JP2005082675A - Flame-retardant thermoplastic polymer composition - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a thermoplastic polymer composition having sufficiently achieved flame retardancy without using a flame retardant. <P>SOLUTION: The thermoplastic polymer composition having flame retardancy of UL94 HB or a higher rating comprises (i) an addition-polymerized block copolymer (I) composed of an aromatic vinyl compound-based polymer block (a-1) and a conjugated diene-based polymer block (b-1), or a hydrogenated product thereof, (ii) a block copolymer (II) having an addition-polymerized block (a) comprising a block copolymer having an aromatic vinyl compound-based polymer block (a-2) and a conjugated diene-based polymer block (b-2), or a hydrogenated product thereof, and a polyurethane block (b), (iii) a thermoplastic polyurethane (III) having ≥0.9 dl/g logarithmic viscosity, and (iv) a paraffin-based oil (IV). <P>COPYRIGHT: (C)2005,JPO&NCIPI

Description

  The present invention relates to a thermoplastic polymer composition having flame retardancy, low hardness and excellent melt moldability. The thermoplastic polymer composition of the present invention is non-tacky and excellent in handleability, and exhibits good melt adhesion to other materials. Therefore, it is effective for the production of various molded products by taking advantage of these properties. used.

  A block copolymer having a styrene polymer block and a conjugated diene polymer block (hereinafter sometimes referred to as “styrene / conjugated diene block copolymer”) and its hydrogenated product are plasticized and melted by heating. Various types of so-called thermoplastic elastomers (thermoplastic elastomers) have been developed in recent years because they can be easily molded, have rubber elasticity at room temperature, and have an excellent balance between flexibility and mechanical properties. Widely used in the field.

Styrene / conjugated diene block copolymer and its hydrogenated product are low-polarity materials, and can be melt-bonded or melt-integrated with the same type of low-polarity plastics. It is difficult to melt and bond.
JP-A-52-150464 (Patent Document 1) describes a composition in which a styrene / conjugated diene block copolymer or a hydrogenated product thereof is blended with a thermoplastic resin having specific physical properties. In this publication, it is disclosed that the composition is particularly suitable as an insulator for a conductor and a wire for soldering, and that a thermoplastic polyurethane is used as one of the thermoplastic resins. However, since the styrene / conjugated diene block copolymer or its hydrogenated product and the thermoplastic polyurethane are incompatible, 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 styrene / conjugated diene block copolymers or hydrogenated products thereof have been proposed in the past. As such conventional techniques, styrene / conjugated diene block copolymer A heat-fusible composition in which a thermoplastic polyurethane is blended with a coalescence or a hydrogenated product thereof is known [JP-A-6-65467 (Patent Document 2), JP-A-6-107898 (Patent Document 3). And Japanese Patent Laid-Open No. 8-72204 (Patent Document 4)]. However, when these heat-fusible compositions are used, there are cases where sufficient adhesive strength may not be obtained depending on the type of material to be laminated with the composition, or there is no sustainability of adhesive strength. Moreover, in these heat-fusible compositions, it cannot be said that the compatibility between the styrene / conjugated diene block copolymer or the hydrogenated product thereof and the thermoplastic polyurethane is sufficiently good. In the laminated molded product obtained by the above, problems such as delamination and adhesive force variation are likely to occur.

  For the purpose of improving the compatibility between the styrene / conjugated diene block copolymer or its hydrogenated product and the thermoplastic polyurethane, and improving the melt adhesion of the composition containing both polymers, the carboxylic acid or its A composition in which a styrene / conjugated diene block copolymer modified with a derivative group, a hydroxyl group, or the like or a hydrogenated product thereof is blended with a thermoplastic polyurethane has been proposed [Japanese Patent Laid-Open No. 63-99257 (Patent Document 5). And JP-A-3-234755 (Patent Document 6)]. Furthermore, in the above-described composition, there has also been proposed a composition containing a phosphorus compound or a phenol compound for the purpose of improving the thermal stability during processing [see JP-A-7-126474 (Patent Document 7). ]. However, satisfactory results have not yet been obtained, and it is insufficient in terms of non-adhesiveness, melt moldability (such as melt retention stability), and melt adhesion when laminated with other resins.

  In order to solve these problems, in JP-A-11-323073 (Patent Document 8), (1) a block copolymer having an aromatic vinyl compound polymer block and a conjugated diene block or a hydrogenated product thereof (2) A block copolymer having a block copolymer having an aromatic vinyl compound polymer block and a conjugated diene polymer block or an addition polymerization block (i) comprising the hydrogenated product and a polyurethane block (b) Compositions comprising coalesced, (3) thermoplastic polyurethane and (4) paraffinic oil have been proposed. This thermoplastic polymer composition is a composition that is flexible, has good elasticity, and can be firmly and easily melt-bonded to various hard materials.

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

In recent years, the range of use of various elastomers including a styrene / conjugated diene block copolymer has been expanded, and accordingly, higher performance has been demanded. For example, when used in the automotive industry or the electronic / electrical industry, a material having flame retardancy is desirable from the viewpoint of safety. As a method for achieving flame retardancy, a flame retardant represented by inorganic compounds such as halogen-containing compounds such as bromine and chlorine, aluminum hydroxide, magnesium hydroxide, and antimony trioxide is generally used. However, it is desirable not to use flame retardants as much as possible because of concerns such as the possibility of adverse effects on the survival of living organisms and the environment.
The present invention has been made in view of such circumstances, and is a thermoplastic polymer composition that achieves sufficient flame retardancy without using a flame retardant, and has low hardness and excellent melt moldability. It is an object of the present invention to provide a thermoplastic polymer composition.

In the course of studying the composition described in Japanese Patent Application Laid-Open No. 11-323073, the present inventor can set the logarithmic viscosity of the thermoplastic polyurethane contained in the composition to a high level to obtain a flame retardant. As a result of obtaining and further studying the unexpected knowledge that a composition having sufficient flame retardancy can be obtained without using the present invention, the present invention has been completed.
That is, the present invention provides (i) an addition polymerization system comprising a block copolymer having an aromatic vinyl compound polymer block (a-1) and a conjugated diene polymer block (b-1) or a hydrogenated product thereof. Block copolymer (I), (ii) Addition comprising block copolymer having aromatic vinyl compound polymer block (a-2) and conjugated diene polymer block (b-2) or hydrogenated product thereof A block copolymer (II) having a polymerization block (A) and a polyurethane block (B), (iii) a thermoplastic polyurethane (III) having a logarithmic viscosity of 0.9 dl / g or more, and (iv) a paraffinic oil ( A thermoplastic polymer composition comprising IV) and having a flame retardancy of UL94HB grade or higher is provided.

  ADVANTAGE OF THE INVENTION According to this invention, the thermoplastic polymer composition which achieved sufficient flame retardance without using a flame retardant is provided. The thermoplastic polymer composition of the present invention is low in hardness and excellent in melt moldability and melt adhesion to various materials, and can be used effectively for the production of various molded products.

The addition polymerization block copolymer (I) used in the present invention is a block copolymer having an aromatic vinyl compound polymer block (a-1) and a conjugated diene polymer block (b-1) or its It consists of at least one selected from hydrogenated products.
The block copolymer (II) used in the present invention is a block copolymer having an aromatic vinyl compound polymer block (a-2) and a conjugated diene polymer block (b-2) or its hydrogen. It is a block copolymer having an addition polymerization block (A) and polyurethane block (B) made of an additive.

  Aromatic vinyl compound polymer block (a-1) in addition polymerization block copolymer (I), and aromatic vinyl compound polymer block in addition polymerization block (a) of block copolymer (II) Examples of the aromatic vinyl compound constituting (a-2) include styrene, α-methylstyrene, β-methylstyrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, and 2,4-dimethylstyrene. 2,4,6-trimethylstyrene, 4-propylstyrene, t-butylstyrene, 4-cyclohexylstyrene, 4-dodecylstyrene, 2-ethyl-4-benzylstyrene, 4- (phenylbutyl) styrene, 1-vinyl Naphthalene, vinylanthracene, indene, acetonaphthylene, monofluorostyrene, difluoros Ren, mention may be made of monochloro styrene, aromatic vinyl compounds such as methoxystyrene. The aromatic vinyl compound-based polymer blocks (a-1) and (a-2) may be composed of one kind of aromatic vinyl compound, or composed of two or more kinds of aromatic vinyl compounds. Also good. The aromatic vinyl compound polymer blocks (a-1) and (a-2) are preferably composed mainly of structural units derived from styrene and / or α-methylstyrene.

  Aromatic vinyl compound-based polymer blocks (a-1) and (a-2) contain a small amount of structural units composed of other copolymerizable monomers as needed together with structural units composed of aromatic vinyl compounds. You may do it. The content of structural units composed of other copolymerizable monomers is preferably 30% by weight or less based on the weight of the aromatic vinyl compound polymer block (a-1) or (a-2). More preferably, it is 10% by weight or less. Examples of other copolymerizable monomers include 1-butene, pentene, hexene, butadiene, 2-methyl-1,3-butadiene (isoprene), methyl vinyl ether, and the like.

  The conjugated diene polymer block (b-1) in the addition polymerization block copolymer (I) and the conjugated diene polymer block (b) in the addition polymerization block (b) of the block copolymer (II) -2) includes 1,3-butadiene, 2-methyl-1,3-butadiene (isoprene), 2,3-dimethyl-1,3-butadiene, 1,3-pentadiene, , 3-hexadiene and the like. The conjugated diene polymer blocks (b-1) and (b-2) may be composed of one type of conjugated diene compound or may be composed of two or more types 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 partially Any of block shape may be sufficient, and also they may be mixed.

  The conjugated diene polymer block (b-1) and / or (b-2) may be not hydrogenated, partially hydrogenated, or entirely hydrogenated. The hydrogenation rate of the conjugated diene polymer block (b-1) and / or (b-2) is preferably 50 mol% or more from the viewpoint of heat resistance, weather resistance and light resistance, and 60 mol. % Or more is more preferable, and it is further more preferable that it is 80 mol% or more.

  In particular, when obtaining a thermoplastic polymer composition excellent in flexibility, mechanical performance and melt moldability, the conjugated diene polymer block (b-1) in the addition polymerization block copolymer (I) and The conjugated diene polymer block (b-2) in the addition polymerization block (b) of the block copolymer (II) may be hydrogenated, mayoprene polymer block, or hydrogenated. It is preferably at least one polymer block selected from a butadiene polymer block and a copolymer block of isoprene and butadiene which may be hydrogenated.

  Bonding form of the aromatic vinyl compound polymer block (a-1) and the conjugated diene polymer block (b-1) in the addition polymerization block copolymer (I), and the block copolymer (II) The bond form of the aromatic vinyl compound polymer block (a-2) and the conjugated diene polymer block (b-2) in the addition polymerization block (a) is not particularly limited, and is linear, branched, Either a radial form or a combined form in which they are combined may be used, but a linear combined form is preferable.

The addition polymerization block (a) of the addition polymerization block copolymer (I) and / or the block copolymer (II) is the above aromatic vinyl compound polymer block (a-1) and (a-2). ) (Hereinafter, both may be represented by X), and conjugated diene polymer blocks (b-1) and (b-2) (hereinafter, both may be represented by Y), The structure includes the formula: (XY) _m -X, (XY) _n , Y- (XY) _p (wherein m, n and p each represent an integer of 1 or more), etc. The form of the block copolymer represented by these can be mentioned. Among these, the diblock copolymer represented by the formula: XY or the triblock copolymer represented by the formula: XYX in terms of flexibility, mechanical performance, melt moldability, and the like. It is preferably in the form, and more preferably in the form of a triblock copolymer represented by the formula: X—Y—X.
Further, the form of the triblock copolymer has a high impregnation ability (oil retention ability) of the paraffinic oil (IV) and is preferable from the viewpoint of preventing migration of the paraffinic oil (IV).

  When the addition polymerization block (a) of the addition polymerization block copolymer (I) and / or the block copolymer (II) contains two or more aromatic vinyl compound polymer blocks X, aromatic vinyl The compound-based polymer block may be a polymer block having the same content, or may be a polymer block having different content. In addition, when the addition polymerization block (a) of the addition polymerization block copolymer (I) and / or the block copolymer (II) contains two or more conjugated diene polymer blocks Y, the conjugated diene The polymer blocks having the same contents may be used, or the polymer blocks having different contents may be used. 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 content of the structural unit derived from the aromatic vinyl compound in the addition polymerization block (a) of the addition polymerization block copolymer (I) and / or block copolymer (II) It is preferable that it is 5 to 90 weight% with respect to all the structural units which comprise addition polymerization type | system | group block (a) of unification (I) and / or block copolymer (II). The content of the structural unit derived from the addition polymerization block copolymer (I) or the aromatic vinyl compound in which the content of the structural unit derived from the aromatic vinyl compound is within the above range is within the above range. When a certain block copolymer (II) is used, a thermoplastic polymer composition excellent in flexibility, mechanical performance and melt moldability can be obtained. The content of the structural unit derived from the aromatic vinyl compound in the addition polymerization block (a) of the addition polymerization block copolymer (I) and the block copolymer (II) is both within the above range. Is desirable.

  The content of the structural unit derived from the aromatic vinyl compound in the addition polymerization block (a) of the addition polymerization block copolymer (I) and / or block copolymer (II) It is more preferably 10 to 90% by weight, and more preferably 20 to 80% by weight, based on all structural units constituting the addition polymerization system block (a) of the union (I) and / or the block copolymer (II). More preferably.

  The number average molecular weight of the aromatic vinyl compound polymer block (a-1) and the conjugated diene polymer block (b-1) in the addition polymerization block copolymer (I) is not particularly limited. The number average molecular weight of the aromatic vinyl compound polymer block (a-1) is in the range of 2,500 to 125,000 in the state before hydrogenation, and the conjugated diene polymer block (b-1). Is preferably in the range of 10,000 to 250,000. An addition polymerization block copolymer (I) comprising an aromatic vinyl compound polymer block (a-1) or a conjugated diene polymer block (b-1) having a number average molecular weight within the above range By using it, a thermoplastic polymer composition having more excellent flexibility, mechanical performance, melt moldability and the like can be obtained.

  Moreover, it is preferable that the whole number average molecular weights of addition polymerization type block copolymer (I) are in the range of 15,000-500,000 in the state before hydrogenation. By using the addition polymerization block copolymer (I) having such a number average molecular weight, it is possible to obtain a thermoplastic polymer composition excellent in various properties such as flexibility, mechanical performance and melt moldability. it can. The number average molecular weight of the addition polymerization block copolymer (I) is more preferably in the range of 80,000 to 400,000. In addition, the number average molecular weight of addition polymerization type block copolymer (I) as used in this specification is the value measured by gel permeation chromatography (GPC) in standard polystyrene conversion.

  The number average molecular weights 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) are: Although not particularly limited, the number average molecular weight of the aromatic vinyl compound polymer block (a-2) is in the range of 2,500 to 75,000 in the state before hydrogenation, and the conjugated diene type The number average molecular weight of the polymer block (b-2) is preferably in the range of 10,000 to 150,000. A block containing an addition polymerization block (A) composed of an aromatic vinyl compound polymer block (a-2) or a conjugated diene polymer block (b-2) having a number average molecular weight within the above range. By using the copolymer (II), a thermoplastic polymer composition having more excellent flexibility, mechanical performance, melt moldability and the like can be obtained.

  Moreover, it is preferable that the whole number average molecular weight of the addition polymerization type | system | group block (a) of block copolymer (II) exists in the range of 15,000-300,000 in the state before hydrogenation. By using the block copolymer (II) containing the addition polymerization block (a) having such a number average molecular weight, a thermoplastic weight excellent in various properties such as flexibility, mechanical performance and melt moldability is obtained. A coalescence composition can be obtained. The number average molecular weight of the addition polymerization block (A) is more preferably in the range of 20,000 to 100,000.

  The addition polymerization block copolymer (I) preferably has a melt flow rate (MFR) measured at 230 ° C. under a load of 2.16 kg within a range of 10 g / 10 min or less. By using the addition polymerization block copolymer (I) having such a melt flow rate (MFR), a thermoplastic polymer composition excellent in various properties such as flexibility, mechanical performance and melt moldability can be obtained. Can be obtained. The melt flow rate (MFR) of the addition polymerization block copolymer (I) measured at 230 ° C. under a load of 2.16 kg is more preferably 5 g / 10 min or less, and 3 g / 10 min or less. More preferably. In addition, the melt flow rate (MFR) of the addition polymerization type block copolymer (I) as used in the present specification is a value measured in accordance with ASTM D-1238.

  Moreover, it is preferable that the JIS A hardness of addition polymerization type block copolymer (I) exists in the range of 30-95. By using the addition polymerization block copolymer (I) having such JIS A hardness, a thermoplastic polymer composition excellent in various properties such as flexibility, mechanical performance and melt moldability can be obtained. it can. The JIS A hardness of the addition polymerization block copolymer (I) is more preferably in the range of 40 to 90, and still more preferably in the range of 50 to 85. In addition, the JIS A hardness of the addition polymerization block copolymer (I) referred to in the present specification is a value measured in accordance with JIS K-6253.

  The block copolymer (II) used in the present invention is a block copolymer containing the above addition polymerization block (A) and polyurethane block (B). In the block copolymer (II), the bond form of the addition polymerization block (a) and the polyurethane block (b) is not particularly limited, and may be any of linear, branched, radial, or a combination form in which they are combined. Although it may exist, it is preferable that it is a linear bond form.

  The structure of the block copolymer (II) is represented by the formula: α-β, α-β-α, β- when the above addition polymerization block (A) is represented by α and the polyurethane block (B) is represented by β. Although it can take various forms such as α-β, an α-β type diblock structure is preferable. By using the diblock type block copolymer (II), a thermoplastic polymer composition having more excellent flexibility, mechanical performance, melt moldability and the like can be obtained.

  When the block copolymer (II) contains two or more addition polymerization blocks (A), the addition polymerization blocks (A) may be blocks having the same contents or different blocks. There may be. Further, when the block copolymer (II) contains two or more polyurethane blocks (b), the polyurethane blocks (b) may be blocks having the same contents or different blocks. Good. For example, two α [addition polymerization block (A)] in a triblock structure represented by α-β-α, or two β [polyurethane blocks in a triblock structure represented by β-α-β (B)] may be the same or different in the types of structural units constituting them, the bonding type, the number average molecular weight, and the like.

  The weight ratio of the addition polymerization block (A) to the polyurethane block (B) in the block copolymer (II) is as follows: addition polymerization block (A) / polyurethane block (B) = 5/95 to 95/5 The addition polymerization block (A) / polyurethane block (B) is more preferably within the range of 10/90 to 90/10, and the addition polymerization block (A) / polyurethane block. (B) More preferably, it is within the range of 20/80 to 80/20, and particularly within the range of addition polymerization system block (a) / polyurethane block (b) = 30/70 to 70/30. preferable.

The polyurethane block (b) in the block copolymer (II) is a block composed of a polymer polyol, a chain extender and an organic diisocyanate compound.
Examples of the polymer polyol constituting the polyurethane block (b) include polyester polyol, polyether polyol, polycarbonate polyol, polyester polycarbonate polyol, polyolefin polyol, conjugated diene polymer polyol, castor oil polyol, silicone polyol, and vinyl polymerization. A systemic polyol etc. can be mentioned. One type of these polymer polyols may be used, or two or more types may be used in combination. Among these, the polymer polyol is preferably one or more of polyester polyol, polyether polyol, and polyolefin polyol, and more preferably polyester polyol and / or polyether polyol.

The polyester polyol can be produced, for example, by subjecting the polyol component and the polycarboxylic acid component directly to an esterification reaction or transesterification reaction, or by ring-opening polymerization of a lactone using the polyol component as an initiator.
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 -Polyhydric alcohols having 3 or more hydroxyl groups per molecule such as hexanetriol, pentaerythritol, and diglycerin. In the production of the polyester polyol, one kind of these polyol components may be used, or two or more kinds may be used in combination.
Among these, in the production of the polyester polyol, 2-methyl-1,4-butanediol, 3-methyl-1,5-pentanediol, 2-methyl-1,8-octanediol, 2,7-dimethyl An aliphatic diol having 5 to 12 carbon atoms having a methyl group as a side chain, such as -1,8-octanediol, 2-methyl-1,9-nonanediol, and 2,8-dimethyl-1,9-nonanediol; It is preferable to use it as a polyol component. In particular, it is preferable to use an aliphatic diol having 5 to 12 carbon atoms having a methyl group as a side chain in a proportion of 30 mol% or more of the total polyol component used in the production of the polyester polyol, and 50 mol% of the total polyol component. It is more preferable to use at the above ratio.

  The polycarboxylic acid component used in the production of the polyester polyol includes polycarboxylic acid components generally used in the production of polyester, such as succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, and 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-dimethyldecanediate Aliphatic dicarboxylic acids having 4 to 12 carbon atoms such as acids; cycloaliphatic dicarboxylic acids such as cyclohexanedicarboxylic acid, dimer acid and hydrogenated dimer acid; aromatic dicarboxylic acids such as terephthalic acid, isophthalic acid, orthophthalic acid and naphthalenedicarboxylic acid Acid; Trifunctional or higher polyvalent cal such as trimellitic acid and pyromellitic acid Phosphate; and ester forming derivatives such as their esters or their anhydrides can be exemplified. These polycarboxylic acid components may be used alone or in combination of two or more. Among these, aliphatic dicarboxylic acids having 6 to 12 carbon atoms, in particular, one or more of adipic acid, azelaic acid, and sebacic acid are preferable 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 include poly (ethylene glycol), poly (propylene glycol), poly (tetramethylene glycol), poly (methyltetramethylene glycol) and the like obtained by ring-opening polymerization of a cyclic ether. Can do. As the polyether polyol, one type may be used, or two or more types may be used in combination. Of these, poly (tetramethylene glycol) and / or poly (methyltetramethylene glycol) are preferred.

Examples of the polycarbonate polyol 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 polyester polycarbonate polyol described above include those obtained by reacting a polyol component, a polycarboxylic acid component and a carbonate compound simultaneously, or those obtained by reacting a polyester polyol and a polycarbonate polyol synthesized in advance with a carbonate compound. Examples thereof include those obtained by reacting a polyester polyol and a polycarbonate polyol synthesized in advance with a polyol component and a polycarboxylic acid component.

  The conjugated diene polymer-based polyol or polyolefin-based polyol described above is obtained by polymerizing a conjugated diene such as butadiene or isoprene, or a conjugated diene and another monomer in the presence of a polymerization initiator by a living polymerization method, and the like. Polyisoprene polyols, polybutadiene polyols, poly (butadiene / isoprene) polyols, poly (butadiene / acrylonitrile) polyols, poly (butadiene / styrene) polyols, or hydrogenated products thereof obtained by reacting an epoxy compound with be able to. As the conjugated diene polymer-based polyol or polyolefin-based polyol, one type may be used, or two or more types may be used in combination.

The number average molecular weight of these polymer polyols is preferably in the range of 500 to 10,000. By using the block copolymer (II) having a polyurethane block (b) made of a polymer polyol having such a number average molecular weight, it is excellent in various properties such as the above-mentioned flexibility, mechanical performance and melt moldability. A thermoplastic polymer composition can be obtained with certainty. The number average molecular weight of the polymer polyol is more preferably in the range of 700 to 8,000, and still more preferably in the range of 800 to 5,000.
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-1577.

  Examples of the chain extender constituting the polyurethane block (b) include chain extenders conventionally used in the production of polyurethane, but the molecular weight having two or more active hydrogen atoms capable of reacting with an isocyanate group in the molecule. A low molecular compound of 400 or less is preferable.

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 Diamines such as adipic acid dihydrazide and isophthalic acid dihydrazide; and amino alcohols such as aminoethyl alcohol and aminopropyl alcohol. One type of these chain extenders may be used, or two or more types may be used in combination. Of these, aliphatic diols having 2 to 12 carbon atoms are preferable as the chain extender, and 1,4-butanediol, 3-methyl-1,5-pentanediol, 2-methyl-1,8-octane are preferable. A diol, 1,9-nonanediol is more preferable.
In addition, when an aliphatic diol having a branch in the molecule and having a number average molecular weight of 100 to 400 is used as a chain extender, the loss factor value is large near room temperature and a large loss factor value is maintained over a wide temperature range. A thermoplastic polymer composition having excellent vibration damping performance can be obtained. The aliphatic diol having such a branch in the molecule is preferably an aliphatic diol having 5 to 12 carbon atoms having a methyl group as a side chain.

  The organic diisocyanate compound constituting the polyurethane block (b) may be an organic diisocyanate compound conventionally used in the production of polyurethane, for example, 4,4′-diphenylmethane diisocyanate, tolylene diisocyanate, phenylene diisocyanate, xylylene diisocyanate. Aromatic diisocyanates such as 1,5-naphthylene diisocyanate and 3,3′-dichloro-4,4′-diphenylmethane diisocyanate; hexamethylene diisocyanate, isophorone diisocyanate, 4,4′-dicyclohexylmethane diisocyanate, hydrogenated xylylene diisocyanate And aliphatic or alicyclic diisocyanates. One type of organic diisocyanate compound may be used, or two or more types may be used in combination. Among these, 4,4'-diphenylmethane diisocyanate is preferable as the organic diisocyanate compound.

  Regarding the proportion of the above-mentioned polymer polyol, chain extender and organic diisocyanate compound in the polyurethane block (b), the nitrogen atom content derived from the organic diisocyanate compound is the total weight of the polymer polyol, chain extender and organic diisocyanate compound. It is preferably within the range of 1 to 6.5% by weight. By using a block copolymer (II) having a polyurethane block (B) in which the nitrogen atom content falls within such a range, various properties such as the above-described flexibility, mechanical performance, and melt moldability are more excellent. A thermoplastic polymer composition can be obtained. The nitrogen atom content derived from the organic diisocyanate compound is more preferably in the range of 1 to 6% by weight based on the total weight of the polymer polyol, the chain extender and the organic diisocyanate compound, and 1.3 to 5.5 More preferably, it is in the range of% by weight, and particularly preferably in the range of 1.6-5% by weight.

  The number average molecular weight of the polyurethane block (b) is preferably in the range of 200 to 300,000. Thermoplastics with superior properties such as flexibility, mechanical performance and melt moldability by using block copolymer (II) with polyurethane block (b) within the range of number average molecular weight A polymer composition can be obtained. The number average molecular weight of the polyurethane block (b) is more preferably in the range of 500 to 150,000, and still more preferably in the range of 1,000 to 100,000.

  In addition, the hardness of the polyurethane block (b) is preferably in the range of 30 to 99 when expressed by the JIS A hardness of the polyurethane corresponding to the block. By using the block copolymer (II) having the polyurethane block (b) having such hardness, a thermoplastic polymer composition having various properties such as flexibility, mechanical performance and melt moldability is obtained. be able to. The JIS A hardness of the polyurethane corresponding to the polyurethane block (b) is more preferably in the range of 45 to 97, and still more preferably in the range of 60 to 95.

The production method of the addition polymerization block copolymer (I) and the block copolymer (II) is not particularly limited, and any method can be used as long as it can form the above structure. Also good.
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, or a radical polymerization method. In the case of the anionic polymerization method, for example, an aromatic vinyl compound and a conjugated diene compound are sequentially polymerized in an inert organic solvent such as n-hexane or cyclohexane using an alkyl lithium compound as a polymerization initiator, After producing a block copolymer having a molecular structure and a 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 an 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, dimethylpropio By adding a lactone compound such as lactone (pivalolactone) or 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.

  The block copolymer (II) has, for example, a structure corresponding to the addition polymerization block (A) and forms a polyurethane block (B) (organic diisocyanate compound, chain extender, polymer polyol, etc.) A block copolymer having a functional group capable of reacting with, that is, an aromatic vinyl compound polymer block (a-2) and a conjugated diene polymer block (b-2), and a polyurethane block (b) A polyurethane-forming reaction is carried out in the presence of a block copolymer having a functional group capable of reacting with the component to be formed or a hydrogenated product thereof (hereinafter sometimes abbreviated as a functional group-containing block copolymer). It can be produced by forming a polyurethane block (b) on the main chain of the block copolymer. The block copolymer (II) can also be produced by reacting a functional group-containing block copolymer with a polyurethane corresponding to the polyurethane block (b).

Examples of the functional group that can react with the component that forms the polyurethane block (b) of the functional group-containing block copolymer include a group that can react with a polymer polyol and / or a chain extender, such as a carboxyl group, an acid An anhydride group, a thiocarboxyl group, an isocyanate group, and the like, and examples of a group capable of reacting with an organic diisocyanate compound include a hydroxyl group, an amino group, a mercapto group, a carboxyl group, an acid anhydride group, a thiocarboxyl group, and an isocyanate group. It is done. The functional group-containing block copolymer may contain two or more of these functional groups.
As the functional group possessed by the functional group-containing block copolymer, a functional group capable of reacting with an organic diisocyanate compound is preferable, and since a uniform polyurethane forming reaction can be performed in the production of the block copolymer (II), a hydroxyl group is more preferred. preferable.

  Moreover, it is preferable that the functional group which can react with the component which forms the polyurethane block (b) in a functional group containing block copolymer is located in the terminal of this functional group containing block copolymer. When a functional group-containing block copolymer having such a functional group at the terminal is used, the functional group is involved in the main chain extension by the polyurethane forming reaction when the block copolymer (II) is produced. When the block copolymer (II) thus obtained is used, a thermoplastic polymer composition excellent in various properties such as flexibility, mechanical performance and melt moldability can be reliably obtained.

  The number of functional groups capable of reacting with the component forming the polyurethane block (b) in the functional group-containing block copolymer is preferably 0.6 or more on an average per molecule of the functional group-containing block copolymer, It is more preferable that it is 0.7 or more, and it is more preferable that it exists in the range of 0.7-1.

A functional group containing block copolymer has a functional group in a molecule | numerator among said addition polymerization type block copolymer (I), and can be manufactured by the said method. The functional group-containing block copolymer has an aromatic vinyl compound polymer block and a conjugated diene polymer block, and a block copolymer having no functional group as described above, depending on the production process. Can be included.
As the functional group-containing block copolymer, a commercially available one can be used.

The number average molecular weight of the functional group-containing block copolymer is preferably in the range of 15,000 to 300,000, and more preferably in the range of 20,000 to 100,000. In addition, the number average molecular weight of a functional group containing block copolymer is the value measured by gel permeation chromatography (GPC) in standard polystyrene conversion.
Moreover, it is preferable that the melt flow rate (MFR) measured under 230 degreeC and 2.16kg load of the functional group containing block copolymer exists in the range of 0.01-100 g / 10min. By using the block copolymer (II) prepared from the functional group-containing block copolymer having such a melt flow rate, a thermoplastic polymer having excellent physical properties such as flexibility, mechanical performance and melt moldability A composition can be obtained. It is more preferable that the melt flow rate (MFR) of the functional group-containing block copolymer measured at 230 ° C. under a load of 2.16 kg is in the range of 0.05 to 80 g / 10 minutes. The melt flow rate of the functional group-containing block copolymer is a value measured according to ASTM D-1238.

  In forming the polyurethane block (ii), the organic diisocyanate compound has 0.9 to 1.3 moles of an isocyanate group per mole of active hydrogen atoms that the polymer polyol and chain extender have. It is preferable to use each component in such a ratio as follows. By using the block copolymer (II) having a polyurethane block (B) obtained by using a polymer polyol, a chain extender and an organic diisocyanate compound in the above proportion, flexibility, mechanical performance and melt molding It is possible to obtain a thermoplastic polymer composition having more excellent various properties such as properties.

  In forming the polyurethane block (b), the nitrogen atom content derived from the organic diisocyanate compound is in the range of 1 to 6.5% by weight based on the total weight of the polymer polyol, the chain extender and the organic diisocyanate compound. It is preferable to use each component in an inner ratio. By using the block copolymer (II) having a polyurethane block (B) obtained by using a polymer polyol, a chain extender and an organic diisocyanate compound in the above proportion, flexibility, mechanical performance and melt molding It is possible to obtain a thermoplastic polymer composition having more excellent various properties such as properties. The nitrogen atom content derived from the organic diisocyanate compound is more preferably in the range of 1 to 6% by weight based on the total weight of the polymer polyol, the chain extender and the organic diisocyanate compound, and 1.3 to 5.5 More preferably, it is in the range of% by weight, and particularly preferably in the range of 1.6-5% by weight.

  The block copolymer (II) can be produced by (A) a functional group-containing block copolymer, a polymer polyol, a chain extender and an organic diisocyanate compound, or (B) a polymer polyol or chain extension. Any method of reacting a reaction product of an agent and an organic diisocyanate compound with a functional group-containing block copolymer is simple and preferred.

  The reaction product in the method (B) may be a reaction mixture of a polymer polyol, a chain extender and an organic diisocyanate compound, or may be a product obtained by post-treating the reaction mixture according to a conventional method. Moreover, as long as it is formed from a polymer polyol, a chain extender, and an organic diisocyanate compound, a commercially available polyurethane can be used as the reaction product. The reaction product of the polymer polyol, the chain extender, and the organic diisocyanate compound is an unreacted polymer polyol or chain depending on the amount of each component used, the reaction rate, other reaction conditions, etc. In some cases, it may contain an extender and an organic diisocyanate compound. In that case, the reaction between the polyurethane formed from the polymer polyol, the chain extender and the organic diisocyanate compound and the functional group of the functional group-containing block copolymer, In addition, the reaction of the functional groups of the polymer polyol, the chain extender, the organic diisocyanate compound, and the functional group-containing block copolymer proceeds.

When the block copolymer (II) is produced by the method (A) above, the ratio of the functional group-containing block copolymer, the polymer polyol, the chain extender and the organic diisocyanate compound is as follows:
[Weight of functional group-containing block copolymer]: [Weight of polymer polyol + weight of chain extender + weight of organic diisocyanate compound] = preferably within the range of 5:95 to 95: 5, the same weight The ratio is more preferably within the range of 10:90 to 90:10, further preferably within the range of 20:80 to 80:20, and preferably within the range of 30:70 to 70:30. Particularly preferred.
Moreover, when manufacturing block copolymer (II) by the method of said (B), the ratio of the reaction product of a high molecular polyol, a chain extender, and an organic diisocyanate compound, and a functional group containing block copolymer,
[Weight of functional group-containing block copolymer]: [Weight of reaction product of polymer polyol, chain extender and organic diisocyanate compound] = preferably within the range of 5:95 to 95: 5, and the same weight ratio Is more preferably in the range of 10:90 to 90:10, more preferably in the range of 20:80 to 80:20, and particularly preferably in the range of 30:70 to 70:30. preferable.

  In the production of the block copolymer (II), a urethanization reaction catalyst may be used. Examples of such a urethanization reaction catalyst include organotin compounds such as dibutyltin diacetate, dibutyltin dilaurate, 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, N, N-dimethylaminoethanol and the like can be mentioned.

  The amount of the urethanization reaction catalyst used is the total weight of the functional group-containing block copolymer, polymer polyol, chain extender and organic diisocyanate compound, or the reaction product and functional group of polymer polyol, chain extender and organic diisocyanate compound. It is preferably within the range of 0.1 ppm to 0.2% by weight, more preferably within the range of 0.5 ppm to 0.02% by weight, based on the total weight of the containing block copolymer. More preferably, it is within the range of 0.01% by weight.

  In the production of the block copolymer (II), the urethanization reaction catalyst is composed of functional group-containing block copolymer, polymer polyol, chain extender, organic diisocyanate compound, or polymer polyol, chain extender and organic diisocyanate compound. Although it can be contained in one or more of the reactants, it is preferably contained in the polymer polyol.

  Moreover, when using a urethanation reaction catalyst in manufacture of block copolymer (II), it is preferable to add a urethanation reaction catalyst deactivator with respect to obtained block copolymer (II). 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 3,5-bis (alpha, alpha-dimethylbenzyl) phenyl] -2H- benzotriazole, 4,4'-octyl-2,2'-but phenolic compounds such as biphenol and the like, phosphorus-based compounds are preferable.

The amount of urethanization catalyst deactivator used is the total weight of functional group-containing block copolymer, polymer polyol, chain extender and organic diisocyanate compound, or the reaction product of polymer polyol, chain extender and organic diisocyanate compound. Is preferably in the range of 1 ppm to 2% by weight, more preferably in the range of 5 ppm to 0.2% by weight, based on the total weight of the functional group-containing block copolymer. More preferably, it is in the range of% by weight.
In addition, the content ratio of the urethanization reaction catalyst and the urethanization reaction catalyst deactivator is based on the amount of metal atom per mole of the urethanization reaction catalyst when a phosphorus compound is used as the urethanization reaction catalyst deactivator. More preferably, it is used in the range of 0.1 to 500 mol as the phosphorus atom of the phosphorus compound, more preferably in the range of 0.2 to 200 mol, and in the range of 0.5 to 100 mol. Is most preferably used. Moreover, when using a phenolic compound for a urethanization reaction catalyst deactivator, it should be used within a range of 1 to 5000 moles as a hydroxyl group of the phenolic compound per mole of metal atoms of the urethanization reaction catalyst. Is more preferable, it is more preferable to use within the range of 2 to 2000 mol, and most preferable to use within the range of 5 to 1000 mol.

  The block copolymer (II) can be produced by using a known polyurethane forming reaction technique, and may be carried out by any of the prepolymer method and the one-shot method.

  The block copolymer (II) is preferably produced substantially in the absence of a solvent, and is produced by melt kneading using a melt kneading apparatus such as a single screw extruder, a twin screw extruder, a kneader, or a Banbury mixer. It is preferable to do. The kneading conditions can be appropriately selected according to the type of raw material to be used, the type of apparatus, etc., but in general, it is preferable to carry out at a temperature of 180 to 260 ° C. for about 1 to 15 minutes.

Specific examples of the polyurethane forming reaction that can be adopted include the following methods [1] to [8].
[1] A functional group-containing block copolymer, a polymer polyol, and a chain extender are mixed and heated to, for example, 40 to 100 ° C., and the resulting mixture is mixed with moles of active hydrogen atoms and isocyanate groups in the mixture. A method in which the organic diisocyanate compound is added in an amount such that the ratio is preferably 1: 0.9 to 1.3 and stirred for a short time, and then heated to 80 to 200 ° C., for example.
[2] A functional group-containing block copolymer, a polymer polyol, a chain extender and an organic diisocyanate compound are mixed in such an amount that the molar ratio of active hydrogen atoms to isocyanate groups is preferably 1: 0.9 to 1.3. For example, a method of kneading while reacting at a high temperature of 180 to 260 ° C.
[3] A polymer polyol, a chain extender, and an organic diisocyanate compound are continuously supplied to an extruder such as a multi-screw extruder, and heated to 90 to 260 ° C., for example, and active hydrogen atoms in the reaction system The functional group-containing block copolymer is continuously fed in an amount such that the molar ratio of the isocyanate group to the isocyanate group is preferably 1: 0.9 to 1.3, and for example, continuous melt polymerization is performed at a high temperature of 180 to 260 ° C. Method.
[4] A functional group-containing block copolymer, a polymer polyol, a chain extender and an organic diisocyanate compound are added to an extruder such as a multi-screw extruder, and the molar ratio of active hydrogen atoms to isocyanate groups is preferably 1: A method in which continuous melt polymerization is carried out at a high temperature of 180 to 260 ° C., for example, by continuously supplying in an amount of 0.9 to 1.3.
[5] A polymer polyol, a chain extender, and an organic diisocyanate compound are continuously supplied to an extruder such as a multi-screw extruder, and heated to 90 to 260 ° C. to form a polyurethane. A method in which a functional group-containing block copolymer is mixed and subjected to continuous melt polymerization at a high temperature of, for example, 180 to 260 ° C.
[6] After kneading the polymer polyol, the chain extender, and the organic diisocyanate compound at a high temperature of, for example, 180 to 260 ° C. to form polyurethane, the functional group-containing block copolymer is mixed, for example, And kneading while reacting at a high temperature of 180 to 260 ° C.
[7] A method in which a functional group-containing block copolymer and polyurethane (commercially available product) are continuously supplied to an extruder such as a multi-screw extruder, and reacted at a high temperature of 180 to 260 ° C., for example.
[8] The functional group-containing block copolymer, the polymer polyol, the chain extender, and the organic diisocyanate compound in an amount such that the molar ratio of the active hydrogen atom to the isocyanate group is preferably 1: 0.9 to 1.3, A method of performing a urethanization reaction in an organic solvent in addition to the organic solvent.

The functional group-containing block copolymer, the polymer polyol, the chain extender and the organic diisocyanate compound, or the reaction product of the polymer polyol, the chain extender and the organic diisocyanate compound and the functional group-containing block copolymer are reacted by the above method. In addition to the block copolymer (II), an unreacted functional group-containing block copolymer and an unreacted polymer are obtained. It may contain a polyol, an unreacted chain extender and an unreacted organic diisocyanate compound. These contents vary depending on the reaction conditions such as the ratio of raw materials used in the reaction and the reaction temperature.
The block copolymer composition may contain a polyurethane formed from a polymer polyol, a chain extender and an organic diisocyanate compound. Furthermore, the block copolymer composition has an aromatic vinyl compound-based polymer block and a conjugated diene-based polymer block, and has no functional group. Corresponding polymer).

The block copolymer (II) is, for example, pulverized to an appropriate size, if necessary, and then treated with a good polyurethane solvent such as dimethylformamide. The polyurethane formed from the polymer polyol, the chain extender and the organic diisocyanate compound, which did not react with the functional group-containing block copolymer (if present in the block copolymer composition), Next, the polymer is treated with a good solvent for the functional group-containing block copolymer such as cyclohexane, and the polymer corresponding to the unreacted functional group-containing block copolymer and the addition polymerization block (a) (in the block copolymer composition) (If present) can be extracted and removed, and the remaining solid can be dried.
In the present invention, as long as the gist of the invention is not impaired, the above block copolymer composition may be used as it is for the production of a thermoplastic polymer composition.

Moreover, the thermoplastic polymer composition of the present invention contains a thermoplastic polyurethane (III) having a logarithmic viscosity of 0.9 dl / g or more. The logarithmic viscosity of the thermoplastic polyurethane (III) needs to be 0.9 dl / g or more. By using such thermoplastic polyurethane (III), a thermoplastic polymer composition having flame retardancy of UL94HB grade or higher can be obtained.
The logarithmic viscosity of the thermoplastic polyurethane (III) is preferably 1.0 dl / g or more, more preferably 1.1 dl / g or more, and further preferably 1.2 dl / g or more.
The logarithmic viscosity of the thermoplastic polyurethane (III) as used herein is calculated based on the flow time measured at 30 ° C. with the thermoplastic polyurethane (III) as a DMF solution having a concentration of 0.5 g / dl. Specifically, it means a value measured by the method described in Examples described later.

As the thermoplastic polyurethane (III), those formed from the above-described polymer polyol, chain extender and organic diisocyanate compound can be used. Further, if the logarithmic viscosity is within the above-mentioned range, a polyurethane that can be produced during the production of the block copolymer (II) may be used as the thermoplastic polyurethane (III).
The thermoplastic polyurethane (III) preferably has the same structure as the polyurethane block (b) in the block copolymer (II).

As the polymer polyol, chain extender and organic diisocyanate compound constituting the thermoplastic polyurethane (III), those described above as the components constituting the polyurethane block (b) in the block copolymer (II) should be used. Can do.
As the polymer polyol constituting the thermoplastic polyurethane (III), it is preferable to use a polyol having a number average molecular weight in the range of 500 to 10,000. By using the thermoplastic polyurethane (III) made of a polymer polyol having such a number average molecular weight, a thermoplastic polymer composition having good flexibility, mechanical performance and melt moldability can be obtained. The number average molecular weight of the polymer polyol constituting the thermoplastic polyurethane (III) is more preferably in the range of 700 to 8,000, and further preferably in the range of 800 to 5,000.

  Moreover, it is preferable that the high molecular polyol which comprises thermoplastic polyurethane (III) exists in the range whose number of hydroxyl groups per molecule is 2.0-2.1. By using a thermoplastic polyurethane (III) comprising a polymer polyol having a number of hydroxyl groups per molecule within the above range, a thermoplastic polymer composition having a flame retardancy of UL94HB grade or higher is reliably obtained. be able to. The polymer polyol constituting the thermoplastic polyurethane (III) is more preferably in the range of 2.0 to 2.05 hydroxyl groups per molecule, and in the range of 2.002 to 2.03. More preferably.

The nitrogen atom content derived from the organic diisocyanate compound in the thermoplastic polyurethane (III) is in the range of 1 to 6.5% by weight based on the total weight of the polymer polyol, the chain extender and the organic diisocyanate compound. preferable.
By using the thermoplastic polyurethane (III) obtained by using the polymer polyol, the chain extender and the organic diisocyanate compound at the above ratio, various properties such as flexibility, mechanical performance and melt moldability are further improved. An excellent thermoplastic polymer composition can be obtained. More preferably, the content of nitrogen atoms derived from the organic diisocyanate compound in the thermoplastic polyurethane (III) is in the range of 1 to 6% by weight based on the total weight of the polymer polyol, the chain extender and the organic diisocyanate compound. Further, it is more preferably within the range of 1.3 to 5.5% by weight, and particularly preferably within the range of 1.6 to 5% by weight.

  Further, the hardness of the thermoplastic polyurethane (III) is preferably in the range of 30 to 99 when expressed in JIS A hardness. By using the thermoplastic polyurethane (III) having such hardness, a thermoplastic polymer composition having more excellent various properties such as flexibility, mechanical performance and melt moldability can be obtained. The JIS A hardness of the thermoplastic polyurethane (III) is more preferably in the range of 45 to 97, and still more preferably in the range of 60 to 95.

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 isocyanate group of the organic diisocyanate compound is 0.9 to 1.3 with respect to 1 mol of active hydrogen atoms of the polymer polyol and the chain extender. It is preferable to use each component in such a ratio that it becomes a mole. By using the thermoplastic polyurethane (III) obtained by using the polymer polyol, the chain extender and the organic diisocyanate compound at the above ratio, various properties such as flexibility, mechanical performance and melt moldability are further improved. An excellent thermoplastic polymer composition can be obtained.

In forming thermoplastic polyurethane (III), there is no sudden rise in melt viscosity during melt molding such as extrusion molding and injection molding, and products such as target molded products and laminated structures can be produced smoothly. Since a thermoplastic polymer composition that can be obtained is obtained, it is preferable to use the polymer polyol, the chain extender, and the organic diisocyanate compound in a proportion that satisfies the following relationship.
[Mole number of polymer polyol]: [Mole number of chain extender] = 1: 0.2 to 8.0 (molar ratio), and [Total number of moles of polymer polyol and chain extender]: [Organic diisocyanate Number of moles of compound] = 1: 0.98 to 1.04

When preparing the thermoplastic polyurethane (III), a urethanization reaction catalyst may be used. As such a urethanization reaction catalyst, those described above can be used.
The amount of the urethanization reaction catalyst used is preferably in the range of 0.1 ppm to 0.2% by weight, based on the total weight of the polymer polyol, the chain extender and the organic diisocyanate compound, and 0.5 ppm to 0. The content is more preferably in the range of 02% by weight, and still more preferably in the range of 1 ppm to 0.01% by weight.
The urethanization reaction catalyst can be contained in one or more of the polymer polyol, chain extender, and organic diisocyanate compound, but is preferably contained in the polymer polyol.

When a urethanization reaction catalyst is used in preparing the thermoplastic polyurethane (III), it is preferable to add a urethanization reaction catalyst deactivator to the obtained thermoplastic polyurethane (III). As the urethanization reaction catalyst deactivator, those described above can be used.
The amount of the urethanization catalyst deactivator used is preferably in the range of 1 ppm to 2 wt% based on the total weight of the polymer polyol, chain extender and organic diisocyanate compound, and 5 ppm to 0.2 wt%. More preferably, it is in the range of 10 ppm to 0.1 wt%.

  In addition, the content ratio of the urethanization reaction catalyst and the urethanization reaction catalyst deactivator is based on the amount of metal atom per mole 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 in the range of 0.2 to 200 mol, and the range of 0.5 to 100 mol. More preferably, it is used in the inside. Moreover, when using a phenol type compound as a urethanization reaction catalyst deactivator, it uses within 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. It is preferable to use within the range of 2 to 2000 mol, and more preferable to use within the range of 5 to 1000 mol.

  The production method of the thermoplastic polyurethane (III) is not particularly limited, and any of the prepolymer method and the one-shot method using a high-molecular 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 produce by continuous melt polymerization using a multi-screw extruder.

  As the paraffinic oil (IV) used in the present invention, a paraffin component (chain hydrocarbon) containing 60% by weight or more is used, but a paraffin component (chain hydrocarbon) containing 80% by weight or more is used. Is preferred. 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) preferably has a kinematic viscosity measured at 40 ° C. in the range of ²⁰ to 800 centistokes [cSt (mm ² / s)]. By using the paraffinic oil (IV) having such a kinematic viscosity, a thermoplastic polymer composition having more excellent various properties such as flexibility, mechanical performance, and melt moldability can be obtained. The kinematic viscosity of the paraffinic oil (IV) measured at 40 ° C. is more preferably in the range of 50 to 600 centistokes [cSt (mm ² / s)]. 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.

  The pour point of the paraffinic oil (IV) is preferably in the range of −40 to 0 ° C. By using the paraffinic oil (IV) having such a pour point, a thermoplastic polymer composition having more excellent various properties such as flexibility, mechanical performance, and melt moldability can be obtained. The pour point of the paraffinic oil (IV) is more preferably within the range of -30 to 0 ° C. 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. By using a paraffinic oil (IV) having such a flash point, it is possible to obtain a thermoplastic polymer composition having various properties such as flame retardancy, flexibility, mechanical performance and melt moldability. it can. The flash point of the paraffinic oil (IV) is more preferably in the range of 250 to 350 ° C. 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 of the present invention contains the above-described components and has flame retardancy of UL94HB grade or higher. Therefore, the thermoplastic polymer composition of the present invention can be suitably used for production of various products satisfying standard safety with respect to flame retardancy, for example, electric products and automobile-related equipment.
Since the thermoplastic polymer composition of the present invention has the flame retardancy described above, the addition polymerization block copolymer (I), the block copolymer (II), the thermoplastic polyurethane (III) and When the weight of the paraffinic oil (IV) is W ₁ , W ₂ , W ₃ and W ₄ respectively, they are present in the composition in such a ratio that they satisfy the following formulas (1) to (3). It is preferable.
5/100 ≦ W ₂ / W ₁ ≦ 200/100 (1)
100/100 ≦ W ₃ / W ₁ ≦ 300/100 (2)
10/100 ≦ W ₄ / W ₁ ≦ 200/100 (3)

If the content of the block copolymer (II) relative to the addition polymerization block copolymer (I) is less than the range represented by the above formula (1), the addition polymerization block copolymer (I) and thermoplasticity The compatibility with polyurethane (III) becomes insufficient, making it difficult to obtain a thermoplastic polymer composition having UL94HB grade flame retardancy. In addition, products such as molded articles and laminated structures obtained using the thermoplastic polymer composition cause surface roughness and lower adhesion between layers. On the other hand, when the content of the block copolymer (II) with respect to the addition polymerization block copolymer (I) exceeds the range represented by the above formula (1), the melt adhesiveness of the thermoplastic polymer composition is lowered. Or the melt fluidity of the thermoplastic polymer composition is lowered, and the molded product obtained using the thermoplastic polymer composition is also roughened.
The ratio between the addition polymerization block copolymer (I) and the block copolymer (II) is:
More preferably, 10/100 ≦ W ₂ / W ₁ ≦ 180/100,
More preferably, 20/100 ≦ W ₂ / W ₁ ≦ 150/100.

Further, when the ratio of the thermoplastic polyurethane (III) to the addition polymerization block copolymer (I) is less than the range represented by the above formula (2), a thermoplastic polymer composition having UL94HB class flame retardancy. It becomes difficult to obtain things. In addition, the compression set of molded articles and laminated structures obtained from the thermoplastic polymer composition is increased, the melt adhesion with other materials is lowered, the molded article surface is roughened, and the moldability is increased. It becomes unstable. On the other hand, when the ratio of the thermoplastic polyurethane (III) to the addition polymerization block copolymer (I) exceeds the range represented by the above formula (2), the non-stickiness of the thermoplastic polymer composition may be reduced. The melt moldability of the thermoplastic polymer composition becomes unstable, and the molded product obtained using the thermoplastic polymer composition may be roughened.
The ratio of the addition polymerization block copolymer (I) to the thermoplastic polyurethane (III) is:
It is more preferable that 150/100 ≦ W ₃ / W ₁ ≦ 280/100.

Further, when the ratio of the paraffinic oil (IV) to the addition polymerization block copolymer (I) is less than the range represented by the above formula (3), a molded product or a laminate obtained from the thermoplastic polymer composition is used. The compression set of the structure or the like increases, and the surface of the molded product becomes rough. On the other hand, when the ratio of the paraffinic oil (IV) to the addition polymerization block copolymer (I) exceeds the range represented by the above formula (3), a thermoplastic polymer composition having UL94HB class flame retardancy. It becomes difficult to obtain. In addition, the thermoplastic polymer composition obtained has decreased melt adhesion with other materials, and has mechanical properties such as tensile strength and tensile breaking elongation of a molded product obtained from the thermoplastic polymer composition. Decrease and surface roughness of the molded product occur. Furthermore, problems such as a spool break during molding occur.
The ratio of addition polymerization block copolymer (I) and paraffinic oil (IV) is:
More preferably, 50/100 ≦ W ₄ / W ₁ ≦ 150/100.

  The thermoplastic polymer composition of the present invention may contain the aforementioned urethanization reaction catalyst or urethanization reaction catalyst deactivator.

The content of the urethanization reaction catalyst is preferably in the range of 0.1 ppm to 0.2% by weight, preferably in the range of 0.5 ppm to 0.02% by weight, based on the weight of the thermoplastic polymer composition. It is more preferable that it is in the range of 1 ppm to 0.01% by weight.
The content of the urethanization catalyst deactivator is preferably in the range of 1 ppm to 2% by weight based on the weight of the thermoplastic polymer composition, and in the range of 5 ppm to 0.2% by weight. More preferably, it is more preferably in the range of 10 ppm to 0.1% by weight.
In addition, the content ratio of the urethanization reaction catalyst and the urethanization reaction catalyst deactivator is such that, when a phosphorus compound is used as the urethanization reaction catalyst deactivator, phosphorus per mol of metal atoms in the urethanization reaction catalyst. The phosphorus atom of the compound is preferably in the range of 0.1 to 500 mol, more preferably in the range of 0.2 to 200 mol, and in the range of 0.5 to 100 mol. Further preferred. Moreover, when using a phenolic compound as a urethanization reaction catalyst deactivator, it is preferably within the range of 1 to 5000 moles as a hydroxyl group of the phenolic compound per mole of metal atoms of the urethanization reaction catalyst. It is more preferably within the range of 2 to 2000 mol, and even more preferably within the range of 5 to 1000 mol.

The thermoplastic polymer composition 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 in the range of 200 parts by weight or less with respect to 100 parts by weight of the addition polymerization block copolymer (I). By blending the olefin polymer (V), the mechanical strength and melt moldability of the resulting thermoplastic polymer composition may be further improved.

Examples of the olefin polymer (V) include homopolymers of olefins such as ethylene, propylene, butylene, olefin copolymers composed of two or more of the above-mentioned olefins, or one or more of the above-mentioned olefins and others. And a copolymer with one or more of these vinyl monomers. Other vinyl monomers include, for example, vinyl cyanide monomers such as acrylonitrile and methacrylonitrile; acrylic acid or methacrylic acid methyl, ethyl, propyl, n-butyl, i-butyl, hexyl, 2- C1-C18 alkyl esters such as ethylhexyl, dodecyl, octadecyl; diol esters such as acrylic acid or methacrylic acid ethylene glycol, propylene glycol, butanediol; C1-C6 carboxylic acids such as acetic acid and propionic acid Vinyl esters; unsaturated carboxylic acids such as acrylic acid, methacrylic acid and maleic acid; anhydrides of unsaturated dicarboxylic acids such as maleic anhydride; (meth) acrylamides such as acrylamide, methacrylamide and N, N-dimethylacrylamide; Maleimide, N-methylmale De, N- ethylmaleimide, N- phenylmaleimide, N- substituted maleimides such as N- cyclohexyl maleimide; butadiene, and the like conjugated dienes isoprene and the like.
Specific examples of the olefin polymer (V) include low density polyethylene, medium density polyethylene, high density polyethylene, polypropylene, polybutylene, ethylene-α-olefin copolymer, ethylene-vinyl acetate copolymer, ethylene-acrylic acid copolymer. Examples thereof include a polymer, an ethylene-maleic anhydride copolymer, a propylene-acrylic acid copolymer, a propylene-maleic anhydride copolymer, and an isobutylene-maleic anhydride copolymer. As the olefin polymer (V), one or more of the olefin homopolymers and olefin copolymers described above can be used.

  In addition, the thermoplastic polymer composition of the present invention is a styrene different from the addition polymerization block copolymer (I) or the block copolymer (II) as necessary within the range not impairing the effects of the present invention. Polymers; Polyphenylene ether resins; Thermosetting polyurethane resins; Polyamide resins; Polyester resins; Polyvinyl chloride resins; Polyvinylidene chloride resins; Polycarbonate resins; Acrylic resins; Saponified ethylene-vinyl acetate copolymers; It may contain a resin such as a copolymer of a compound and a vinyl cyanide compound; a copolymer of an aromatic vinyl compound, a vinyl cyanide compound and an olefin compound.

Furthermore, the thermoplastic polymer composition of the present invention can contain an inorganic filler as required. The inorganic filler is useful for increasing the hardness of the thermoplastic polymer composition of the present invention and improving the economy as an extender. As the inorganic filler, for example, one or more of calcium carbonate, talc, clay, synthetic silicon, titanium oxide, carbon black, barium sulfate and the like can be used. The blending amount of the inorganic filler is preferably 100 parts by weight or less with respect to 100 parts by weight of the addition polymerization block copolymer (I).
Furthermore, the thermoplastic polymer composition of the present invention can be used as necessary with lubricants, pigments, impact resistance improvers, processing aids, crystal nucleating agents, colorants, flame retardants, weather resistance improvers, ultraviolet absorbers, oxidation agents. Various additives such as inhibitors, hydrolysis resistance improvers, fungicides, antibacterial agents, light stabilizers, antistatic agents, silicone oils, antiblocking agents, mold release agents, foaming agents, and fragrances; various coupling agents Arbitrary components such as can be blended as necessary.

The thermoplastic polymer composition of the present invention may be produced by any method as long as the above-described constituent components can be uniformly mixed, but the melt-kneading method is simple and preferable.
The thermoplastic polymer composition of the present invention, for example, each component is usually 150 to 220 ° C. using a melt kneader such as a single screw extruder, a twin screw extruder, a kneader, a mixing roll, or a Banbury mixer. For about 30 seconds to 5 minutes.
It is desirable to perform melt-kneading without cooling to 150 ° C. or lower, more preferably 170 ° C. or lower, and even more preferably 190 ° C. or lower because a thermoplastic polymer composition having desired physical properties can be reliably obtained.
In the melt-kneading, it is important to employ conditions under which the logarithmic viscosity of the thermoplastic polyurethane in the thermoplastic polymer composition is maintained at 0.9 or more.

As a method for producing the thermoplastic polymer composition of the present invention, in order to reliably produce a thermoplastic polymer composition excellent in flame retardancy, the procedures shown in the following [1] to [6], especially production It is recommended to manufacture according to the procedure shown in [1], [2], [5] and [6] from the viewpoint of properties.
[1] A polymer polyol, a reaction product of a chain extender and an organic diisocyanate compound, an addition polymerization block copolymer (I), a block copolymer (II) and a paraffinic oil (IV) are melt-kneaded.
[2] Addition polymerization type block copolymer (I), block copolymer (II), paraffinic oil (IV), polymer polyol, chain extender and organic diisocyanate compound are melt-kneaded.
[3] A block copolymer composition containing a block copolymer (II) is prepared by kneading a functional group-containing block copolymer, a polymer polyol, a chain extender and an organic diisocyanate compound, and then paraffinic oil (IV), further comprising a block copolymer having an aromatic vinyl compound polymer block and a conjugated diene polymer block and a hydrogenated product thereof, if necessary, a high molecular polyol, a chain extender or an organic diisocyanate compound An addition polymerization block copolymer having no functional group reactive with is blended by melt kneading.
[4] A block copolymer composition containing a block copolymer (II) is prepared by kneading a reaction product of a polymer polyol, a chain extender and an organic diisocyanate compound and a functional group-containing block copolymer, Paraffinic oil (IV), further comprising a block copolymer having an aromatic vinyl compound-based polymer block and a conjugated diene-based polymer block and a hydrogenated product thereof, if necessary, a polymer polyol, a chain extender or An addition polymerization block copolymer having no functional group reactive with the organic diisocyanate compound is blended by melt kneading.
[5] Functional group-containing block copolymer, polymer polyol, chain extender, organic diisocyanate compound and paraffinic oil (IV), and if necessary, aromatic vinyl compound polymer block and conjugated diene polymer An addition polymerization block copolymer comprising a block copolymer having a block and a hydrogenated product thereof and having no functional group reactive with a polymer polyol, a chain extender or an organic diisocyanate compound is melt-kneaded.
[6] Polymer polyol, reaction product of chain extender and organic diisocyanate compound, functional group-containing block copolymer and paraffin oil (IV), and if necessary, aromatic vinyl compound polymer block and conjugated diene A block copolymer having a polymer block and a hydrogenated product thereof, and melt-kneading an addition polymerization block copolymer having no functional group reactive with a polymer polyol, a chain extender or an organic diisocyanate compound .

In the melt-kneading, there is no particular limitation on the blending order of each component.
A specific example is as follows.
(A) 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) and a paraffin oil ( IV) are melt-kneaded all together [Procedure 1]
(B) Addition polymerization block copolymer (I), block copolymer (II), paraffinic oil (IV), polymer polyol, chain extender and organic diisocyanate compound are melt-kneaded together [Procedure 2 ]
(C) The block copolymer (II), the polymer polyol, the chain extender and the organic diisocyanate compound are melt-kneaded all at once, and then the addition polymerization block copolymer (I) and paraffin separately prepared by melt-kneading. A composition comprising a base oil (IV) is added and melt kneaded [Procedure 3]
(D) A functional group-containing block copolymer, a polymer polyol, a chain extender, an organic diisocyanate compound, and a paraffinic oil are melt-kneaded together (procedure 4).
(E) A functional group-containing block copolymer, a polymer polyol, a chain extender and an organic diisocyanate compound are kneaded, and paraffinic oil is added to the resulting composition and melt-kneaded (procedure 5).
(F) A polymer polyol, a chain extender and an organic diisocyanate compound are kneaded to perform a polyurethane forming reaction, then a functional group-containing block copolymer is added and kneaded, and paraffinic oil is added to the resulting composition And kneading (procedure 6).
(G) A functional group-containing block copolymer, a polymer polyol, a chain extender and a paraffinic oil are melt-kneaded, and then an organic diisocyanate compound is added and kneaded. (Procedure 7)
(H) A thermoplastic polyurethane prepared in advance as a reaction product of a polymer polyol, a chain extender and an organic diisocyanate compound, a functional group-containing block copolymer, and a separately prepared aromatic vinyl compound polymer block and conjugated diene polymer Comprising a block copolymer having a combined block and a hydrogenated product thereof, comprising a polymer polyol, a chain extender or an addition polymerization block copolymer having no functional group reactive with an organic diisocyanate compound and a paraffinic oil The composition is melt kneaded. (Procedure 8)

When a urethanization reaction catalyst is used, it should be contained in one or more of a polymer polyol, a chain extender, an organic diisocyanate compound, or a reaction product of a polymer polyol, a chain extender and an organic diisocyanate compound. However, it is preferably contained in the polymer polyol.
Moreover, when using a urethanation reaction catalyst deactivator, it is preferable to add when the physical property of a thermoplastic polymer composition becomes a desired value.

Furthermore, the olefin polymer (V), the other thermoplastic polymer, the other resin, the inorganic filler and other optional components are added to the addition polymerization block copolymer (I), the block copolymer (II). ), A composition containing a thermoplastic polyurethane (III) and a paraffinic oil (IV), or at any stage after the preparation.
When blended when preparing a composition containing an addition polymerization block copolymer (I), block copolymer (II), thermoplastic polyurethane (III) and paraffinic oil (IV), an olefin polymer (V ), Other thermoplastic polymers, other resins, inorganic fillers and other optional components described above are added polymerization block copolymer (I), block copolymer (II) [or the above block copolymer Combined composition], thermoplastic polyurethane (III) and paraffinic oil (IV) may be supplied separately to a melt-kneading apparatus and kneaded, or addition polymerization block copolymer (I), block copolymer The mixture (II) [or the above block copolymer composition], thermoplastic polyurethane (III), and paraffinic oil (IV) are contained in at least one kind, and then supplied to a melt kneader and kneaded. Yo .

  The thermoplastic polymer composition of the present invention prepared by melt kneading may be used for molding in a molten state, or may be used once for molding after being formed into pellets.

  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. Can be manufactured smoothly. The molded article made of the thermoplastic polymer resin composition of the present invention thus obtained includes articles of any shape such as a film shape, a sheet shape, a tube shape, and a three-dimensional shape. When the thermoplastic polymer composition of the present invention is used, a molded product having excellent flame retardancy and various properties such as flexibility and mechanical performance can be obtained.

Furthermore, the thermoplastic polymer composition of the present invention has high melt adhesion to various materials in combination with flame retardancy, and can be firmly bonded to various other materials under melting. It can be effectively used for the production of a composite molded body with members made of these other materials.
Examples of the other material include various thermoplastic resins other than the thermoplastic polymer composition of the present invention or a composition thereof, thermosetting resin, paper, fabric, metal, wood, ceramics, and the like.

  The thermoplastic polymer composition of the present invention is particularly excellent in melt adhesion with a material having polarity, among other 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 composite molded body is typically a laminated body such as a film or a sheet, but may take a tube, an irregular shape, or any other three-dimensional shape.
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 comprising 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 producing 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 and 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, it is preliminarily formed into a predetermined shape and size by a conventional general-purpose method for manufacturing a metal product (casting, rolling, cutting, machining, grinding, etc.). Form it.

Moreover, when manufacturing a composite molded body by the above-described two-color injection molding method, after two or more injection devices are used to inject other materials into 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 a gap formed between a molded product made of another 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 a 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 product, 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. Further, in the case of press molding, a composite molded body can be produced by performing melt pressing using the thermoplastic polymer composition of the present invention under the arrangement of other materials.

  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, vacuum cleaner bumpers, remote control switches and knobs, various key tops for office automation equipment; underwater products such as underwater glasses and underwater camera covers; various cover parts; sealing, waterproof, soundproof, vibration proof Industrial parts with various packing for the purpose of safety; 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, silencer gears; ; Building materials such as doors and window frames; Various joints ; It can be mentioned the so surgical cast various products; valve parts. 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 these examples.
In Examples and Comparative Examples, the logarithmic viscosity of the thermoplastic polyurethane in the thermoplastic polymer composition, the melt viscosity of the thermoplastic polymer composition, flame retardancy, hardness, tensile breaking strength, tensile breaking elongation, and lamination The adhesion strength in the body was measured or evaluated by the following method.

(1) Logarithmic viscosity of thermoplastic polyurethane:
The thermoplastic polyurethane is dissolved in DMF so as to have a concentration of 0.5 g / dl, and the flow time of the polyurethane solution at 30 ° C. is measured using an Ubbelohde viscometer. (Η _inh ) was determined.
Logarithmic viscosity of thermoplastic polyurethane (η _inh ) = [ln (t / t ₀ )] / c
[Wherein t is the flow time (seconds) of the DMF solution of thermoplastic polyurethane, t ₀ is the flow time (seconds) of the solvent (DMF), and c is the concentration of the thermoplastic polyurethane in the DMF solution (g / dl) Represents. ]
In addition, about the thermoplastic polyurethane in a thermoplastic polymer composition, the logarithmic viscosity of what was obtained by extracting as follows was measured.
N, N-dimethylformamide (DMF) is added to the thermoplastic polymer composition at a rate of 200 ml per gram of the composition, and the mixture is stirred at room temperature for 24 hours, followed by filtration to recover a DMF solution. Further, DMF is added to the insoluble part, and the mixture is stirred for 1 hour and subjected to filtration. Repeat this operation three times. The recovered DMF solutions are combined and the DMF is distilled off, and then the residue is vacuum dried at 40 ° C. for 24 hours to obtain a thermoplastic polyurethane.

(2) 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 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.
(3) Flame retardancy:
The thermoplastic polymer composition was melted at 200 ° C. for 3 minutes using a press molding machine [manufactured by Shinto Metal Industry Co., Ltd., “Compression molding machine AYS-10” (trade name)], A molded article (test piece) having a thickness of 1 mm was produced by holding at 200 ° C. under a load of 50 kgf for 3 minutes.
Using the obtained molded product (test piece), the molded product was tested in accordance with “Horizontal Combustion Test for HB Classification” (established by UNDERWRITERS LABORATORIES INC.) Described in “UL94 Plastic Material Combustion Test”. Flame retardancy was measured.
Those satisfying the conditions of UL94HB grade were evaluated as “◯”. Moreover, the thing which does not satisfy UL94HB grade conditions was evaluated as "x".

(4) Hardness:
A disk-shaped molded product (diameter: 120 mm, thickness: 2 mm) was manufactured by injection molding (cylinder temperature: 180 to 205 ° C., mold temperature: 35 ° C.) using a mold having a mirror-finished surface. The obtained molded article was allowed to stand at 23 ° C. for 7 days, and then the Shore A hardness of the molded article was measured according to JIS K-6301 using a laminate of two molded articles.
(5) 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 above-described evaluation of injection moldability. 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 produce a test piece. -500D "was used to measure tensile break strength and tensile break elongation.

(6) Adhesive strength in the laminate:
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 peeled in accordance with “180 degree peel test” described in JISK 6854. The 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)
SEBS :
Hydrogenated product of triblock copolymer having a structure of polystyrene block-polybutadiene block-polystyrene block type [manufactured by Kuraray Co., Ltd., "Septon 8006" (trade name)]
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)]

(Functional group-containing block copolymer)
F-SEEPS :
Hydrogenated product of a triblock copolymer having a polystyrene block-poly (isoprene / butadiene) block-polystyrene block type structure and having a hydroxyl group at one end of the molecule [number average molecular weight: 50,000, styrene content: 30%, hydrogenation rate in poly (isoprene / butadiene) block: 98%, ratio of isoprene to butadiene: 50/50 (molar ratio), average number of hydroxyl groups per molecule: 0.9; poly (isoprene / butadiene) ) Total amount of 1,2-bonds and 3,4-bonds in the block: 8 mol%; produced from styrene, isoprene and butadiene as raw materials according to the method described in Reference Example 1 of JP-A-10-139963 did. ]
F-SEEPS is a block copolymer having a hydroxyl group at one end of the molecule [SEEPS-OH [polystyrene block-poly (isoprene / butadiene) block-polyblock copolymer hydrogenated structure having a polystyrene block type structure, Number average molecular weight: 50,000, styrene content: 30%, hydrogenation rate in poly (isoprene / butadiene) block: 98%, ratio of isoprene to butadiene: 50/50 (molar ratio), poly (isoprene / butadiene) Block copolymer having no hydroxyl group in the molecule [SEEPS-2 [polystyrene block-poly (isoprene / butadiene) block- Hydrogenation of triblock copolymer with polystyrene block structure , Number average molecular weight: 50,000, styrene content: 30%, hydrogenation rate in poly (isoprene / butadiene) block: 98%, ratio of isoprene to butadiene: 50/50 (molar ratio), poly (isoprene / butadiene) ) Total amount of 1,2-bond and 3,4-bond in the block: 8 mol%]] [SEEPS-OH / SEEPS-2 = 9/1 (molar ratio)].

(Thermoplastic polyurethane)
TPU-1:
Polyester-based thermoplastic polyurethane [manufactured by Kuraray Co., Ltd., “Cramiron U8165” (trade name): Polyester-based thermoplastic polyurethane having poly (3-methyl-1,5-pentanediol adipate) as a soft segment; logarithmic viscosity: 1 .09dl / g]
TPU-2:
Polyurethane composed of 3-methyl-1,5-pentanediol and adipic acid (number average molecular weight: 3500), 4,4′-diphenylmethane diisocyanate and 1,4-butanediol (nitrogen atom content: 1.9% by weight; manufactured according to the method described in Example 2 of JP-A-47-34494.)

(Paraffinic oil)
PL : Paraffinic oil [Idemitsu Kosan Co., Ltd., “Diana Process PW-380” (trade name)]
(Polymer polyol)
POH-1 :
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 :
Polyester polyol produced by reacting 3-methyl-1,5-pentanediol, trimethylolpropane and adipic acid and having 3.00 hydroxyl groups per molecule (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 (urethanization reaction catalyst)
CAT : Tetraisopropyl titanate (urethanization catalyst deactivator)
INACT : Distearyl phosphate

(Synthetic resin that constitutes the synthetic resin plate used to manufacture the laminate)
ABS : Acrylonitrile-butadiene-styrene copolymer resin (manufactured by Nippon Synthetic Rubber Co., Ltd., “JSR ABS12” (trade name))
PA6 : nylon 6 (manufactured by Ube Industries, “UBE nylon 1013B” (trade name))

  In Example 3 and Comparative Example 3, the composition (PU-SEEPS Compound) obtained in the following Reference Example was used as the composition containing the block copolymer (II).

Reference Example [Production of Composition Containing Block Copolymer (II)]
100 parts by weight of the above TPU-2 and 100 parts by weight of F-SEEPS are premixed, and the resulting mixture is rotated in the same direction in a twin screw extruder [30 mmφ, L / D = 36; “BT-30” (trade name)] was melt-kneaded under the conditions of a cylinder temperature of 220 ° C. and a screw rotation speed of 150 rpm, and the resulting reaction mixture (melt) was continuously in water as a strand. Extruding and then cutting with a pelletizer to obtain pellets. The resulting pellet was dehumidified and dried at 80 ° C. for 4 hours to obtain a block copolymer composition (PU-SEEPS Compound).

(1) Polymer polyol containing 10 ppm of urethanization reaction catalyst (CAT) [mixture of POH-1 and POH-3; POH-1: POH-3 = 30: 70 (molar ratio)], chain extender (BD ) And organic diisocyanate compound (MDI), (Mixture of POH-1 and POH-3): BD: MDI molar ratio of 1.00: 1.09: 2.08 (nitrogen atom content is 1.9 wt. And a twin screw extruder (30 mmφ, L / D = 36; heating zone is at the front and center), and the total feed rate is 137.5 g / min. , Divided into three zones at the rear, and continuously fed to the front of the heating zone, and the polyurethane forming reaction was carried out by continuous melt polymerization at 260 ° C. A mixture of block copolymer (SEBS) and paraffinic oil (PL) [SEBS: PL = 1: 1 (weight ratio)] was 90 g / min (SEBS was 18 wt%, PL was 18 wt%), and block copolymer Twin screw extruder connected to the center of the heating zone of the above twin screw extruder so that the polymer (F-SEEPS) is 22.5 g / min (F-SEEPS is 9% by weight) (30 mmφ, L / D = 36; heated at 220 ° C.) and continuously reacted with the reaction mixture obtained by the polyurethane formation reaction, and the resulting melt is continuously extruded into water as a strand. Then, it was cut with a pelletizer, and the pellets were dehumidified and dried at 70 ° C. for 4 hours to obtain a thermoplastic polymer composition 1. When the logarithmic viscosity of the thermoplastic polyurethane in the thermoplastic polymer composition 1 was measured by the method described above, it was as shown in Table 1 below. The thermoplastic polymer composition 1 was measured for melt viscosity, flame retardancy, hardness, tensile rupture strength, and tensile rupture elongation by the methods described above, and the results were as shown in Table 1 below.

(2) A portion of the thermoplastic polymer composition 1 was taken and the polyurethane in the composition was extracted and removed using dimethylformamide. Subsequently, unreacted SEEPS-OH, SEEPS-2, SEBS and PL were extracted and removed using cyclohexane, and the remaining solid was dried to obtain a block copolymer. As a result of analysis by ¹ H-NMR, the obtained block copolymer was a polymer block having a structure of polystyrene block-hydrogenated poly (isoprene / butadiene) block-polystyrene block type [addition polymerization block (ii)]. And a poly (3-methyl-1,5-pentanediol adipate) unit, a polytetramethylene glycol unit, a 4,4′-diphenylmethane diisocyanate unit and a 1,4-butanediol unit [polyurethane block (b) It was found that it was a block copolymer consisting of
In addition, when the weight of the polymer component (including unreacted SEEPS-OH, SEEPS-2 and SEBS) in the extract of cyclohexane is W, the weight (W ₂ ) of the above-mentioned block copolymer, dimethyl The ratio of the weight of polyurethane extracted with formamide [corresponding to thermoplastic polyurethane (III): W ₃ ] and the weight of PL [corresponding to paraffinic oil (IV): W ₄ ] is W ₂ / W = 29, W ₃ / W = 235, W ₄ / W = 80.
(3) Furthermore, using the thermoplastic polymer composition 1, ABS, PA6, a laminate was produced by the method described above, and the adhesive strength of the obtained laminate was measured by the method described above. As shown in FIG.

(1) Polymer polyol containing 15 ppm of urethanization reaction catalyst (CAT) [POH-1, POH-3 and POH-2 mixture, POH-1: POH-3: POH-2 = 29.4: 68. 6: 2.0 (molar ratio); average number of hydroxyl groups per molecule = 2.02], chain extender (BD) and organic diisocyanate compound (MDI) are converted into (POH-1 / POH-3 / POH-2). Mixture): BD: MDI molar ratio is 1.00: 1.25: 2.22 (nitrogen atom content is 2.0 wt%), and the total feed amount thereof is 131.25 g / min. In this way, a twin screw extruder (30 mmφ, L / D = 36; the heating zone is divided into three zones, the front, the center and the rear) is rotated continuously at 260 ° C. Polyurethane form by continuous melt polymerization of The reaction was carried out. A mixture of block copolymer (SEEPS-1) and paraffinic oil (PL) [SEEPS-1: PL = 1: 1 (weight ratio)] is 95 g / min (SEEPS-1 is 19% by weight, PL is 19% by weight) %), And a block copolymer (F-SEEPS) at 23.75 g / min (F-SEEPS is 9.5% by weight) connected to the center of the heating zone of the twin screw extruder. Was continuously fed to the twin screw type extruder (30 mmφ, L / D = 36; heated at 220 ° C.) to continuously react with the reaction mixture by the polyurethane forming reaction. Next, 0.05% by weight (feed amount: 0.125 g / min) of a urethanization reaction catalyst deactivator (INACT) was added to the rear part of the above twin screw extruder, and the resulting melt was converted into a strand. The thermoplastic polymer composition 2 was obtained by continuously extruding it into water and then cutting with a pelletizer and dehumidifying and drying the pellets at 70 ° C. for 4 hours. When the logarithmic viscosity of the thermoplastic polyurethane in the thermoplastic polymer composition 2 was measured by the method described above, it was as shown in Table 1 below. The thermoplastic polymer composition 2 was measured for melt viscosity, flame retardancy, hardness, tensile strength at break, and tensile elongation at break as shown in Table 1 below.

(2) A part of the thermoplastic polymer composition 2 was taken and the polyurethane in the composition was extracted and removed using dimethylformamide. Subsequently, unreacted SEEPS-OH, SEEPS-2, SEEPS-1 and PL were extracted and removed using cyclohexane, and the remaining solid was dried to obtain a block copolymer. As a result of analysis by ¹ H-NMR, the obtained block copolymer was a polymer block having a structure of polystyrene block-hydrogenated poly (isoprene / butadiene) block-polystyrene block type [addition polymerization block (ii)]. And a poly (3-methyl-1,5-pentanediol adipate) unit, a polytetramethylene glycol unit, a 4,4′-diphenylmethane diisocyanate unit and a 1,4-butanediol unit [polyurethane block (b) )] Was found to be a block copolymer.
As a result of GPC analysis, the cyclohexane extract was obtained as a result of two polymer blocks [addition polymerization system block (A)] having a structure of polystyrene block-hydrogenated poly (isoprene / butadiene) block-polystyrene block type. Polyurethane block composed of (3-methyl-1,5-pentanediol adipate) unit, polytetramethylene glycol unit, 4,4′-diphenylmethane diisocyanate unit and 1,4-butanediol unit [polyurethane block (b)] It was found to contain a triblock copolymer having a single number.
Weight of polyurethane extracted with dimethylformamide [corresponding to thermoplastic polyurethane (III): W ₃ ] and total weight of unreacted SEEPS-OH, SEEPS-2 and SEEPS-1 extracted with cyclohexane [ The ratio of the addition polymerization block copolymer (I): W ₁ ] and the weight of PL [equivalent to paraffinic oil (IV): W ₄ ] are W ₃ / W ₁ = 254, W ₄ / W. ₁ = 95. Further, the total weight (W ₂ ) of the diblock copolymer and triblock copolymer having the above addition polymerization system block (a) and polyurethane block (b) and unreacted SEEPS-OH, SEEPS-2 and SEEPS The ratio of the total weight (W ₁ ) of −1 was W ₂ / W ₁ = 52.
(3) Further, using the thermoplastic polymer composition 2, ABS, PA6, a laminate was produced by the method described above, and the adhesive strength of the obtained laminate was measured by the method described above. 1 as shown.

(1) Polymer polyol containing 10 ppm of urethanization reaction catalyst (CAT) [POH-1 and POH-2 mixture, POH-1: POH-2 = 99.0: 1.0 (molar ratio); 1 molecule Average number of hydroxyl groups per unit = 2.01], chain extender (BD) and organic diisocyanate compound (MDI) (mixture of POH-1 and POH-2): BD: MDI molar ratio is 1.00: 2. .45: 3.42 (nitrogen atom content is 2.1% by weight), and a twin screw extruder (30 mmφ, L) rotating coaxially so that the total supply amount thereof is 100 g / min. / D = 36; The heating zone was divided into three zones (front, center and rear), and the polyurethane formation reaction was carried out by continuous melt polymerization at 260 ° C. Mixture of block copolymer (SEBS) and paraffinic oil (PL) [SEBS: PL = 1: 1 (weight ratio)] at 100 g / min (SEBS is 20 wt%, PL is 20 wt%), and Reference Example The block copolymer composition (PU-SEEPS Compound) obtained in step 1 is connected to the center of the heating zone of the above twin screw extruder so as to be 50 g / min (PU-SEEPS Compound is 20% by weight). Was continuously fed to the twin screw type extruder (30 mmφ, L / D = 36; heated at 220 ° C.) to continuously react with the reaction mixture by the polyurethane forming reaction. Next, 0.03% by weight of a urethanization reaction catalyst deactivator (INACT) (feed amount: 0.075 g / min) was added to the rear part of the above twin screw extruder, and the resulting melt was converted into a strand. The resultant was continuously extruded into water, cut with a pelletizer, and the pellets were dehumidified and dried at 70 ° C. for 4 hours to obtain a thermoplastic polymer composition 3. When the logarithmic viscosity of the thermoplastic polyurethane in the thermoplastic polymer composition 3 was measured by the method described above, it was as shown in Table 1 below. The thermoplastic polymer composition 3 was measured for melt viscosity, flame retardancy, hardness, tensile strength at break and tensile elongation at break as shown in Table 1 below.

(2) A part of the thermoplastic polymer composition 3 was taken and the polyurethane in the composition was extracted and removed using dimethylformamide. Subsequently, unreacted SEEPS-OH, SEEPS-2, SEBS and PL were extracted and removed using cyclohexane, and the remaining solid was dried to obtain a block copolymer. As a result of analysis by ¹ H-NMR, the obtained block copolymer was a polymer block having a structure of polystyrene block-hydrogenated poly (isoprene / butadiene) block-polystyrene block type [addition polymerization block (ii)]. And a polyurethane block [polyurethane block (b)] comprising a poly (3-methyl-1,5-pentanediol adipate) unit, a 4,4′-diphenylmethane diisocyanate unit and a 1,4-butanediol unit. It was found to be a polymer.
In addition, as a result of GPC analysis, the extract with cyclohexane was found to contain two polymer blocks [addition polymerization block (ii)] having a structure of polystyrene block-hydrogenated poly (isoprene / butadiene) block-polystyrene block type, Triblock having one polyurethane block [polyurethane block (b)] composed of (3-methyl-1,5-pentanediol adipate) unit, 4,4′-diphenylmethane diisocyanate unit and 1,4-butanediol unit It was found to contain a copolymer.
Weight of polyurethane extracted with dimethylformamide [corresponding to thermoplastic polyurethane (III): W ₃ ] and total weight of unreacted SEEPS-OH, SEEPS-2 and SEBS extracted with cyclohexane [addition polymerization The ratio of the system block copolymer (I): W ₁ ] and the weight of PL [corresponds to paraffinic oil (IV): W ₄ ] are W ₃ / W ₁ = 183, W ₄ / W ₁ = 79. Further, the total weight (W ₂ ) of the diblock copolymer and triblock copolymer having the above addition polymerization system block (a) and polyurethane block (b) and unreacted SEEPS-OH, SEEPS-2 and SEBS The ratio of the total weight (W ₁ ) was W ₂ / W ₁ = 32.
(3) Further, using the thermoplastic polymer composition 3, ABS, PA6, a laminate was produced by the method described above, and the adhesive strength of the obtained laminate was measured by the method described above. As shown in FIG.

Comparative Example 1
(1) Polymer polyol containing 10 ppm of urethanization reaction catalyst (CAT) [mixture of POH-1 and POH-3, POH-1: POH-3 = 30: 70 (molar ratio)], chain extender (BD ) And an organic diisocyanate compound (MDI), (Mixture of POH-1 / POH-3): BD: MDI molar ratio of 1.00: 1.09: 2.08 (nitrogen atom content is 1.9 wt. And a twin screw extruder (30 mmφ, L / D = 36; heating zone is front, middle, rear), and the total feed rate is 125 g / min. The polyurethane formation reaction was carried out by continuous melt polymerization at 260 ° C. A mixture of block copolymer (SEBS) and paraffinic oil (PL) [SEBS: PL = 1: 1 (weight ratio)] was adjusted to 125 g / min (SEBS 25 wt%, PL 25 wt%). Continuously fed to a twin screw extruder (30 mmφ, L / D = 36; heated at 220 ° C.) connected to the central part of the heating zone of the twin screw extruder, and by the above polyurethane forming reaction A thermoplastic polymer composition is obtained by continuously reacting with the reaction mixture, continuously extruding the resulting melt into water in a strand, then cutting with a pelletizer, and dehumidifying and drying the pellets at 70 ° C. for 4 hours. C-1 was obtained. When the logarithmic viscosity of the thermoplastic polyurethane in the thermoplastic polymer composition C-1 was measured by the method described above, it was as shown in Table 1 below. The thermoplastic polymer composition C-1 was measured for melt viscosity, flame retardancy, hardness, tensile strength at break, and tensile elongation at break as shown in Table 1 below.
Furthermore, using the thermoplastic polymer composition C-1, ABS, PA6, a laminate was produced by the method described above, and the adhesive strength of the obtained laminate was measured by the method described above. It was as shown in.
The thermoplastic polymer composition C-1 does not contain a polymer corresponding to the block copolymer (II). Further, when the composition of the thermoplastic polymer composition C-1 is calculated based on the weight of the raw material used, SEBS / PL / thermoplastic polyurethane = 100/100/200 (weight ratio).

Comparative Example 2
(1) Polymer polyol containing 15 ppm of urethanization reaction catalyst (CAT) [POH-1, POH-3 and POH-2 mixture, POH-1: POH-3: POH-2 = 29.4: 68. 6: 2.0 (molar ratio); average number of hydroxyl groups per molecule = 2.02], chain extender (BD) and organic diisocyanate compound (MDI) are converted into (POH-1 / POH-3 / POH-2). A molar ratio of BD: MDI is 1.00: 1.25: 2.22 (nitrogen atom content is 2.0% by weight), and the total feed amount thereof is 137.5 g / min. In this way, a twin screw extruder (30 mmφ, L / D = 36; the heating zone is divided into three zones, the front, the center and the rear) is rotated continuously at 260 ° C. Polyurethane formation by continuous melt polymerization The response was carried out. A mixture of block copolymer (SEBS) and paraffinic oil (PL) [SEBS: PL = 1: 3 (weight ratio)] is 100 g / min (SEBS is 10 wt%, PL is 30 wt%), and block copolymer Twin screw type connected to the center of the heating zone of the above twin screw type extruder so that the polymer (F-SEEPS) is 12.5 g / min (F-SEEPS is 5.0% by weight). The mixture was continuously fed to an extruder (30 mmφ, L / D = 36; 220 ° C. warming), and continuously reacted with the reaction mixture obtained by the polyurethane formation reaction. Subsequently, 0.05 wt% (feed amount: 0.125 g / min) of a urethanization reaction catalyst deactivator (INACT) was added to the rear part of the above twin screw extruder, and the resulting thermoplastic polymer was obtained. The melt of the composition was continuously extruded into water in the form of strands, then cut with a pelletizer, and the pellets were dehumidified and dried at 70 ° C. for 4 hours to obtain a thermoplastic polymer composition C-2. When the logarithmic viscosity of the thermoplastic polyurethane in the thermoplastic polymer composition C-2 was measured by the method described above, it was as shown in Table 1 below. The thermoplastic polymer composition C-2 was measured for melt viscosity, flame retardancy, hardness, tensile strength at break, and tensile elongation at break as shown in Table 1 below.

(2) The polyurethane in the composition was extracted and removed from the thermoplastic polymer composition C-2 using dimethylformamide. Subsequently, unreacted SEEPS-OH, SEEPS-2, SEBS and PL were extracted and removed using cyclohexane, and the remaining solid was dried to obtain a block copolymer. As a result of analysis by ¹ H-NMR, the obtained block copolymer was a polymer block having a structure of polystyrene block-hydrogenated poly (isoprene / butadiene) block-polystyrene block type [addition polymerization block (ii)]. And a poly (3-methyl-1,5-pentanediol adipate) unit, a polytetramethylene glycol unit, a 4,4′-diphenylmethane diisocyanate unit and a 1,4-butanediol unit [polyurethane block (b) It was found to be a diblock copolymer consisting of
As a result of GPC analysis, the cyclohexane extract was obtained as a result of two polymer blocks [addition polymerization system block (A)] having a structure of polystyrene block-hydrogenated poly (isoprene / butadiene) block-polystyrene block type. Polyurethane block composed of (3-methyl-1,5-pentanediol adipate) unit, polytetramethylene glycol unit, 4,4′-diphenylmethane diisocyanate unit and 1,4-butanediol unit [polyurethane block (b)] It was found to contain a triblock copolymer having a single number.
Weight of polyurethane extracted with dimethylformamide [corresponding to thermoplastic polyurethane (III): W ₃ ] and total weight of unreacted SEEPS-OH, SEEPS-2 and SEBS extracted with cyclohexane [addition polymerization The ratio of the weight of the block copolymer (I): W ₁ ] and the weight of PL [corresponding to the paraffinic oil (IV): W ₄ ] is W ₃ / W ₁ = 514, W ₄ / W ₁ = 286. Further, the total weight (W ₂ ) of the diblock copolymer and triblock copolymer having the above addition polymerization block (a) and polyurethane block (b) and unreacted SEEPS-OH, SEEPS-2 and SEBS The ratio of the total weight (W ₁ ) was W ₂ / W ₁ = 52.
(3) Further, using the thermoplastic polymer composition C-2, ABS, PA6, a laminate was produced by the method described above, and the adhesive strength of the resulting laminate was measured by the method described above. As shown in Table 1.

Comparative Example 3
80 g / min of block copolymer (SEBS) and paraffinic oil (PL) [SEBS: PL = 1: 1 (weight ratio)], 80 g / min of thermoplastic polyurethane (TPU-1) The obtained block copolymer composition (PU-SEEPS Compound) is supplied to a twin-screw extruder (30 mmφ, L / D = 36) that rotates coaxially at 40 g / min and is 220 ° C. The resulting melt is continuously extruded into water as a strand, then cut with a pelletizer, and the pellets are dehumidified and dried at 70 ° C. for 4 hours to obtain a thermoplastic polymer composition C-3. Obtained. When the logarithmic viscosity of the thermoplastic polyurethane in the thermoplastic polymer composition C-3 was measured by the method described above, it was as shown in Table 1 below. The thermoplastic polymer composition C-3 was measured for melt viscosity, flame retardancy, hardness, tensile strength at break, and tensile elongation at break as shown in Table 1 below.
Furthermore, using the thermoplastic polymer composition C-3, ABS, PA6, a laminate was produced by the method described above, and the adhesive strength of the obtained laminate was measured by the method described above. It was as shown in.

Note 1) Molar ratio of polymer polyol, chain extender, organic diisocyanate compound 2) Polymer polyol, chain extender, organic diisocyanate compound, functional group-containing block copolymer, addition polymerization block copolymer, block copolymer Percentage of total weight of coalescence composition, thermoplastic polyurethane and paraffinic oil

Comparative Example 4
Polymer polyol containing 10 ppm of urethanization reaction catalyst (CAT) [POH-1 and POH-2 mixture, POH-1: POH-2 = 99.0: 1.0 (molar ratio); average per molecule Hydroxyl number = 2.01], chain extender (BD) and organic diisocyanate compound (MDI) (mixture of POH-1 and POH-2): BD: MDI molar ratio is 1.00: 0.07: A twin screw extruder (30 mmφ, L / D = 1.07 (nitrogen atom content is 0.8% by weight) and rotating in a coaxial direction so that the total supply amount thereof is 100 g / min. 36; the heating zone was divided into three zones, a front part, a central part and a rear part), and a polyurethane forming reaction was carried out by continuous melt polymerization at 260 ° C. Mixture of block copolymer (SEBS) and paraffinic oil (PL) [SEBS: PL = 1: 1 (weight ratio)] at 100 g / min (SEBS is 20 wt%, PL is 20 wt%), and Reference Example Connected to the center of the heating zone of the above twin screw extruder so that the block copolymer composition (PU-SEEPS Compound) obtained in step 1 is 50 g / min (PU-SEEPS Compound is 20% by weight). The resulting mixture was continuously supplied to the twin screw extruder (30 mmφ, L / D = 36; heated at 220 ° C.) and continuously reacted with the reaction mixture by the polyurethane formation reaction. Next, 0.03% by weight of urethanization reaction catalyst deactivator (INACT) (feed amount: 0.075 g / min) was added to the rear part of the above twin screw extruder. The melt of the obtained thermoplastic polymer composition was continuously extruded into water, but because of its strong tackiness, it could not be introduced into a strand shape, and it was a pellet-shaped thermoplastic weight suitable for use in molding. A coalescence composition could not be obtained.

Comparative Example 5
Polymer polyol containing 10 ppm of urethanization reaction catalyst (CAT) [POH-1 and POH-2 mixture, POH-1: POH-2 = 99.0: 1.0 (molar ratio); average per molecule Number of hydroxyl groups = 2.01], chain extender (BD) and organic diisocyanate compound (MDI) (mixture of POH-1 and POH-2): BD: MDI molar ratio is 1.00: 56.59: 56.59 (nitrogen atom content is 7.0 wt%) and the twin screw extruder (30 mmφ, L / D = rotation in the coaxial direction so that the total supply amount thereof is 100 g / min) 36; the heating zone was divided into three zones, a front part, a central part and a rear part), and a polyurethane forming reaction was carried out by continuous melt polymerization at 260 ° C. Mixture of block copolymer (SEBS) and paraffinic oil (PL) [SEBS: PL = 1: 1 (weight ratio)] at 100 g / min (SEBS is 20 wt%, PL is 20 wt%), and Reference Example Connected to the center of the heating zone of the above twin screw extruder so that the block copolymer composition (PU-SEEPS Compound) obtained in step 1 is 50 g / min (PU-SEEPS Compound is 20% by weight). The resulting mixture was continuously supplied to the twin screw extruder (30 mmφ, L / D = 36; heated at 220 ° C.) and continuously reacted with the reaction mixture by the polyurethane formation reaction. Next, 0.03% by weight of urethanization reaction catalyst deactivator (INACT) (feed amount: 0.075 g / min) was added to the rear part of the above twin screw extruder. The melt of the obtained thermoplastic polymer composition was continuously extruded into water, but because of its low spinnability, it could not be introduced into a strand shape, making it a pellet-shaped thermoplastic suitable for use in molding processing A polymer composition could not be obtained.

ADVANTAGE OF THE INVENTION According to this invention, the thermoplastic polymer composition which achieved sufficient flame retardance without using a flame retardant is provided. The thermoplastic polymer composition of the present invention is low in hardness and excellent in melt moldability and melt adhesion to various materials, and can be used effectively for the production of various molded products.

Claims (15)

(I) 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) ), (Ii) Addition polymerization block (a) comprising a block copolymer having an aromatic vinyl compound polymer block (a-2) and a conjugated diene polymer block (b-2) or a hydrogenated product thereof And block copolymer (II) having polyurethane block (b), (iii) thermoplastic polyurethane (III) having a logarithmic viscosity of 0.9 dl / g or more, and (iv) paraffinic oil (IV). A thermoplastic polymer composition having a flammability of UL94HB or higher. The thermoplastic polymer composition according to claim 1, wherein the thermoplastic polyurethane (III) is composed of a polymer polyol having a number average molecular weight of 500 to 10,000, a chain extender, and an organic diisocyanate compound. The thermoplastic polymer composition according to claim 2, wherein the average number of functional groups per molecule of the polymer polyol is 2.0 to 2.1. The nitrogen atom content derived from the organic diisocyanate compound in the thermoplastic polyurethane (III) is in the range of 1 to 6.5% by weight based on the total weight of the polymer polyol, the chain extender and the organic diisocyanate compound. 4. The thermoplastic polymer composition according to 2 or 3. The polyurethane block (b) in the block copolymer (II) is a polyurethane block composed of a polymer polyol having a number average molecular weight of 500 to 10,000, a chain extender and an organic diisocyanate compound. The thermoplastic polymer composition according to any one of the above. 6. The nitrogen atom content derived from the organic diisocyanate compound in the polyurethane block (b) is in the range of 1 to 6.5% by weight based on the total weight of the polymer polyol, the chain extender and the organic diisocyanate compound. The thermoplastic polymer composition described in 1. When the weights of addition polymerization block copolymer (I), block copolymer (II), thermoplastic polyurethane (III) and paraffinic oil (IV) are W ₁ , W ₂ , W ₃ and W ₄ , respectively. The thermoplastic polymer composition according to any one of claims 1 to 6, which satisfies the following formulas (1) to (3).
5/100 ≦ W ₂ / W ₁ ≦ 200/100 (1)
100/100 ≦ W ₃ / W ₁ ≦ 300/100 (2)
10/100 ≦ W ₄ / W ₁ ≦ 200/100 (3) 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, aromatic Block copolymer (a) comprising an aromatic vinyl compound polymer block (a-2) and a conjugated diene polymer block (b-2) or a hydrogenated product thereof and a polyurethane block (b) A thermoplastic polymer composition obtained by melt-kneading block copolymer (II), paraffinic oil (IV), polymer polyol, chain extender and organic diisocyanate compound having a polymer polyol, chain The logarithmic viscosity of the polyurethane produced from the extender and the organic diisocyanate compound is 0.9 dl / g or more, and the flame retardant in the entire composition A thermoplastic polymer composition having a property of UL94HB grade or higher. It consists of a block copolymer having an aromatic vinyl compound polymer block and a conjugated diene polymer block or a hydrogenated product thereof, terminated with a functional group reactive with a polymer polyol, a chain extender or an organic diisocyanate compound. Addition polymerization block copolymer (I ′), paraffinic oil, polymer polyol, chain extender and organic diisocyanate compound, and if necessary, aromatic vinyl compound polymer block and conjugated diene polymer block Melting and kneading an addition polymerization block copolymer (I ″) that has no functional group reactive with a polymer polyol, chain extender or organic diisocyanate compound A thermoplastic polymer composition obtained by polymerizing a polymer polyol, a chain extender and With inherent viscosity of polyurethane to be produced from an organic diisocyanate compound is 0.9 dl / g or more, thermoplastic polymer composition flame retardancy in the overall composition is UL94HB grade or more. High molecular polyol, reaction product of chain extender and organic diisocyanate compound, paraffin oil, and block copolymer having aromatic vinyl compound polymer block and conjugated diene polymer block or its hydrogenated product, Addition polymerization block copolymer (I ′) having a functional group reactive with a molecular polyol, a chain extender or an organic diisocyanate compound, and, if necessary, an aromatic vinyl compound block and a conjugated diene. Addition polymerization block copolymer (I '') comprising a block copolymer having a polymer block and a hydrogenated product thereof and having no functional group reactive with a polymer polyol, a chain extender or an organic diisocyanate compound Is a thermoplastic polymer composition obtained by melt-kneading and presenting in the composition With inherent viscosity of the polyurethane is 0.9 dl / g or more, thermoplastic polymer composition flame retardancy in the overall composition is UL94HB grade or more. The thermoplastic polymer composition according to any one of claims 8 to 10, wherein the polymer polyol has a number average molecular weight of 500 to 10,000. The thermoplastic polymer composition according to any one of claims 8 to 11, wherein the average number of functional groups per molecule of the polymer polyol is 2.0 to 2.1. The nitrogen atom content derived from the organic diisocyanate compound is in the range of 1 to 6.5% by weight based on the total weight of the polymer polyol, the chain extender and the organic diisocyanate compound. The thermoplastic polymer composition according to item. The molded article which consists of a thermoplastic polymer composition of any one of Claims 1-13. The composite molded object which consists of a thermoplastic polymer composition of any one of Claims 1-14, and another material.