JP5111851B2 - Thermoplastic polymer composition - Google Patents

Description

  The present invention relates to a thermoplastic polymer composition, a molded article comprising the same, and a composite molded body. The thermoplastic polymer composition of the present invention is excellent in handleability and melt moldability, and a melted product such as an extrudate adheres to or adheres to a molding apparatus part, particularly a die part in melt extrusion molding, at the time of melt molding. Can be molded with good productivity, and thereby various mechanical properties such as appearance, dimensional stability, flexibility and strength, and excellent properties such as wear resistance and light resistance. Since a molded product can be produced smoothly and is firmly melt-bonded to various materials, it can be effectively used for producing various molded products and composite molded articles by utilizing these properties.

  A block copolymer having a styrene polymer block and a conjugated diene polymer block and a hydrogenated product thereof (hereinafter sometimes collectively referred to as “(hydrogenated) styrene / conjugated diene block copolymer”) Since it can be easily plasticized and melted by heating, it can be molded easily, has rubber elasticity at room temperature, and has an excellent balance between flexibility and mechanical properties, so-called thermoplastic elastomer ( In recent years, it has been widely used as a kind of thermoplastic elastomer) in various fields.

(Hydrogenated) Styrene / conjugated diene block copolymer has low polarity, so it can be melt-bonded or integrally formed with other polymers with low polarity. Melt bonding is difficult.
So far, a composition in which an engineering plastic having a specific crystalline melting point and viscosity is blended with a (hydrogenated) styrene / conjugated diene block copolymer is known, and thermoplastic polyurethane is one of the engineering plastics. Used (see Patent Document 1). This Patent Document 1 describes that the composition is suitable as an insulator for a conductor or a wire for soldering. However, when a thermoplastic polyurethane is used as the engineering plastic, ) Since the compatibility between the styrene / conjugated diene block copolymer and the thermoplastic polyurethane is poor, the properties of both polymers are not sufficiently exhibited, and a useful composition cannot be obtained.

  In addition, various techniques for improving the heat-fusibility of (hydrogenated) styrene / conjugated diene block copolymers have been proposed in the past. As such conventional techniques, (hydrogenated) styrene / conjugated diene has been proposed. A heat-fusible composition in which a thermoplastic polyurethane is blended into a block copolymer is known (see Patent Documents 2 to 4). However, these heat-fusible compositions have a problem that, depending on the material to be heat-sealed, sufficient adhesive strength cannot be obtained and the adhesive strength is not sustained. Moreover, in these heat-fusible compositions, the compatibility between the (hydrogenated) styrene / conjugated diene block copolymer and the thermoplastic polyurethane cannot be said to be sufficiently good. In the laminated molded product obtained by the above, problems such as delamination and adhesive force variation are likely to occur.

  (Hydrogenated) Carboxylic acid groups and hydroxyl groups for the purpose of improving the compatibility between the styrene / conjugated diene block copolymer and the thermoplastic polyurethane, and improving the melt adhesion of the composition containing both polymers. In addition, a composition in which a thermoplastic polyurethane is blended with a (hydrogenated) styrene / conjugated diene block copolymer modified with another polar group is known (see Patent Documents 5 and 6). In addition, a composition consisting of a styrene / conjugated diene block copolymer modified with a carboxylic acid group and a thermoplastic polyurethane is used to improve the thermal stability during the molding process, using hindered phenol and phosphite. A composition to which a system compound is added is known (see Patent Document 7). However, these compositions are liable to adhere to and adhere to a molding device such as a die part during melt molding, and accordingly, a molded product having a predetermined dimension and excellent in surface smoothness and appearance cannot be obtained. In some cases, it is not satisfactory in terms of handleability, melt moldability, etc., and it is difficult to say that it is sufficiently excellent in terms of melt adhesion with other materials.

  (Hydrogenated) Styrene / conjugated diene block copolymer and (polyhydrogenated) styrene / conjugated diene block copolymer can be used to solve the problems in the above-described conventional compositions containing thermoplastic polyurethane. ) A block copolymer having an addition polymerization block composed of a styrene / conjugated diene block copolymer and a polyurethane block, a thermoplastic polyurethane and a thermoplastic polymer composition containing paraffinic oil are known (Patent Document 8). reference). This thermoplastic polymer composition has good flexibility, elasticity, mechanical properties, oil resistance, molding processability, and excellent melt adhesiveness, and firmly adheres to various materials under melting. It has an excellent property of Therefore, the present inventors further examined the thermoplastic polymer composition, and found that an addition polymerization block composed of a (hydrogenated) styrene / conjugated diene block copolymer used in the thermoplastic polymer composition and A block copolymer having a polyurethane block may be dissociated at the joint between the addition polymerization block and the polyurethane block depending on the thermal conditions at the time of molding processing. From the viewpoint of improving heat resistance at the time of molding processing, etc. From this, it was found that there was room for further improvement. Moreover, there was room for further improvement from the viewpoint of obtaining a thermoplastic polymer composition having higher tensile breaking strength.

JP-A-52-150464 JP-A-6-65467 JP-A-6-107898 JP-A-8-72204 JP-A-63-99257 JP-A-3-234755 Japanese Patent Laid-Open No. 7-126474 JP 11-323073 A JP 2001-220505 A JP 2001-220506 A JP-A-10-139963

As described above, the range of use of various types of thermoplastic elastomers including (hydrogenated) styrene / conjugated diene block copolymers has been expanded, and with this, molding processability is further improved and high performance. Has come to be required.
The object of the present invention is to solve the above-described problems in the prior art, and is excellent in melt moldability and handleability without adhesion or adhesion to a molding apparatus during melt molding, and particularly melt extrusion including inflation molding. No extrudate sticks to the die part during molding, thickness irregularities, cracks, streaks, etc. do not occur in the molded product, and it is possible to smoothly produce a molded product with excellent appearance and dimensional stability with high productivity. Moreover, it is possible to produce molded products and composite molded articles that are excellent in mechanical properties such as flexibility, tensile breaking strength, abrasion resistance, light resistance, heat resistance, and melt adhesion with other materials. It is to provide a thermoplastic polymer composition.
Furthermore, the objective of this invention is providing the molded article which consists of the said thermoplastic polymer composition, and the composite molded object of this thermoplastic polymer composition and another material.

  In the course of studying the thermoplastic polymer composition described in Patent Document 8, the present inventors include an addition polymerization block composed of a (hydrogenated) styrene / conjugated diene block copolymer contained therein, and 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 part during melt extrusion molding can be prevented or reduced, and the I came up with the idea that defective phenomena such as thick spots, streaks, and cracks could be improved. And in the thermoplastic polymer composition described in Patent Document 8, a block copolymer having an addition polymerization block composed of a (hydrogenated) styrene / conjugated diene block copolymer and a polyurethane block used therein. Was made into a block copolymer having an addition polymerization block composed of a (hydrogenated) styrene / conjugated diene block copolymer and a polycarbonate block, and the handleability of the composition, The melt moldability and physical properties were examined. As a result, the thermoplastic polymer composition containing an addition polymerization block composed of a (hydrogenated) styrene / conjugated diene block copolymer and a block copolymer having a polycarbonate block adheres to a molding apparatus during melt molding. Excellent extrudability and handling, and extrudate does not adhere to the die part during melt extrusion, especially including inflation molding, resulting in thickness spots, streaks, cracks, etc. It has also been found that it has excellent mechanical properties such as flexibility and tensile breaking strength, abrasion resistance, light resistance, heat resistance, and melt adhesion to other materials.

In the thermoplastic polymer composition described above, the present invention provides a polycarbonate as a block copolymer having an addition polymerization block composed of a (hydrogenated) styrene / conjugated diene block copolymer and a polycarbonate block. Reactive functional group-containing (hydrogenated) block copolymer prepared by reacting styrene / conjugated diene block copolymer and polycarbonate under melt kneading, or polycarbonate-reactive functional group (hydrogenated) ) A block copolymer prepared by reacting a styrene / conjugated diene block copolymer, a compound having two hydroxyl groups, and a carbonate precursor under melt kneading is preferably used, in order to prepare the block copolymer. It has been found that the reaction in the melt kneading is preferably carried out in the presence of a catalyst.
Further, the inventors of the thermoplastic polymer composition described in Patent Document 8 mentioned above include an addition polymerization block and a polyurethane block comprising a (hydrogenated) styrene / conjugated diene block copolymer used therein. A reaction mixture prepared by reacting a polycarbonate with a reactive functional group (hydrogenated) styrene / conjugated diene block copolymer having a reactive functional group and the polycarbonate under melt kneading, or a polycarbonate Even when using a reaction mixture prepared by reacting (hydrogenated) styrene / conjugated diene block copolymer having a reactive functional group, a compound having two hydroxyl groups, and a polycarbonate precursor under melt kneading, It has been found that a thermoplastic polymer composition having the above-described various characteristics can be obtained.

In the thermoplastic polymer composition, the present inventors comprise, as polyurethane, a polymer polyol, a chain extender and an organic diisocyanate compound, wherein the content of nitrogen atoms derived from the organic diisocyanate compound is a polymer polyol, It has been found that a thermoplastic polyurethane formed using a reaction raw material of 1 to 6.5% by mass based on the total mass of the chain extender and the organic diisocyanate compound is preferably used.
Furthermore, the present inventors performed melt-kneading using 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. In this case, the present inventors have found that a thermoplastic polymer composition having the above-described excellent characteristics can be obtained, and the present invention has been completed based on these various findings.

That is, the present invention
(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) ), A block copolymer having an aromatic vinyl compound polymer block (a-2) and a conjugated diene polymer block (b-2) or an addition polymerization block (i) comprising a hydrogenated product thereof and a polycarbonate system A thermoplastic polymer composition comprising a block copolymer (II) having a polymer block (b), a thermoplastic polyurethane (III), and a paraffinic oil (IV) [hereinafter referred to as "heat It may be referred to as “plastic polymer composition (i)”].

And this invention,
(2) The thermoplastic polymer composition according to (1), wherein the block copolymer (II) is at least one of the following block copolymer (IIA) and block copolymer (IIB).
Block copolymer (IIA) :
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 reacting with a polycarbonate polymer (b-1) A block copolymer prepared by reacting an addition polymerization block copolymer (A-1) having a functional group capable of being reacted with a polycarbonate polymer (RO-1) under melt kneading.
Block copolymer (IIB) :
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 reacting with a polycarbonate polymer (b-1) Block copolymer prepared by reacting a compound having two functional groups (i-1), a compound having two hydroxyl groups, and a carbonate precursor under melt kneading.

The present invention also provides:
(3) The thermoplastic polymer composition of the above (2), wherein the block copolymer (IIA) and the block copolymer (IIB) are prepared by reacting in the presence of a catalyst under melt kneading; and ,
(4) per 100 parts by mass of 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 paraffinic oil (IV ) In a proportion of 10 to 200 parts by mass, the thermoplastic polymer composition according to any one of (1) to (3);
It is.

Furthermore, the present invention provides
(5) 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) ), A thermoplastic polymer composition obtained by melt-kneading at least one of the following reaction mixture (IIa) and reaction mixture (IIb), thermoplastic polyurethane (III), and paraffinic oil (IV) [hereinafter this May be referred to as “thermoplastic polymer composition (ii)”.
Reaction mixture (IIa) :
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 reacting with a polycarbonate polymer (b-1) A reaction mixture obtained by reacting an addition polymerization block copolymer (A-1) having a functional group capable of undergoing reaction with a polycarbonate polymer (RO-1) under melt kneading.
Reaction mixture (IIb) :
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 reacting with a polycarbonate polymer (b-1) A reaction mixture obtained by reacting an addition polymerization block copolymer having a functional group (i-1), a compound having two hydroxyl groups, and a carbonate precursor under melt kneading.

And this invention,
(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 (I). ), A thermoplastic polymer obtained by melt-kneading at least one of the following reaction mixture (IIa) and reaction mixture (IIb), a polymer polyol, a chain extender, an organic diisocyanate compound, and paraffinic oil (IV) This is a composition [hereinafter this may be referred to as “thermoplastic polymer composition (iii)”].
Reaction mixture (IIa) :
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 reacting with a polycarbonate polymer (b-1) A reaction mixture obtained by reacting an addition polymerization block copolymer (A-1) having a functional group capable of undergoing reaction with a polycarbonate polymer (RO-1) under melt kneading.
Reaction mixture (IIb) :
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 reacting with a polycarbonate polymer (b-1) A reaction mixture obtained by reacting an addition polymerization block copolymer having a functional group (i-1), a compound having two hydroxyl groups, and a carbonate precursor under melt kneading.

Furthermore, the present invention provides
(7) The thermoplastic polymer composition according to any one of (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 (7), wherein the addition polymerization block copolymer (A-1) has an average of 0.6 or more hydroxyl groups per molecule at the terminals;
It is.

And this invention,
(9) The thermoplastic polyurethane (III) is a reaction raw material for forming a thermoplastic polyurethane comprising a polymer polyol, a chain extender and an organic diisocyanate compound, and the content of nitrogen atoms derived from the organic diisocyanate compound is a polymer. The above-mentioned (1) to (5), (7) and (7), which are thermoplastic polyurethanes formed using a reaction raw material of 1 to 6.5% by mass based on the total mass of the polyol, the chain extender and the organic diisocyanate compound. The thermoplastic polymer composition according to any one of 8).
Furthermore, the present invention provides
(10) The thermoplastic resin according to any one of (1) to (9), wherein a tensile strength at break measured in accordance with JIS K-7311 is 8 MPa or more in a dumbbell-shaped test piece defined in JIS No. 3. It is a polymer composition.
And this invention,
(11) A molded article comprising the thermoplastic polymer composition according to any one 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 thermoplastic polymer composition of the present invention is excellent in melt moldability and handleability without adhesion or sticking to a molding apparatus at the time of melt molding, and particularly in the die part during melt extrusion molding including inflation molding. Extrudates do not adhere, and no thick spots, streaks, cracks, etc. occur during extrusion molding, and a high-quality molded product excellent in 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, 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 used for various molded products and products, for example, electrical products, synthetic leather, automobile-related devices, etc. It can be effectively used for the production of various molded articles bonded to other materials, such as shaped articles, hose-like articles, tube-like articles, and other molded articles.

The present invention is described in detail below.
The present invention
(I) a thermoplastic polymer composition comprising an addition polymerization block copolymer (I), a block copolymer (II), a thermoplastic polyurethane (III) and a paraffinic oil (IV) [thermoplastic polymer composition Thing (i)];
(Ii) Heat obtained by melt-kneading at least one of addition polymerization block copolymer (I), reaction mixture (IIa) and reaction mixture (IIb), thermoplastic polyurethane (III) and paraffinic oil (IV) A plastic polymer composition [thermoplastic polymer composition (ii)]; and
(Iii) Melting at least one of addition polymerization block copolymer (I), reaction mixture (IIa) and reaction mixture (IIb), polymer polyol, chain extender, organic diisocyanate compound, and paraffinic oil (IV) Thermoplastic polymer composition obtained by kneading [thermoplastic polymer composition (iii)];
Is included.

Used in the thermoplastic polymer compositions (i) to (iii) of the present invention [hereinafter, the thermoplastic polymer compositions (i) to (iii) may be collectively referred to as “thermoplastic polymer compositions”). The addition polymerization block copolymer (I) has an aromatic vinyl compound polymer block (a-1).
Further, it can be used as an addition polymerization block (a) in the block copolymer (II) used in the thermoplastic polymer composition (i) and as a block copolymer (II) in the thermoplastic polymer composition (i). Addition polymerization type block copolymer (I-1) used for forming the block copolymer (IIA) and the block copolymer (IIB), and the reaction mixture in the thermoplastic polymer compositions (ii) and (iii) ( The addition polymerization block copolymer (I-1) used for the formation of IIa) and reaction mixture (IIb) both has an aromatic vinyl compound polymer block (a-2).
Examples of the aromatic vinyl compound constituting the aromatic vinyl compound polymer blocks (a-1) and (a-2) include styrene, α-methylstyrene, β-methylstyrene, o-methylstyrene, m -Methylstyrene, p-methylstyrene, 2,4-dimethylstyrene, 2,4,6-trimethylstyrene, 4-propylstyrene, t-butylstyrene, 4-cyclohexylstyrene, 4-dodecylstyrene, 2-ethyl-4 -Aromatic vinyl compounds such as benzylstyrene, 4- (phenylbutyl) styrene, 1-vinylnaphthalene, vinylanthracene, indene, acetonaphthylene, monofluorostyrene, difluorostyrene, monochlorostyrene, and methoxystyrene. The aromatic vinyl compound-based polymer blocks (a-1) and (a-2) may be formed from one kind of aromatic vinyl compound, or may be formed from two or more kinds of aromatic vinyl compounds. Also good. The aromatic vinyl compound polymer blocks (a-1) and (a-2) are preferably formed mainly from structural units derived from styrene and / or α-methylstyrene.

  The aromatic vinyl compound-based polymer blocks (a-1) and (a-2) are one or two of other copolymerizable monomers as necessary, together with the structural unit derived from the aromatic vinyl compound. The structural unit derived from the above may be contained in a small amount. The content of structural units derived from other copolymerizable monomers is 30% by mass or less, particularly 10% by mass based on the mass of the aromatic vinyl compound polymer block (a-1) or (a-2). % Or less is more preferable. Examples of other copolymerizable monomers include 1-butene, 1-pentene, 1-hexene, butadiene, 2-methyl-1,3-butadiene (isoprene), methyl vinyl ether, and the like.

Further, the addition polymerization block copolymer (I) used in the thermoplastic polymer compositions (i) to (iii) of the present invention is a conjugated diene polymer block (b-1) mainly derived from a conjugated diene. have. Further, it can be used as an addition polymerization block (a) in the block copolymer (II) used in the thermoplastic polymer composition (i) and as a block copolymer (II) in the thermoplastic polymer composition (i). Addition polymerization type block copolymer (I-1) used for forming the block copolymer (IIA) and the block copolymer (IIB), and the reaction mixture in the thermoplastic polymer compositions (ii) and (iii) ( The addition polymerization block copolymer (I-1) used for the formation of IIa) and reaction mixture (IIb) both has a conjugated diene polymer block (b-2).
Examples of the conjugated diene compound constituting the conjugated diene polymer blocks (b-1) and (b-2) include 1,3-butadiene, 2-methyl-1,3-butadiene (isoprene), 2,3- Examples thereof include dimethyl-1,3-butadiene, 1,3-pentadiene, and 1,3-hexadiene. The conjugated diene polymer blocks (b-1) and (b-2) may be formed from one kind of conjugated diene compound or may be formed from two or more kinds of conjugated diene compounds. When the conjugated diene polymer block (b-1) and / or (b-2) contains a structural unit derived from two or more kinds of conjugated diene compounds, their bonding form is random, tapered, or one Any of partial blocks may be used, and they may be mixed.

  The conjugated diene polymer block (b-1) and / or (b-2) may be not hydrogenated, partially hydrogenated, or entirely hydrogenated. As the hydrogenation rate of the conjugated diene polymer block (b-1) and / or (b-2), from the viewpoint of heat resistance, weather resistance and light resistance, 50 mol% or more, more preferably 60 mol% or more, In particular, it is preferably 80 mol% or more. In addition, this hydrogenation rate (mol%) is a ratio with respect to the total number of moles of the double bond which exists in the conjugated diene polymer block (b-1) or (b-2) before hydrogenation.

  In particular, the conjugated diene polymer block (b-1) and the conjugated diene polymer block (b) are obtained from the point that a thermoplastic polymer composition excellent in flexibility, mechanical performance and melt moldability can be obtained more smoothly. -2) is at least one selected from an optionally hydrogenated isoprene polymer block, an optionally hydrogenated butadiene polymer block and an optionally hydrogenated isoprene and butadiene copolymer block. The polymer block is preferably.

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, more preferably 10%, based on the mass of the addition polymerization block copolymer (I). It is preferable that it is -90 mass%, especially 20-80 mass%.
The content of the structural unit derived from the aromatic vinyl compound in the addition polymerization system block (a) of the block copolymer (II) is 5 to 90% by mass with respect to the mass of the addition polymerization system block (a). Is preferably 10 to 90% by mass, more preferably 20 to 80% by mass.
Further, the content of the structural unit derived from the aromatic vinyl compound in the addition polymerization block copolymer (I-1) used for forming the block copolymer (IIA) and the block copolymer (IIB), and the reaction mixture The content of the structural unit derived from the aromatic vinyl compound in the addition polymerization block copolymer (I-1) used for forming the reaction mixture (IIa) and the reaction mixture (IIb) is the addition polymerization block copolymer (I- It is preferable that it is 5-90 mass% with respect to the mass of 1), Furthermore, it is 10-90 mass%, Especially 20-80 mass%.
Use of addition polymerization block copolymer (I), block copolymer (II), and addition polymerization block copolymer (I-1) in which the content of the structural unit derived from the aromatic vinyl compound is in the above range. By doing so, it is possible to obtain a thermoplastic polymer composition that is superior in flexibility, mechanical performance, melt moldability and the like.

  Bonding form of aromatic vinyl compound polymer block (a-1) and conjugated diene polymer block (b-1) in addition polymerization block copolymer (I), addition of block copolymer (II) Bond form of the aromatic vinyl compound polymer block (a-2) and the conjugated diene polymer block (b-2) in the polymerization block (a), the block copolymer (IIA) and the block copolymer ( IIB) a combination form of the aromatic vinyl compound polymer block (a-2) and the conjugated diene polymer block (b-2) in the addition polymerization block copolymer (a-1) used for the formation of IIB), and The aromatic vinyl compound-based polymer block (a-2) and the conjugated diene-based polymer block in the addition polymerization block copolymer (I-1) used for forming the reaction mixture (IIa) and the reaction mixture (IIb). The binding form with the lac (b-2) is not particularly limited, and may be any of linear, branched, radial, or a combination thereof, and among them, a linear bond The form is preferable from the viewpoint that a thermoplastic polymer composition excellent in flexibility, mechanical performance, melt moldability and the like can be obtained.

Addition Polymerization Block Copolymer (I), Addition Polymerization Block (i) in Block Copolymer (II), Addition Polymerization Block Used for Formation of Block Copolymer (IIA) and Block Copolymer (IIB) As the copolymer (I-1) and the addition polymerization block copolymer (I-1) used for forming the reaction mixture (IIa) and the reaction mixture (IIb), an aromatic vinyl compound polymer block (a -1) and (a-2) are represented by X, and conjugated diene polymer blocks (b-1) and (b-2) are represented by Y, for example, the following formula:
(XY) _m -X
(XY) _n
Y- (XY) _p
(In the formula, m, n and p each represent an integer of 1 or more)
Can be mentioned.
Among these, addition polymerization block copolymer (I), block copolymer (from the point that the thermoplastic polymer composition of the present invention is excellent in melt moldability, flexibility, mechanical performance, etc. II) addition polymerization block (a), addition copolymer block copolymer (II-1) used to form block copolymer (IIA) and block copolymer (IIB), and reaction mixture (IIa) and The addition polymerization block copolymer (I-1) used for forming the reaction mixture (IIb) is a diblock copolymer represented by the formula: XY or a triblock represented by the formula: XYX. It is preferably in the form of a copolymer, and more preferably in the form of a triblock copolymer represented by the formula: XYX. In particular, in the form of a triblock copolymer represented by the formula: XYX, the impregnation ability (oil retention ability) of paraffinic oil (IV) in the thermoplastic polymer composition is increased, It is also preferable from the viewpoint that paraffinic oil (IV) migration (bleed out, etc.) can be more effectively prevented.

When the addition polymerization block copolymer (I) contains two or more aromatic vinyl compound polymer blocks X, the addition polymerization block (I) of the block copolymer (II) is an aromatic vinyl compound heavy polymer. When two or more coalescence blocks X are contained, the addition polymerization block copolymer (I-1) used for forming the block copolymer (IIA) and the block copolymer (IIB) is an aromatic vinyl compound polymer. When two or more blocks X are contained and / or the addition polymerization block copolymer (I-1) used for forming the reaction mixture (IIa) and the reaction mixture (IIb) is an aromatic vinyl compound polymer block X When two or more are contained, the aromatic vinyl compound-based polymer block may be a polymer block having the same content or may be a polymer block having different content.
When the addition polymerization block copolymer (I) contains two or more conjugated diene polymer blocks Y, the addition polymerization block (A) of the block copolymer (II) contains two or more conjugates. When the diene polymer block Y is contained, the addition polymerization block copolymer (I-1) used for forming the block copolymer (IIA) and the block copolymer (IIB) has two or more conjugated diene systems. Conjugated diene polymer block having two or more addition polymerization block copolymers (I-1) used for forming the polymer block Y and / or forming the reaction mixture (IIa) and the reaction mixture (IIb) When Y is contained, the conjugated diene polymer block may be a polymer block having the same contents or a polymer block having different contents.
For example, two aromatic vinyl compound polymer blocks X in a triblock structure represented by XYX, or two conjugated diene polymers in a triblock structure represented by YXY The block Y may be the same or different in the type of aromatic vinyl compound or conjugated diene compound constituting the block Y, the bonding type thereof, the number average molecular weight of the polymer block, and the like.

  The number average molecular weights of the aromatic vinyl compound polymer block (a-1) and the conjugated diene polymer block (b-1) in the addition polymerization block copolymer (I) are not particularly limited, In a state before hydrogenation, the aromatic vinyl compound polymer block (a-1) has a number average molecular weight in the range of 2,500 to 125,000, particularly 10,000 to 100,000, and is a conjugated diene type. The number average molecular weight of the polymer block (b-1) is preferably in the range of 10,000 to 250,000, particularly 20,000 to 200,000. An addition polymerization block copolymer (I) comprising an aromatic vinyl compound polymer block (a-1) having a number average molecular weight within the above range and a conjugated diene polymer block (b-1). By using the thermoplastic polymer composition of the present invention, the melt moldability, flexibility, mechanical performance, and the like become better.

  The total number average molecular weight of the addition polymerization block copolymer (I) is preferably in the range of 15,000 to 500,000, particularly 80,000 to 400,000, in a state before hydrogenation. By using the addition polymerization block copolymer (I) having such a number average molecular weight, the melt moldability, flexibility, mechanical performance, etc. of the thermoplastic polymer composition of the present invention are further improved. .

Further, the number average molecular weight of the aromatic vinyl compound polymer block (a-2) and the conjugated diene polymer block (b-2) in the addition polymerization block (a) of the block copolymer (II), the block copolymer Aromatic vinyl compound polymer block (a-2) and conjugated diene polymer block in addition polymerization block copolymer (I-1) used for forming polymer (IIA) and block copolymer (IIB) Number average molecular weight of (b-2), aromatic vinyl compound polymer block (a-2) in addition polymerization block copolymer (I-1) used for formation of reaction mixture (IIa) and reaction mixture (IIb) ) And the conjugated diene polymer block (b-2) are not particularly limited in number average molecular weight, but both are aromatic vinyl compound polymer blocks in the state before hydrogenation. The number average molecular weight of the lock (a-2) is in the range of 2,500 to 75,000, particularly 5,000 to 50,000, and the number average molecular weight of the conjugated diene polymer block (b-2) is 10 It is preferable that it is in the range of 10,000 to 150,000, particularly 10,000 to 100,000.
When the number average molecular weights of the aromatic vinyl compound polymer block (a-2) and the conjugated diene polymer block (b-2) are within the above range, the melt moldability of the thermoplastic polymer composition of the present invention is as follows. , Flexibility, mechanical performance, etc. will be better.

  Further, the total number average molecular weight of the addition copolymerization block (a) of the block copolymer (II), the addition polymerization block copolymer used for the formation of the block copolymer (IIA) and the block copolymer (IIB) The total number average molecular weight of (a-1), the total number average molecular weight of the addition polymerization block copolymer (I-1) used for forming the reaction mixture (IIa) and the reaction mixture (IIb) are as follows. It is preferable that all fall within the range of 15,000 to 300,000, particularly 20,000 to 100,000. By using a block copolymer (II) containing an addition polymerization block (A) having such a number average molecular weight, or using an addition polymerization block copolymer (A-1) having such a number average molecular weight Of the thermoplastic polymer composition of the present invention by using the block copolymer (IIA), the block copolymer (IIB), the reaction mixture (IIa) and / or the reaction mixture (IIb). Property, flexibility, mechanical performance, etc. are improved.

  The number average molecular weights of the aromatic vinyl compound polymer block (a-1) and the conjugated diene polymer block (b-1), the addition polymerization block copolymer (I), as used herein. The total number average molecular weight, 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 total number of the addition polymerization system block (a) Average molecular weight, number average molecular weight of addition of aromatic vinyl compound polymer block (a-2) and conjugated diene polymer block (b-2) in addition polymerization block copolymer (I-1), and addition The total number average molecular weight of the polymerization block copolymer (I-1) is a value measured in terms of standard polystyrene by gel permeation chromatography (GPC). A.

  The addition polymerization block copolymer (I) used in the thermoplastic polymer compositions (i) to (iii) of the present invention has a melt flow rate (MFR) measured at 230 ° C. under a load of 2.16 kg of 10 g / It is preferably 10 minutes or less, more preferably 5 g / 10 minutes or less, and particularly preferably 3 g / 10 minutes or less. By using the addition polymerization block copolymer (I) having such a melt flow rate (MFR), the thermoplastic polymer composition of the present invention has more excellent melt moldability, flexibility, mechanical performance and the like. It will be a thing.

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 (IIA) usable as the block copolymer (II) ) And the block copolymer (IIB), the addition polymerization block copolymer (I-1), and the reaction mixture (IIa) in the thermoplastic polymer compositions (ii) and (iii) of the present invention and The addition polymerization block copolymer (I-1) used for the formation of the reaction mixture (IIb) has a melt flow rate (MFR) of 0.01 to 100 g / m measured at 230 ° C. under a load of 2.16 kg. It is preferably within a range of 10 minutes, particularly 0.05 to 80 g / 10 minutes. Thereby, the block copolymer (II), the block copolymer (IIA), the block copolymer (IIB) or the reaction mixture (IIa) and / or the reaction mixture (IIb) and the addition polymerization block copolymer ( The compatibility with I) and the thermoplastic polyurethane (III) is improved, and a thermoplastic polymer composition excellent in mechanical performance, melt moldability and the like is obtained.
In addition, the melt flow rate (MFR) of the addition polymerization block copolymer (I) and the addition polymerization block copolymer (I-1) in this specification is measured in accordance with ASTM D-1238. It is the value.
In addition, the melt flow rate (MFR) of the addition polymerization block (A) in the present specification uses a polymer in which the polycarbonate polymer block (B) is replaced with a hydrogen atom in the block copolymer (II). The value measured in accordance with ASTM D-1238.

The JIS A hardness of the addition polymerization block copolymer (I) used in the thermoplastic polymer compositions (i) to (iii) of the present invention is 30 to 95, more preferably 40 to 90, and particularly 50 to 85. It is preferable to be within. By using the addition polymerization block copolymer (I) having such JIS A hardness, the melt moldability, flexibility, mechanical performance and the like of the thermoplastic polymer composition of the present invention become better.
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 (IIA) usable as the block copolymer (II) ) And the block copolymer (IIB), the addition polymerization block copolymer (I-1), and the reaction mixture (IIa) in the thermoplastic polymer compositions (ii) and (iii) of the present invention and The addition polymerization block copolymer (I-1) used for forming the reaction mixture (IIb) has a JIS A hardness of 30 to 95, more preferably 40 to 90, and particularly 50 to 85. Is preferable, whereby 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 according to JIS K-6253. is there.
Further, the JIS A hardness of the addition polymerization block (A) in the present specification is determined according to JIS using a polymer obtained by replacing the polycarbonate polymer block (B) with a hydrogen atom in the block copolymer (II). It is the value measured based on K-6253.

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. You may manufacture by any method which can manufacture.
The addition polymerization block copolymer (I) can be produced, for example, by an ion polymerization method such as anionic polymerization or cationic polymerization, a single site polymerization method, a radical polymerization method, or the like. In the case of anionic polymerization, for example, an aromatic vinyl compound and a conjugated diene compound are sequentially polymerized in an inert organic solvent such as n-hexane or cyclohexane using an alkyl lithium compound as a polymerization initiator, After producing a block copolymer having a molecular structure and molecular weight, it can be produced by adding an active hydrogen-containing compound such as alcohols, carboxylic acids and water to stop the polymerization. And the obtained block copolymer is preferably present in an inert organic solvent such as n-hexane or cyclohexane in the presence of a hydrogenation reaction catalyst such as a Ziegler catalyst comprising an alkylaluminum compound and cobalt, nickel or the like. The hydrogenated product may be obtained by hydrogenation under the conditions of a reaction temperature of 20 to 150 ° C. and a hydrogen pressure of 0.1 to 15 MPa.

In the above, before adding the active hydrogen-containing compound to stop the polymerization, for example, a compound having an oxirane skeleton such as ethylene oxide, propylene oxide, styrene oxide, ε-caprolactone, β-propiolactone, dimethylpropiolactone ( By adding a lactone compound such as pivalolactone and methylvalerolactone, 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 a 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 union (I) can also be produced.
In addition, as addition polymerization type block copolymer (I), you may use what is marketed.

  As the polycarbonate polymer block (b) constituting the block copolymer (II) used in the thermoplastic polymer composition (i), for example, it was produced by reacting a compound having two hydroxyl groups with a carbonate precursor. Mention may be made of blocks made of polycarbonate. Further, a polycarbonate-based polymer (B-1) used for forming a block copolymer (IIA) that can be used as the block copolymer (II), and a reaction mixture in the thermoplastic polymer compositions (ii) and (iii) Examples of the polycarbonate-based polymer (B-1) used for forming (IIa) include a polycarbonate produced by reacting a compound having two hydroxyl groups with a carbonate precursor.

Examples of the compound having two hydroxyl groups used in the production of polycarbonate include dihydric phenols and aliphatic diols.
As typical examples of the dihydric phenol in that case, 2,2-bis (4-hydroxyphenyl) propane [bisphenol A], 1,1-bis (4-hydroxyphenyl) ethane, 1,1-bis ( 4-hydroxyphenyl) cyclohexane, 2,2-bis (4-hydroxy-3,5-dimethylphenyl) propane, 2,2-bis (4-hydroxy-3,5-dibromophenyl) propane, 2,2-bis (4-hydroxy-3,5-chlorophenyl) propane, 2,2-bis (4-hydroxy-3-methylphenyl) propane, hydroquinone, 4,4′-dihydroxydiphenyl, bis (4-hydroxyphenyl) sulfide, bis (4-hydroxyphenyl) sulfone, bis (4-hydroxyphenyl) sulfoxide, etc. wear. Among these, bis (4-hydroxyphenyl) alkane is preferable as the dihydric phenol, and 2,2-bis (4-hydroxyphenyl) propane (common name: bisphenol A) is particularly preferable.

  Examples of the aliphatic diol used in the production of polycarbonate include ethylene glycol, propylene glycol, hexylene glycol, and 3-methyl-1,5-pentanediol.

  Polycarbonate polymer block (II) in the block copolymer (II), polycarbonate polymer (B-1) used for forming the block copolymer (IIA) that can be used as the block copolymer (II), reaction mixture The polycarbonate-based polymer (B-1) used for the formation of (IIa) consists of a polycarbonate-based polymer obtained by the reaction of one of the two hydroxyl group-containing compounds with a carbonate precursor. Alternatively, it may be made of a polycarbonate polymer obtained by a reaction between two or more of the above-mentioned compounds having two hydroxyl groups and a carbonate precursor.

Examples of the carbonate precursor include carbonyl halide, carbonate ester, and haloformate. Specific examples include phosgene, diphenyl carbonate, methyl chlorocarbonate, dihaloformate of dihydric phenol, and the like. Among these, phosgene is preferable as the carbonate precursor.
Polycarbonate polymer block (II) in the block copolymer (II), polycarbonate polymer (B-1) used for forming the block copolymer (IIA) that can be used as the block copolymer (II), reaction mixture The polycarbonate-based polymer (B-1) used for the formation of (IIa) may be formed using one type of carbonate precursor, or formed using two or more types of carbonate precursors. It may be a thing.

The molecular weight of the polycarbonate polymer (B-1) used to form the block copolymer (IIA) that can be used as the block copolymer (II), and the polycarbonate polymer (B) used to form the reaction mixture (IIa) The melt weight of the thermoplastic polymer composition of the present invention is such that the molecular weight of 1) is in the range of 10,000 to 100,000, particularly 15,000 to 60,000, in terms of viscosity average molecular weight. From the viewpoints of flexibility, mechanical performance and the like.
The viscosity average molecular weight of the polycarbonate polymer (B-1) in this specification is a value measured by a solution viscosity method (measurement temperature = 20 ° C., solvent = methylene chloride).

In the block copolymer (II) used in the thermoplastic polymer composition (i) of the present invention, the bonding form of the addition polymerization block (A) and the polycarbonate polymer block (B) is not particularly limited, and is linear. May be any of a linear, branched, radial, or combined form thereof, but the linear combined form is a melt moldability and flexibility of the thermoplastic polymer composition (i). From the standpoint of mechanical performance and the like.
When the addition polymerization block (A) is represented by α and the polycarbonate polymer block (B) is represented by β, the linear block copolymer is represented by, for example, the formula: α-β Examples include various block copolymers such as a diblock copolymer, a formula; a triblock copolymer represented by α-β-α, and a formula; a triblock copolymer represented by β-α-β. Can do.
Among them, when the block copolymer (II) is a diblock copolymer represented by the formula: α-β, the melt moldability, flexibility, and mechanical performance of the thermoplastic polymer composition (i) Etc. are preferable because they are more excellent.

  In the block copolymer (II), the mass ratio of the addition polymerization block (a) to the polycarbonate polymer block (b) is from 20:80 to 80:20, further from 30:70 to 70:30, particularly 35. Is preferably in the range of 65 to 65:35 from the viewpoints of melt moldability, flexibility, mechanical performance, and the like of the thermoplastic polymer composition (i).

  The block copolymer (II) used in the thermoplastic polymer composition (i) of the present invention is known, and the compatibility between the polycarbonate resin and the rubber-reinforced styrene resin is improved. The polycarbonate resin and the polyester resin are used. It is conventionally used for the purpose of improving the compatibility of the resin (see Patent Documents 9 and 10). However, it has not been conventionally known that the block copolymer (II) is used in combination with the addition polymerization block copolymer (I) and the thermoplastic polyurethane (III).

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, flexibility, and mechanical performance of the thermoplastic polymer composition. In view of the above, the block copolymer (II) is preferably at least one block copolymer of the following block copolymer (IIA) and block copolymer (IIB) prepared by a specific method. used.
Block copolymer (IIA) :
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 reacting with a polycarbonate polymer (b-1) A block copolymer prepared by reacting an addition polymerization block copolymer (A-1) having a functional group capable of being reacted with a polycarbonate polymer (RO-1) under melt kneading.
Block copolymer (IIB) :
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 reacting with a polycarbonate polymer (b-1) Block copolymer prepared by reacting a compound having two functional groups (i-1), a compound having two hydroxyl groups, and a carbonate precursor under melt kneading.
In the block copolymer (IIB), a polycarbonate polymer block (b) is formed by a reaction between a compound having two hydroxyl groups and a carbonate precursor.

Addition-polymerized block copolymer (I-1) and thermoplastic polymer composition used for the preparation of the block copolymer (IIA) and the block copolymer (IIB) that can be used in the thermoplastic polymer composition (i) It can react with the polycarbonate polymer (b-1) of the addition polymerization block copolymer (b-1) used for forming the reaction mixtures (IIa) and (IIb) in the products (ii) and (iii) Examples of the functional group include a carboxyl group, an acid anhydride group, an alkoxycarbonyl group, a thiocarboxyl group, an isocyanate group, a hydroxyl group, an amino group, and a mercapto group. The addition polymerization block copolymer (I-1) may have one of these functional groups, or may have two or more thereof, and a hydroxyl group is preferable among the functional groups described above. .
Further, the above addition polymerization block copolymer (I-1) preferably has a functional group capable of reacting with the polycarbonate polymer (B-1) at the molecular end of the copolymer. .

Addition-polymerized block copolymer (I-1) and thermoplastic polymer composition used for the preparation of the block copolymer (IIA) and the block copolymer (IIB) that can be used in the thermoplastic polymer composition (i) Functional group capable of reacting with the polycarbonate polymer (b-1) in the addition polymerization block copolymer (b-1) used for forming the reaction mixtures (IIa) and (IIb) in the products (ii) and (iii) In any case, the number of the addition polymerization block copolymer (A-1) is 0.6 or more on average, more preferably 0.7 or more, and particularly 0.7 to 1 per molecule. preferable.
Depending on the production process, the addition polymerization block copolymer (A-1) has a functional group capable of reacting with the polycarbonate polymer (B-1) (the functional group). Hydrogenated or non-hydrogenated block copolymer having an aromatic vinyl compound-based polymer block and a conjugated diene-based polymer block) may be included. As 1), the number of functional groups capable of reacting with the polycarbonate-based polymer (ro-1) is 0.6 or more, more preferably 0.7 or more, particularly 0.7 or more on average per molecule. The block copolymer (II), the block copolymer (IIA), the block copolymer (IIB), the reaction mixture (IIa) or (IIb) can be smoothly prepared by using one to ˜ be able to.

The production method of the addition polymerization block copolymer (A-1) is not limited in any way, and for example, it is produced by an ion polymerization method such as anionic polymerization or cationic polymerization, a single site polymerization method, a radical polymerization method, or the like. be able to. In the case of anionic polymerization, for example, an aromatic vinyl compound and a conjugated diene compound are sequentially polymerized in an inert organic solvent such as n-hexane or cyclohexane using an alkyl lithium compound as a polymerization initiator, When the molecular structure and molecular weight are reached, compounds having an oxirane skeleton such as ethylene oxide, propylene oxide, and styrene oxide, and lactones such as ε-caprolactone, β-propiolactone, dimethylpropiolactone (pivalolactone), and methylvalerolactone It can be produced by adding a compound or the like and then adding an active hydrogen-containing compound such as alcohols, carboxylic acids or water to stop the polymerization. The block copolymer thus obtained is preferably present in an inert organic solvent such as n-hexane or cyclohexane in the presence of a hydrogenation reaction catalyst such as a Ziegler catalyst comprising an alkylaluminum compound and cobalt, nickel or the like. Further, a hydrogenated product may be obtained by hydrogenation under conditions of a reaction temperature of 20 to 150 ° C. and a hydrogen pressure of 0.1 to 15 MPa. If desired, the block copolymer before or after hydrogenation may be modified with maleic anhydride or the like.
In addition, as addition polymerization type block copolymer (I-1), you may use what is marketed.

  The polycarbonate-based polymer (B-1) used for the preparation of the block copolymer (IIA) that can be used in the thermoplastic polymer composition (i) and the reaction mixture in the thermoplastic polymer compositions (ii) and (iii) ( The polycarbonate-based polymer (B-1) used for the formation of IIa) can be produced by reacting a compound having two hydroxyl groups and a carbonate precursor by a solution method or a melting method. In preparing the block copolymer (IIA) and the reaction mixture (IIa), a reaction mixture containing a polycarbonate polymer (B-1) obtained by reacting a compound having two hydroxyl groups with a carbonate precursor is used as it is. The polycarbonate-based polymer (B-1) may be separated from the reaction mixture and used. Further, the block copolymer (IIA) and the reaction mixture (IIa) may be prepared using a commercially available polycarbonate as the polycarbonate polymer (b-1).

  As the polycarbonate-based polymer (B-1), a polycarbonate produced using a molecular weight regulator, a branching agent, a catalyst or the like may be used as necessary. The polycarbonate-based polymer (B-1) is optionally added as an additive, for example, a heat stabilizer such as phosphite, phosphate, phosphonate; triazole, acetophenone, salicylate, etc. Ultraviolet absorber; low molecular weight polycarbonate of tetrabromobisphenol A, tetrabromobisphenol A; flame retardant such as decabromodiphenyl ether; colorant, fluorescent brightener and the like.

  In addition, it has two hydroxyl groups used for the preparation of the reaction mixture (IIb) in the block copolymer (IIB) and the thermoplastic polymer compositions (ii) and (iii) that can be used in the thermoplastic polymer composition (i). As the compound and the carbonate precursor, the two hydroxyl groups specifically exemplified above for the polycarbonate and the polycarbonate polymer (b-1) constituting the polycarbonate polymer block (b) in the block copolymer (II) are used. Compounds (for example, bisphenol A and other various dihydric phenols, aliphatic diols, etc.), carbonate precursors (for example, carbonyl halides, carbonate esters, haloformates, etc. (specific examples are phosgene, diphenyl carbonate, methyl chlorocarbonate, 2 Dihaloformate of dihydric phenol )] Can be used.

In preparing the block copolymer (IIA) that can be used for the thermoplastic polymer composition (i) and the reaction mixture (IIa) used for the thermoplastic polymer compositions (ii) and (iii), the block copolymer ( Since the compatibility of IIA) or the reaction mixture (IIa) with the addition polymerization block copolymer (I) and the thermoplastic polyurethane (III) is improved, the addition polymerization block copolymer (I-1) ) And polycarbonate polymer (B-1) [mass of addition polymerization block copolymer (A-1)]: [mass of polycarbonate polymer (B-1)] = 20: 80-80: 20, more preferably 30:70 to 70:30, and particularly preferably 35:65 to 65:35.
In preparing the block copolymer (IIB) that can be used for the thermoplastic polymer composition (i) and the reaction mixture (IIb) used for the thermoplastic polymer compositions (ii) and (iii), block copolymer Since the compatibility of the polymer (IIB) or the reaction mixture (IIb) with the addition polymerization block copolymer (I) and the thermoplastic polyurethane (III) is improved, the addition polymerization block copolymer (I -1) A compound having two hydroxyl groups and a carbonate precursor, [mass of addition polymerization block copolymer (I-1)]: [total mass of compound having two hydroxyl groups and carbonate precursor] = 20 : 80 to 80:20, more preferably 30:70 to 70:30, and particularly preferably 35:65 to 65:35.

  The above reaction for preparing the block copolymer (IIA), the block copolymer (IIB), the reaction mixture (IIa) and the reaction mixture (IIb) is preferably carried out in the presence of a catalyst. Examples of the catalyst used in this case include organic titanium compounds, organic antimony compounds, organic germanium compounds, organic manganese compounds, organic tin compounds, organic zinc compounds, organic calcium compounds, organic lead compounds, organic samarium compounds, organic lanthanum compounds, and organic compounds. An organometallic compound such as an ytterbium compound, an organic cobalt compound, an organic cadmium compound, or an organomagnesium compound can be given, and one or more of these can be used. Among these, one or more of an organic titanium compound, an organic tin compound, and an organic samarium compound are preferably used. When using 2 or more types of catalysts together, the metals contained in each catalyst may be the same or different.

  The type of the organic titanium compound that is preferably used as the catalyst is not particularly limited, and examples thereof include tetraisopropyl titanate, tetrabutyl titanate, tetra-2-ethylhexyl titanate, ethylene glycol titanate, butylene glycol titanate, potassium potassium oxalate, and potassium potassium tartrate. , Titanium acetylacetonate, dibutoxybis (triethanolaminate) 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.

  Further, the kind of the above-described organotin compound that is preferably used as a catalyst is not particularly limited, and examples thereof include monomethyltin oxide, monoethyltin oxide, monopropyltin oxide, monobutyltin oxide, di-2-ethylhexyltin oxide, and dibutyltin oxide. , Phenylmethyltin oxide, monobutyltin trichloride, dibutyltin dichloride, dimethyltin dibromide, monobutyltin monoacetate, monobutyltin monobutyrate, dibutyltin diacetate, dibutyltin sulfide, diphenyltin sulfide, and the like. Or 2 or more types can be used. Among them, one or two of tin oxides such as monomethyltin oxide, monoethyltin oxide, monopropyltin oxide, dibutyltin oxide; and tin carboxylates such as monobutyltin monoacetate, monobutyltin monobutyrate, dibutyltin diacetate The above is preferably used.

  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. These 1 type (s) or 2 or more types can be used. Among them, samarium acetylacetonate is particularly preferably used.

  The amount of the catalyst used is the total mass of the addition polymerization block copolymer (A-1) and the polycarbonate polymer (B-1), or the addition polymerization block copolymer (A-1), Based on the total mass of the compound having a hydroxyl group and the carbonate precursor, 0.1 ppm to 0.2 mass%, more preferably 0.5 ppm to 0.02 mass%, particularly 1 ppm to 0.01 mass%. It is preferable.

  When a catalyst is used in preparing the block copolymer (IIA), the block copolymer (IIB), the reaction mixture (IIa) and the reaction mixture (IIb), the addition polymerization block copolymer (I) and Unless the compatibility with the thermoplastic polyurethane (III) is impaired, the resulting block copolymer (IIA), block copolymer (IIB), reaction mixture (IIa) and reaction mixture (IIb) are subjected to catalyst loss. It is preferable to add an activator. Examples of the catalyst deactivator include lauryl phosphate, oleyl phosphate, stearyl phosphate, dilauryl phosphate, dioleyl phosphate, distearyl phosphate, tris (2-ethylhexyl) phosphate, bis (octadecyl) pentaerythritol diphosphate, phenylphosphonic acid Phosphorus compounds such as diethyl, diethyl 3,5-di-t-butyl-4-hydroxybenzylphosphonate; 2,2′-methylenebis (4-methyl-6-t-butylphenol), 2,2′-methylenebis ( 4-ethyl-6-t-butylphenol), 2-hydroxy-4-benzyloxybenzophenone, 2- (2′-hydroxy-3 ′, 5′-t-butylphenyl) benzotriazole, 2- [2-hydroxy- 3,5-bis alpha, alpha-dimethylbenzyl) phenyl] -2H- benzotriazole, 4,4'-octyl-2,2'-phenolic compounds such as biphenol like can be mentioned, phosphorus compounds Among the preferably used.

  The amount of the catalyst deactivator used is the total mass of the addition polymerization block copolymer (A-1) and the polycarbonate polymer (B-1), or the addition polymerization block copolymer (A-1), 2 Based on the total mass of the compound having two hydroxyl groups and the carbonate precursor, it is preferably in the range of 1 ppm to 2 mass%, more preferably 5 ppm to 0.2 mass%, and particularly preferably 10 ppm to 0.1 mass%.

In preparing the block copolymer (IIA) that can be used for the thermoplastic polymer composition (i), for example, an addition polymerization block copolymer (I-1) and a polycarbonate polymer (B-1) Block by adopting a method of melt kneading usually at 180-300 ° C. for 3-15 minutes with a kneader such as a single screw extruder, twin screw extruder, kneader, Banbury mixer, etc. in the presence of a catalyst as necessary. A copolymer (IIA) can be obtained.
In preparation of the block copolymer (IIB) that can be used for the thermoplastic polymer composition (i), for example, an addition polymerization block copolymer (I-1), a compound having two hydroxyl groups, and a carbonate precursor are used. Adopting a method of melt-kneading the body at 180 to 300 ° C. for 3 to 15 minutes with a kneader such as a single screw extruder, a twin screw extruder, a kneader, or a Banbury mixer, if necessary, in the presence of a catalyst. Thus, the block copolymer (IIB) can be obtained.
In addition, when using a catalyst deactivator, it is preferable to add the addition after the end of the carbonate bond formation reaction and the end of the melt kneading.

When the block copolymer (IIA) is prepared by reacting the addition polymerization block copolymer (A-1) with the polycarbonate polymer (B-1), and the addition polymerization block copolymer (A-1). ) When a block copolymer (IIB) is prepared by reacting a compound having two hydroxyl groups and a carbonate precursor, the block copolymer (IIA) or block is contained in the reaction product obtained by the reaction. In addition to the copolymer (IIB), an unreacted addition polymerization block copolymer (I-1), an unreacted polycarbonate polymer (B-1), a compound having two hydroxyl groups and a carbonate precursor. A functional group reactive with a polycarbonate polymer (B-1) comprising a polycarbonate, an aromatic vinyl compound polymer block and a conjugated diene polymer block to be formed It may contain one or more components such as block copolymers that do not have, and the content of these components varies depending on the reaction conditions such as the ratio of raw materials used in the reaction, reaction temperature, etc. To do.
In the thermoplastic polymer composition (i) of the present invention, even if the reaction product containing the above-mentioned other components together with the block copolymer (IIA) or the block copolymer (IIB) is used as it is, there is generally no particular problem. Often does not occur. Therefore, the reaction product containing the block copolymer (IIA) or the block copolymer (IIB) without separating and recovering the block copolymer (IIA) or the block copolymer (IIB) from the reaction product. When the thermoplastic polymer composition (i) of the present invention is produced using the above, the production process of the thermoplastic polymer composition (i) can be simplified.

In the thermoplastic polymer composition (i), when the above-mentioned reaction product containing other components together with the block copolymer (IIA) or the block copolymer (IIB) is used, an addition polymerization type block copolymer In order to have good compatibility with both (I) and the thermoplastic polyurethane (III), the reaction product having a tensile breaking strength of 10 MPa or more, further 12 MPa or more, particularly 15 MPa or more is used. It is preferable to use it.
In addition, the tensile breaking strength as used in this specification is the value measured based on JISK-7311.

In the thermoplastic polymer composition (i), when the above-mentioned reaction product containing other components together with the block copolymer (IIA) or the block copolymer (IIB) is used, the thermoplastic polymer of the present invention is used. In order to improve the melt moldability, flexibility, mechanical performance and the like of the composition (i), the reaction has a JIS A hardness of 40 to 99, more preferably 50 to 95, particularly 60 to 95. It is preferred to use the product.
In addition, the JIS A hardness of the said reaction product as used in this specification is the value measured based on JIS K-6253.

In preparing the reaction mixture (IIa) used for the thermoplastic polymer compositions (ii) and (iii), for example, an addition polymerization block copolymer (I-1) and a polycarbonate polymer (B-1) ) Is usually melted and kneaded at 180 to 300 ° C. for 3 to 15 minutes using a kneader such as a single screw extruder, twin screw extruder, kneader, or Banbury mixer in the presence of a catalyst as necessary. As a result, the reaction mixture (IIa) can be obtained.
Further, in preparing the reaction mixture (IIb) used in the thermoplastic polymer compositions (ii) and (iii), for example, an addition polymerization block copolymer (I-1), a compound having two hydroxyl groups, and a carbonate A method is adopted in which the precursor is melt-kneaded 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 Banbury mixer in the presence of a catalyst as necessary. As a result, the reaction mixture (IIb) can be obtained.
In addition, when using a catalyst deactivator, it is preferable to add the addition after the end of the carbonate bond formation reaction and the end of the melt kneading.

The reaction mixture (IIa) and reaction mixture (IIb) used in the thermoplastic polymer compositions (ii) and (iii) are used for both the addition polymerization block copolymer (I) and the thermoplastic polyurethane (III). In order to have good compatibility, it is preferable to use the reaction mixture having a tensile breaking strength of 10 MPa or more, further 12 MPa or more, particularly 15 MPa or more.
The reaction mixture (IIa) and reaction mixture (IIb) used in the thermoplastic polymer compositions (ii) and (iii) are the melt moldability and flexibility of the thermoplastic polymer compositions (ii) and (iii). In order to improve the mechanical performance, 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 addition, the JIS A hardness of the said reaction mixture as used in this specification is the value measured based on JIS K-6253.

The thermoplastic polymer compositions (i) to (iii) of the present invention include the above addition polymerization block copolymer (I), block copolymer (II), reaction mixture (IIa) or reaction mixture (IIb). ) And thermoplastic polyurethane (III).
As the thermoplastic polyurethane (III), those formed from a polymer polyol, a chain extender and an organic diisocyanate compound are preferable.

  Examples of the polymer polyol used for forming the thermoplastic polyurethane (III) include polyester polyol, polyether polyol, polycarbonate polyol, polyester polycarbonate polyol, polyolefin polyol, conjugated diene polymer polyol, castor oil polyol, and silicone polyol. A polyol, a vinyl polymer system polyol, etc. can be mentioned, These 1 type (s) or 2 or more types can be used. Among them, as the polymer polyol, one or more of polyester polyol, polyether polyol, and polyolefin-based polyol are preferably used, and polyester polyol and / or polyether polyol are more preferably used.

  The above-described polyester polyol preferably used for forming the thermoplastic polyurethane (III) is, for example, a method in which a polyol component and a polycarboxylic acid component are directly subjected to an esterification reaction or a transesterification reaction, or a lactone is opened using a polyol component as an initiator. It can be produced by ring polymerization.

  As the polyol component used in the production of the polyester polyol, those generally used in the production of polyester, for example, ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, 1,3-propanediol, 2-methyl-1 , 3-propanediol, 2,2-diethyl-1,3-propanediol, 1,3-butanediol, 1,4-butanediol, 2-methyl-1,4-butanediol, neopentyl glycol, 1, 5-pentanediol, 3-methyl-1,5-pentanediol, 1,6-hexanediol, 1,7-heptanediol, 1,8-octanediol, 2-methyl-1,8-octanediol, 2, 7-dimethyl-1,8-octanediol, 1,9-nonane C2-C15 aliphatic diol such as 2-methyl-1,9-nonanediol, 2,8-dimethyl-1,9-nonanediol, 1,10-decanediol; 1,4-cyclohexane Alicyclic diols such as diol, cyclohexanedimethanol and cyclooctanedimethanol; Aromatic diols such as 1,4-bis (β-hydroxyethoxy) benzene; Trimethylolpropane, trimethylolethane, glycerin, 1,2,6 -One or more polyhydric alcohols having 3 or more hydroxyl groups per molecule, such as hexanetriol, pentaerythritol, diglycerin and the like can be used.

  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, 3 to 12 carbon atoms having a methyl group as a side chain such as 2,7-dimethyl-1,8-octanediol, 2-methyl-1,9-nonanediol, and 2,8-dimethyl-1,9-nonanediol It is preferable to use one or more aliphatic diols. Particularly, 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, further 30 mol% or more, particularly 50 mol% or more of all polyol components used for the production of polyester polyol. It is preferable to use at a ratio of mol% or more.

  In addition, as the polycarboxylic acid component used in the production of the above-described polyester polyol, 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-methylglutaric acid, 3-methylglutaric acid, trimethyladipic acid, 2-methyloctanedioic acid, 3,8-dimethyldecanedioic acid, 3,7-dimethyl C4-C12 aliphatic dicarboxylic acid such as decanedioic acid; cycloaliphatic dicarboxylic acid such as cyclohexanedicarboxylic acid, dimer acid, hydrogenated dimer acid; aroma such as terephthalic acid, isophthalic acid, orthophthalic acid, naphthalenedicarboxylic acid Group dicarboxylic acids; trifunctional or higher functional groups such as trimellitic acid and pyromellitic acid Valence carboxylic acids; and the like can be illustrated their esters or ester forming derivatives such as their anhydrides, may be used alone or two or more of these. 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.

  Moreover, (epsilon) -caprolactone, (beta) -methyl-delta-valerolactone etc. can be mentioned as said lactone used for manufacture of a polyester polyol.

  Examples of the polyether polyol preferably used for forming the thermoplastic polyurethane (III) include, for example, poly (ethylene glycol), poly (propylene glycol), poly (tetramethylene) obtained by ring-opening polymerization of a cyclic ether. Glycol), poly (methyltetramethylene glycol) and the like, and one or more of these can be used. Of these, poly (tetramethylene glycol) and / or poly (methyltetramethylene glycol) are preferably used.

Examples of the polycarbonate polyol that can be used for forming the thermoplastic polyurethane (III) include those obtained by a reaction between a polyol component and a carbonate compound such as dialkyl carbonate, alkylene carbonate, and diaryl carbonate.
As a polyol component which comprises a polycarbonate polyol, the polyol component illustrated as a structural component of a polyester polyol can be used. Examples of the dialkyl carbonate include dimethyl carbonate and diethyl carbonate. Examples of the alkylene carbonate include ethylene carbonate. Examples of the diaryl carbonate include diphenyl carbonate. Can do.

  Examples of the above-described polyester polycarbonate polyol that can be used for forming the thermoplastic polyurethane (III) include those obtained by simultaneously reacting a polyol component, a polycarboxylic acid component and a carbonate compound, or a polyester polyol and a polycarbonate polyol synthesized in advance. And a compound obtained by reacting a polyester polyol and a polycarbonate polyol synthesized in advance with a polyol component and a polycarboxylic acid component.

  In the presence of a polymerization initiator, a conjugated diene such as butadiene or isoprene, or a conjugated diene and another monomer can be used in the presence of a polymerization initiator as the conjugated diene polymer-based polyol or polyolefin-based polyol that can be used to form the thermoplastic polyurethane (III). Polyisoprene polyol, polybutadiene polyol, poly (butadiene / isoprene) polyol, poly (butadiene / acrylonitrile) polyol, poly (butadiene / styrene) obtained by reacting an epoxy compound with the polymerization active terminal after polymerization by a polymerization method or the like Examples thereof include polyols and hydrogenated products thereof, and one or more of these can be used.

The number average molecular weight of the polymer polyol used to form the thermoplastic polyurethane (III) is 500 to 10,000, more 700～8,000, particularly preferably in the range of 800 to 5,000. By containing a thermoplastic polyurethane (III) produced using a polymer polyol having a number average molecular weight within the above range, the melt moldability, flexibility, mechanical performance, etc. of the thermoplastic polymer composition of the present invention are improved. Excellent characteristics.
In addition, the number average molecular weight of the polymer polyol as used in the present specification is a number average molecular weight calculated based on a hydroxyl value measured in accordance with JIS K-1557.

The polymer polyol used for forming the thermoplastic polyurethane (III) has a number of hydroxyl groups per molecule of 2.0 to 2.1, more preferably 2.0 to 2.05, particularly 2.002 to It is preferably within the range of 2.03. By containing a thermoplastic polyurethane (III) formed using a polymer polyol having a number of hydroxyl groups per molecule within the above range, the melt moldability, flexibility and dynamics of the thermoplastic polymer composition of the present invention Excellent characteristics such as mechanical performance and wear resistance.
In addition, when using a plurality of types of polymer polyols, the number of hydroxyl groups per molecule and the average number of hydroxyl groups per molecule calculated from the amount used (number of moles) are determined per molecule. The number of hydroxyl groups.

  The chain extender used for forming the thermoplastic polyurethane (III) may be any chain extender conventionally used in the production of polyurethane, and among them, an active hydrogen atom capable of reacting with an isocyanate group is contained in the molecule. Two or more low molecular weight compounds having a molecular weight of 400 or less are preferably used.

Examples of the chain extender include ethylene glycol, propylene glycol, 1,4-butanediol, 1,6-hexanediol, 2-methyl-1,3-propanediol, and 2,2-diethyl-1,3-propane. Diol, 2-butyl-2-ethyl-1,3-propanediol, 1,3-butanediol, 2-methyl-1,4-butanediol, neopentyl glycol, 3-methyl-1,5-pentanediol, 2,4-diethyl-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 (β-hydroxyethoxy) benzene, 1, -Cyclohexanediol, bis (β-hydroxyethyl) terephthalate, xylylene glycol, 1,4-cyclohexanedimethanol, 1,4 (or 5) -cyclooctanedimethanol, 3 (or 4), 8 (or 9)- diols such as dihydroxy methyltricyclo (5,2,1,0 ^2,6) decane; hydrazine, ethylenediamine, propylenediamine, xylylenediamine, isophoronediamine, piperazine and its derivatives, phenylenediamine, tolylenediamine, xylylenediamine And diamines such as adipic acid dihydrazide and isophthalic acid dihydrazide; amino alcohols such as aminoethyl 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 1,4-butanediol, 3-methyl-1,5-pentanediol, 2-methyl-1,8-octanediol and 1,9- One or more of nonanediol is more preferably used.
Further, when a thermoplastic polyurethane (III) produced using an aliphatic diol having a number average molecular weight of 100 to 400 having a branch in the molecule is used as a chain extender, the value of the loss factor is large near room temperature, In addition, a thermoplastic polymer composition excellent in vibration damping performance that maintains a large loss factor value over a 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.

Examples of the organic diisocyanate compound used for forming the thermoplastic polyurethane (III) include organic diisocyanate compounds conventionally used in the production of polyurethane, such as 4,4′-diphenylmethane diisocyanate, tolylene diisocyanate, phenylene diisocyanate, xylylene. Aromatic diisocyanates such as diisocyanate, 1,5-naphthylene diisocyanate, 3,3′-dichloro-4,4′-diphenylmethane diisocyanate; hexamethylene diisocyanate, isophorone diisocyanate, 4,4′-dicyclohexylmethane diisocyanate, hydrogenated xyly Aliphatic or alicyclic diisocyanates such as range isocyanate can be used, and one or more of these can be used.
Among them, since the thermoplastic polymer composition of the present invention has excellent melt moldability, flexibility, mechanical performance and the like, thermoplastic polyurethane (III) formed using 4,4′-diphenylmethane diisocyanate (III ) Is preferably contained. Further, a thermoplastic polyurethane (III) formed using an aliphatic or alicyclic diisocyanate is preferably used because of its excellent light resistance.

  In forming the thermoplastic polyurethane (III), the nitrogen atom content derived from the organic diisocyanate compound is 1 to 6.5% by mass 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 in the range of 1 to 6% by mass, particularly 1.3 to 5.5% by mass. By containing 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.

  Further, as the thermoplastic polyurethane (III), the thermoplastic polymer composition of the present invention may have a JIS A hardness of 30 to 99, more preferably 45 to 97, particularly 60 to 95. This is preferable because the melt moldability, flexibility, mechanical performance, etc. of the product become better.

As the thermoplastic polyurethane (III), commercially available products may be used, or those prepared by reacting the above-described polymer polyol, chain extender and organic diisocyanate compound may be used.
In forming the thermoplastic polyurethane (III), the organic diisocyanate compound has an isocyanate group content of 0.9 to 1.3 moles per mole of active hydrogen atoms of the polymer polyol and chain extender. It is preferable to use each component in such a ratio as follows. By containing the thermoplastic polyurethane (III) formed using each component in the above proportion, the melt moldability, flexibility, mechanical performance, etc. of the thermoplastic polymer compositions (i) to (iii) of the present invention The characteristics of this will be better.

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 chain elongation] the total number of moles of agent: [moles] = 1 of the organic diisocyanate compound: 0.98 to 1.04 when containing those formed in the Suyo was satisfy the condition that (molar ratio), the thermoplastic of the present invention When melt molding such as extrusion molding and injection molding is performed using a polymer composition, a sharp increase in melt viscosity does not occur, and products such as target molded products and laminated structures can be produced smoothly. it can.

In the formation of the thermoplastic polyurethane (III), a urethanization reaction catalyst may be used. Examples of the urethanization reaction catalyst include organotin compounds such as dibutyltin diacetate, dibutyltin dilaurate, and dibutyltin bis (3-mercaptopropionic acid ethoxybutyl ester) salt; titanic acid; tetraisopropyl titanate, tetra-n-butyl titanate Organic titanium compounds such as polyhydroxytitanium stearate and titanium acetylacetonate; triethylenediamine, N-methylmorpholine, N, N, N ′, N′-tetramethylethylenediamine, N, N, N ′, N′— Tertiary amine compounds such as tetramethylhexamethylenediamine, triethylamine, and N, N-dimethylaminoethanol can be used, and one or more of these 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, particularly 1 ppm, based on the total mass of the polymer polyol, the chain extender and the organic diisocyanate compound. It is preferable to be within the range of -0.01% by mass.
The urethanization reaction catalyst can be contained in one or more of the polymer polyol, the chain extender, and the organic diisocyanate compound, but is preferably contained in the polymer polyol.

When thermoplastic polyurethane (III) is produced using a urethanization reaction catalyst, it is preferable to add a urethanization reaction catalyst deactivator to the obtained thermoplastic polyurethane (III). Examples of the urethanization catalyst deactivator include lauryl phosphate, oleyl phosphate, stearyl phosphate, dilauryl phosphate, dioleyl phosphate, distearyl phosphate, tris (2-ethylhexyl) phosphate, bis (octadecyl) pentaerythritol diphosphate, Phosphorus compounds such as diethyl phenylphosphonate, diethyl 3,5-di-t-butyl-4-hydroxybenzylphosphonate; 2,2′-methylenebis (4-methyl-6-tert-butylphenol), 2,2 ′ -Methylenebis (4-ethyl-6-t-butylphenol), 2-hydroxy-4-benzyloxybenzophenone, 2- (2'-hydroxy-3 ', 5'-t-butylphenyl) benzotriazole, 2- [2 -Hydroxy-3, -Phenolic compounds such as -bis (α, α-dimethylbenzyl) phenyl] -2H-benzotriazole, 4,4'-octyl-2,2'-biphenol, etc. Among them, phosphorus compounds are preferred. Used.
The amount of the urethanization catalyst deactivator used is 1 ppm to 2% by mass based on the total mass of the polymer polyol, chain extender and organic diisocyanate compound used to form the thermoplastic polyurethane (III), and more preferably 5 ppm to It is preferable to be within a range of 0.2% by mass, particularly 10 ppm to 0.1% by mass.

Moreover, the use ratio of the urethanization reaction catalyst deactivator to the urethanization reaction catalyst is based on 1 mole of metal atoms of the urethanization reaction catalyst when a phosphorus compound is used as the urethanization reaction catalyst deactivator. 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, particularly preferably 0.5 to 100 mol. Moreover, when using a phenol type compound as a urethanization reaction catalyst deactivator, 1-5000 mol as a hydroxyl group of a phenol type compound with respect to 1 mol of metal atoms of a urethanation reaction catalyst, Furthermore, 2-2000 mol In particular, it is preferably used within the range of 5 to 1000 mol.
Urethane reaction catalyst deactivator includes addition polymerization block copolymer (I), block copolymer (II), reaction mixture (IIa) or reaction mixture (IIb), thermoplastic polyurethane (III), Paraffinic oil (IV) and other components as necessary are mixed and melt-kneaded to produce a thermoplastic polymer composition. When the properties of the thermoplastic polymer composition reach desired values Is preferably added from the viewpoints of melt moldability, flexibility, mechanical performance and the like of the thermoplastic polymer composition of the present invention.

  The method for forming the thermoplastic polyurethane (III) is not particularly limited, and any one of the prepolymer method and the one-shot method using a polymer polyol, a chain extender, and an organic diisocyanate compound and utilizing a known urethanization reaction. May be manufactured. Among them, it is preferable to perform melt polymerization in the substantial absence of a solvent, and it is particularly preferable to form the polymer by continuous melt polymerization using a multi-screw extruder.

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

  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 paraffin components (chain hydrocarbons) are used. What contains 80 mass% or more of (chain hydrocarbon) is preferable. The paraffinic oil (IV) may contain a component having an aromatic ring such as a benzene ring or a naphthene ring as another component.

The paraffinic oil (IV) has a kinematic viscosity measured at 40 ° C. of 20 to 800 centistokes [cSt (mm ² / s)], particularly 50 to 600 centistokes [cSt (mm ² / s)]. It is preferable to use those in By using the paraffinic oil (IV) having such a kinematic viscosity, the thermoplastic polymer composition of the present invention has more excellent properties such as melt moldability, flexibility and mechanical performance.
In addition, the kinematic viscosity of the paraffinic oil (IV) referred to in the present specification is a value measured according to JIS K-2283.

In the present invention, it is preferable to use 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 has more excellent properties such as melt moldability, flexibility and mechanical performance.
In addition, the pour point of paraffinic oil (IV) as used in this specification is the value measured based on JIS K-2269.

The flash point of the paraffinic oil (IV) is preferably in the range of 200 to 400 ° C, particularly 250 to 350 ° C. 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 properties such as melt moldability, flexibility and mechanical performance. .
In addition, the flash point of paraffinic oil (IV) as used herein is a value measured in accordance with JIS K-2265.

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

  In the thermoplastic polymer composition (i), when 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), the addition polymerization system The compatibility between the block copolymer (I) and the thermoplastic polyurethane (III) becomes insufficient, making it difficult to obtain a thermoplastic polymer composition having flexibility, mechanical performance and melt moldability. In some cases, products such as molded articles and laminated structures obtained using the thermoplastic polymer composition tend to be prone to surface roughness and lower adhesion between layers. On the other hand, in the thermoplastic polymer composition (i), when the content of the block copolymer (II) exceeds 200 parts by mass with respect to 100 parts by mass of the addition polymerization block copolymer (I), The melt fluidity and melt adhesion of the coalesced 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). It is more preferable that it is contained at a ratio of 20 to 150 parts by mass.

Further, in the thermoplastic polymer composition (i), when 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), the flexibility and dynamics are increased. It is difficult to obtain a thermoplastic polymer composition having mechanical performance and melt moldability, and the compression set of a molded product or a laminated structure obtained from the thermoplastic polymer composition is likely to be increased. The melt adhesion with other materials is lowered, the surface of the molded 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), moldability may be deteriorated. 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), the thermoplastic polymer is melt-molded. The polymer composition tends to adhere to the molding apparatus and tends to cause instability of melt moldability and surface roughness in the molded product.
The thermoplastic polymer composition (i) of the present invention may contain 150 to 800 parts by mass of thermoplastic polyurethane (III) with respect to 100 parts by mass of the addition polymerization type block copolymer (I). More preferably, it is more preferably contained in a proportion of 200 to 700 parts by mass, particularly preferably 350 to 700 parts by mass.

In the thermoplastic polymer composition (i), when 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 block copolymer (I), the thermoplastic polymer There is a tendency that compression set of a molded product or a laminated structure obtained from the composition is increased, or that the surface of the molded product is easily 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 is difficult to melt-mold the product, and the melt adhesion with other materials is lowered, and the mechanical properties such as tensile breaking strength and tensile breaking elongation of the molded product obtained from the thermoplastic polymer composition are reduced, There is a tendency that problems such as roughness of the 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 may contain 50 to 150 parts by mass of paraffinic oil (IV) with respect to 100 parts by mass of the addition polymerization block copolymer (I). More preferably, it is more preferably 75 to 125 parts by mass.

In the production of the thermoplastic polymer composition (i) of the present invention, a block copolymer obtained by reacting an addition polymerization block copolymer (I-1) and a polycarbonate polymer (B-1) ( A reaction product containing IIA) and / or an addition polymerization block copolymer (A-1), a block copolymer (IIB) obtained by reacting a compound having two hydroxyl groups and a carbonate precursor When the reaction product is used as it is, in the reaction product, in addition to the block copolymer (IIA) or the block copolymer (IIB), an unreacted addition polymerization type block copolymer ( A-1), an unreacted polycarbonate polymer (B-1), a polycarbonate formed from a compound having two hydroxyl groups and a carbonate precursor, an aromatic vinyl compound polymer block Sometimes and polycarbonate-based polymer made from a conjugated diene polymer block (B -1) and one or more kinds of components such as the block copolymer having no reactive functional group is contained.
In such a case, the addition polymerization block copolymer (I-1) [corresponding to the addition polymerization block copolymer (I)] contained in the reaction product, the block copolymer (II) In consideration of the amount of polycarbonate polymer (B-1) and the like, addition polymerization block copolymer (I), block copolymer (II), thermoplastic polyurethane (III) in the thermoplastic polymer composition ) And the paraffinic oil (IV) are preferably adjusted so that the content ratio of the reaction product and other components is adjusted so as to be within the above-described preferable range.

  Further, in the thermoplastic polymer compositions (ii) and (iii) of the present invention, the obtained thermoplastic polymer composition has melt moldability, anti-adhesion to a molding machine, flexibility, mechanical properties, etc. From the point that various properties such as melt adhesion to the material are improved, 5 to 5000 parts by mass of the reaction mixture (IIa) and / or (IIb) per 100 parts by mass of the addition polymerization block copolymer (I) [When both reaction mixture (IIa) and reaction mixture (IIb) are used, the total mass of both], 100 to 13600 parts by mass of thermoplastic polyurethane (III) and 10 to 3400 parts by mass of paraffinic oil (IV) It is preferable to use in the ratio.

In the thermoplastic polymer compositions (ii) and (iii), the amount of the reaction mixture (IIa) and / or reaction mixture (IIb) used is 5 with respect to 100 parts by mass of the addition polymerization block copolymer (I). If it is less than part by mass, the compatibility between the addition polymerization block copolymer (I) and the thermoplastic polyurethane (III) becomes insufficient, and the thermoplastic weight excellent in flexibility, mechanical performance and melt moldability is obtained. There is a case where it is difficult to obtain a coalesced composition, and further, a product such as a molded product or a laminated structure obtained by using a thermoplastic polymer composition tends to easily cause surface roughness and lower adhesion between layers. It is in. On the other hand, in the thermoplastic polymer compositions (ii) and (iii), the amount of the reaction mixture (IIa) and / or reaction mixture (IIb) used is 100 parts by mass of the addition polymerization block copolymer (I). When the amount exceeds 5000 parts by mass, the melt fluidity of the thermoplastic polymer composition is lowered and the melt adhesiveness is lowered, and the surface of the molded product is easily roughened. Tend to be.
In the thermoplastic polymer compositions (ii) and (iii), 10 to 450 parts by mass of the reaction mixture (IIa) and / or the reaction mixture (IIb) with respect to 100 parts by mass of the addition polymerization block copolymer (I). More preferably, it is used at a ratio of 20 parts to 300 parts by weight.

In the thermoplastic polymer compositions (ii) and (iii), the amount of the thermoplastic polyurethane (III) used is less than 100 parts by mass with respect to 100 parts by mass of the addition polymerization block copolymer (I). In addition, it is difficult to obtain a thermoplastic polymer composition having flexibility, mechanical performance, and melt moldability, and the compression set of a molded product or a laminated structure obtained from the thermoplastic polymer composition is large. Further, the melt adhesiveness with other materials is lowered, the surface of the molded product is roughened, and the moldability tends to become 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 (iii), when the amount of the thermoplastic polyurethane (III) used exceeds 13600 parts by mass with respect to 100 parts by mass of the addition polymerization block copolymer (I), The thermoplastic polymer composition tends to adhere to the molding apparatus during melt molding, and the melt moldability tends to become unstable and the surface roughness of the molded product tends to occur.
In the thermoplastic polymer compositions (ii) and (iii), the thermoplastic polyurethane (III) should be used at a ratio of 150 to 1500 parts by mass with respect to 100 parts by mass of the addition polymerization block copolymer (I). It is more preferable to use it in the ratio of 200-1100 mass parts, and it is still more preferable to use it in the ratio of 350-1100 mass parts.

In addition, in the thermoplastic polymer compositions (ii) and (iii), the amount of the paraffinic oil (IV) used is less than 10 parts by mass with respect to 100 parts by mass of the addition polymerization block copolymer (I). 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 be rough. On the other hand, in the thermoplastic polymer compositions (ii) and (iii), when the amount of the paraffinic oil (IV) used exceeds 3400 parts by mass with respect to 100 parts by mass of the addition polymerization block copolymer (I), Mechanical properties such as tensile breaking strength and tensile breaking elongation of molded products obtained from thermoplastic polymer compositions, which are likely to be difficult to melt mold thermoplastic polymer compositions, and also have poor melt adhesion to other materials. There is a tendency that problems such as deterioration in performance, roughness of the surface of the molded product, and running out of the spool during molding tend to occur.
In the thermoplastic polymer compositions (ii) and (iii), the paraffinic oil (IV) should be used in a proportion of 50 to 300 parts by mass with respect to 100 parts by mass of the addition polymerization block copolymer (I). Is more preferable, and it is still more preferable to use it in the ratio of 75-200 mass parts.

  The thermoplastic polymer compositions (i) to (iii) of the present invention may contain an olefin polymer (V) as necessary within a range not impairing the effects of the invention. The content of the olefin polymer (V) is preferably 200 parts by mass or less, particularly preferably 0 to 100 parts by mass with respect to 100 parts by mass of the addition polymerization block copolymer (I). By containing the olefin polymer (V), the mechanical strength and melt moldability of the thermoplastic polymer composition may be further improved.

  Examples of the olefin polymer (V) include homopolymers of olefins such as ethylene, propylene and butylene, olefin copolymers composed of two or more of the olefins described above, or one or more of the olefins described above and others. And a copolymer with one or more of these vinyl monomers. Examples of other vinyl monomers in this case include vinyl cyanide monomers such as acrylonitrile and methacrylonitrile; methyl, ethyl, propyl, n-butyl, i-butyl, hexyl of acrylic acid or methacrylic acid Alkyl esters having 1 to 18 carbon atoms such as 2-ethylhexyl, dodecyl and octadecyl; diol esters such as ethylene glycol, propylene glycol and butanediol of acrylic acid or methacrylic acid; 1 to 6 carbon atoms such as acetic acid and propionic acid Vinyl ester of carboxylic acid; unsaturated carboxylic acid such as acrylic acid, methacrylic acid, maleic acid; anhydride of unsaturated dicarboxylic acid such as maleic anhydride; (meth) such as acrylamide, methacrylamide, N, N-dimethylacrylamide Acrylamides; maleimide, N-methyl Maleimide, N- ethylmaleimide, N- phenylmaleimide, N- cyclohexyl N- substituted maleimides such as maleimide; butadiene, a conjugated diene such as isoprene and the like.

  More specifically, examples of the olefin polymer (V) include low density polyethylene, medium density polyethylene, high density polyethylene, polypropylene, polybutylene, ethylene-α-olefin copolymer, and ethylene-vinyl acetate copolymer. , Ethylene-acrylic acid copolymer, ethylene-maleic anhydride copolymer, propylene-acrylic acid copolymer, propylene-maleic anhydride copolymer, isobutylene-maleic anhydride copolymer, and the like. These 1 type (s) or 2 or more types can be used.

  Further, the thermoplastic polymer compositions (i) to (iii) of the present invention may be added within the range not impairing the effects of the present invention, if necessary, by addition polymerization block copolymer (I), block copolymer. Polystyrene ether resin; Thermosetting polyurethane resin; Polyamide resin; Polyester resin; Polyvinyl chloride resin; Polyvinylidene chloride resin; Acrylic resin; Ethylene-vinyl acetate copolymer Ken A copolymer of an aromatic vinyl compound and a vinyl cyanide compound; containing one or more of other polymers such as a copolymer of an aromatic vinyl compound, a vinyl cyanide compound and an olefin compound. Also good.

  The thermoplastic polymer compositions (i) to (iii) of the present invention can contain an inorganic filler as necessary, and the inorganic filler can increase the hardness of the thermoplastic polymer composition of the present invention. It is useful for improving economy 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 one or more of these can be contained. The content of the inorganic filler is preferably 100 parts by mass or less, particularly preferably 0 to 50 parts by mass with respect to 100 parts by mass of the addition polymerization block copolymer (I).

  The thermoplastic polymer compositions (i) to (iii) of the present invention may contain, if necessary, a lubricant, pigment, impact resistance improver, processing aid, crystal nucleating agent, colorant, flame retardant, and weather resistance improver. , UV absorbers, antioxidants, hydrolysis resistance improvers, antifungal agents, antibacterial agents, light stabilizers, antistatic agents, silicone oil, antiblocking agents, mold release agents, foaming agents, fragrances, etc. Agent: One or more of various coupling agents and other optional components can be contained.

  According to the present invention, a thermoplastic polymer composition having a high tensile breaking strength can be obtained. For example, a thermoplastic polymer composition having a tensile strength at break of 8 MPa or more, further 11 MPa or more can be obtained. The tensile strength at break is a value measured in accordance with JIS K-7311 using a thermoplastic polymer composition as a dumbbell-shaped test piece specified in JIS No. 3, and details are given in the examples. This will be explained in the item.

The method for producing the thermoplastic polymer compositions (i) to (iii) of the present invention is not particularly limited and may be produced by any method as long as the above-described constituent components can be uniformly mixed. However, the melt-kneading method is simple and preferably employed.
For example, the thermoplastic polymer compositions (i) to (iii) of the present invention are prepared using a melt kneader such as a single-screw extruder, a twin-screw extruder, a kneader, a mixing roll, or a Banbury mixer. Usually, it can be produced by melt-kneading at a temperature of 150 to 220 ° C. for about 30 seconds to 5 minutes.

Among these, as a method for producing the thermoplastic polymer composition (i), from the viewpoint of reliably producing the thermoplastic polymer composition (i) excellent in melt moldability, flexibility, mechanical performance, etc., the following The method shown in [1] or [2] is preferably employed.
[1] Addition polymerization type block copolymer (I), block copolymer (II) [or the above reaction product containing other components together with the block copolymer (II) {hereinafter referred to as “block copolymer (II) ) Containing reaction product}], polymer polyol, chain extender and organic diisocyanate compound reacted to pre-manufactured thermoplastic polyurethane (III) and paraffinic oil (IV) to mix and knead how to.
[2] Addition polymerization block copolymer (I), block copolymer (II) [or block copolymer (II) -containing reaction product], paraffinic oil (IV), polymer polyol, chain extender And an organic diisocyanate compound are mixed and melt-kneaded.

In the production of the thermoplastic polymer composition (i), the blending order and melt-kneading order of each component are not particularly limited. It can be carried out.
(1) Thermoplastic polyurethane (III) prepared by reacting a polymer polyol, a chain extender and an organic diisocyanate compound, an addition polymerization block copolymer (I), a block copolymer (II) [or block copolymer Combined (II) -containing reaction product] and paraffinic oil (IV) are mixed together and melt-kneaded.
(2) Addition polymerization type block copolymer (I), block copolymer (II) [or block copolymer (II) -containing reaction product], paraffinic oil (IV), polymer polyol, chain extender And an organic diisocyanate compound are mixed together and melt-kneaded.
(3) Block copolymer (II) [or block copolymer (II) -containing reaction product], polymer polyol, chain extender and organic diisocyanate compound are mixed and melt-kneaded. A method in which the 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 polymerization block copolymer (I), block copolymer (II) [or block copolymer (II) -containing reaction product] and paraffinic oil (IV) are mixed and melt-kneaded, A method in which a polymer polyol, a chain extender, and an organic diisocyanate compound are added to the melt-kneaded product and further melt-kneaded.
(5) Addition block copolymer (I), block copolymer (II) [or block copolymer (II) -containing reaction product], polymer polyol, chain extender and organic diisocyanate compound are mixed. After melt-kneading, a paraffinic oil (IV) is added thereto and further melt-kneaded.
(6) A thermoplastic polyurethane obtained by kneading and reacting a polymer polyol, a chain extender and an organic diisocyanate compound is produced, and then an addition polymerization block copolymer (I) and a block copolymer (II) [or a block copolymer Polymer (II) -containing reaction product] is melt kneaded, and paraffinic oil (IV) is further added thereto and melt kneaded.
(7) Addition polymerization type block copolymer (I), 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) Along with thermoplastic polyurethane (III) and block copolymer (II) [or block copolymer (II) -containing reaction product] prepared in advance by reacting a polymer polyol, a chain extender and an organic diisocyanate compound And a method of mixing and melt-kneading a composition comprising a separately prepared addition polymerization block copolymer (I) and paraffinic oil (IV).

Moreover, the thermoplastic polymer composition (ii) of the present invention can be produced by the following method [3].
[3] A method of melt-kneading at least one of addition polymerization block copolymer (I), reaction mixture (IIa) and reaction mixture (IIb), thermoplastic polyurethane (III), and paraffinic oil (IV).
Furthermore, the thermoplastic polymer composition (iii) of the present invention can be produced by the following method [4].
[4] Melt at least one of addition polymerization block copolymer (I), reaction mixture (IIa) and reaction mixture (IIb), polymer polyol, chain extender, organic diisocyanate compound, and paraffinic oil (IV) Kneading method.

  In addition, in the method [4] described above, while the polymer polyol, the chain extender, and the organic diisocyanate compound are reacted to form a thermoplastic polyurethane, the addition polymerization block copolymer (I), A method in which at least one of the reaction mixture (IIa) and the reaction mixture (IIb) and 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 a part of the components are first melt-kneaded and then the remaining components are added to the melt-knead. May be.

The olefin polymer (V), other polymers, inorganic fillers, and other optional components are addition polymerization block copolymer (I), block copolymer (II) or reaction mixture (IIa). The reaction mixture (IIb), the thermoplastic polyurethane (III), and the paraffinic oil (IV) may be added at the time of melt mixing or after the melt mixing.
The optional components are added to the addition polymerization block copolymer (I), the block copolymer (II) or the reaction mixture (IIa) and / or the reaction mixture (IIb), the thermoplastic polyurethane (III), and the paraffinic oil ( In the case of addition at the time of melt mixing of IV), the addition polymerization block copolymer (I), block copolymer (II), reaction mixture (IIa) and / or reaction mixture (IIb), thermoplastic polyurethane (III) In addition, the paraffinic oil (IV) may be supplied separately to the melt kneader and kneaded, or the addition polymerization block copolymer (I), the block copolymer (II) or the reaction mixture (IIa) and / Or may be contained in at least one of the reaction mixture (IIb), the thermoplastic polyurethane (III) and the paraffinic oil (IV) and then supplied to the melt-kneading apparatus and kneaded. .

  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 formed into a pellet, the molded product or a composite molded product. May be used in the manufacture of

The thermoplastic polymer composition of the present invention can be melt-molded and heat-processed. Various molded products can be obtained by any molding method such as extrusion molding, injection molding, press molding, blow molding, calendar molding, and casting. And a composite molded body can be produced smoothly. Thereby, 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 manufactured, 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 part during melt extrusion molding including inflation molding can be greatly reduced. High-quality molded products free from defects such as streaks can be produced with good productivity, and the resulting molded products are excellent in various properties such as flexibility and mechanical performance.
Moreover, when what was formed using aliphatic diisocyanate or alicyclic diisocyanate as thermoplastic polyurethane (III) is used, the molded article which is excellent also in light resistance with the above-mentioned characteristic can be obtained.

Furthermore, the thermoplastic polymer composition of the present invention has high melt adhesion to various materials in addition to the above-described excellent melt moldability, and firmly adheres to various other materials under melting. Therefore, it can be effectively used for the production of a composite molded body with a member made of another material.
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 resins, paper, fabrics, and metals. , Wood, ceramics and the like.

  Among these, 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-vinyl acetate copolymer, polyurethane, polyamide, polyester, polycarbonate, polyphenylene sulfide, polyacrylate, polymethacrylate, polyether, polysulfone, Acrylonitrile / styrene copolymer (AS resin), styrene / maleic anhydride copolymer (SMA resin), rubber-reinforced polystyrene (HIPS resin), acrylonitrile / butadiene / styrene copolymer (ABS resin), methyl methacrylate / styrene Copolymer (MS resin), methyl methacrylate / butadiene / styrene copolymer (MBS resin), vinyl chloride polymer, vinylidene chloride polymer, vinyl chloride / vinyl acetate copolymer, polyvinylidene fluoride phenol Various synthetic resins such as oil and epoxy resin; various synthetic rubbers such as isoprene rubber, butadiene rubber, butadiene-styrene rubber, butadiene-acrylonitrile rubber, chloroprene rubber, butyl rubber, urethane rubber, silicone rubber, fluorine rubber, acrylonitrile rubber; Examples thereof include metals such as iron, aluminum, and copper, and various alloys such as stainless steel, tinplate, and tin.

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. be able to.
Although it is not limited at all, examples of the laminate obtained by using the thermoplastic polymer composition of the present invention include, for example, one layer composed of the thermoplastic polymer composition of the present invention and other materials. A two-layer structure in which one layer is laminated, and a three-layer structure 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 Body, 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 another one Examples thereof include a multilayer structure in which layers of seeds or two or more materials are alternately laminated 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. Further, when the laminate has two or more layers made of the thermoplastic polymer composition of the present invention, the thermoplastic polymer compositions constituting each layer may be the same or different from each other. Also good.

The production method of the composite molded body of the thermoplastic polymer composition of the present invention and other materials is not particularly limited, and any method may be adopted as long as it is a method for producing a composite molded body by melt adhesion. . Among them, in the production of 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 molding methods, coextrusion molding methods, and extrusion coating methods; blow molding methods; calendar molding methods; molding methods involving melting such as press molding methods and melt casting methods can be employed.
Among the molding methods described above, when the insert injection molding method is used, another material previously formed in a predetermined shape and size is inserted into a mold, and the thermoplastic polymer composition of the present invention is inserted therein. Generally, a method of manufacturing a composite molded body by injection molding an object is employed. In this case, the formation method of the other material 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, cutting to a predetermined dimension, press molding, casting, etc. 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 (casting, rolling, cutting, machining, grinding, etc.) is used to obtain a predetermined shape and size It only has to be formed.

In the case of producing a composite molded body by the above-described two-color injection molding method, by using two or more injection devices, after injection molding other materials in the mold, the mold is rotated or moved. The mold cavity is exchanged, and the thermoplastic polymer composition of the present invention is injected into the gap formed between the molded product made of the other material formed by the first injection molding and the second mold wall. A method of forming a composite molded body by 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, another material is first injection molded into the mold to form a molded product, and then the mold is used. In general, a method of producing a composite molded body by enlarging a mold cavity and injection-molding the thermoplastic polymer composition of the present invention therein is generally employed.
Further, 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 article, and then another material (heat A composite molded body may be manufactured by injection molding a plastic resin or the like.

In the case of producing a composite molded body having a layer of the thermoplastic polymer composition of the present invention and a layer of another thermoplastic material by the above-described extrusion molding, the inner and outer sides, the upper side and the lower side, and the left side and the right side Uses a method in which the thermoplastic polymer composition of the present invention and other materials (thermoplastic resin, etc.) are melt-extruded into two or more layers at the same time through a die (extrusion die part, etc.) divided into layers or more. it can. When 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 and laminated on another material in a melt plasticized state or in a solid state. Thus, the intended composite molded body can be produced. 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.

  The composite molded body of the present invention can be used as various industrial products and parts. Specific examples include automotive panels such as instrument panels, center panels, center console boxes, door trims, pillars, and assist grips; automotive exterior parts such as malls; electric tool grips, refrigerator doors, cameras Home appliance parts such as grips, bumpers and hoses for vacuum cleaners, remote control switches and knobs, various key tops for OA equipment; underwater products such as underwater glasses and underwater camera covers; various cover parts; sealing, waterproof, soundproof, Industrial parts with various types of packing for the purpose of vibration proofing; automotive functional parts such as rack and pinion boots, suspension boots, constant velocity joint boots, etc .; electrical and electronic parts such as curled cord wire coverings, belts, hoses, tubes, and silencer gears Sporting goods; synthetic leather; doors, window frames, etc. Building materials; various fittings; valve parts; can be exemplified various products like surgical cast. And in the product in which the layer comprising 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 exhibits a soft and good feel when touched, has shock absorption (cushioning properties), and is excellent in impact resistance, so it is also excellent in terms of safety.

EXAMPLES The present invention will be specifically described below with reference to examples and comparative examples, but the present invention is not limited to the following examples.
In the following examples, the melt viscosity, extrusion moldability, hardness, tensile breaking strength, tensile breaking elongation, and adhesive strength in the laminate of the thermoplastic polymer composition were measured or evaluated by the following methods.

Melt viscosity :
The melt viscosity of the thermoplastic polymer composition dried under reduced pressure (1333.2 Pa or less) at 80 ° C. for 1 hour was measured using a Koka type flow tester (manufactured by Shimadzu Corporation) with a load of 50 kgf and a nozzle size = diameter of 1 mm. × Measured under conditions of length 10 mm and temperature 200 ° C.

Extrudability :
About 3 kg of the thermoplastic polymer composition is obtained from an extruder (25 mmφ, cylinder temperature = 200 to 215 ° C., die temperature = 205 ° C.) equipped with a sheet die (width = 25 mm, thickness = 0.3 mm). During the continuous discharge at the discharge speed of / hour, the deposit (hereinafter referred to as “grease”) adhering to the die part was sampled three times every 20 minutes, and the average mass was measured. As a standard, it was used as an index of extrusion moldability.
A: 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.

Hardness :
Injection molding (cylinder temperature = 180-205 ° C., mold temperature = 35 ° C.) using a mold having a mirror-finished surface, and a disk-shaped molded product (diameter = 120 mm, made of a thermoplastic polymer composition) (Thickness = 2 mm). The obtained molded product was allowed to stand at 23 ° C. for 7 days, and then the JIS A hardness of the molded product was measured according to JIS K-6301 using a laminate of two molded products.

Tensile breaking strength and tensile breaking elongation :
A disk-shaped molded product (diameter = 120 mm, thickness = 2 mm) was manufactured by performing the same operation as in the evaluation of the hardness. The obtained molded product was allowed to stand at 25 ° C. for 7 days, and then punched into a dumbbell mold defined in JIS No. 3 to prepare a test piece. According to JIS K-7311, “Autograph Measuring Device IS” manufactured by Shimadzu -500D "was used to measure tensile break strength and tensile break elongation.

Adhesive strength in laminated structures :
A synthetic resin plate (dimensions: length x width x thickness = 200 mm x 150 mm x 1 mm) is placed in the mold, and an injection molding machine (manufactured by Nissei Plastic Industry Co., Ltd .; 80 ton injection molding machine) is used. A laminate in which a thermoplastic polymer composition is 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 is laminated on one surface of a resin plate (dimensions: length × width) × thickness = 200 mm × 150 mm × 2 mm).
A test piece for measuring peel strength (dimension: length × width × thickness = 80 mm × 25 mm × 2 mm) was cut out from the obtained laminate, and used in accordance with “180 degree peel test” described in JIS K-6854. The peel strength was measured.

  The abbreviations and / or contents of the compounds used in the following Reference Examples, Examples and Comparative Examples, as well as the abbreviations of the synthetic resins constituting the synthetic resin plates used to produce the laminates in the following Examples and Comparative Examples The contents are as follows.

<< Addition polymerization block copolymer (I) >>
SEBS :
Hydrogenated triblock copolymer having a structure of polystyrene block-polybutadiene block-polystyrene block type [manufactured by Kuraray Co., Ltd., “Septon 8006” (trade name), content of structural unit derived from styrene = 33 mass %].
SEEPS-1 :
Hydrogenated product of a triblock copolymer having a polystyrene block-poly (isoprene / butadiene) block-polystyrene block type structure [manufactured by Kuraray Co., Ltd., "Septon 4055" (trade name), a structural unit derived from styrene Content = 30% by mass].

<< Addition polymerization block copolymer (I-1) >>
F-SEEPS :
Hydrogenated product of triblock copolymer having a structure of polystyrene block-poly (isoprene / butadiene) block-polystyrene block type and having a hydroxyl group at one end of the molecule. [Number average molecular weight = 50,000, styrene content = 30 mass%, hydrogenation rate in poly (isoprene / butadiene) block = 98%, ratio of isoprene to butadiene = 50/50 (molar ratio) per molecule Average number of hydroxyl groups = 0.9, total amount of 1,2-bonds and 3,4-bonds in poly (isoprene / butadiene) block = 8 mol%; in the method described in Reference Example 1 of Patent Document 11 Accordingly, styrene, isoprene and butadiene were produced as raw materials. ]
In addition, this F-SEEPS is a block copolymer having a hydroxyl group at one end of the molecule. Hydrogenated product: number average molecular weight = 50,000, styrene content = 30% by mass, hydrogenation rate in poly (isoprene / butadiene) block = 98%, ratio of isoprene to butadiene = 50/50 (molar ratio), poly (Total amount of 1,2-bond and 3,4-bond amount in (isoprene / butadiene) block = 8 mol%) and SEEPS-2 [polystyrene block-poly (block copolymer having no hydroxyl group in the molecule) (Isoprene / Butadiene) block-polystyrene block type structure Hydrogenated block copolymer; number average molecular weight = 50,000, styrene content = 30% by mass, hydrogenation rate in poly (isoprene / butadiene) block = 98%, ratio of isoprene to butadiene = 50/50 ( [SEEPS-OH / SEEPS-2 = 9/1 (molar ratio), containing a total amount of 1,2-bond and 3,4-bond amount in poly (isoprene / butadiene) block = 8 mol%]] ]].

F-HVSIS :
Hydrogenated product of a triblock copolymer having a structure of polystyrene block-polyisoprene block-polystyrene block type and having a hydroxyl group at one end of the molecule.
(Number average molecular weight = 63,000, styrene content = 30% by mass, hydrogenation rate in polyisoprene block = 90%, average number of hydroxyl groups per molecule = 0.8, 1,4-bond in polyisoprene block Amount = 45 mol%, total amount of 1,2-bond and 3,4-bond amount = 55 mol%; manufactured according to the method described in Reference Example 3 of Patent Document 11 using styrene and isoprene as raw materials .)
This F-HVSIS is a block copolymer having a hydroxyl group at one end of the molecule, HVSIS-OH (hydrogenated product of a triblock copolymer having a polystyrene block-polyisoprene block-polystyrene block type structure; Number average molecular weight = 63,000, styrene content = 30% by mass, hydrogenation rate in polyisoprene block = 90%, total amount of 1,2-bond and 3,4-bond amount in polyisoprene block = 55 mol% ) And HVSIS [polystyrene block-polyisoprene block-polyblock block hydrogenated structure having a hydroxyl group in the molecule; number average molecular weight = 63,000, Styrene content = 30% by mass in the polyisoprene block Iodized rate = 90%, the total amount of 1,2-bond and 3,4-bond content in the polyisoprene block = 55 mol%) containing [HVSIS-OH / HVSIS = 8/2 (molar ratio)].

SEPS :
Hydrogenated triblock copolymer having a structure of polystyrene block-polyisoprene block-polystyrene block type and having no hydroxyl group in the molecule [manufactured by Kuraray Co., Ltd., "Septon 2002" (trade name), styrene Content of structural unit derived = 30% by mass, MFR = 70 g / 10 min, JIS A hardness = 80].

<< Polycarbonate polymer (B-1) >>
PC :
Polycarbonate [manufactured by Teijin Chemicals Ltd., “Panlite L-1225” (trade name), viscosity average molecular weight = 22,500].

<< Thermoplastic polyurethane (III) >>
TPU-1 :
Polyester-based thermoplastic polyurethane [Kuraray Co., Ltd., “Cramiron U8165” (trade name), poly (3-methyl-1,5-pentanediol adipate) as a soft segment, 1,4-butanediol and 4,4 Polyester thermoplastic polyurethane having a segment made of '-diphenylmethane diisocyanate (MDI) as a hard segment; logarithmic viscosity (measured in DMF solvent at a concentration of 0.5 g / dl at 30 ° C.) = 1.09 dl / g, JIS A hardness = 65].

<Polymer polyol>
POH-1 :
A polyester diol produced by reacting 3-methyl-1,5-pentanediol and adipic acid and having a number of hydroxyl groups per molecule 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 having a number of hydroxyl groups per molecule of 2.00 (number average molecular weight = 2,000).

《Chain extender》
BD : 1,4-butanediol.

<Organic diisocyanate compound>
MDI : 4,4′-diphenylmethane diisocyanate.

《Paraffin oil (IV)》
PL : Paraffinic oil [manufactured by Idemitsu Kosan Co., Ltd., “Diana Process PW-380” (trade name), kinematic viscosity (40 ° C.): 382 cSt, pour point: −15 ° C., flash point: 300 ° C.].

《Synthetic resin (other materials) constituting the synthetic resin plate used for manufacturing the laminated structure》
ABS : Acrylonitrile-butadiene-styrene copolymer resin (manufactured by Nippon Synthetic Rubber Co., Ltd., “JSR ABS12” (trade name)).

<< Reference Example 1 >>
[Production of Composition Containing Block Copolymer (II) (PC-SEEPS Compound E1)]
(1) 600 parts by mass of a block copolymer (F-SEEPS), 400 parts by mass of a polycarbonate polymer (PC) and 0.4 parts by mass of a catalyst (dibutyltin oxide) are premixed, and the resulting mixture is coaxially arranged. rotating twin-screw extruder [30mmφ, L / D = 36; plastics Engineering Research Laboratory, "BT-30" (trade name)] using, under the conditions of cylinder temperature 275 ° C. and a screw rotation speed of 150rpm The resulting reaction mixture (melt) was continuously extruded into water as a strand, and then cut with a pelletizer to obtain pellets. The obtained pellet was dehumidified and dried at 80 ° C. for 12 hours to obtain a composition (PC-SEEPS Compound E1) containing the block copolymer (II). The melt viscosity of this composition (PC-SEEPS Compound E1) was 890 Pa · s.
(2) Dumbbell No. 1 type by injection molding (cylinder temperature = 200-220 ° C., mold temperature = 30 ° C.) using the composition (PC-SEEPS Compound E1) obtained in (1) above. A molded product having a thickness of 3 mm was manufactured. The molded article had a JIS A hardness of 80, and the tensile fracture strength measured according to JIS K-7113 (test speed = 5 mm / min, distance between chucks = 110 mm) was 17 MPa.

<< Reference Example 2 >>
[Production of Composition Containing Block Copolymer (II) (PC-SEEPS Compound E2)]
(1) 350 parts by mass of a block copolymer (F-SEEPS), 650 parts by mass of a polycarbonate polymer (PC) and 0.4 parts by mass of a catalyst (dibutyltin oxide) are premixed, and the resulting mixture is coaxially rotating twin-screw extruder [30mmφ, L / D = 36; plastics Engineering Research Laboratory, "BT-30" (trade name)] using, under the conditions of cylinder temperature 275 ° C. and a screw rotation speed of 150rpm The resulting reaction mixture (melt) was continuously extruded into water as a strand, and then cut with a pelletizer to obtain pellets. The obtained pellet was dehumidified and dried at 80 ° C. for 12 hours to obtain a composition (PC-SEEPS Compound E2) containing the block copolymer (II). The melt viscosity of this composition (PC-SEEPS Compound E2) was 630 Pa · s.
(2) Dumbbell No. 1 type by injection molding (cylinder temperature = 200-220 ° C., mold temperature = 30 ° C.) using the composition (PC-SEEPS Compound E2) obtained in (1) above. A molded article having a thickness of 3 mm was manufactured. The molded article had a JIS A hardness of 97, and had a tensile strength at break of 33 MPa as measured according to JIS K-7113 (test speed = 5 mm / min, distance between chucks = 110 mm).

<< Reference Example 3 >>
[Production of Composition Containing Block Copolymer (II) (PC-HVSIS Compound E3)]
(1) 500 parts by mass of a block copolymer (F-HVSIS), 500 parts by mass of a polycarbonate polymer (PC) and 0.4 parts by mass of a catalyst (dibutyltin oxide) are premixed, and the resulting mixture is coaxially arranged. rotating twin-screw extruder [30mmφ, L / D = 36; plastics Engineering Research Laboratory, "BT-30" (trade name)] using, under the conditions of cylinder temperature 275 ° C. and a screw rotation speed of 150rpm The resulting reaction mixture (melt) was continuously extruded into water as a strand, and then cut with a pelletizer to obtain pellets. The obtained pellet was dehumidified and dried at 80 ° C. for 12 hours to obtain a composition (PC-HVSIS Compound E3) containing a block copolymer (II). The melt viscosity of this composition (PC-HVSIS Compound E3) was 610 Pa · s.
(2) Dumbbell No. 1 type by injection molding (cylinder temperature = 200-220 ° C., mold temperature = 30 ° C.) using the composition (PC-HVSIS Compound E3) obtained in (1) above. A molded product having a thickness of 3 mm was manufactured. The molded article had a JIS A hardness of 80, and the tensile fracture strength measured according to JIS K-7113 (test speed = 5 mm / min, distance between chucks = 110 mm) was 14 MPa.

<< Reference Example 4 >>
[Production of composition not containing block copolymer (II) (PC / SEEPS Compound))
(1) A twin-screw type extruder [30 mmφ, L / L] in which 600 parts by mass of a block copolymer (SEPS) and 400 parts by mass of a polycarbonate-based polymer (PC) are premixed and the resulting mixture is rotated in the coaxial direction. D = 36; plastics Engineering Research Laboratory, using "BT-30" (trade name)], and melt-kneaded under the conditions of cylinder temperature 275 ° C. and a screw rotation speed of 150 rpm, the resulting reaction mixture (molten The product 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). The melt viscosity of this composition (PC / SEEPS Compound) was 54 Pa · s.
(2) By using the composition (PC / SEEPS Compound) obtained in (1) above, injection molding (cylinder temperature = 200 to 220 ° C., mold temperature = 30 ° C.) allows dumbbell No. 1 type ( A molded article having a thickness of 3 mm was manufactured. The JIS A hardness of the molded product was 89, and the tensile strength at break measured by JIS K-7113 (test speed = 5 mm / min, distance between chucks = 110 mm) was 8 MPa.

Example 1
(1) Polymer polyol containing 10 ppm of urethanization reaction catalyst (tetraisopropyl titanate) [mixture of POH-1 and POH-3, POH-1 / POH-3 = 30/70 (molar ratio) per molecule Average number of hydroxyl groups = 2.00], chain extender (BD) and organic diisocyanate compound (MDI), molar ratio of polymer polyol: BD: MDI = 1.0: 1.1: 2.1 (containing nitrogen atom) The rate is 1.9% by mass), and the total supply amount thereof is 140 g / min [the amount in which the content of the thermoplastic polyurethane (III) in the thermoplastic polymer composition is 70% by mass]] in the coaxial direction. Continuously feeding to the front of the heating zone of a rotating twin screw extruder (30 mmφ, L / D = 36, heating zone divided into three zones: front, center, and rear). Continuous melt weight In was carried out polyurethane-forming reaction.
(2) At the same time as (1) above, a mixture of block copolymer (SEBS) and paraffinic oil (PL) [SEBS: PL = 1: 1 (mass ratio)] is supplied at a rate of 40 g / min [thermoplastic weight The composition (PC-SEEPS) having the block copolymer (II) obtained in Reference Example 1 in such a manner that the SEBS content in the coalescence composition is 10% by mass and the PL content is 10% by mass]. Compound E1) at a feed rate of 20 g / min (the amount in which the content of PC-SEEPS Compound E1 in the thermoplastic polymer composition is 10% by mass), the heating zone of the twin screw extruder of (1) above Are continuously fed to a twin screw extruder (30 mmφ, L / D = 36, heated at 190 ° C.) connected to the center of the melt and kneaded, and the resulting melt is continuously put into water in a strand form. Extrusion was followed by cutting with a pelletizer, and the pellets were dehumidified and dried at 70 ° C. for 4 hours to obtain a thermoplastic polymer composition 1.
(3) With respect to 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, and as shown in Table 1 below. there were.
Moreover, when the laminated structure was manufactured by the above-described method using the thermoplastic polymer composition 1 and ABS, and the adhesive strength of the obtained laminated structure was measured by the above-described method, it is shown in Table 1 below. It was as follows.

Example 2
(1) Polymer polyol containing 15 ppm of urethanization reaction catalyst (tetraisopropyl titanate) [mixture of POH-2 and POH-3; POH-2 / POH-3 = 1/99 (molar ratio); Average number of hydroxyl groups = 2.01], chain extender (BD), and organic diisocyanate compound (MDI), molar ratio of polymer polyol: BD: MDI = 1.0: 1.03: 2.03 (containing nitrogen atom) And the total supply amount thereof is 130 g / min (the amount of the thermoplastic polyurethane (III) in the thermoplastic polymer composition is 65% by mass), which rotates in the coaxial direction. Is continuously fed to a twin screw type extruder (30 mmφ, L / D = 36, the heating zone is divided into three zones: front, center, and rear) The urethane formation reaction was carried out.
(2) Simultaneously with the above (1), a supply amount of a block copolymer (SEEPS-1) and a paraffinic oil (PL) mixture [SEEPS-1: PL = 1: 1 (mass ratio)] at 50 g / min. (The amount of SEEPS-1 in the thermoplastic polymer composition is 12.5% by mass, the amount of PL is 12.5% by mass), and the block copolymer obtained in Reference Example 2 ( II) at a feed rate of 20 g / min (PC-SEEPS Compound E2) (in which the content of PC-SEEPS Compound E2 in the thermoplastic polymer composition is 10% by mass) (1) ) Was continuously supplied to a twin screw extruder (30 mmφ, L / D = 36, 190 ° C. heating) connected to the center of the heating zone of the twin screw extruder. Subsequently, 0.05 mass% (feed amount = 0.125 g / min) of the urethanization reaction catalyst deactivator (distearyl phosphate) was added to the rear part of the above twin screw extruder, and the resulting melt was obtained. Was extruded into water in the form of strands, cut with a pelletizer, and the pellets were dehumidified and dried at 70 ° C. for 4 hours to obtain a thermoplastic polymer composition 2.
(3) With respect to 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. there were.
Moreover, when the laminated structure was manufactured 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-described method, it is shown in Table 1 below. It was as follows.

Example 3
(1) Polymer polyol containing 10 ppm of urethanization reaction catalyst (tetraisopropyl titanate) [mixture of POH-1 and POH-2; POH-1 / POH-2 = 98.5 / 1.5 (molar ratio); Average number of hydroxyl groups per molecule = 2.015], chain extender (BD) and organic diisocyanate compound (MDI), molar ratio of polymer polyol: BD: MDI = 1.0: 2.4: 3.4 (Nitrogen atom content = 2.1% by mass), and the total supply amount thereof is 120 g / min (the amount of thermoplastic polyurethane (III) in the thermoplastic polymer composition is 60% by mass) in the coaxial direction. Is continuously fed to a twin screw extruder (30 mmφ, L / D = 36, heating zone is divided into three zones: front, center and rear), and polyurethane is melted at 260 ° C. form The reaction was carried out.
(2) Simultaneously with the above (1), a supply amount of a mixture of block copolymer (SEEPS-1) and paraffinic oil (PL) [SEEPS-1: PL = 1: 1 (mass ratio)] at 60 g / min. (The amount of SEEPS-1 in the thermoplastic polymer composition is 15% by mass and the amount of PL is 15% by mass) and the block copolymer (II) obtained in Reference Example 3 in compositions with the supply amount of (PC-HVSIS compound E3) a 20 g / min (amount of content of the PC-HVSIS C ompound E3 of the thermoplastic polymer composition is 10 mass%), the above (1) This was continuously supplied 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 urethanization reaction catalyst deactivator (distearyl phosphate) (feed amount = 0.075 g / min) was added to the rear part of the above twin screw extruder, and the resulting melt was obtained. Was extruded into water in the form of strands, cut with a pelletizer, and the pellets were dehumidified and dried at 70 ° C. for 4 hours to obtain a thermoplastic polymer composition 3.
(3) With respect to the thermoplastic polymer composition 3 obtained in ( 2 ) above, the melt viscosity, hardness, tensile breaking strength, and tensile breaking elongation were measured by the methods described above, and as shown in Table 1 below. there were.
Moreover, when the laminated structure was manufactured by the above-described method using the thermoplastic polymer composition 3 and ABS, and the adhesive strength of the obtained laminated structure was measured by the above-described method, it is shown in Table 1 below. It was as follows.

<< Comparative Example 1 >>
(1) Polymer polyol containing 10 ppm of urethanization reaction catalyst (tetraisopropyl titanate) [mixture of POH-1 and POH-3; POH-1 / POH-3 = 30/70 (molar ratio)], chain extender (BD) and the organic diisocyanate compound (MDI) are polymer polyol: BD: MDI molar ratio = 1.0: 1.1: 2.1 (nitrogen atom content is 1.9 mass%), and these A twin screw extruder (30 mmφ, L) rotating in the coaxial direction at a total feed rate of 125 g / min [amount in which the content of thermoplastic polyurethane (III) in the thermoplastic polymer composition is 50% by mass) / D = 36, the heating zone was divided into three zones of the front, the center and the rear), and the polyurethane formation reaction was carried out by continuous melt polymerization at 260 ° C.
(2) Simultaneously with the above (1), a mixture of block copolymer (SEBS) and paraffinic oil (PL) [SEBS: PL = 1: 1 (mass ratio)] is supplied at 125 g / min (thermoplastic weight). The amount of SEBS in the coalesced composition is 25% by mass and the amount of PL is 25% by mass), which is connected to the central part of the heating zone of the twin screw extruder of (1) above. Continuously feeding to an axial screw type extruder (30 mmφ, L / D = 36, heating at 220 ° C.), the obtained melt was continuously extruded into water in a strand form, and then cut with a pelletizer. A thermoplastic polymer composition C-1 was obtained by dehumidifying and drying at 70 ° C. for 4 hours.
(3) The thermoplastic polymer composition C-1 obtained in (2) above was measured for melt viscosity, hardness, tensile breaking strength, and tensile breaking elongation by the methods described above, and the results are shown in Table 1 below. It was as follows.
Furthermore, using the thermoplastic polymer composition C-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 shown in.

<< Comparative Example 2 >>
(1) Supply amount of block copolymer (SEBS) and paraffinic oil (PL) [SEBS: PL = 1: 1 (mass ratio)] at 60 g / min (SEBS in thermoplastic polymer composition) A content of 15% by mass and an amount of PL of 15% by mass), and a feed amount of thermoplastic polyurethane (TPU-1) of 120 g / min [a thermoplastic polyurethane in a thermoplastic polymer composition (III ) Content of 60% by mass], and a supply amount of 20 g / min of the block copolymer composition (PU / SEEPS Compound) obtained in Reference Example 4 (in the thermoplastic polymer composition). PU / SEEPS Compound content is 10% by mass), which is supplied to a twin screw extruder (30 mmφ, L / D = 36) rotating in the same direction and melt-kneaded at 220 ° C. Melting Objects in the water continuously extruded in a strand form and then cut by a pelletizer to obtain a thermoplastic polymer composition C-2 by the pellets for 4 hours dehumidified and dried at 70 ° C..
(2) With respect to the thermoplastic polymer composition C-2 obtained in (1) above, the melt viscosity, hardness, tensile breaking strength, and tensile breaking elongation were measured by the methods described above, and the results are shown in Table 1 below. It was as follows.
Furthermore, using the thermoplastic polymer composition C-2 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 in.

As shown in Table 1 above, an addition polymerization block comprising a hydrogenated product of a block copolymer having an aromatic vinyl compound polymer block (a-1) and a conjugated diene polymer block (b-1) Addition polymerization block comprising a hydrogenated product of block copolymer having copolymer (I), aromatic vinyl compound polymer block (a-2) and conjugated diene polymer block (b-2) ) And a polycarbonate copolymer block (b) -containing block copolymer (II), thermoplastic polyurethane (III) and paraffinic oil (IV), the thermoplastic polymer composition of the present invention of Examples 1-3 When the product is melt-extruded, the adherence of the extrudate to the die portion (the amount of grease) is extremely small and excellent in extrusion moldability. Moreover, the molded articles obtained from the thermoplastic polymer compositions of Examples 1 to 3 are excellent in mechanical properties such as tensile breaking strength and tensile breaking elongation, and are further strongly melt bonded to the ABS resin plate. Yes.
On the other hand, the thermoplastic resin of Comparative Example 1 containing the addition polymerization block copolymer (I), the thermoplastic polyurethane (III) and the paraffinic oil (IV) and not containing the block copolymer (II). Comparative example containing a polymer composition and the addition polymerization block copolymer (I), thermoplastic polyurethane (III), paraffinic oil (IV) and polycarbonate, but not the block copolymer (II) All of the thermoplastic polymer compositions of No. 2 are inferior to extrusion molding because of large adhesion of the extrudate to the die portion (amount of grease) when melt extrusion molding is performed. Moreover, the molded articles obtained from the thermoplastic polymer compositions of Comparative Examples 1 and 2 have low tensile fracture strength and poor mechanical properties, and also poor melt adhesion with the ABS resin plate. .

The thermoplastic polymer composition of the present invention is excellent in melt moldability, and particularly when melt extrusion molding including inflation molding is performed, adherence of extrudate (amount of grease) to a die portion of an extrusion molding machine. High quality molded products can be manufactured 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 has excellent properties such as light resistance, and also has excellent melt adhesion with other materials. Utilizing these properties, it can be applied to various products such as electrical products, synthetic leather, and automobile-related equipment. It can be effectively used for producing a film-like material, a sheet-like material, a hose-like material, a tube-like material, and the like.

Claims (11)

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) comprising a hydrogenated product thereof 100 mass Per part;
A block copolymer having an aromatic vinyl compound polymer block (a-2) and a conjugated diene polymer block (b-2) or an addition polymerization block (i) comprising a hydrogenated product thereof and a polycarbonate polymer 5 to 200 parts by mass of the block copolymer (II) having a block (b) ;
100 to 800 parts by weight of the thermoplastic polyurethane (III); and,
10-200 parts by weight of paraffinic oil (IV) ;
A thermoplastic polymer composition characterized by comprising: The thermoplastic polymer composition according to claim 1, wherein the block copolymer (II) is at least one of the following block copolymer (IIA) and block copolymer (IIB).
Block copolymer (IIA) :
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 reacting with a polycarbonate polymer (b-1) A block copolymer prepared by reacting an addition polymerization block copolymer (A-1) having a functional group capable of being reacted with a polycarbonate polymer (RO-1) under melt kneading.
Block copolymer (IIB) :
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 reacting with a polycarbonate polymer (b-1) Block copolymer prepared by reacting a compound having two functional groups (i-1), a compound having two hydroxyl groups, and a carbonate precursor under melt kneading.   The thermoplastic polymer composition according to claim 2, wherein the block copolymer (IIA) and the block copolymer (IIB) are prepared by reacting in the presence of a catalyst under melt kneading. 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) comprising a hydrogenated product thereof, hereinafter The thermoplastic resin according to claim 1, which is obtained by melt-kneading at least one of the reaction mixture (IIa) and the reaction mixture (IIb), thermoplastic polyurethane (III), and paraffinic oil (IV). Polymer composition.
Reaction mixture (IIa) :
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 reacting with a polycarbonate polymer (b-1) A reaction mixture obtained by reacting an addition polymerization block copolymer (A-1) having a functional group capable of undergoing reaction with a polycarbonate polymer (RO-1) under melt kneading.
Reaction mixture (IIb) :
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 reacting with a polycarbonate polymer (b-1) A reaction mixture obtained by reacting an addition polymerization block copolymer having a functional group (i-1), a compound having two hydroxyl groups, and a carbonate precursor under melt kneading. 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) comprising a hydrogenated product thereof, hereinafter at least one of the reaction mixture (IIa) and the reaction mixture (IIb) in claim 1 polymer polyol, a chain extender, organic diisocyanate, and is obtained by melt kneading a paraffin oil (IV) The thermoplastic polymer composition described in 1 .
Reaction mixture (IIa) :
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 reacting with a polycarbonate polymer (b-1) A reaction mixture obtained by reacting an addition polymerization block copolymer (A-1) having a functional group capable of undergoing reaction with a polycarbonate polymer (RO-1) under melt kneading.
Reaction mixture (IIb) :
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 reacting with a polycarbonate polymer (b-1) A reaction mixture obtained by reacting an addition polymerization block copolymer having a functional group (i-1), a compound having two hydroxyl groups, and a carbonate precursor under melt kneading. The thermoplastic polymer composition according to any one of claims 2 to 5 , wherein the functional group capable of reacting with the polycarbonate polymer in the addition polymerization block copolymer (I-1) is a hydroxyl group. The thermoplastic polymer composition according to claim 6 , wherein the addition polymerization block copolymer (A-1) has an average of 0.6 or more hydroxyl groups per molecule per terminal. The thermoplastic polyurethane (III) is a reaction raw material for forming a thermoplastic polyurethane comprising a polymer polyol, a chain extender and an organic diisocyanate compound, and the content of nitrogen atoms derived from the organic diisocyanate compound is high. It is a thermoplastic polyurethane formed using the reaction raw material which is 1-6.5 mass% based on the total mass of an extending | stretching agent and an organic diisocyanate compound, The any one of Claims 1-4, 6 and 7 Thermoplastic polymer composition. The thermoplastic polymer according to any one of claims 1 to 8 , wherein a tensile strength at break measured in accordance with JIS K-7311 is 8 MPa or more as a dumbbell-shaped test piece defined in JIS No. 3. Composition. A molded article comprising the thermoplastic polymer composition according to any one of claims 1 to 9 . A composite molded body comprising the thermoplastic polymer composition according to any one of claims 1 to 9 and another material.