polymer composition (i) of the present invention, the block copolymer obtained by reacting the addition polymerization block copolymer (I-1) and the polycarbonate polymer (Rho 1). A reaction product containing a polymer (ΠΑ), and a block copolymer (ΠΒ) obtained by reacting Z or an addition block copolymer (I-1), a compound having two hydroxyl groups and a carbonate precursor. ) Containing reaction products, In the composition, in addition to the block copolymer (共) or block copolymer (成), an unreacted addition polymerization block copolymer (I-1), an unreacted polycarbonate polymer (low) 1) A compound having two hydroxyl groups and a carbonate precursor, formed polycarbonate, aromatic vinyl compound polymer block and conjugated gen polymer block, and also reacts with polycarbonate polymer (Roh 1). One or more components such as a block copolymer having no functional group may be contained.

In such a case, the addition polymerization block copolymer (I-1) [equivalent to the addition polymerization block copolymer (I)] contained in those reaction products, the block copolymer (11) In consideration of the amount of selenium-polyborate polymer (Rho 1), etc., addition polymerization block copolymer (1), block copolymer (11), thermoplastics in the thermoplastic polymer composition Content Ratio of Polyurethane (III) and Paraffinic Oil (IV) It is preferable to adjust the blending ratio of the reaction product and other components so as to be within the above-mentioned range.

[0104] Further, in the thermoplastic polymer compositions (ii) and (iii) of the present invention, the obtained thermoplastic polymer composition has a melt moldability, an adhesion preventing property to a molding machine, a flexibility, a mechanical property. From the point that the characteristics and various properties such as melt adhesion to other materials are improved, the reaction mixture (Ila) and Z or (lib) per 100 parts by mass of the addition polymerization block copolymer (I) 5 to 5000 parts by mass [If both reaction mixture (Ila) and reaction mixture (lib) are used, the total mass of both], 100 to 13600 parts by mass of thermoplastic polyurethane (III) and paraffinic oil (IV ) Is preferably used in a proportion of 10 to 3400 parts by mass.

[0105] In the thermoplastic polymer compositions (ii) and (m), an addition polymerization block copolymer (I)

When the use amount of the reaction mixture (Ila) and Z or the reaction mixture (lib) is less than 5 parts by mass with respect to 100 parts by mass, the addition polymerization block copolymer (I) and the thermoplastic polyurethane (III) Insufficient compatibility may be difficult, and it may be difficult to obtain a thermoplastic polymer composition having excellent flexibility, mechanical performance, and melt moldability. Further, the thermoplastic polymer composition may be used. Products such as molded products and laminated structures tend to be prone to surface roughness and interlaminar adhesion degradation. On the other hand, in the thermoplastic polymer compositions (ii) and (m), the reaction mixture (Ila) and Z or the reaction mixture (lib) are added to 100 parts by mass of the addition polymerization block copolymer (I). When the amount of use exceeds 5000 parts by mass, the thermoplastic polymer composition Decrease in melt fluidity and decrease in melt adhesiveness tend to cause surface roughness in the molded product, and poor adhesion between layers in the laminated structure.

In the thermoplastic polymer compositions (ii) and (m), the reaction mixture (Ila) and Z or the reaction mixture (lib) are added in an amount of 10 to 450 parts by mass relative to the addition polymerization block copolymer (I) loo parts by mass. More preferably, it is used in a proportion of 20 parts by weight, and more preferably in a proportion of 20 to 300 parts by mass.

[0106] In addition, in the thermoplastic polymer compositions (i) and (m), the amount of the thermoplastic polyurethane (III) used is 100 parts by mass with respect to 100 parts by mass of the addition polymerization block copolymer (I). If the amount is less than part by mass, it is difficult to obtain a thermoplastic polymer composition having flexibility, mechanical performance and melt moldability, and the strength of the thermoplastic polymer composition is easily obtained. The compression set tends to be large, and the melt adhesion with other materials is lowered, the surface of the molded product is roughened, and the moldability tends to be unstable. In particular, when performing melt extrusion molding including inflation molding using the thermoplastic polymer composition (ii) or (iii), the moldability may be lowered. On the other hand, in the thermoplastic polymer compositions (ii) and (m), the amount of the thermoplastic polyurethane (III) used is 13600 parts by mass with respect to the addition polymerization block copolymer (I) loo part by mass. If it exceeds 1, the thermoplastic polymer composition tends to adhere to the molding apparatus at the time of melt molding, so that the melt moldability tends to become unstable and the surface of the molded product tends to become rough.

In thermoplastic polymer compositions (ii) and (m), thermoplastic polyurethane (III) should be used at a ratio of 150 to 1500 parts by mass with respect to addition polymerization block copolymer (I) loo parts by mass. More preferably 200 to: L It is particularly preferable to use at a ratio of 100 to 100 parts by mass, and particularly preferable to use at a ratio of 350 to 1100 parts by mass.

[0107] In addition, in the thermoplastic polymer compositions (ϋ) and (m), the amount of the paraffinic oil (IV) used is 10 per 100 parts by mass of the addition polymerization block copolymer (I). If the amount is less than part by mass, the compression set of a molded product or a laminated structure obtained from the thermoplastic polymer composition tends to increase, or the surface of the molded product tends to become rough. On the other hand, in the thermoplastic polymer compositions (ii) and (m), the amount of the paraffinic oil (IV) used is 3400 parts by mass with respect to 100 parts by mass of the addition polymerization block copolymer (I). Exceeding thermoplastic polymer Melt molding of the composition is difficult, and melt adhesion with other materials is reduced, and mechanical properties such as tensile breaking strength and tensile breaking elongation of molded products obtained from thermoplastic polymer compositions are reduced. There is a tendency that problems such as lowering, roughness of the molded product surface, and running out of the spool during molding tend to occur.

In the thermoplastic polymer compositions (ii) and (m), the nophine oil (IV) is used at a ratio of 50 to 300 parts by mass with respect to the addition polymerization type block copolymer (I) loo part by mass. It is more preferable to use it at a ratio of 75 to 200 parts by mass.

[0108] The thermoplastic polymer composition ω to (m) of the present invention does not impair the effects of the invention!

If necessary, it may contain an olefin polymer (V). The content of the olefin polymer (V) is preferably 200 parts by mass or less, particularly 0 to L00 parts by mass with respect to 100 parts by mass of the addition polymerization block copolymer (I). By including the olefin polymer (V), the mechanical strength and melt moldability of the thermoplastic polymer composition may be further improved.

[0109] Examples of the olefin-based polymer (V) include homopolymers of olefins such as ethylene, propylene and butylene, olefin copolymers composed of two or more of the above-mentioned olefins, or one or two of the olefins described above. Examples thereof include a copolymer of at least one species and one or more of other bule monomers. Examples of other bur monomers include cyanobyl monomers such as acrylo-tolyl and meta-tallow-tolyl; methyl, ethyl, propyl, n-butyl of acrylic acid or methacrylic acid, C1-C18 alkyl esters such as i-butyl, hexyl, 2-ethylhexyl, dodecyl, octadecyl; diol esters such as acrylic acid or methacrylic acid ethylene glycol, propylene glycol, butanediol; acetic acid and propionic acid Vinyl esters of carboxylic acids having 1 to 6 carbon atoms such as; unsaturated carboxylic acids such as acrylic acid, methacrylic acid and maleic acid; anhydrides of unsaturated dicarboxylic acids such as maleic anhydride; acrylamide, methacrylamide, N, N — (Meth) acrylamides such as dimethylacrylamide; maleimide, N-methylmaleimi And N-substituted maleimides such as N-ethylmaleimide, N-phenylmaleimide and N-cyclohexylmaleimide; conjugated gens such as butadiene and isoprene.

[0110] More specifically, as the olefin-based polymer (V), for example, low density polyethylene, medium Density polyethylene, high density polyethylene, polypropylene, polybutylene, ethylene (X-olefin copolymer, ethylene acetate butyl copolymer, ethylene acrylic acid copolymer, ethylene maleic anhydride copolymer, propylene acrylic acid copolymer, propylene Examples thereof include maleic anhydride copolymers and isobutylene maleic anhydride copolymers, and one or more of these can be used.

[Oil 1] In addition, the thermoplastic polymer compositions (i) to (iii) of the present invention may be added within the range of the addition polymerization block copolymer (1 ), A styrene polymer different from the block copolymer (II); a polyphenylene ether resin; a thermosetting polyurethane resin; a polyamide resin; a polyester resin; a polyvinyl chloride resin; Vinylidene resin; Acrylic resin; Ethylene acetate copolymer Copolymer; Copolymer of aromatic vinyl compound and vinyl silane compound; Aromatic vinyl compound, cyanide vinyl compound and Olefinich One kind or two or more kinds of other polymers such as a copolymer of the compound may be contained.

[0112] The thermoplastic polymer composition ω to (m) of the present invention can contain an inorganic filler as required, and the inorganic filler is a high polymer of the thermoplastic polymer composition of the present invention. It is useful for improving hardness and economic efficiency as a bulking agent. Examples of the inorganic filler include calcium carbonate, talc, clay, synthetic silicon, titanium oxide, carbon black, barium sulfate, and the like, and can contain one or more of these. . The content of the inorganic filler is preferably 100 parts by mass or less, more preferably 0 to 50 parts by mass with respect to 100 parts by mass of the addition polymerization block copolymer (I).

[0113] The thermoplastic polymer composition ω to (m) of the present invention may be a lubricant, a pigment, an impact resistance improver, a processing aid, a crystal nucleating agent, a colorant, a flame retardant, and a weather resistance improvement as necessary. Agents, ultraviolet absorbers, antioxidants, hydrolysis resistance improvers, antifungal agents, antibacterial agents, light stabilizers, antistatic agents, silicone oils, antiblocking agents, mold release agents, foaming agents, fragrances, etc. 1 type or 2 types or more of various coupling agents and other arbitrary components.

[0114] According to the present invention, a thermoplastic polymer composition having high bow I tensile strength can be obtained. For example, a thermoplastic polymer composition having a tensile strength at break of 8 MPa or more, and further lMPa or more can be obtained. The tensile strength at break is the thermoplastic polymer composition. Is a dumbbell-type test piece specified in JIS 3 and measured in accordance with JIS K-7311. Details will be described in the item of the example.

[0115] The method for producing the thermoplastic polymer composition ω to (m) of the present invention is not particularly limited, and any method can be used as long as the above-described constituent components can be uniformly mixed. Of these, the melt-kneading method is simple and preferably employed.

In the thermoplastic polymer compositions (i) to (iii) of the present invention, for example, each constituent component is melt-kneaded equipment such as a single screw extruder, a twin screw extruder, a kneader, a mixing roll, a Banbury mixer, and the like. In general, it can be produced by melt kneading at a temperature of 150 to 220 ° C. for about 30 seconds to 5 minutes.

[0116] Among them, as a method for producing the thermoplastic polymer composition (i), the thermoplastic polymer composition (i) excellent in melt moldability, flexibility, mechanical performance, etc. can be reliably produced. The following method [1] or [2] is preferably employed.

[1] Addition polymerization type block copolymer (I), block copolymer (II) or block copolymer (II) and other reaction components as described above (hereinafter referred to as “block copolymer ( II) Containing reaction product "]], mixing high molecular weight polyol, chain extender and organic diisocyanate compound, pre-manufactured thermoplastic polyurethane (ΠΙ) and paraffinic oil (IV) And then melt-kneading.

[2] Addition-polymerized block copolymer (I), block copolymer (II) or block copolymer (II) -containing reaction product], paraffinic oil (IV), polymer polyol, chain elongation A method in which an agent and an organic diisocyanate compound are mixed and melt-kneaded.

[0117] In the production of the thermoplastic polymer composition (i), the blending order and melt-kneading order of each component are not particularly limited. For example, blending is performed by the method shown in the following (1) to (8). Melting and kneading can be performed.

(1) Thermoplastic polyurethane (111), addition-polymerized block copolymer (1), block copolymer (II) prepared by reacting polymer polyol, chain extender and organic diisocyanate compound ) A block copolymer (II) -containing reaction product] and paraffinic oil (IV) are mixed together and melt-kneaded.

(2) Addition polymerization block copolymer (1), block copolymer (II) Hot block copolymer Body (II) -containing reaction product], paraffinic oil (IV), polymer polyol, chain extender and organic diisocyanate compound are mixed together and melt-kneaded.

(3) A block copolymer (II) or a block copolymer (II) -containing reaction product], a polymer polyol, a chain extender and an organic diisocyanate compound are mixed and melt-kneaded. Separately, the addition polymerization block copolymer (I) and the paraffinic oil (IV) are separately mixed and melt-kneaded, and both melt-kneaded materials are mixed and further melt-kneaded.

(4) Addition-polymerized block copolymer (1), block copolymer (II) or block copolymer (Π) containing reaction product] and paraffinic oil (IV) are mixed and melt-kneaded. A method of adding a polymer polyol, a chain extender and an organic diisocyanate compound to the melt-kneaded product and further melt-kneading.

(5) Addition-polymerized block copolymer (1), block copolymer (II) or block copolymer (II) -containing reaction product], polymer polyol, chain extender and organic diisocyanate compound are mixed Then, after melt-kneading, paraffinic oil (IV) is added thereto and further melt-kneading.

(6) A thermoplastic polyurethane is produced by kneading and reacting a polymer polyol, a chain extender and an organic diisocyanate compound, followed by addition polymerization block copolymer (I) and block copolymer ( II) Almost the block copolymer (II) -containing reaction product] is melt-kneaded, and paraffinic oil (IV) is further added thereto and melt-kneaded.

(7) Addition-polymerized block copolymer (1), block copolymer (II) or block copolymer (II) -containing reaction product], polymer polyol, chain extender and paraffinic oil (IV ) Are mixed and melt-kneaded, and then an organic diisocyanate compound is added thereto and further melt-kneaded.

(8) Thermoplastic polyurethane (III) and block copolymer (II) prepared by reacting high molecular polyol, chain extender and organic diisocyanate compound (II) A method of mixing and melt-kneading a composition comprising separately prepared addition polymerization block copolymer (I) and paraffinic oil (IV) together with (i) containing reaction product].

Further, the thermoplastic polymer composition (ii) of the present invention can be produced by the following method [3]. [3] A method in which at least one of addition polymerization block copolymer (I), reaction mixture (Ila) and reaction mixture (lib), thermoplastic polyurethane (III), and paraffinic oil (IV) is melt-kneaded.

Furthermore, the thermoplastic polymer composition (m) of the present invention can be produced by the following method [4].

[4] Addition polymerization block copolymer (I), at least one of reaction mixture (Ila) and reaction mixture (lib), polymer polyol, chain extender, organic diisocyanate compound, and paraffinic oil A method of melt-kneading (IV).

[0119] In the above-mentioned method [4], addition polymerization is carried out while reacting a polymer polyol, a chain extender, and an organic diisocyanate compound to form a thermoplastic polyurethane. A method in which at least one of the system block copolymer (I), the reaction mixture (Ila) and the reaction mixture (lib), and the paraffinic oil (IV) are added and melt-kneaded. In the above methods [3] and [4], the components to be used may be melt-kneaded all at once, or some of the components may be melted and kneaded first, then the remaining components are added and melted. It may be kneaded.

[0120] Further, the olefin-based polymer (V), other polymers, inorganic fillers, and other optional components include addition-polymerized block copolymer (I), block copolymer (II) or Can be added during or after melt mixing of reaction mixtures (Ila) and Z or reaction mixture (lib), thermoplastic polyurethane (III) and paraffinic oil (IV)! ! / The above optional components are added to the addition polymerization block copolymer (1), block copolymer (II) or reaction mixture (Ila) and Z or reaction mixture (lib), thermoplastic polyurethane (III) and paraffin. When adding it during the melt mixing of the base oil (IV), the addition polymerization system block copolymer (I), block copolymer (II) or reaction mixture (Ila) and Z or reaction mixture (lib), heat Separately from the plastic polyurethane (III) and the paraffinic oil (IV), they may be supplied to a melt-kneader and kneaded, or the addition polymerization block copolymer (1), block copolymer (II) or reaction The mixture (Ila) and Z or the reaction mixture (lib), the thermoplastic polyurethane (III), and the paraffinic oil (IV) are contained in at least one kind, and then supplied to the melt-kneader to knead. . [0121] The thermoplastic polymer composition of the present invention produced by melt-kneading may be used directly in the production of a molded product or a composite molded product in a molten state, or once molded into a pellet. It may also be used for the production of composite molded bodies.

[0122] The thermoplastic polymer composition of the present invention can be melt-molded and heat-processed, and may be any molding method such as extrusion molding, injection molding, press molding, blow molding, calender molding, and casting. Thus, various molded products and composite molded bodies can be produced smoothly. Accordingly, a molded product having an arbitrary shape such as a film shape, a sheet shape, a tube shape, or a three-dimensional shape can be produced, and the present invention includes those molded products.

The thermoplastic polymer composition of the present invention is excellent in melt moldability, and in particular, adhesion of the extrudate to the die portion during melt extrusion molding including inflation molding can be greatly reduced. High-quality molded products free from defects such as cracks and streaks can be produced with high productivity, and the resulting molded products are excellent in various properties such as flexibility and mechanical performance.

In addition, when a thermoplastic polyurethane (III) formed using an aliphatic diisocyanate or an alicyclic diisocyanate is used, a molded product having excellent light resistance in combination with the above-described characteristics can be obtained. .

[0123] Furthermore, the thermoplastic polymer composition of the present invention has high melt adhesiveness to various materials in combination with the above-described excellent melt moldability, and is strong with various other materials under melting. Therefore, it can be used effectively in the manufacture of composite molded bodies with members made of other materials.

Examples of other materials that can be combined with the thermoplastic polymer composition of the present invention include various thermoplastic polymers other than the thermoplastic polymer composition of the present invention or compositions thereof, thermosetting resin, paper, and fabric. , Metal, wood, ceramics and the like.

[0124] Among them, the thermoplastic polymer composition of the present invention is excellent in melt adhesion with other polar materials. Specific examples of other polar materials include polyoxymethylene, saponified ethylene acetate butyl copolymer, polyurethane, polyamide, polyester, polycarbonate, polyphenylene sulfide, polyacrylate, polymetatalylate, and polyester. , Polysulfone, acrylonitrile Z styrene copolymer (AS resin), styrene Z Maleic anhydride copolymer (SMA resin), Rubber reinforced polystyrene (HIPS resin), Atari mouth-tolyl Z butadiene Z styrene copolymer (ABS resin), Methyl methacrylate Z styrene copolymer (MS Resin), methyl methacrylate Z butadiene Z styrene copolymer (MBS resin), vinyl chloride polymer, vinylidene chloride polymer, salt salt Z vinyl acetate copolymer, poly (vinylidene fluoride) 榭Various synthetic resins such as fat and epoxy resin; various synthetic rubbers such as isoprene rubber, butadiene rubber, butadiene styrene rubber, butadiene allylononitrile rubber, chloroprene rubber, butyl rubber, urethane rubber, silicone rubber, fluorine rubber, and acrylo-tolyl rubber ; Metals such as iron, aluminum and copper, various alloys such as stainless steel, tinplate and tin. it can.

The type and shape of the composite molded body of the thermoplastic polymer composition of the present invention and other materials are not particularly limited, and typical examples include film-like, sheet-like or plate-like laminates. In addition, for example, a tube, a deformed product, and other arbitrary three-dimensional shapes can be used.

In the laminate obtained by using the thermoplastic polymer composition of the present invention, the number of layers, the thickness, shape, and structure of each layer are not particularly limited, and are appropriately adjusted according to the use of the laminate. That's right.

Although not limited at all, the laminate obtained by using the thermoplastic polymer composition of the present invention includes, for example, one layer composed of the thermoplastic polymer composition of the present invention and another material. A two-layer structure in which one layer is laminated, and three layers in which a layer made of the thermoplastic polymer composition of the present invention exists as an intermediate layer between two surface layers (front and back layers) made of other materials A structure, a three-layer structure in which a layer made of the thermoplastic polymer composition of the present invention is laminated on the front and back surfaces of one layer made of another material, a layer made of the thermoplastic polymer composition of the present invention, and others Examples include a multilayer structure in which layers of one or more materials are alternately stacked in four or more layers.

And when a laminated body has two or more layers which consist of another material, the other material which comprises each layer may be the same, and may mutually differ. When the laminate has two or more layers made of the thermoplastic polymer composition of the present invention, the thermoplastic polymer composition constituting each layer may be the same or different from each other. Even Yes.

[0126] The method for producing a composite molded body of the thermoplastic polymer composition of the present invention and other materials is not particularly limited, and any method can be used as long as it is a method for producing a composite molded body by melt adhesion. May be. Among them, in producing the composite molded body of the present invention, for example, an injection molding method such as an insert injection molding method, a two-color injection molding method, a core back injection molding method, a sandwich injection molding method, an injection press molding method; Extrusion molding methods such as a laminate molding method, coextrusion molding method, and extrusion coating method; blow molding method; calender molding method; press molding method and melt casting method such as a melt casting method can be employed.

Among the molding methods described above, in the case of the insert injection molding method, another material that has been formed in a predetermined shape and size in advance is inserted into a mold, and the thermoplastic weight of the present invention is inserted there. A method of producing a composite molded body by injection molding of the combined composition is generally employed. In this case, the method for forming other materials inserted in the mold is not particularly limited. When the other material to be inserted is a synthetic resin or rubber product, for example, it is manufactured by any method such as injection molding, extrusion molding and cutting to a predetermined dimension, press molding, casting, etc. It may be. In addition, when the other material to be inserted is a metal material, for example, a conventional general-purpose method for manufacturing a metal product (forging, rolling, cutting, machining, grinding, etc.) can be used to obtain a predetermined shape and size. What is necessary is just to form beforehand.

[0127] Further, when a composite molded body is manufactured by the above-described two-color injection molding method, other materials are injected into the mold using two or more injection devices, and then the rotation of the mold is performed. The thermoplastic resin composition of the present invention is formed in a gap formed between a molded product made of another material formed by the first injection molding and the second mold wall by exchanging the mold cavity by movement or the like. A method of producing a composite molded body by injection molding is generally employed. In the case of the core back injection molding method described above, after using one injection molding machine and one mold, other materials are first injection molded into the mold to form a molded product, and then the mold is used. A method is generally employed in which the mold cavity is expanded and the thermoplastic polymer composition of the present invention is injection molded therein to produce a composite molded body.

In the injection molding method described above, the injection order of the materials is reversed, and the thermoplastic polymer composition of the present invention is first injected into a mold to produce a first molded product, and then another material. Composite moldings may be manufactured by injection molding of materials (such as thermoplastic resin).

[0128] When a composite molded body having a layer of the thermoplastic polymer composition of the present invention and a layer of another thermoplastic material is produced by the above-described extrusion molding, the inner side and the outer side, the upper side and the lower side, the left side and the right side The thermoplastic polymer composition of the present invention and other materials (such as thermoplastic resin) are simultaneously melt-extruded into two or more layers and joined through a mold (extrusion die portion or the like) divided into two or more layers. Methods can be adopted. If the other material is not thermoplastic, a composite molded body can be produced by extrusion-coating the thermoplastic polymer composition of the present invention under melting on or around the other material. .

Further, for example, when calendering is performed, the thermoplastic polymer composition of the present invention is calendered and coated on a melt plastic force or other material in a solid state under melting. By laminating, a desired composite molded body can be produced. Further, in the case of press molding, a composite molded body can be produced by performing melt pressing using the thermoplastic polymer composition of the present invention under the arrangement of other materials.

[0129] The composite molded article of the present invention can be used as various industrial products and parts. Examples of such equipment include instrument panels, center panels, center console boxes, door trims, pillars, various interior parts for vehicles such as assist grips; automotive exterior parts such as malls; electric tool grips, refrigerator doors, cameras Home appliance parts such as grips, vacuum cleaner bumpers and hoses, remote control switches and various key tops for office equipment; underwater products such as underwater glasses and underwater camera covers; various cover parts; sealing, waterproof, soundproof, Industrial parts with various packings for anti-vibration performance; automotive functional parts such as rack & pion boots, suspension boots, constant velocity joint boots, etc .; Electronic parts; Sporting goods; Synthetic leather; Doors, window frame materials, etc. Built for materials; various fittings; valve parts; can be exemplified various products like surgical cast. In a product in which the layer composed of the thermoplastic polymer composition of the present invention appears on at least one surface of the composite molded body, the thermoplastic polymer composition is elastic and flexible. It shows a soft and good touch when touched, and the collar also has shock absorption (cushioning) properties and excellent impact resistance, so it is also excellent in terms of safety. Example

[0130] The ability of the present invention to be specifically described below with reference to Examples and Comparative Examples The present invention is not limited to the following examples.

In the following examples, the melt viscosity, extrusion moldability, hardness, tensile rupture strength, tensile rupture elongation, and adhesive strength in the laminate of the thermoplastic polymer composition were measured or evaluated by the following methods.

[0131] mm &:

The melt viscosity of the thermoplastic polymer composition dried at 80 ° C for 1 hour under reduced pressure (133.32 Pa or less) was measured using a Koka flow tester (manufactured by Shimadzu Corporation) with a load of 50 kgf and nozzle dimensions. = Measured under the conditions of diameter lmm X length 10 mm, temperature 200 ° C.

[0132] Extrusion molding:

Whether the thermoplastic polymer composition is an extruder (25 mm φ, cylinder temperature = 200 to 215 ° C, die temperature = 205 ° C) with a sheet die (width = 25 mm, thickness = 0.3 mm) During the continuous discharge at a discharge speed of about 3 kgZ time, deposits adhered to the die part (hereinafter referred to as “grease”) were sampled 3 times every 20 minutes and the average mass was measured. The following criteria were used as indicators of extrusion moldability.

◯: The average mass of the collected eye grease is 5 mg or less.

X: The average mass of the collected eye grease exceeds 5 mg.

[0133] MS .:

Injection molding (cylinder temperature = 180 to 205 ° C, mold temperature = 35 ° C) using a mold with a mirror-finished surface, and a disk-shaped molded product (diameter = 120 mm, thickness = 2 mm). After the resulting molded product is left at 23 ° C for 7 days, measure the JIS A hardness of the molded product in accordance with JIS K-6301 using a stack of two molded products.

[0134] Tensile strength at break and tensile elongation at break:

A disk-shaped molded product (diameter = 120 mm, thickness = 2 mm) was manufactured in the same manner as in the evaluation of the hardness described above. The obtained molded product was left at 25 ° C for 7 days, and then punched into a dumbbell mold specified in JIS No. 3 to produce a test piece. According to JIS K-7311, Shimadzu Using an “autograph measuring device IS-500DJ” manufactured by Seisakusho, the tensile strength at break and tensile elongation at break were measured.

[0135] Glue structure;

A synthetic resin plate (dimensions: vertical X horizontal X thickness = 200 mm X 150 mm X lmm) is placed in the mold, and an injection molding machine (manufactured by Nissei Sewa Kogyo Co., Ltd .; 80-ton injection molding machine) is used. The thermoplastic polymer composition was injected under conditions of a cylinder temperature of 220 ° C and a mold temperature of 40 ° C, and a layer of the thermoplastic polymer composition was laminated on one surface of the resin board. (Dimensions: vertical X horizontal X thickness = 200 mm X 150 mm X 2 mm) were manufactured.

A test piece for measuring peel strength (dimension: length X width X thickness = 80 mm X 25 mm X 2 mm) was cut out from the obtained laminate, and it was used in the "180 degree peel test" described in JIS K-6854. The peel strength was measured accordingly.

[0136] The abbreviations and Z or contents of the compounds used in the following Reference Examples, Examples and Comparative Examples, and the synthetic resin boards used to produce laminates in the following Examples and Comparative Examples The abbreviations and contents of the synthetic resins are as follows.

[0137] 《Addition polymerization block copolymer (1)》

SEBS:

Polystyrene block Polybutadiene block Hydrogenated triblock copolymer having a polystyrene block structure [Kuraray Co., Ltd., “Septon 8006” (trade name), content of structural units derived from styrene = 33 mass %].

SEEPS- 1:

Polystyrene block Poly (isoprene Z butadiene) block Polystyrene block Hydrogenated triblock copolymer with structure [Kuraray Co., Ltd., "Septon 4055" (trade name), content of structural units derived from styrene = 30% by mass].

[0138] 《Addition polymerization block copolymer (1)》

F—SEEPS:

Polystyrene block Poly (isoprene z butadiene) block Polystyrene block A hydrogenated product of a triblock copolymer having a structure of the type and having a hydroxyl group at one end of the molecule. [Number average molecular weight = 50, 000, styrene content = 30 mass ^_0/0, poly (isoprene / pig Gen) block hydrogenation rate = 98%, isoprene to butadiene ratio = 50Z 50 (molar ratio), average number of hydroxyl groups per molecule = 0.9, 1, 2 in poly (isoprene butadiene) block The total amount of bonds and 3, 4 bonds = 8 mol%; according to the method described in Reference Example 1 of Patent Document 11, styrene, isoprene and butadiene were used as raw materials. ]

This F-SEEPS is a block copolymer having a hydroxyl group at one end of the molecule. SEEPS-OH [polystyrene block poly (isoprene Z butadiene) block poly styrene block type triblock copolymer structure] hydrogenated products; number-average molecular weight = 50, 000, styrene content = 30 mass ^_0/0, poly (isoprene Z butadiene) hydrogen添Ka卩率= 98% in the block, the ratio of isoprene and butadiene = 50Z50 (molar ratio ), Poly (isopreneΖbutadiene) block, total amount of 1,2 bonds and 3,4 bonds = 8 mol%], and SEEPS-2 [a block copolymer without hydroxyl groups in the molecule] Hydrogenated triblock copolymer with a structure of polystyrene block poly (isoprene Z butadiene) block polystyrene block type; number average molecular weight = 50,000, steel Ren content = 30 mass ^_0/0, poly (isoprene Z butadiene) hydrogenation ratio in the block = 98%, the ratio of isoprene and butadiene = 50Z50 (molar ratio), 1 in the poly (isoprene Ζ butadiene) block, 2 bond And 3, 4 total amount of bonds = 8 mol%] [SEEPS-OH / SEEPS-2 = 9/1 (molar ratio)].

F-HVSIS:

Polystyrene block Polyisoprene block A hydrogenated product of a triblock copolymer having a polystyrene block type structure and having a hydroxyl group at one end of the molecule.

(Number average molecular weight = 63, 000, styrene content = 30 mass ^_0/0, hydrogenation ratio definitive polyisoprene block = 90%, the average number of hydroxyl groups per molecule zero. 8, 1 in polyisoprene block , 4 bond content = 45 mole ^_0/0, 1, 2 coupling and 3, 4 bonds of the total amount = 55 mol%; according to the method described in example 3 of Patent Document 11, the raw material styrene and I isoprene Manufactured as.)

This F-HVSIS is a block copolymer having a hydroxyl group at one end of the molecule. HVSIS-OH (polystyrene block polyisoprene block polystyrene block Hydrogenated triblock copolymer having a type structure; number average molecular weight = 63,000, styrene content = 30% by mass, hydrogenation rate in polyisoprene block = 90%, 1, 2 in polyisoprene block binding and 3, and 4 binding amount of the total amount = 55 mole ^_0/0), tri-block copolymer having the structure HVSIS [polystyrene block-polyisoprene block polystyrene block type is no block copolymer a hydroxyl group in the molecule Hydrogenation product: number average molecular weight = 63,000, styrene content = 30% by mass, hydrogenation rate in polyisoprene block = 90%, 1, 2 and 3, 4 bonds in polyisoprene block containing an amount total amount = 55 mole ^_0/0) [HVSIS- OH / HVSIS = 8Z2 ( molar ratio)].

[0140] SEPS:

Polystyrene block Polyisoprene block A hydrogenated product of a triblock copolymer having a polystyrene block type structure and no hydroxyl group in the molecule [Kuraray Co., Ltd., "Septon 2002" (trade name), derived from styrene the content of the structural unit = 30 mass ^{_{_{0/0, MFR = 70 8}}} 10 min,] 13 a hardness = 80.

[0141] << Polycarbonate polymer (Roh 1) >>

PC:

Polycarbonate [Teijin Chemicals, “Panlite L-1225” (trade name), viscosity average molecular weight = 22,500].

[0142] 《Thermoplastic polyurethane (111)》

TPU-1:

Polyester-based thermoplastic polyurethane [Kuraray Co., Ltd., “Curamylon U8165” (trade name), poly (3-methyl-1,5-pentanediol adipate), 1, 4-butanediol and 4, 4'— Polyester thermoplastic polyurethane with a segment of diphenylmethane diisocyanate (MDI) force as a node segment; logarithmic viscosity (measured in DMF solvent at a concentration of 0.5 gZdl, 30 ° C) = 1. 09 dlZg, JIS A hardness = 65].

[0143] Polymer polyol

POH- 1:

One molecule per molecule produced by reacting 3-methyl-1,5-pentanediol with adipic acid. A polyester diol having a number of hydroxyl groups of 2.00 (number average molecular weight = 3,500). POH- 2:

A polyester polyol having a number of hydroxyl groups per molecule of 3.00, produced by reacting 3-methyl-1,5-pentanediol, trimethylolpropane and adipic acid (number average molecular weight = 2,000).

POH- 3:

Polytetramethylene glycol (number average molecular weight) with 2.00 hydroxyl groups per molecule

= 2,000).

[0144] 《Chain extender》

BP: 1, 4 Butanediol.

[0145] 《Organic diisocyanate compound》

MDI: 4, 4'-diphenylmethane diisocyanate.

[0146] 《Paraffin oil (IV)》

PL: Rohine oil [made by Idemitsu Kosan Co., Ltd., “Diana Process PW—380” (trade name), kinematic viscosity (40 ° C): 382cSt, pour point: —15 ° C, flash point: 300 ° C].

[0147] <Synthetic resin constituting the synthetic resin plate used for manufacturing the laminated structure (other materials)>

ABS: Acrylonitrile-butadiene-styrene copolymer resin (manufactured by Nippon Synthetic Rubber Co., Ltd.)

RjSR ABS12 "(trade name)).

[0148] << Reference Example 1 >>

[Production of Composition (PC—SEEPS Compound El) Containing Block Copolymer (Π)) (1) Block copolymer (F—SEEPS) 600 parts by mass, polycarbonate polymer (PC) 400 parts by mass Catalyst (dibutyltinoxide) 0.4 parts by weight are premixed, and the resulting mixture is a twin screw extruder (30πιπι φ, LZD = 36; manufactured by Plastic Industrial Laboratory, “BT— 30 ”(trade name)] and melt kneading under the conditions of a cylinder temperature of 275 ° C. and a screw rotation speed of 150 rpm, and the resulting reaction mixture (melt) is continuously put into water as a strand. It was extruded and then cut with a pelletizer to obtain pellets. The obtained pellets were dehumidified and dried at 80 ° C. for 12 hours to obtain a composition (PC—SEEPS Compound El) containing a block copolymer (Π). This composition (PC—S The melt viscosity of EEPS Compound El) was 890 Pa's.

(2) By using the composition (PC—SEEPS Compound El) obtained in (1) above, injection molding (cylinder temperature = 200 to 220 ° C, mold temperature = 30 ° C) will result in dumbbells. No. 1 mold (thickness = 3mm) was produced. The JIS A hardness of the molded product was 80, and the tensile breaking strength measured according to JIS K-7113 (test speed = 5 mmZ min., Distance between chucks = 11 Omm) was 17 MPa.

[0149] <Reference Example 2>

[Composition of block copolymer (Π) (Production of PC—SEEPS Compound E2)]

(1) Block copolymer (F—SEEPS) 350 parts by weight, polycarbonate polymer (PC) 650 parts by weight and catalyst (dibutyltinoxide) 0.4 parts by weight, and the resulting mixture is coaxially Using a twin screw extruder (30πιπι φ, LZD = 36; manufactured by Plastic Industrial Laboratory, “BT-30” (trade name)) with a cylinder temperature of 275 ° C and a screw speed of 150 rpm The obtained reaction mixture (melt) was continuously extruded into water in the form of strands and then cut with a pelletizer to obtain pellets. The obtained pellets were dehumidified and dried at 80 ° C. for 12 hours to obtain a composition (PC—SEEPS Compound E2) containing a block copolymer (Π). The melt viscosity of this composition (PC-S EEPS Compound E2) was 630 Pa's.

(2) Using the composition obtained in (1) above (PC—SEEPS Compound E2), injection molding (cylinder temperature = 200 to 220 ° C, mold temperature = 30 ° C) allows dumbbells. No. 1 mold (thickness = 3mm) was manufactured. The JIS A hardness of the molded product was 97, and the tensile breaking strength measured according to JIS K-7113 (test speed = 5 mmZ min, distance between chucks = 110 mm) was 33 MPa.

[0150] << Reference Example 3 >>

[Production of Composition Containing Block Copolymer (（) (PC—HVSIS Compound E3)] (1) 500 parts by mass of block copolymer (F—HVSIS), 500 parts by mass of polycarbonate-based polymer (PC) and Catalyst (dibutyltinoxide) 0.4 parts by weight are premixed, and the resulting mixture is a twin screw extruder (30πιπι φ, LZD = 36; manufactured by Plastic Industrial Laboratory, “BT— 30 ”(trade name)] and a cylinder temperature of 275 ° C and The mixture was melt-kneaded under conditions of 150 rpm of the screw and the resulting reaction mixture (melt) was continuously extruded into water in the form of strands, and then cut with a pelletizer to obtain pellets. The obtained pellets were dehumidified and dried at 80 ° C. for 12 hours to obtain a composition (PC-HVSIS Compound E3) containing a block copolymer (Π). The melt viscosity of this composition (PC—HVSIS Compound E3) was 610 Pa ′s.

(2) Using the composition (PC—HVSIS Compound E3) obtained in (1) above, injection molding (cylinder temperature = 200 to 220 ° C, mold temperature = 30 ° C) was used to A molded product of Le No. 1 type (thickness = 3 mm) was manufactured. The JIS A hardness of the molded product was 80, and the tensile fracture strength measured according to JIS K-7113 (test speed = 5 mmZ min., Distance between chucks = 110 mm) was 14 MPa.

[0151] << Reference Example 4 >>

[Does not contain block copolymer (II) !, manufacture of composition (PCZSEEPS Compound)]

(1) 600 parts by mass of block copolymer (SEPS) and 400 parts by mass of polycarbonate polymer (PC) are premixed, and the resulting mixture is rotated in the same direction as a twin-screw extruder [30 mm φ , L / D = 36; “BT-30” (trade name) manufactured by Plastic Industry Research Institute] was obtained by melt-kneading under conditions of a cylinder temperature of 275 ° C. and a screw rotation speed of 150 rpm. The reaction mixture (melt) was continuously extruded into water as a strand, and then cut with a pelletizer to obtain pellets. The obtained pellets were dehumidified and dried at 80 ° C. for 12 hours to obtain a composition (PCZSEEPS Compound). The melt viscosity of this composition (PCZS EEPS Compound) was 54 Pa's.

(2) By using the composition (PCZSEEPS Compound) obtained in (1) above, injection molding (cylinder temperature = 200 to 220 ° C, mold temperature = 30 ° C), dumbbell No. 1 type ( A molded article having a thickness of 3 mm) was produced. The JIS A hardness of the molded product was 89, and the tensile breaking strength measured according to JIS K-7113 (test speed = 5 mmZ min, distance between chucks = 110 mm) was 8 MPa.

[0152] << Example 1 >>

(1) Polymer polyol containing lOppm of urethanization reaction catalyst (tetraisopropyl titanate) [mixture of POH-1 and POH-3, POH-1 / POH— 3 = 30/70 (mol Ratio), average number of hydroxyl groups per molecule = 2.00], chain extender (BD) and organic diisocyanate compound (MDI), high molecular polyol: BD: MDI molar ratio = 1.0: 1.1 : 2.1 (nitrogen atom content is 1.9% by mass), and total supply amount of 140gZ [The content of thermoplastic polyurethane (III) in the thermoplastic polymer composition is 70% by mass Volume]], continuous to the front of the heating zone of the twin screw extruder (30mmφ, LZD = 36, heating zone divided into three zones: front, middle and rear) rotating in the same axis direction The polyurethane formation reaction was carried out by continuous melt polymerization at 260 ° C.

(2) Supply amount of block copolymer (SEBS) and paraffinic oil (PL) [SEBS: PL = 1: 1 (mass ratio)] for 40gZ at the same time as (1) above [Thermoplastic polymer In the composition, the SEBS content is 10% by mass and the PL content is 10% by mass], and further the composition having the block copolymer (II) obtained in Reference Example 1 (PC-SEEPS Compo und El) at a feed rate of 20 gZ (the amount of PC—SEEPS Compound El content in the thermoplastic polymer composition is 10% by mass), heating the twin screw extruder of (1) above Continuously supplied to a twin screw extruder (30mmφ, L / D = 36, 190 ° C heating) connected to the center of the zone, melted and kneaded. The thermoplastic polymer composition 1 was obtained by continuously extruding, then cutting with a pelletizer, and dehumidifying and drying the pellets at 70 ° C for 4 hours.

(3) For the thermoplastic polymer composition 1 obtained in (2) above, the melt viscosity, hardness, tensile strength at break and tensile elongation at break were measured by the methods described above. It was as shown.

Further, using the thermoplastic polymer composition 1 and ABS, a laminated structure was produced by the method described above, and the adhesive strength of the obtained laminated structure was measured by the method described above. It was as follows.

Example 2

(1) Polymer polyol containing 15ppm of urethanization catalyst (tetraisopropyl titanate) [mixture of POH-2 and POH-3; POH-2 / POH—3 = lZ99 (mole ratio); average per molecule Number of hydroxyl groups = 2.01], chain extender (BD) and organic disoocyanate compound (MDI), high molecular polyol: BD: MDI molar ratio = 1.0: 1.03: 2. 03 (the nitrogen atom content is 2.2% by mass) and the total supply amount thereof is 130 gZ (the amount of the thermoplastic polyurethane (III) in the thermoplastic polymer composition is 65% by mass)) , Feed continuously to a twin-screw extruder (30mmφ, LZD = 36, heating zone divided into three zones: front, center, and rear) that rotate in the same direction. The polyurethane formation reaction was carried out by continuous melt polymerization.

(2) At the same time as (1) above, supply a block copolymer (SEEPS-1) and a paraffinic oil (PL) mixture [SEEPS-1: PL = 1: 1 (mass ratio)] for 50 gZ ( The block copolymer obtained in Reference Example 2 (SEEPS-1 content in the thermoplastic polymer composition is 12.5 mass% and PL content is 12.5 mass%). II) (PC SEEPS Compound E2) in a supply amount of 20 gZ (the amount of PC-SEEPS Compound E2 in the thermoplastic polymer composition is 10% by mass) This was continuously supplied to a twin screw extruder (30 mιηφ, LZD = 36, 190 ° C heating) connected to the center of the heating zone of the twin screw extruder. Next, 0.05% by mass of urethanization catalyst deactivator (distearyl phosphate) (feed amount = 0.125 gZ) was added to the rear part of the above twin screw extruder, and the resulting melt was A thermoplastic polymer composition 2 was obtained by continuous extrusion into water in the form of a strand, followed by cutting with a pelletizer and dehumidifying and drying the pellets at 70 ° C. for 4 hours.

(3) Regarding the thermoplastic polymer composition 2 obtained in (2) above, the melt viscosity, hardness, tensile strength at break and tensile elongation at break were measured by the methods described above, and as shown in Table 1 below. Met.

Further, when the laminated structure was produced by the above-described method using the thermoplastic polymer composition 2 and ABS, and the adhesive strength of the obtained laminated structure was measured by the above-mentioned method, it was shown in Table 1 below. It was as follows.

Example 3

(1) Polymer polyol containing lOppm of urethanization reaction catalyst (tetraisopropyl titanate) [mixture of? 011-1 and 1 ³ 011-2; 011—17? 011— 2 = 98.5Z1.5 (molar ratio); average number of hydroxyl groups per molecule = 2.015], chain extender (BD) and organic diisocyanate compound (MDI) Polyol: BD: MDI molar ratio = 1. 0: 2.4: 3 4 (nitrogen atom content = 2.1% by mass), and the total supply amount thereof is 120 gZ (the amount of thermoplastic polyurethane (III) in the thermoplastic polymer composition is 60% by mass), Continuous melt feed at 260 ° C with continuous supply to twin screw extruder (30mmφ, LZD = 36, heating zone divided into three zones: front, center and rear) rotating in the same direction Polyurethane formation reaction was carried out by polymerization.

(2) At the same time as (1) above, supply a block copolymer (SEEPS-1) and paraffinic oil (PL) mixture [SEEPS-1: PL = 1: 1 (mass ratio)] for 60gZ ( The content of SEEPS-1 in the thermoplastic polymer composition is 15% by mass and the PL content is 15% by mass), and the block copolymer (II) obtained in Reference Example 3 is used. in compositions with the supply amount of (PC- HVSI S compound E3) the 20gZ fraction (amount content of PC- HVSI S compound E3 of the thermoplastic polymer composition is 10 mass ^_0/0), (1 ) Was continuously fed to a twin screw extruder (30 mmφ, L / D = 36, 220 ° C heating) connected to the center of the heating zone of the twin screw extruder. Next, 0.03% by mass of a urethanization reaction catalyst deactivator (distearyl phosphate) (feed amount = 0.075 gZ) was added to the rear part of the above twin screw extruder, and the resulting melt was obtained. Is extruded into water as a strand

Subsequently, the pellet was cut with a pelletizer, and the pellet was dehumidified and dried at 70 ° C. for 4 hours to obtain a thermoplastic polymer composition 3.

(3) For the thermoplastic polymer composition 3 obtained in (3) above, the melt viscosity, hardness, tensile strength at break and tensile elongation at break were measured by the methods described above. It was as shown.

Further, using the thermoplastic polymer composition 3 and ABS, a laminated structure was produced by the method described above, and the adhesive strength of the obtained laminated structure was measured by the method described above. It was as follows.

(1) Polymer polyol containing lOppm of urethanization catalyst (tetraisopropyl titanate) [mixture of POH-1 and POH-3; POH-1 / POH-3 = 30/70 (molar ratio)], chain extender (BD) and organic diisocyanate compound (MDI) are polymer polyols: BD: MDI molar ratio = 1. 0: 1. 1: 2.1 (nitrogen atom content is 1. 9% by mass) and The total supply amount of these components is 125gZ (the amount of the thermoplastic polyurethane (I II) in the thermoplastic polymer composition is 50% by mass), and the twin screw extruder (30mm φ , LZD = 36, and the heating zone was divided into three zones: front, center, and rear). The polyurethane formation reaction was carried out by continuous melt polymerization at 260 ° C.

(2) At the same time as (1) above, supply a block copolymer (SEBS) and paraffinic oil (PL) mixture [SEBS: PL = 1: 1 (mass ratio)] for 125gZ (thermoplastic polymer The SEBS content in the composition is 25% by mass and the PL content is 25% by mass), and is connected to the center of the heating zone of the twin screw extruder of (1) above. Continuously fed into an axial screw type extruder (30 mmφ, LZD = 36, 220 ° C heating), the resulting melt was continuously extruded into water in a strand, and then cut with a pelletizer. The pellets were dehumidified and dried at 70 ° C. for 4 hours to obtain a thermoplastic polymer composition C-1.

(3) The melt viscosity, hardness, tensile strength at break and tensile elongation at break of the thermoplastic polymer composition C 1 obtained in (2) above were measured by the methods described above. It was as shown in.

Furthermore, using the thermoplastic polymer composition C1 and ABS, a laminated structure was produced by the method described above, and the adhesive strength of the obtained laminated structure was measured by the method described above. It was as shown.

(1) Supply amount of block copolymer (SEBS) and paraffinic oil (PL) [SEBS: PL = 1: 1 (mass ratio)] for 60gZ (SEBS content in thermoplastic polymer composition) Amount of 15 mass% and PL content of 15 mass%), and supply amount of thermoplastic polyurethane (TPU-1) for 120 gZ [of thermoplastic polyurethane (ΠΙ) in thermoplastic polymer composition] In addition, the block copolymer composition (PU / SEEPS Compound) obtained in Reference Example 4 was fed in an amount of 20 gZ (PUZ SEEPS in the thermoplastic polymer composition). It is obtained by feeding to a twin screw extruder (30mmφ, L / D = 36) that rotates in the same direction at the compound temperature, and melt kneading at 220 ° C. The molten material is continuously extruded into water in the form of strands and then cut with a pelletizer. The pellets were dehumidified and dried at 70 ° C. for 4 hours to obtain a thermoplastic polymer composition C-2.

(2) For the thermoplastic polymer composition C 2 obtained in the above (1), the melt viscosity, hardness, tensile breaking strength and tensile breaking elongation were measured by the methods described above. It was as shown in.

Furthermore, using the thermoplastic polymer composition C2 and ABS, a laminated structure was produced by the method described above, and the adhesive strength of the obtained laminated structure was measured by the method described above. It was as shown.

[table 1]

Example 1 Example 2 Example 3 Comparative Example 1 Comparative Example 2

[Production raw materials]

Polymer t ° Rio [Molar ratio] 1)

P0H-1 0.300 0.985 0.300

P0H-2 0.010 0.015

P0H-3 0.700 0.990 0.700

Chain extender (BD) (ratio) << 1.1 2.4 1.1

Organic compounds (MDI) (ratio) n 2.1 3.4 2.1

Elemental atomic content (mass%) 1.9 2.2 2.1 1.9

Thermoplastic resin [Large%] * 70 65 60 50

D Fuku copolymer composition [mass%] «

PC-SEEPS Compound El 10

PC-SEEPS Compound E2 10

PC-HVSIS Compound E3 10

PC / SEEPS Compound 10 Addition Polymerization 7 'D Copolymer [mass%] 2)

SEBS 10 25 15

SEEPS- 1 12.5 15

Thermoplastic E 'ij Urethane (TPU-1) [H content ¾] a 60 half rough; [mass%] »10 12.5 15 25 15

[Thermoplastic polymer composition]

Melt fit viscosity [Heiss] 10,200 8,600 3,650 6,780 1,500 Extrudability ○ o ○ X X

[Molded product of thermoplastic polymer composition]

Hardness [JIS A] 55 63 60 46 55 Tensile rupture ¾ degree CMPa) 19 23 11 3 4 Tensile rupture elongation [%] 860 675 930 610 720

[Adhesive strength in the footwear]

A B S Ckgf / 25mm] 5.0 4,4 5.3 1.4 2.2

1) Molar ratio of polymer polyol, chain extender, organic diisocyanate compound,

2) Combined mass of polymer polyol, chain extension 劑, organic diisocyanate compound or thermoplastic polyurethane (ΙΠ), block copolymer (II), addition-polymerized block copolymer (I), and roseffin-based oil (IV) As shown in Table 1 above, hydrogenation of a block copolymer having an aromatic vinyl compound polymer block (a-1) and a conjugated diene polymer block (b-1) Hydrogenated block copolymer having a polymerized block copolymer (I), an aromatic vinyl compound polymer block (a-2) and a conjugated diene polymer block (b-2). Calorie with additives Examples 1 to 3 of the present invention containing a block copolymer (Π) having a polymer block (ii) and a polycarbonate polymer block (mouth), thermoplastic polyurethane (III) and paraffinic oil (IV) The thermoplastic polymer composition has excellent extrudability when the extrudate adheres to the die part (amount of grease) when melt extrusion is performed. The molded products obtained from the thermoplastic polymer compositions of Examples 1 to 3 are also excellent in mechanical properties such as tensile breaking strength and tensile breaking elongation, and are firmly melt bonded to the ABS resin board. is doing.

On the other hand, it contains the above addition polymerization block copolymer (1), thermoplastic polyurethane (III) and paraffinic oil (IV), and does not contain the block copolymer (Π) !, Comparative Example The thermoplastic polymer composition of 1 and the addition polymerization block copolymer (1), the thermoplastic polyurethane (111), the paraffinic oil (IV), and the polycarbonate, the block copolymer (Π ) The thermoplastic polymer composition of Comparative Example 2 was inferior to the extrusion molding in which the adhesion (extrusion amount) of the extrudate to the die part was large when melt extrusion was performed. ing. In addition, molded articles obtained from the thermoplastic polymer compositions of Comparative Examples 1 and 2 have low tensile fracture strength and inferior mechanical properties, and also have good melt adhesion to the ABS resin board. Is also inferior.

Industrial applicability

The thermoplastic polymer composition of the present invention is excellent in melt moldability, and particularly when melt extrusion including inflation molding is performed, the extrudate is attached to the die part of an extruder (the amount of grease). ) Can be produced with high productivity without causing defects such as thick spots, streaks, and cracks, and the resulting molded products have flexibility, mechanical performance, and wear resistance. It excels in properties such as light resistance and light resistance, and also has excellent melt adhesion with other materials. By taking advantage of these properties, various products such as electrical products, synthetic leather, automobiles, etc. It can be used effectively in the production of film-like materials, sheet-like materials, hose-like materials, tube-like materials and the like used for equipment.

Claims

The scope of the claims

[1] Aromatic vinyl compound polymer block (a— 1) and conjugated diene polymer block (b—

The block copolymer having 1) or its hydrogenated product addition block copolymer (I), aromatic vinyl compound block (a-2) and conjugate polymer block (b-2) ) Or a block copolymer (II) having a polycarbonate polymer block (mouth), a thermoplastic polyurethane (III), and a paraffin type. A thermoplastic polymer composition comprising an oil (IV).

[2] Block copolymer (Π) force The thermoplastic polymer composition according to claim 1, which is at least one of the following block copolymer (ΠΑ) and block copolymer (II B).

Block book (ΠΑ):

Aromatic beluie compound polymer block (a— 2) and conjugated diene polymer block (b—

2) a block copolymer having a functional group capable of reacting with the block copolymer or its hydrogenated product and capable of reacting with the polycarbonate polymer (Rho 1), and a polycarbonate polymer (1) A block copolymer prepared by reacting Rho 1) with melt kneading.

Block copolymer (IIB):

[3] The thermoplastic polymer composition according to claim 2, wherein the block copolymer (ΠΑ) and the block copolymer (ΠΒ) are prepared by reacting in the presence of a catalyst under melt-kneading. .

[4] Addition polymerization block copolymer (I) 5 to 200 parts by mass of block copolymer (II), 100 to 800 parts by mass of thermoplastic polyurethane (III) and paraffin oil (100 parts by mass) The thermoplastic polymer composition according to any one of claims 1 to 3, comprising IV) in a proportion of 10 to 200 parts by mass.

[5] Aromatic vinyl compound polymer block (a— 1) and conjugated diene polymer block (b—

A block copolymer having 1) or an addition polymerization type block copolymer (1), which is a hydrogenated product thereof, at least one of the following reaction mixture (Ila) and reaction mixture (lib), thermoplastic thermoplastic polyurethane (III), And a thermoplastic polymer composition obtained by melt-kneading paraffinic oil (IV).

'' Kun 馳 a):

2) a block copolymer having a functional group capable of reacting with the block copolymer or its hydrogenated product and capable of reacting with the polycarbonate polymer (Rho 1), and a polycarbonate polymer (1) A reaction mixture obtained by reacting Rho 1) with melt kneading. A block copolymer having a polymer block (a-2) and a conjugated diene polymer block (b-2), or a hydrogenated product thereof, and a polycarbonate polymer (Roh 1) A reaction mixture obtained by reacting an addition polymerization block copolymer having a functional group capable of reacting with (I-1), a compound having two hydroxyl groups, and a carbonate precursor under melt kneading.

[6] Aromatic vinyl compound polymer block (a— 1) and conjugated diene polymer block (b—

1) or a block copolymer having a hydrogenated product (1), at least one of the following reaction mixture (Ila) and reaction mixture (lib), a high molecular polyol, a chain extender A thermoplastic polymer composition obtained by melt-kneading an organic diisocyanate compound and paraffinic oil (IV).

'' Kun 馳 a):

2) a block copolymer having a functional group capable of reacting with the block copolymer or its hydrogenated product and capable of reacting with the polycarbonate polymer (Rho 1), and a polycarbonate polymer (1) A reaction mixture obtained by reacting Rho 1) with melt kneading. 'Kun 馳 b):

[7] The thermoplastic polymer composition according to any one of claims 2 to 6, wherein the functional group capable of reacting with the polycarbonate polymer in the addition polymerization block copolymer (I-1) is a hydroxyl group. .

[8] The thermoplastic polymer composition according to [7], wherein the addition polymerization block copolymer (I-1) has an average of 0.6 or more hydroxyl groups per molecule per terminal.

[9] The thermoplastic polyurethane (III) is a reaction raw material for forming a thermoplastic polyurethane that also has a polymer polyol, a chain extender, and an organic diisocyanate compound, and contains nitrogen atoms derived from the organic diisocyanate compound. It is a thermoplastic polyurethane formed using a reaction raw material whose amount is 1 to 6.5% by mass based on the total mass of the polymer polyol, the chain extender and the organic diisocyanate compound. The thermoplastic polymer composition according to any one of claims 1 to 5, 7, and 8.

[10] The dumbbell-type test piece defined in JIS No. 3 and having a tensile strength at break of 8 MPa or more measured according to JIS Κ-7311, according to any one of claims 1 to 9. Thermoplastic polymer composition.

[11] A molded article comprising the thermoplastic polymer composition according to any one of claims 1 to 10.

[12] Claims 1 to: A composite molded article comprising the thermoplastic polymer composition according to any one of LO and another material.