JP2016183289A - Thermoplastic resin composition, molded body and wire covering material - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a thermoplastic resin composition excellent in oil resistance, low temperature flexibility, non-migration property to an ASA resin (acryl-styrene-acrylonitrile copolymer resin), moldability or the like, and a molded body and a wire obtained by using the thermoplastic resin composition.SOLUTION: There is provided a thermoplastic resin composition which contains following components (A), (B) and (C), and contains the component (B) of 50 to 150 pts.wt, based on 100 pts.wt. of the component (A), and in which a ratio of [weight of the component (B)]/[weight of the component (C)] is 0.1 to 20. Component (A): vinyl chloride resin. Component (B): a polyester-based plasticizer containing a 3-methyl-1,5-pentane diol unit of 50 mol% or more based on the total diol unit and an adipic acid unit of 50 mol% or more based on total dicarboxylic acid unit. Component (C):a polyester-based thermoplastic elastomer.SELECTED DRAWING: None

Description

  The present invention relates to a thermoplastic resin composition, and a molded body and an electric wire obtained using the thermoplastic resin composition. More specifically, the present invention relates to a resin composition that is excellent in oil resistance, low-temperature flexibility, molding processability and the like and does not adversely affect the surface appearance even when it comes into contact with an ASA resin.

  BACKGROUND ART A vinyl chloride resin composition containing a vinyl chloride resin, a plasticizer, and the like has been widely used for a long time in applications such as electric wire coating, tubes, tapes, building materials, automobile parts, and home appliance parts.

In particular, the electric wire may be used in a low temperature environment, in an environment where various fat-soluble liquids exist, and in an environment where ASA resin exists. However, none of the conventional vinyl chloride resin compositions can cope with these conditions at the same time.
As a method for improving the cold resistance of a vinyl chloride resin, it is generally known that fatty acid esters are used as a plasticizer, but this method has a decrease in heat resistance and bleed resistance in terms of performance, Although the low-temperature impact resistance is improved, there are problems that the low-temperature flexibility is not greatly improved and that the cost is high in terms of economy.

As a method for improving oil resistance, as disclosed in Non-Patent Document 1, a method using a polyester plasticizer condensed with various dicarboxylic acids and diols is known. As a method for solving the problem of low temperature flexibility, Patent Document 1 proposes a method of blending a polyester elastomer which is excellent in rubber elasticity and low temperature flexibility and has good compatibility with soft polyvinyl chloride. In addition, it gives high flexibility to vinyl chloride resin and has heat resistance, oil resistance, cold resistance, polystyrene resin and ABS resin (acrylonitrile-butadiene-styrene).
A polyester plasticizer using 3-methyl-1,5-pentanediol as a polyhydric alcohol component as a plasticizer composition capable of giving a composition having excellent performance such as migration resistance to a copolymer resin) A plasticizer composition obtained by mixing trimellitic acid triester or pyromellitic acid tetraester has also been proposed.

JP-A-4-11647 JP-A-8-337700

Endo, Akinori, Sudo, edited by Plastics -Basics and Applications- Taiseisha (1996)

  According to the detailed study of the present inventors, the electric wire may be used in an environment where it comes into contact with an ASA resin (acryl-styrene-acrylonitrile copolymer resin), and the conventional vinyl chloride-based thermoplastic resin composition is used. In such a case, the present inventors have found that there is a problem that the plasticizer moves to the surface of the ASA resin and the surface appearance is remarkably impaired.

  The object of the present invention is to solve the above-mentioned problems in the prior art and to provide a thermoplastic resin composition excellent in oil resistance, low temperature flexibility, non-migration to ASA resin, molding processability, etc., and this thermoplastic resin composition It is providing the molded object and electric wire which are obtained using this.

  As a result of intensive studies in view of the above problems, the present inventors have solved the above problems with a thermoplastic resin composition containing a vinyl chloride resin, a polyester plasticizer having a specific structure, and a polyester thermoplastic elastomer in a specific blending ratio. I found out. That is, the gist of the present invention resides in the following [1] to [6].

[1] The following component (A), component (B) and component (C) are included, and component (B) is included in an amount of 50 to 150 parts by weight with respect to 100 parts by weight of component (A), and [of component (B) The weight] / [weight of component (C)] is 0.1-20.
Component (A): Vinyl chloride resin Component (B): 50 mol% or more of 3-methyl-1,5-pentanediol unit with respect to all diol units, and 50 mol of adipic acid units with respect to all dicarboxylic acid units % Polyester-based plasticizer component (C): polyester-based thermoplastic elastomer

[2] The thermoplastic resin composition according to [1], wherein the viscosity of the component (B) at 25 ° C. is 2,500 to 10,000 mPa · s.

[3] The thermoplastic resin composition according to [1] or [2], wherein the component (C) has a hard segment made of polybutylene terephthalate and a soft segment made of polytetramethylene glycol.

[4] A molded article formed by molding the thermoplastic resin composition according to any one of [1] to [3].

[5] The molded article according to [4], which is formed by extrusion molding.

[6] An electric wire covering material comprising the thermoplastic resin composition according to any one of [1] to [3].

  According to the present invention, it is possible to provide a thermoplastic resin composition excellent in oil resistance, low temperature flexibility, non-migration to ASA resin, molding processability and the like. Since the thermoplastic resin composition of the present invention is excellent in the above properties, it is particularly suitable for electric wires, and can be suitably used for extruded products in the field of automobile wind molding and building materials.

  Hereinafter, the present invention will be described in detail. However, the following description is an example of an embodiment of the present invention, and the present invention is not limited to the following description unless it exceeds the gist. In addition, when using the expression “to” in the present invention, it is used as an expression including numerical values or physical property values before and after the expression.

[Thermoplastic resin composition]
The thermoplastic resin composition of the present invention includes the following component (A), component (B) and component (C), and includes 100 to 100 parts by weight of component (A), 50 to 150 parts by weight of component (B), [Weight of component (B)] / [Weight of component (C)] is 0.1-20.
Component (A): Vinyl chloride resin Component (B): 50 mol% or more of 3-methyl-1,5-pentanediol unit with respect to all diol units, and 50 mol of adipic acid units with respect to all dicarboxylic acid units % Polyester-based plasticizer component (C): polyester-based thermoplastic elastomer

[Component (A)]
The thermoplastic resin composition of the present invention contains a vinyl chloride resin as component (A). The type of the vinyl chloride resin is not limited as long as it is a homopolymer of vinyl chloride monomer or a copolymer of vinyl chloride monomer and a monomer copolymerizable with vinyl chloride monomer.

Examples of monomers copolymerizable with vinyl chloride monomer include vinyl esters such as vinyl acetate, vinyl propionate and vinyl laurate; acrylic acid esters such as methyl acrylate, ethyl acrylate and butyl acrylate; methyl methacrylate and ethyl methacrylate. Methacrylic acid esters such as dibutyl maleate and diethyl maleate; fumaric acid esters such as dibutyl fumarate and diethyl fumarate; vinyl ethers such as vinyl methyl ether, vinyl butyl ether and vinyl octyl ether; Vinyl cyanides such as acrylonitrile and methacrylonitrile; α-olefins such as ethylene, propylene and styrene; vinyl halides other than vinyl chloride such as vinylidene chloride and vinyl bromide Isopropylidene or vinyl halides; diallyl phthalate, although polyfunctional monomers such as ethylene glycol dimethacrylate, a monomer is not limited to those described above to be used. These monomers may be used individually by 1 type, and may use 2 or more types together. In the production of vinyl chloride resin, when the above monomer is used, the monomer is preferably used so as to be in the range of 30% by weight or less, and in the range of 20% by weight or less in the constituents of the vinyl chloride resin. More preferably, it is used. The vinyl chloride resin of component (A) in the present invention includes chlorinated polyvinyl chloride after the post-chlorination of a (co) polymer of vinyl chloride and a copolymerizable monomer that is used if necessary. A cross-linked vinyl chloride resin containing a cross-linked gel component insoluble in tetrahydrofuran (hereinafter referred to as THF) cross-linked by adding a cross-linking agent sometimes is also included.

  The production method of the vinyl chloride resin is not particularly limited, and for example, usual methods such as a suspension polymerization method, a bulk polymerization method, a fine suspension polymerization method, and an emulsion polymerization method can be used.

  The average degree of polymerization of the vinyl chloride resin of the component (A) is preferably 700 to 6,500, more preferably 1, based on JIS K6721, from the viewpoint of processability, moldability and physical properties. 300 to 4,000. When the average degree of polymerization is not less than the above lower limit value, physical properties of the obtained thermoplastic resin composition tend to be better, and when it is not more than the above upper limit value, workability and moldability tend to be better. Because.

  In the present invention, for the purpose of controlling the design surface of the molded product, a crosslinked vinyl chloride resin containing the aforementioned crosslinked gel can be used as the vinyl chloride resin. When the crosslinked vinyl chloride resin contains a THF-insoluble crosslinked gel content, the crosslinked gel content is desirably 60% by weight or less, preferably 50% by weight or less, and the average degree of polymerization of the portion dissolved in THF is as described above. It is desirable to be in range. In addition, the cross-linked vinyl chloride resin may be used as it is for the cross-linked gel, or a product exceeding the above-mentioned gel content is produced, and this is appropriately blended with a vinyl chloride resin to contain the cross-linked gel content. May be adjusted. If the cross-linked gel content exceeds the upper limit, mechanical properties such as tensile strength tend to decrease. In the present invention, the THF-insoluble cross-linked gel component was charged with 2 g of vinyl chloride resin in 30 ml of THF while being stirred and allowed to stand at a temperature of 25 ° C. for 24 hours. It is the percentage which calculated | required the undissolved part weight after filtering using this, and repeating this operation 3 times.

[Component (B)]
The polyester plasticizer of component (B) used in the thermoplastic resin composition of the present invention contains 50 mol% or more of 3-methyl-1,5-pentanediol units with respect to all diol units, and contains all dicarboxylic acid units. On the other hand, it is a polyester plasticizer containing 50 mol% or more of adipic acid units. In the thermoplastic resin composition of the present invention, the component (B) contributes to non-migration and oil resistance to the ASA resin.

  The polyester plasticizer of component (B) has an adipic acid unit content of 50 mol% or more, preferably 60 mol% or more, more preferably 70 mol% or more, based on all dicarboxylic acid units. . The upper limit is 100 mol%. In the polyester plasticizer of component (B), the higher the content of adipic acid units, the more preferable in terms of non-migration to ASA resin.

Examples of dicarboxylic acid units other than adipic acid units that can be contained in the polyester plasticizer of component (B) include 1,4-cyclohexanedicarboxylic acid units, 1,2-cyclohexanedicarboxylic acid units, 1,3- Cycloaliphatic dicarboxylic acid units, 1,4-decahydronaphthalenedicarboxylic acid units, 1,5-decahydronaphthalenedicarboxylic acid units and other alicyclic dicarboxylic acid units; terephthalic acid units, phthalic acid units, isophthalic acid units, phenylenedioxy Dicarboxylic acid units, 4,4′-diphenyldicarboxylic acid units, 4,4′-diphenyl ether dicarboxylic acid units, 4,4′-diphenyl ketone dicarboxylic acid units, 4,4′-diphenoxyethanedicarboxylic acid units, 4,4 '-Diphenylsulfone dicarboxylic acid unit, 2,6-naphthalenedica Aromatic dicarboxylic acid units such as bonic acid units; succinic acid units, glutaric acid units, adipic acid units, pimelic acid units, suberic acid units, azelaic acid units, sebacic acid units, undecadicarboxylic acid units, dodecadicarboxylic acid units, etc. A chain aliphatic dicarboxylic acid unit of the above; a dicarboxylic acid derivative unit such as an alkyl ester unit having 1 to 4 carbon atoms or a halide of these dicarboxylic acid units. These may contain 1 type independently and may contain 2 or more types.

  The polyester plasticizer of component (B) has a content of 3-methyl-1,5-pentanediol units of 50 mol% or more, preferably 60 mol% or more, more preferably based on all diol units. Is 70 mol% or more. The upper limit is 100 mol%. In the polyester plasticizer of component (B), the higher the content of 3-methyl-1,5-pentanediol units, the more preferable in terms of non-migration to the ASA resin.

On the other hand, examples of the diol unit other than the 3-methyl-1,5-pentanediol unit that can be contained in the component (B) include 1,2-cyclopentanediol unit, 1,3-cyclopentanediol unit, 1,2-cyclopentanedimethanol bis (hydroxymethyl) tricyclo [5.2.1.0] decane unit, 1,3-cyclopentanedimethanol bis (hydroxymethyl) tricyclo [5.2.1.0] decane 5-membered ring diol units such as units; 1,2-cyclohexanediol units, 1,3-cyclohexanediol units, 1,4-cyclohexanediol units, 1,2-cyclohexanedimethanol units, 1,3-cyclohexanedimethanol units 6-membered ring diols such as 2,2-bis- (4-hydroxycyclohexyl) -propane Position: ethylene glycol unit, trimethylene glycol unit, 1,2-propanediol unit, 1,2-butanediol unit, 1,3-butanediol unit, 1,4-butanediol unit, 2-methyl-1,3 -Propanediol unit, tetramethylene glycol unit, pentamethylene glycol unit, hexamethylene glycol unit, octamethylene glycol unit, decamethylene glycol unit, neopentyl glycol unit, diethylene glycol unit, polyethylene glycol unit, chain aliphatic diol unit; poly Polyalkylene ether glycol units such as tetramethylene ether glycol; xylylene glycol units, 4,4′-dihydroxybiphenyl units, 2,2-bis (4′-hydroxyphenyl) propane units, 2,2 -Aromatic diol units such as bis (4′-β-hydroxyethoxyphenyl) propane unit, bis (4-hydroxyphenyl) sulfone unit, and bis (4-β-hydroxyethoxyphenyl) sulfonic acid unit. These may be used alone or in combination of two or more.

  The polyester plasticizer of component (B) is used so that adipic acid is 50 mol% or more based on the total dicarboxylic acid raw material, and 3-methyl-1,5-pentanediol is used based on the total diol raw material. It can be obtained by carrying out esterification or transesterification and polycondensation reaction using 50 mol% or more. The temperature condition of the esterification reaction or transesterification reaction is usually 200 to 300 ° C. In order to obtain a sufficient reaction rate, it is preferable to use a catalyst. The catalyst is not particularly limited as long as it is a catalyst used in ordinary esterification reaction or transesterification reaction, and polycondensation reaction, and widely known catalysts can be adopted. Specific examples include titanium compounds, antimony compounds, tin compounds, and the like. When polycondensation is performed using a transesterification reaction, the dicarboxylic acid raw material is derived from the corresponding dimethyl dicarboxylate.

  In addition, as a polyester plasticizer of a component (B), 1 type of resin may be used independently, and 2 or more types from which a dicarboxylic acid unit and a diol component differ may be mixed and used.

  Component (B) preferably has a viscosity at 25 ° C. of 500 to 10,000 mPa · s, more preferably 1,500 to 7,000 mPa · s, and 2,000 to 5,000 mPa · s. More preferably. When the viscosity at 25 ° C. is in the above range, it is preferable from the viewpoint of oil resistance and molding processability.

  The polyester plasticizer of component (B) can also be obtained as a commercial product. For example, an appropriate product can be selected from Adekaizer (registered trademark) PN series manufactured by ADEKA or Polycizer (registered trademark) manufactured by DIC.

[Component (C)]
The polyester-based thermoplastic elastomer of component (C) used in the thermoplastic resin composition of the present invention is usually a block copolymer having a crystalline hard segment and an amorphous soft segment, The hard segment is made of polyester.

  The polyester-based thermoplastic elastomer of component (C) usually has a melting peak based on a hard segment when the thermal properties are measured by the DSC method. This melting peak temperature is preferably 140 ° C. or higher, more preferably 150 ° C. or higher, while preferably 220 ° C. or lower, more preferably 210 ° C. or lower.

  Further, the polyester-based thermoplastic elastomer of component (C) has flexibility based on a soft segment. Specifically, at least one of Duro D hardness and Duro A hardness can usually be measured, and the hardness is Duro D hardness. This is a range satisfying at least one of (JIS K6253-1993) 60 or less and Duro A hardness (JIS K6253-1993) 70 or more.

The polyester-based thermoplastic elastomer is from a cyclic polyester (in the present invention, “cyclic polyester” means a dicarboxylic acid or alkyl ester thereof containing dicarboxylic acid having a cyclic structure or an alkyl ester thereof). Block segments having a hard segment (hereinafter sometimes referred to as “cyclic polyester unit”) and a soft segment (hereinafter sometimes referred to as “polyalkylene ether glycol unit”) composed of polyalkylene ether glycol. A polymer (hereinafter sometimes referred to as “cyclic polyester-polyalkylene ether glycol block copolymer”), a hard segment comprising a cyclic polyester and a chain aliphatic polyester (in the present invention, “chain aliphatic polyester”). "Tell" means that the raw dicarboxylic acid or alkyl ester thereof is a dicarboxylic acid having only a chain structure or an alkyl ester thereof (hereinafter referred to as "chain aliphatic polyester unit"). And the like (hereinafter, sometimes referred to as “cyclic polyester-chain aliphatic polyester block copolymer”). Among these, a cyclic polyester-polyalkylene ether glycol block copolymer is preferable.

  As the cyclic polyester-polyalkylene ether glycol block copolymer, a block copolymer having a hard segment made of an aromatic polyester (hereinafter sometimes referred to as “aromatic polyester unit”) and a polyalkylene ether glycol unit ( Hereinafter, it may be referred to as “aromatic polyester-polyalkylene ether glycol block copolymer”), a hard segment composed of an alicyclic polyester (hereinafter sometimes referred to as “alicyclic polyester unit”). And a block copolymer having a polyalkylene ether glycol unit (hereinafter, sometimes referred to as “alicyclic polyester-polyalkylene ether glycol block copolymer”). Polyalkylene ether glycolate - Le block copolymer.

  The aromatic polyester-polyalkylene ether glycol block copolymer is a known thermoplastic elastomer as described in JP-A-10-130451 or the like and is a polymer containing a polyalkylene ether glycol unit. Each block may be a single polymer or a copolymer.

The raw material of the aromatic polyester unit will be described in detail below. However, since the compatibility with the vinyl chloride resin of component (A) is particularly good, it is preferable to contain polybutylene terephthalate as a hard segment, The glycol unit raw material is also described in detail below, but includes a soft segment (hereinafter sometimes referred to as “polytetramethylene glycol unit”) made of polytetramethylene ether glycol from the viewpoint of low-temperature flexibility. It is preferable. As the polyester thermoplastic elastomer used in the present invention, a polybutylene terephthalate-polyalkylene ether glycol block copolymer is preferable, and a polybutylene terephthalate-polytetramethylene ether glycol block copolymer is particularly preferable.

  In addition, as the alicyclic polyester-polyalkylene ether glycol block copolymer, an alicyclic dicarboxylic acid (in the present specification, “alicyclic dicarboxylic acid” means that two carboxyl groups are directly bonded to a cyclic aliphatic hydrocarbon. ), And those obtained using alicyclic diol and polyalkylene ether glycol as a raw material can be cited as representative examples. If the polymer contains a polyalkylene ether glycol unit, each block is The polymer may be a single polymer or a copolymer. The alicyclic polyester unit preferably includes a hard segment obtained using cyclohexanedicarboxylic acid and cyclohexanedimethanol as raw materials. The polyalkylene ether glycol unit of the alicyclic polyester-polyalkylene ether glycol block copolymer preferably includes a soft segment (polytetramethylene ether glycol unit) obtained using polytetramethylene ether glycol as a raw material.

As the cyclic polyester-chain aliphatic polyester block copolymer, a block copolymer having a hard segment composed of an aromatic polyester and a soft segment composed of a chain aliphatic polyester (hereinafter referred to as “aromatic polyester-chain aliphatic”). A block copolymer having a hard segment composed of an alicyclic polyester and a soft segment composed of a chain aliphatic polyester (hereinafter referred to as “alicyclic polyester-chain fatty acid”). In some cases, aromatic polyester-chain aliphatic polyester block copolymers are preferable. Among the aromatic polyester-chain aliphatic polyester block copolymers, a polybutylene terephthalate-chain aliphatic polyester block copolymer in which the aromatic polyester unit is made of polybutylene terephthalate is more preferable. The chain aliphatic polyester unit is preferably obtained from a chain aliphatic dicarboxylic acid having 4 to 10 carbon atoms typified by sebacic acid and adipic acid and a chain aliphatic diol.

  As a raw material for the soft segment having amorphous properties, polyalkylene ether glycol is preferable, polymethylene ether glycol, polyethylene ether glycol, poly (1,2- and 1,3-) propylene ether glycol, polytetramethylene ether glycol, In addition to linear and branched aliphatic ethers such as polyhexamethylene ether glycol, homopolymers or copolymers of alicyclic ethers such as cyclohexanediol condensates and cyclohexanedimethanol condensates may be mentioned. Moreover, the random copolymer in these ether units may be sufficient. A block copolymer having a polyalkylene ether glycol unit can also be used. These may be used alone or in combination of two or more.

  The number average molecular weight of the polyalkylene ether glycol unit contained in the cyclic polyester-polyalkylene ether glycol block copolymer is preferably 600 to 4,000, particularly preferably 800 to 2,500, and particularly preferably 900 to 2,100. . Here, the number average molecular weight of the polyalkylene ether glycol unit refers to a polystyrene-converted value measured by gel permeation chromatography (GPC).

  One of these polyalkylene ether glycol units may be contained in the cyclic polyester-polyalkylene ether glycol block copolymer, and two or more of those having different number average molecular weights and constituent components are contained. Also good.

  There is no restriction | limiting in particular as a manufacturing method of a polyester-type thermoplastic elastomer, For example, among cyclic polyester-polyalkylene ether glycol block copolymers, aromatic polyester-polyalkylene ether using aromatic polyester and polyalkylene ether glycol is used. If it is a glycol block copolymer, a chain aliphatic and / or alicyclic diol having 2 to 12 carbon atoms, an aromatic dicarboxylic acid or an alkyl ester thereof, and a polyalkylene ether glycol are used as raw materials, and an esterification reaction is performed. Alternatively, it can be obtained by polycondensing an oligomer obtained by a transesterification reaction.

  As said C2-C12 chain | strand-shaped aliphatic and / or alicyclic diol, what is normally used as a raw material of polyester can be used. For example, chain aliphatic diols include ethylene glycol, propylene glycol, trimethylene glycol, 1,3-butylene glycol, 1,4-butylene glycol, 1,6-hexene glycol and the like, among which 1,4 -Butylene glycol is preferred. Examples of the alicyclic diol include 1,4-cyclohexene glycol and 1,4-cyclohexanedimethanol, and 1,4-cyclohexanedimethanol is preferable. These C2-C12 chain aliphatic and / or alicyclic diols may be used alone or in a mixture of two or more.

  As the aromatic dicarboxylic acid or an alkyl ester thereof, those generally used as a raw material for polyester can be used. For example, terephthalic acid and its lower component (in this specification, “lower” means 4 or less carbon atoms). ) Alkyl esters, isophthalic acid, phthalic acid, 2,5-norbonane dicarboxylic acid, 1,4-naphthalenedicarboxylic acid, 1,5-naphthalenedicarboxylic acid, 2,6-naphthalenedicarboxylic acid and their lower alkyl esters Can be mentioned. Among these, terephthalic acid and isophthalic acid are preferable, and terephthalic acid is particularly preferable. These aromatic dicarboxylic acids or alkyl esters thereof may be used alone or in combination of two or more.

  Examples of the polyalkylene ether glycol include polymethylene ether glycol, polyethylene ether glycol, poly (1,2- and 1,3-) propylene ether glycol, polytetramethylene ether glycol, polyhexamethylene ether glycol and the like. In addition to chain and branched aliphatic ether glycols, there may be mentioned homopolymers or copolymers of alicyclic ethers such as cyclohexanediol condensates and cyclohexanedimethanol condensates. Moreover, the random copolymer in these ether units may be sufficient. Among these, linear and branched such as polymethylene ether glycol, polyethylene ether glycol, poly (1,2- and 1,3-) propylene ether glycol, polytetramethylene ether glycol, polyhexamethylene ether glycol and the like are preferable. More preferred are polymethylene ether glycol, polyethylene ether glycol, poly (1,2- and 1,3-) ether propylene glycol, polytetramethylene ether glycol, and particularly preferred are polymethylene ether glycol, polytetramethylene ether glycol, and polytetramethylene ether glycol. Tetramethylene ether glycol. These may be used alone or in combination of two or more.

  Further, when producing an alicyclic polyester-polyalkylene ether glycol block copolymer, an aromatic dicarboxylic acid used as a raw material for producing the above aromatic polyester-polyalkylene ether glycol block copolymer or its Instead of the alkyl ester, an alicyclic dicarboxylic acid or an alkyl ester thereof may be used. That is, it is obtained by esterification reaction or transesterification reaction using a chain aliphatic and / or alicyclic diol having 2 to 12 carbon atoms, an alicyclic dicarboxylic acid or an alkyl ester thereof, and a polyalkylene ether glycol as raw materials. The obtained oligomer can be obtained by polycondensation.

  As the alicyclic dicarboxylic acid or alkyl ester thereof, those generally used as raw materials for polyesters can be used, and examples thereof include cyclohexane dicarboxylic acid and lower alkyl esters thereof, cyclopentane dicarboxylic acid and lower alkyl esters and the like. . Among these, cyclohexanedicarboxylic acid and lower alkyl esters thereof are preferable, and cyclohexanedicarboxylic acid is particularly preferable. One of these alicyclic dicarboxylic acids may be used alone, or two or more thereof may be used in combination.

  The content of each of the cyclic polyester unit and the polyalkylene ether glycol unit in the cyclic polyester-polyalkylene ether glycol block copolymer is not limited, but it is usually less than or equal to the balance between the crystallinity of the hard segment and the flexibility of the soft segment. It becomes the range like this.

That is, the lower limit of the content of the cyclic polyester unit in the cyclic polyester-polyalkylene ether glycol block copolymer is usually 10% by weight or more, preferably 20% by weight or more. The upper limit of the content of the cyclic polyester unit is usually 95% by weight or less, preferably 90% by weight or less, more preferably 80% by weight or less. The lower limit of the content of the polyalkylene ether glycol unit in the cyclic polyester-polyalkylene ether glycol block copolymer is not limited, but is usually 5% by weight or more, preferably 10% by weight or more, more preferably 20% by weight. That's it. The upper limit of the content of the polyalkylene ether glycol unit is not limited, but is usually 90% by weight or less, preferably 80% by weight or less. In addition, the content of the cyclic polyester unit in the block copolymer having the cyclic polyester unit can be calculated based on the chemical shift of the hydrogen atom and the content using nuclear magnetic resonance spectroscopy (NMR). it can. Similarly, the content of the polyalkylene ether glycol unit in the block copolymer having the polyalkylene ether glycol unit is based on the chemical shift of the hydrogen atom and the content thereof using nuclear magnetic resonance spectroscopy (NMR). Can be calculated.

  As the aromatic polyester-polyalkylene ether glycol block copolymer, a polybutylene terephthalate-polyalkylene ether glycol block copolymer is preferred because of its particularly high crystallization speed and excellent moldability. 2-12 are preferable, as for carbon number of the alkylene group of a glycol unit, 2-8 are more preferable, 2-5 are still more preferable, and 4 is especially preferable.

  The cyclic polyester-polyalkylene ether glycol block copolymer represented by the aromatic polyester-polyalkylene ether glycol block copolymer according to the present invention includes trifunctional alcohol, tricarboxylic acid and / or other than the above components. Alternatively, one or two or more of the esters may be copolymerized in a small amount, and a chain aliphatic dicarboxylic acid such as adipic acid or a dialkyl ester thereof may be introduced as a copolymerization component.

  Said cyclic polyester-polyalkylene ether glycol block copolymer can also be obtained as a commercial item. Examples of such commercially available products include “Primalloy (registered trademark)” (manufactured by Mitsubishi Chemical Corporation), “Perprene (registered trademark)” (manufactured by Toyobo Co., Ltd.), and “Hytrel (registered trademark)” (manufactured by DuPont). ) And the like.

  Polyester thermoplastic elastomers such as cyclic polyester-polyalkylene ether glycol block copolymers may be used singly or in combination of two or more.

[Combination ratio]
The thermoplastic resin composition of the present invention contains 50 to 150 parts by weight of component (B) with respect to 100 parts by weight of component (A). It is necessary for the content of component (B) to be 50 parts by weight or more with respect to 100 parts by weight of component (A) in order to obtain non-migratory properties to ASA resin and cold resistance (low temperature flexibility). The content of (B) is preferably 60 parts by weight or more, more preferably 70 parts by weight or more. On the other hand, from the viewpoint of moldability, the content of component (B) is 150 parts by weight or less with respect to 100 parts by weight of component (A), and from this viewpoint, it is preferably 130 parts by weight or less.

  In the thermoplastic resin composition of the present invention, [weight of component (B)] / [weight of component (C)] is 0.1-20. From the viewpoint of moldability, [weight of component (B)] / [weight of component (C)] is 0.1 or more, and from this viewpoint, it is preferably 0.5 or more, more preferably 0.8. That's it. On the other hand, from the viewpoint of low temperature flexibility, [weight of component (B)] / [weight of component (C)] is 20 or less, and from this viewpoint, it is preferably 15 or less, more preferably 10 or less.

[Other ingredients]
The thermoplastic resin composition of the present invention includes a stabilizer in addition to the component (A), the component (B) and the component (C), a plasticizer other than the component (B), a lubricant, an antioxidant, and an ultraviolet absorber. In addition, various additives such as flame retardants, antistatic agents, colorants, foaming agents, impact modifiers, fillers, thermoplastic resins other than component (A) and component (C), etc. do not significantly impair the effects of the present invention. As long as it can be blended as needed.

  Stabilizers include inorganic salts such as tribasic lead sulfate, lead silicate and basic lead carbonate, metal soaps mainly composed of organic acid salts of metals such as lead, cadmium, barium, calcium and zinc, and the aforementioned metals. Containing at least two kinds, for example, fatty acid complexes such as Ba-Zn, Ca-Zn, and Cd-Ba, fatty acid (phosphite) -based, carboxylate (phosphite) -based composite metal soap or composite liquid metal soap, organic Examples thereof include tin compounds. These stabilizers may be used alone or in combination of two or more. When a stabilizer is blended in the thermoplastic resin composition of the present invention, the blending amount of the stabilizer is usually 0.1 to 30 parts by weight, preferably 1 to 15 parts by weight with respect to 100 parts by weight of the component (A). It is.

  Examples of plastic other than component (B) include di-2-ethylhexyl phthalate (DEHP), di-n-octyl phthalate, diisononyl phthalate (DINP), diisodecyl phthalate (DIDP), diundecyl phthalate (DUP), or carbon. Phthalate plasticizers such as phthalates of higher alcohols or mixed alcohols having about 10 to 13 atoms; di-2-ethylhexyl adipate, di-n-octyl adipate, di-n-decyl adipate, diisodecyl adipate, di Aliphatic dibasic acid ester plasticizers such as 2-ethylhexyl azelate, dibutyl sebacate, di-2-ethylhexyl sebacate; tri-2-ethylhexyl trimellitate (TOTM), tri-n-octyl trimellitate , Tridecyl trimelli , Triisodecyl trimellitate, di-n-octyl-n-decyl trimellrate and other trimellitic acid ester plasticizers; tributyl phosphate, tricresyl phosphate (TCP), triphenyl phosphate, trixylyl phosphate , Trioctyl phosphate, octyl diphenyl phosphate, cresyl diphenyl phosphate, tributoxyethyl phosphate, trichloroethyl phosphate, tris (2-chloropropyl) phosphate, tris (2,3-dichloropropyl) phosphate, tris (2,3-dibromo Propyl) phosphate, tris (bromochloropropyl) phosphate, bis (2,3-dibromopropyl) -2,3-dichloropropyl phosphate, bis (chloropropyl) monooctyl Phosphate ester plasticizers such as phosphate; Biphenyltetracarboxylic acid tetraalkyl ester plasticizers such as 2,3,3 ′, 4′-biphenyltetracarboxylic acid tetraheptyl ester; Polyester polymer plasticizers; Large epoxidation Examples include bean oil, epoxidized linseed oil, epoxidized cottonseed oil, and epoxy plasticizers such as liquid epoxy resins; chlorinated paraffins; chlorinated fatty acid esters such as pentachlorostearic acid alkyl esters. Plasticizers other than component (B) may be used alone or in combination of two or more.

  The filler that can be used in the thermoplastic resin composition of the present invention is not particularly limited. For example, carbon black, calcium carbonate, titanium oxide, talc, aluminum hydroxide, magnesium hydroxide, hydrotalcite, clay, silica, An example is white carbon. These fillers may be used alone or in combination of two or more. When a filler is blended in the thermoplastic resin composition of the present invention, the blending amount of the filler is usually 1 to 100 parts by weight, preferably 5 to 50 parts by weight with respect to 100 parts by weight of the chlorine-based resin component (A). It is.

[Method for producing thermoplastic resin composition]
The thermoplastic resin composition of the present invention is a temperature range in which the component (A), the component (B), the component (C) and other components are charged into a predetermined kneader or mixer and the component (A) is not deteriorated, For example, it can be prepared by uniformly mixing or kneading while heating to a temperature of 100 to 230 ° C, preferably 130 to 200 ° C. The mixer or kneader used for mixing or kneading the above-described components is not particularly limited as long as it is a device that can substantially uniformly mix and knead the compound. Examples of the mixer include a Henschel mixer, a ribbon blender, and a planetary mixer. Examples of the kneader include a single screw extruder, a twin screw extruder, a mill roll, a Banbury mixer, a kneader, and an intensive mixer. And those that can be kneaded under shear force.

[Physical properties]
The hardness of the thermoplastic resin composition of the present invention is preferably 30 to 90, more preferably 50 to 80 in terms of hardness measurement (Duro-A) based on JIS K6253.

  The thermoplastic resin composition of the present invention is excellent in cold resistance (low temperature flexibility). In the present invention, cold resistance (low temperature flexibility) can be evaluated based on JIS K6261 by a 50% impact embrittlement temperature at a low temperature using a low temperature embrittlement tester. The 50% impact embrittlement temperature based on JIS K6261 is evaluated as being excellent in cold resistance (low temperature flexibility) as the value is lower, and is preferably −50 ° C. or lower, more preferably −55 ° C. or lower.

[Molded body]
The thermoplastic resin composition of the present invention can be formed into a molded body by various molding methods such as extrusion molding, injection molding and compression molding. Among these, from the viewpoint of fluidity in the molten state of the thermoplastic resin composition, a method of forming a molded body by extrusion molding is preferable. Although there is no restriction | limiting in particular as shaping | molding conditions, Molding temperature 130-220 degreeC is suitable, and it is preferable from viewpoints of a moldability, a designability, etc. that it is more than the said lower limit. On the other hand, it is preferable from the viewpoint of preventing decomposition of the vinyl chloride resin contained in the thermoplastic resin composition to be not more than the above upper limit value.

[Usage]
The thermoplastic resin composition of the present invention is excellent in oil resistance and low-temperature flexibility, and has properties such that the plasticizer does not migrate to the ASA resin. For this reason, it can be suitably used in various industrial fields, and in particular, automotive exterior materials such as window moldings, door lower moldings, side moldings, automotive interior materials such as knobs and grips, building materials such as packings, sealing materials, and gaskets. It can be suitably used as a wire covering material, and is suitable for a wire covering material.

  EXAMPLES Hereinafter, although an Example demonstrates this invention more concretely, this invention is not limited to a following example at all. In addition, the values of various production conditions and evaluation results in the following examples have meanings as preferable values of the upper limit or the lower limit in the embodiment of the present invention, and the preferable range is the above-described upper limit or lower limit value. A range defined by a combination of values of the following examples or values of the examples may be used.

[material]
In the following Examples and Comparative Examples, the raw materials used for the production of the thermoplastic resin composition are as follows.

<Component (A)>
A-1:
Shin-Etsu Chemical Co., Ltd. vinyl chloride resin average polymerization degree: 2,500

<Component (B)>
B-1:
Polyester plasticizer viscosity containing 100 mol% of 3-methyl-1,5-pentanediol unit as diol unit and 100 mol% of adipic acid unit as dicarboxylic acid unit: 3,000 mPa · s
B-2:
It contains 70 mol% of 3-methyl-1,5-pentanediol units as diol units, 10 mol% of neopentyl glycol units and 20 mol% of 1,4-butanediol, and 100 mol of adipic acid units as dicarboxylic acid units. % Polyester-based plasticizer viscosity: 3,000 mPa · s

b-1 (for comparative example):
30 mol% of 3-methyl-1,5-pentanediol unit, 50 mol% of 2-methylpropanediol unit and 20 mol% of 1,4-butanediol as diol units, and adipic acid units as dicarboxylic acid units Polyester plasticizer viscosity containing 100 mol%: 3,000 mPa · s
b-2 (for comparative example):
Polyester plasticizer containing 60 mol% 1,4-butanediol as diol units, 40 mol% 1,3-butanediol and 100 mol% adipic acid units as dicarboxylic acid units Viscosity: 3,000 mPa · s
b-3 (for comparative example):
Polyester plasticizer viscosity containing 50 mol% 1,2-butanediol as diol units, 50 mol% 1,4-butanediol, and 100 mol% adipic acid units as dicarboxylic acid units Viscosity: 700 mPa · s
b-4 (for comparative example):
Trimellitic acid tris (2-ethylhexyl): TOTM

<Ingredient (C)>
C-1:
Polyester thermoplastic elastomer (obtained by copolycondensation of polybutylene terephthalate prepolymer (hard segment) and polytetramethylene ether glycol (soft segment))
Melting peak temperature: 165 ° C
Duro D hardness: 35

<Other ingredients>
D-1:
Ca / Mg / Zn stabilizer (manufactured by Adeka, ADK STAB RUP-106)

[Evaluation method]
In the following Examples and Comparative Examples, the raw materials used for the production of the thermoplastic resin composition and the evaluation methods of the obtained thermoplastic resin composition are as follows.

1) Low-temperature flexibility Based on JIS K6261, a low-temperature torsion test was performed, a change in torsion modulus at −55 to 25 ° C. was measured, and an evaluation was performed according to the following criteria.
○: The torsion modulus hardly changes in the range of −30 ° C. to 25 ° C.
Δ: Torsional modulus slightly changes in the range of −30 ° C. to 25 ° C.
X: The torsion modulus changes remarkably in the entire measurement region.

2) Oil resistance An oil resistance test was performed based on JIS K6723.
○: The residual ratio of tensile strength and the residual ratio of elongation are both 90% or more.
Δ: Residual rate of tensile strength and residual rate of elongation are both 80% or more, and any of them is less than 90%.
X: At least one of the residual ratio of tensile strength and the residual ratio of elongation is less than 80%.

3) ASA transferability A test piece having a width of 6 mm and a length of 40 mm was punched out from a press sheet in which the thermoplastic resin composition was adjusted to a thickness of 2 mm using a forging blade. ASA resin was stuck to the entire surface of the test piece, and a load of 500 g was applied. In this state, the sample was allowed to stand in an atmosphere of 60 ° C. for 24 hours, and evaluation was performed based on whether or not traces were observed on the ASA surface.
○: No trace is observed.
Δ: Slight traces are observed.
X: A clear trace is recognized.

[Examples 1-8 and Comparative Examples 1-9]
Among the blending raw materials shown in Table-1 or Table-2, components other than the polyester-based thermoplastic elastomer of component (C) are charged into a high-speed mixer in the blending amounts described in Table-1 or Table-2, and the temperature is changed to 110 ° C. Stir until discharged. The polyester thermoplastic elastomer of component (C) was added to the discharged mixture at the blending amount described in Table-1 or Table-2, kneaded with a kneader, and discharged when it reached 170 ° C.

Regarding the low temperature flexibility, oil resistance, and ASA transferability, this thermoplastic resin composition was molded by a press molding machine at a molding temperature of 180 ° C. and a molding pressure of 200 kg / cm ² and used as a sample for evaluation. Each evaluation result is shown in Table-1 or Table-2.

[Evaluation results]
As can be seen from Tables 1 and 2, Examples 1 to 8 corresponding to the thermoplastic resin composition of the present invention have low temperature flexibility, oil resistance, and ASA migration compared to Comparative Examples 1 to 9. It turns out that it is excellent in balance.

Comparative Examples 1 to 3 are examples in which any of “b-1” to “b-3” was used without using the component (B), but in comparison with Examples 1 to 8, an ASA resin was used. It turns out that it is inferior to the non-transferability to. Moreover, although the comparative example 4 is an example which did not use a component (B) and used "b-4" instead, it turns out that it is inferior to oil resistance. Further, Comparative Examples 5 and 6 are examples in which the component (A) to the component (C) are used, but the amount of the component (B) is reduced, but these are inferior in low-temperature flexibility. I know that there is. Comparative Examples 7 and 8 are components (B
)), But the material could not be uniformly kneaded. Furthermore, although Comparative Example 9 uses components (A) to (C), [weight of component (B)] / [weight of component (C)] is 125/5 (= 25). It is an example that does not correspond to the thermoplastic resin composition of the present invention, and is found to be inferior in low-temperature flexibility.

Claims (6)

The following component (A), component (B), and component (C) are included, component (A) is included in an amount of 50 to 150 parts by weight, and [weight of component (B)] / The thermoplastic resin composition whose [weight of a component (C)] is 0.1-20.
Component (A): Vinyl chloride resin Component (B): 50 mol% or more of 3-methyl-1,5-pentanediol unit with respect to all diol units, and 50 mol of adipic acid units with respect to all dicarboxylic acid units % Polyester-based plasticizer component (C): polyester-based thermoplastic elastomer   The thermoplastic resin composition of Claim 1 whose viscosity in 25 degreeC of a component (B) is 500-10,000 mPa * s.   The thermoplastic resin composition according to claim 1 or 2, wherein the component (C) has a hard segment composed of polybutylene terephthalate and a soft segment composed of polytetramethylene glycol.   The molded object formed by shape | molding the thermoplastic resin composition of any one of Claims 1 thru | or 3.   The molded product according to claim 4, which is formed by extrusion molding.   An electric wire covering material comprising the thermoplastic resin composition according to any one of claims 1 to 3.