JP2008297329A - High heat resistant resin composition - Google Patents

Abstract

An object of the present invention is to provide a material having an excellent balance of rigidity, impact resistance and heat resistance by improving a thermoplastic resin blend.
(A) 100 parts by mass of a thermoplastic resin blend comprising 1 to 99% by mass of a thermoplastic resin a1 to 99% by mass of a thermoplastic resin b, and (B) 0.1 to 100 parts by mass of a block copolymer; (C) The thermoplastic resin composition containing 0.1-50 mass parts of polycarbodiimide which consists of polycarbonate diol and excess aromatic diisocyanate.
[Selection figure] None

Description

  The present invention relates to a thermoplastic resin used as a material for various industrial parts such as automobile parts and electrical / electronic parts.

Up to now, various techniques relating to thermoplastic resin blends obtained by melting and kneading two or more different thermoplastic resins have been developed as materials for industrial parts such as automobile parts and electrical / electronic parts.
For example, a technique related to a thermoplastic resin blend made of a polyphenylene ether resin and a polystyrene resin is disclosed in Patent Document 1, and a thermoplastic resin blend based on this technique is widely used as a component material in the electric / electronic field.
Moreover, the technique regarding the thermoplastic resin blend which consists of a polyphenylene ether resin and a polyamide resin is disclosed by patent document 2, and the thermoplastic resin blend by this technique is widely used as components materials, such as a motor vehicle field | area.
Further, a technique relating to a thermoplastic resin blend made of a polyphenylene ether resin and a polyphenylene sulfide resin is disclosed in Patent Document 3, and the thermoplastic resin blend based on this technique is widely used as a component material in the fields of automobiles and electrical equipment.
Furthermore, a technique related to a thermoplastic resin blend made of a polyphenylene ether resin and an aromatic polyester resin is disclosed in Patent Document 4, and the thermoplastic resin blend based on this technique is widely used as a component material in the electric / electronic field.
However, these thermoplastic resin blends do not have sufficient tensile properties, impact resistance, and rigidity, and are advanced materials required for manufacturing various industrial parts in the electric / electronic field, automobile field, etc. as a substitute for metal. It has not yet reached the point of combining material properties.

JP 05-186681 A Japanese Patent Laid-Open No. 02-201811 JP 2001-302916 A Japanese Patent Laid-Open No. 5-117505

  An object of the present invention is to provide a material having an excellent balance of rigidity, impact resistance and heat resistance by improving a thermoplastic resin blend.

In order to achieve the above-mentioned object, the present inventor has conducted studies on a thermoplastic resin blend obtained by melt-kneading two or more different thermoplastic resins, and as a result, a specific block has been added to the thermoplastic resin blend. By blending a copolymer with a specific polycarbodiimide,
It has been found that a thermoplastic resin composition having a very high balance of rigidity, impact resistance and heat resistance can be obtained, and the present invention has been made.

（式１中、ｋは０〜３０の整数、ｍは２〜１００の整数、ｎは０〜３０の整数、Ｒ₁は炭素数２〜１０のアルキレン基、Ｒ₂は芳香族ジイソシアネート残基、Ｒ₃は芳香族モノイソシアネート残基を意味する。） That is, the present invention is as follows.
(A) 100 parts by mass of a thermoplastic resin blend consisting of thermoplastic resin a1 to 99% by mass and thermoplastic resin b99 to 1% by mass;
(B) 0.1-100 parts by mass of a block copolymer;
(C) 0.1 to 50 parts by mass of polycarbodiimide represented by the formula (1);
A thermoplastic resin composition comprising:
Formula (1)

(In Formula 1, k is an integer of 0 to 30, m is an integer of 2 to 100, n is an integer of 0 to 30, R ₁ is an alkylene group having 2 to 10 carbon atoms, R ₂ is an aromatic diisocyanate residue, R ₃ means an aromatic monoisocyanate residue.)

  According to the present invention, a thermoplastic resin composition having an improved balance of tensile properties, impact resistance, rigidity, etc. can be provided without impairing the moldability of conventional thermoplastic resin blends.

Hereinafter, the present invention will be specifically described.
1. (A) Thermoplastic resin blend 1-1 Thermoplastic resins a and b
First, (A) the thermoplastic resin a and the thermoplastic resin b constituting the thermoplastic resin blend will be described.
In the present invention, (A) the thermoplastic resin a and the thermoplastic resin b constituting the thermoplastic resin blend are different types of thermoplastic resins.
The combination of the thermoplastic resin a and the thermoplastic resin b can be any combination as long as it is a combination of different types of thermoplastic resins.
In the present invention, the different types of thermoplastic resins are thermoplastic resins having different types of polymers constituting the thermoplastic resin; either the number average molecular weight, viscosity average molecular weight or weight average molecular weight of the polymer constituting the thermoplastic resin. Thermoplastic resins that differ by 20% or more; Thermoplastic resins that differ in melt viscosity or solution viscosity by 100% or more; When the thermoplastic resin is made of a copolymerized polymer, thermoplastic resins that differ in copolymerization ratio by 10% or more A thermoplastic resin corresponding to any one or more of thermoplastic resins having different monomer sequences in the copolymer (sequences such as random copolymerization, alternating copolymerization, block copolymerization, and graft copolymerization);

Examples of the thermoplastic resins a and b used in the present invention include polyolefin resin, polystyrene resin, acrylic resin, polyphenylene ether resin, polycarbonate resin, polyamide resin, polyphenylene sulfide resin, thermoplastic elastomer, phenol resin, polyacetal resin, and polyethylene. Examples include terephthalate resin, polybutylene terephthalate resin, aromatic polyester resin, and polyetherimide resin.
The thermoplastic resins a and b used in the present invention are preferably those having a melting point of 140 to 340 ° C or a glass transition temperature of 80 to 250 ° C.

In the present invention, polyphenylene ether resins can be preferably used as the thermoplastic resins a and b.
Examples of the polyphenylene ether resin that can be preferably used as the thermoplastic resins a and b in the present invention include a homopolymer or a copolymer having a repeating unit represented by the formula (3).

Formula (3)

In formula (3), R ₁ and R ₄ each independently represent hydrogen, primary or secondary lower alkyl, phenyl, aminoalkyl, or hydrocarbonoxy. R ₂ and R ₃ each independently represent hydrogen, primary or secondary lower alkyl, or phenyl.

Specific examples of the homopolymer of polyphenylene ether resin include, for example, poly (2,6-dimethyl-1,4-phenylene) ether, poly (2-methyl-6-ethyl-1,4-phenylene) ether, poly (2,6-diethyl-1,4-phenylene) ether, poly (2-ethyl-6-n-propyl-1,4-phenylene) ether, poly (2,6-di-n-propyl-1,4) -Phenylene) ether, poly (2-methyl-6-n-butyl-1,4-phenylene) ether, poly (2-ethyl-6-isopropyl-1,4-phenylene) ether, poly (2-methyl-6) -Hydroxyethyl-1,4-phenylene) ether, poly (2-methyl-6-chloroethyl-1,4-phenylene) ether and the like.
Of these, poly (2,6-dimethyl-1,4-phenylene) ether is particularly preferred.

  The polyphenylene ether resin copolymer is a copolymer containing a phenylene ether unit as a single unit. Specific examples thereof include, for example, a copolymer of 2,6-dimethylphenol and 2,3,6-trimethylphenol, a copolymer of 2,6-dimethylphenol and o-cresol, Examples thereof include a copolymer of dimethylphenol, 2,3,6-trimethylphenol, and o-cresol.

Examples of the method for producing the polyphenylene ether resin used in the present invention include a method of oxidative polymerization of 2,6-xylenol using a complex of cuprous salt and amine described in US Pat. No. 3,306,874 as a catalyst. It is done.
The methods described in U.S. Pat. No. 3,306,875, U.S. Pat. No. 3,257,357, U.S. Pat. It is preferable as a production method.

Further, it is proposed that the polyphenylene ether resin used in the present invention may be present in the conventional polyphenylene ether resin in addition to the repeating unit represented by the formula (3) unless it is contrary to the gist of the present invention. Various other phenylene ether units may be included as a partial structure.
Examples of the phenylene ether unit proposed to coexist in a small amount include 2- (dialkylaminomethyl) -6-methylphenylene ether unit described in JP-A-63-301222, 2- ( N-alkyl-N-phenylaminomethyl) -6-methylphenylene ether unit and the like.

  The polyphenylene ether resin used in the present invention may be one in which a small amount of diphenoquinone or the like is bonded in the main chain.

In the present invention, polystyrene resins can be preferably used as the thermoplastic resins a and b.
As the polystyrene resin that can be preferably used as the thermoplastic resins a and b in the present invention, a homopolymer of an aromatic vinyl monomer or an aromatic vinyl monomer unit of 50% by mass or more and Examples thereof include copolymers with other vinyl monomers or rubbery polymers that can be copolymerized.

Examples of the aromatic vinyl monomer include styrene, α-methylstyrene, 2,4-dimethylstyrene, monochlorostyrene, o-methylstyrene, p-methylstyrene, m-methylstyrene, p-tert-butylstyrene. And ethyl styrene.
Examples of other vinyl monomers or rubbery polymers copolymerizable with aromatic vinyl monomers include methacrylic acid esters such as methyl methacrylate and ethyl methacrylate; acrylonitrile, methacrylonitrile and the like. Unsaturated nitrile compounds; acid anhydrides such as maleic anhydride.

In the present invention, polyamide resins can be preferably used as the thermoplastic resins a and b.
Examples of the polyamide resin that can be preferably used as the thermoplastic resins a and b in the present invention include those having an amide bond {—NH—C (═O) —} in the polymer main chain. In general, the polyamide resin is obtained by ring-opening polymerization of lactams, polycondensation of diamine and dicarboxylic acid, polycondensation of aminocarboxylic acid, and the like, but is not limited thereto.

  Examples of the diamine that can be used as a raw material for the polyamide resin include aliphatic, alicyclic and aromatic diamines, and specific examples include tetramethylene diamine, hexamethylene diamine, undecamethylene diamine, and dodecamethylene. Diamine, tridecamethylenediamine, 2,2,4-trimethylhexamethylenediamine, 2,4,4-trimethylhexamethylenediamine, 5-methylnanomethylenediamine, 1,3-bisaminomethylcyclohexane, 1,4-bis Examples include aminomethylcyclohexane, m-phenylenediamine, p-phenylenediamine, m-xylylenediamine, and p-xylylenediamine.

Dicarboxylic acids are roughly classified into aliphatic, alicyclic and aromatic dicarboxylic acids. Specific examples include adipic acid, suberic acid, azelaic acid, sebacic acid, dodecanedioic acid, 1,1,3-tridecane. Examples include diacid, 1,3-cyclohexanedicarboxylic acid, terephthalic acid, isophthalic acid, naphthalenedicarboxylic acid, dimer acid and the like.
Specific examples of lactams include ε-caprolactam, enantolactam, and ω-laurolactam.
Specific examples of the aminocarboxylic acid include ε-aminocaproic acid, 7-aminoheptanoic acid, 8-aminooctanoic acid, 9-aminonanoic acid, 11-aminoundecanoic acid, 12-aminododecanoic acid, and 13-amino. And tridecanoic acid.

In the present invention, any of copolyamides obtained by polycondensation of lactams, diamines, dicarboxylic acids, and ω-aminocarboxylic acids alone or in a mixture of two or more can be used.
Moreover, what polymerized lactam, diamine, dicarboxylic acid, and (omega) -aminocarboxylic acid to the low molecular-weight oligomer stage in the polymerization reactor, and high molecular weight with the extruder etc. can be used conveniently.
The method for polymerizing the polyamide resin used in the present invention is not particularly limited, and any of melt polymerization, interfacial polymerization, solution polymerization, bulk polymerization, solid phase polymerization, and a combination thereof may be used. Among these, melt polymerization is more preferably used.

Specific examples of the polyamide resin that can be preferably used in the present invention include, for example, polyamide-6, polyamide-6,6, polyamide 4,6, polyamide 11, polyamide 12, polyamide 6,10, polyamide 6,12, polyamide 6 / 6,6, polyamide 6 / 6,12, polyamide MXD (m-xylylenediamine), 6, polyamide 6, T, polyamide 6, I, polyamide 6/6, T, polyamide 6/6, I, polyamide 6,6 / 6, T, polyamide 6,6 / 6, I, polyamide 6/6, T / 6, I, polyamide 6,6 / 6, T / 6, I, polyamide 6/12/6, T Polyamides such as polyamide 6, 6/12/6, T, polyamide 6/12/6, I, polyamide 6, 6/12/6, I, polyamide 9, T, etc. It can also be used an extruder and copolymerizing perform transamidation reaction and polyamide.
In the present invention, particularly preferred polyamide resins are polyamide-6, polyamide-6,6, polyamide 6 / 6,6, polyamide 9, T, and mixtures thereof, and the most preferred polyamide resins are polyamide 6, polyamide 6, 6, polyamide 9, T, or a mixture thereof.

A preferable viscosity range of the polyamide resin that can be used in the present invention is a viscosity number measured in 96% sulfuric acid according to ISO 307, and is in the range of 50 to 300 ml / g. More preferably, it is the range of 80-180 ml / g.
In the present invention, even if the polyamide resin is a mixture of polyamide resins having a viscosity number outside the above range, it can be preferably used if the viscosity number of the mixture is within the above range. Examples thereof include a mixture of a polyamide resin having a viscosity of 150 ml / g and a polyamide resin having a viscosity of 80 ml / g, a mixture of a polyamide resin having a viscosity of 120 ml / g and a polyamide resin having a viscosity of 115 ml / g, and the like. It is done. Whether or not the viscosity number of the polyamide resin mixture is within the above range can be easily confirmed by dissolving the polyamide resin in 96% sulfuric acid at the same ratio as the mixing ratio and measuring the viscosity number according to ISO307. Can do.
A particularly preferable mixed form among the polyamide resins is a mixture of polyamide resins in which each polyamide resin has a viscosity number of 90 to 150 ml / g and different viscosity numbers.

In this invention, it is preferable that the molar ratio of the amino group terminal of a polyamide resin and the carboxyl group terminal, ie, terminal amino group / terminal carboxyl group ratio, is 0.10-10, More preferably, it is 0.12-5. 0, more preferably 0.15 to 1.0, particularly preferably 0.17 to 0.80.
As a method for adjusting the end group of the polyamide resin, a known method that will be apparent to those skilled in the art can be used. For example, a method of adding one or more selected from a diamine compound, a monoamine compound, a dicarboxylic acid compound, a monocarboxylic acid compound and the like at a predetermined end group concentration at the time of polymerization of the polyamide resin can be mentioned.
In the present invention, as a method for quantifying the amino group terminal and carboxyl group terminal of a polyamide resin, E. Waltz, Guy B. Taylor, “Dedication of the molecular Weight of Nylon”, Ind. Eng. Chem. Anal. Ed. , 19, 448 (1947).
When a plurality of polyamide resins are used as the thermoplastic resins a and b, the terminal amino group / terminal carboxyl group ratio of the entire polyamide resin is given by the following formula.
Terminal amino group / terminal carboxyl group ratio of the entire polyamide resin = Σ ((addition amount of polyamide i) × (amino group end of polyamide i)) / Σ ((addition amount of polyamide i) × (carboxyl group end of polyamide i) ))

In the present invention, the metal stabilizer described in JP-A-1-163262 can be used without any problem for the purpose of improving the heat resistance stability of the polyamide resin.
Among these metal stabilizers, those that can be particularly preferably used include CuI, CuCl ₂ , copper acetate, cerium stearate, and the like. Further, halogenated salts of alkyl metals typified by potassium iodide, potassium bromide and the like can also be suitably used. Of course, these may be added together.
The preferable compounding amount of the metal stabilizer and / or the halogenated salt of the alkyl metal is 0.001 to 1 part by mass with respect to 100 parts by mass of the total amount of the polyamide resin.

Moreover, in this invention, a well-known organic stabilizer other than the metal stabilizer mentioned above can be used without a problem. Specific examples of the organic stabilizer include, for example, hindered phenol antioxidants represented by Irganox 1098, phosphorus processing heat stabilizers represented by Irgaphos 168, and lactones represented by HP-136. Examples thereof include a processing heat stabilizer, a sulfur heat stabilizer, a hindered amine light stabilizer, and the like.
Among these organic stabilizers, a hindered phenol antioxidant, a phosphorus processing heat stabilizer, or a combination thereof is preferable.
A preferable blending amount of these organic stabilizers is 0.001 to 1 part by mass with respect to 100 parts by mass of the polyamide resin.

  Furthermore, in addition to the above, known additives that can be added to the polyamide resin can be added to the polyamide resin. The amount of such an additive added is preferably less than 10 parts by mass with respect to 100 parts by mass of the polyamide resin.

In the present invention, polycarbonate resins can be preferably used as the thermoplastic resins a and b.
Examples of the polycarbonate resin that can be preferably used as the thermoplastic resins a and b in the present invention include a polymer having a repeating unit represented by the following formula (4).

Formula (4)

In Formula (4), Z, alkylene or C1-8 shows a single bond, alkylidene of 2 to 8 carbon atoms, cycloalkylene of 5 to 15 carbon atoms, SO _2, SO, O, CO, or And means a group represented by formula (5). Moreover, X shows hydrogen or a C1-C8 saturated alkyl group, a and b show the integer of 0-4.

Formula (5)

This polycarbonate resin is, for example, a reaction between a dihydric phenol and a carbonate precursor such as phosgene or a dihydric phenol in the presence of a known acid acceptor or molecular weight modifier in a solvent method, that is, a solvent such as methylene chloride. It can be produced by a transesterification reaction with a carbonate precursor such as diphenyl carbonate.
Examples of the dihydric phenol that can be used here include 2,2-bis (4-hydroxyphenyl) propane [commonly known as bisphenol A], hydroquinone, 4,4′-dihydroxydiphenyl, and bis (4-hydroxyphenyl) alkane. Bis (4-hydroxyphenyl) cycloalkane, bis (4-hydroxyphenyl) sulfide, bis (4-hydroxyphenyl) sulfone, bis (4-hydroxyphenyl) sulfoxide, bis (4-hydroxyphenyl) ether, etc. Can do. In particular, bisphenol A is preferably used alone or mixed with other dihydric phenols. These dihydric phenols may be homopolymers of dihydric phenols or two or more kinds of copolymers or blends. Furthermore, the polycarbonate resin used in the present invention may be a thermoplastic random polycarbonate obtained by reacting a polyfunctional aromatic compound with a dihydric phenol and / or a carbonate precursor.

In the present invention, polyphenylene sulfide resins can be preferably used as the thermoplastic resins a and b.
Examples of the polyphenylene sulfide resin (PPS resin) that can be preferably used as the thermoplastic resins a and b in the present invention include those containing 70 mol% or more of a structural unit represented by the following formula (6). When the structural unit represented by the formula (6) is less than 70 mol%, it tends to be difficult to obtain a thermoplastic resin composition having excellent characteristics.

Formula (6)

  As a polymerization method of the PPS resin, a method in which sodium sulfide and p-dichlorobenzene are reacted in an amide solvent such as N-methylpyrrolidone or dimethylacetamide or a sulfone solvent such as sulfolane can be mentioned as a preferred example. At this time, an alkali metal salt of carboxylic acid or sulfonic acid can be added to adjust the degree of polymerization, or an alkali hydroxide, an alkali metal carbonate, or an alkaline earth metal oxide can be added. As a copolymerization component, meta bond, ortho bond, ether bond, sulfone bond, biphenyl bond, substituted phenylene sulfide bond (substituents are alkyl group, nitro group, phenyl group, alkoxy group, carboxylic acid group, carboxylic acid metal Even if it contains a trifunctional bond or the like, it may be in a range that does not greatly affect the crystallinity of the polymer, but preferably the copolymerization component is less than 30 mol%, more preferably 10 mol%. It is as follows. The PPS resin is usually used after thermal crosslinking at a temperature of 200 to 250 ° C. in the presence of oxygen to adjust the melt viscosity.

In the present invention, aromatic polyester resins can be preferably used as the thermoplastic resins a and b.
Examples of the aromatic polyester resin that can be preferably used as the thermoplastic resins a and b in the present invention include polyester resins that form an anisotropic molten phase. The polyester forming the anisotropic melt phase is called a thermotropic liquid crystal polyester resin by those skilled in the art and has a melting point of 180 to 360 ° C. measured by a differential scanning calorimeter. The property of the anisotropic molten phase can be confirmed by a normal deflection inspection method using an orthogonal deflector, that is, by observing a sample placed on a hot stage in a nitrogen atmosphere.

In the present invention, as the aromatic polyester resin, either a semi-aromatic polyester having an aliphatic group in a molecular chain or a fully aromatic polyester in which the molecular chain is entirely composed of an aromatic group may be used. Of these aromatic polyester resins, wholly aromatic polyesters are preferred because of their good flame retardancy and mechanical properties.
Examples of the repeating unit constituting the aromatic polyester resin used in the present invention include an aromatic oxycarbonyl repeating unit, an aromatic dicarbonyl repeating unit, an aromatic dioxy repeating unit, an aromatic oxydicarbonyl repeating unit, and an aliphatic dioxy Examples include repeating units.

  Specific examples of the monomer giving the aromatic oxycarbonyl repeating unit include, for example, parahydroxybenzoic acid, metahydroxybenzoic acid, orthohydroxybenzoic acid, 6-hydroxy-2-naphthoic acid, and 5-hydroxy-2-naphthoic acid. Acid, 3-hydroxy-2-naphthoic acid, 4′-hydroxyphenyl-4-benzoic acid, 3′-hydroxyphenyl-4-benzoic acid, 4′-hydroxyphenyl-3-benzoic acid, their alkyl, alkoxy or Halogen-substituted products and ester-forming derivatives thereof such as acylated products, ester derivatives, acid halides and the like can be mentioned. Among these, parahydroxybenzoic acid and 6-hydroxy-2-naphthoic acid are preferable.

  Specific examples of the monomer that gives an aromatic dicarbonyl repeating unit include, for example, terephthalic acid, isophthalic acid, 2,6-naphthalenedicarboxylic acid, 1,6-naphthalenedicarboxylic acid, 2,7-naphthalenedicarboxylic acid, 1 , 4-Naphthalenedicarboxylic acid, 4,4′-dicarboxybiphenyl, aromatic dicarboxylic acids such as bis (4-carboxyphenyl) ether, bis (3-carboxyphenyl) ether, alkyl, alkoxy or halogen substitution thereof And ester-forming derivatives such as ester derivatives and acid halides thereof, among which terephthalic acid and 2,6-naphthalenedicarboxylic acid are preferred.

  Specific examples of the monomer that gives an aromatic dioxy repeating unit include, for example, hydroquinone, resorcin, 2,6-dihydroxynaphthalene, 2,7-dihydroxynaphthalene, 1,6-dihydroxynaphthalene, 1,4-dihydroxynaphthalene, Aromatic diols such as 4,4′-dihydroxybiphenyl, 3,3′-dihydroxybiphenyl, 3,4′-dihydroxybiphenyl, 4,4′-dihydroxybiphenyl ether, alkyl, alkoxy or halogen substituents thereof, And ester-forming derivatives such as acylated products thereof, among which hydroquinone and 4,4′-dihydroxybiphenyl are preferred.

  Specific examples of monomers that give aromatic oxydicarbonyl repeating units include, for example, hydroxy aromatic dicarboxylic acids such as 3-hydroxy-2,7-naphthalenedicarboxylic acid, 4-hydroxyisophthalic acid, and 5-hydroxyisophthalic acid. Examples thereof include acid, alkyl, alkoxy or halogen-substituted products thereof, and ester-forming derivatives such as acylated products, ester derivatives, and acid halides thereof.

Specific examples of the monomer that gives the aliphatic dioxy repeating unit include aliphatic diols such as ethylene glycol, 1,4-butanediol, 1,6-hexanediol, and acylated products thereof.
Also, polyesters having aliphatic dioxy repeating units such as polyethylene terephthalate and polybutylene terephthalate react with aromatic oxycarboxylic acids, aromatic dicarboxylic acids, aromatic diols and their acylated products, ester derivatives, acid halides, etc. It is possible to obtain an aromatic polyester resin containing an aliphatic dioxy repeating unit.

  Among these combinations of repeating units, examples of suitable combinations having a low melting point and good mechanical properties are shown below. In addition, the number of a repeating unit represents the mol% of each repeating unit in aromatic polyester resin.

  Among these, combinations of repeating units shown below are particularly preferable.

The aromatic polyester resin used in the present invention may contain an amide bond or a thioester bond as long as the object of the present invention is not impaired. Examples of the monomer that gives such a bond include aromatic hydroxyamines, aromatic diamines, aromatic aminocarboxylic acids, mercaptoaromatic carboxylic acids, aromatic dithiols, and mercaptoaromatic phenols. It is preferable that the usage-amount of these monomers is 10 mol% or less with respect to the total amount of all the monomers.
The aromatic polyester resin used in the present invention may be a blend of two or more aromatic polyester resins.

1-2 Thermoplastic Resin Blend Next, the (A) thermoplastic resin blend composed of the thermoplastic resin a and the thermoplastic resin b will be described.
The thermoplastic resin blend (A) in the present invention can be produced by melting and kneading different types of thermoplastic resin a and thermoplastic resin b.
As long as the combination of the thermoplastic resin a and the thermoplastic resin b is a combination of different types of thermoplastic resins, any combination is possible.

In this invention, (A) thermoplastic resin blend consists of thermoplastic resin a1-99 mass% and thermoplastic resin b99-1 mass%.
In the present invention, a preferred (A) thermoplastic resin blend comprises 10 to 90% by mass of a thermoplastic resin a and 90 to 10% by mass of a thermoplastic resin b.
In the present invention, the more preferable (A) thermoplastic resin blend comprises 30 to 70% by mass of the thermoplastic resin a and 70 to 30% by mass of the thermoplastic resin b.
In the present invention, a particularly preferable (A) thermoplastic resin blend is composed of 40 to 60% by mass of the thermoplastic resin a and 60 to 40% by mass of the thermoplastic resin b.

As long as the combination of the thermoplastic resin a and the thermoplastic resin b is a combination of different types of thermoplastic resins, any combination is possible.
In the present invention, (A) a preferable combination of the thermoplastic resin blend is a combination of a polyphenylene ether resin and a polystyrene resin, a combination of a polyphenylene ether resin and a polyamide resin, a combination of a polyphenylene ether resin and a polyphenylene sulfide resin, a polyphenylene ether resin and an aromatic resin. A combination of polyesters.
Among these, a combination of polyphenylene ether resin and polyamide resin, a combination of polyphenylene ether resin and polyphenylene sulfide resin is preferable, and a combination of polyphenylene ether resin and polyamide resin is particularly preferable. Among these, the case where the polyamide resin is polyamide 6, polyamide 6,6, polyamide 9, T, or a mixture thereof is most preferable.

It is preferable that the thermoplastic resin a and the thermoplastic resin b are compatible.
As a method of compatibilizing the thermoplastic resin a and the thermoplastic resin b, a method of originally selecting the compatible thermoplastic resin a and the thermoplastic resin b and melt-kneading them is preferable.
A specific example of such a method is a method of melt-kneading a polystyrene resin and a polyphenylene ether resin.

Further, as a method of compatibilizing the thermoplastic resin a and the thermoplastic resin b, a method of compatibilizing the originally incompatible thermoplastic resin a and the thermoplastic resin b using a compatibilizer is also preferable. Applicable.
As a specific example of such a method, a polyamide resin and a polyphenylene ether resin are mixed with a compatibilizer such as maleic anhydride, itaconic acid, citric acid, a liquid diene polymer, an epoxy compound, an oxidized polyolefin wax, a quinone, and an organosilane compound. The method of adding and melt-kneading is mentioned.
As another specific example of such a method, a compatibilizer such as maleic anhydride, itaconic acid, citric acid, liquid diene polymer, epoxy compound, oxidized polyolefin wax, quinone, organosilane compound, etc. is added to polyphenylene ether resin. There is also a method in which after adding and melt-kneading to obtain a modified polyphenylene ether resin, the polyamide resin and the modified polyphenylene ether resin are melt-kneaded.

Furthermore, as a method of compatibilizing the thermoplastic resin a and the thermoplastic resin b, a block copolymer or a graft copolymer is used for the thermoplastic resin a and the thermoplastic resin b which are not originally compatible. Thus, the compatibilizing method can also be preferably applied.
As a specific example of such a method, there is a method in which a polyolefin resin and a polystyrene resin are melt-kneaded by adding a SEBS (styrene-ethylene-butene-styrene) block copolymer.
As a method of compatibilizing the thermoplastic resin a and the thermoplastic resin b, a method of compatibilizing a known thermoplastic resin can be widely applied and is not limited to the above method.

  The thermoplastic resin composition using the thermoplastic resin blend (A) in which the thermoplastic resin a and the thermoplastic resin b are compatible has particularly improved mechanical properties such as impact strength and tensile elongation.

The compatibilizing agent is preferably added in an amount of 0.1 to 10 parts by mass with respect to 100 parts by mass of the (A) thermoplastic resin blend.
The amount of the compatibilizer added is more preferably 0.2 parts by mass to 5 parts by mass with respect to 100 parts by mass of the (A) thermoplastic resin blend.
A particularly preferable amount of the compatibilizer is 0.3 to 3 parts by mass with respect to 100 parts by mass of the (A) thermoplastic resin blend.

2. (B) Block copolymer In this invention, there is no limitation in (B) block copolymer.
In the present invention, a preferred block copolymer (B) is a block copolymer of a conjugated diene and an aromatic vinyl compound, a block copolymer of a hydrogenated conjugated diene and an aromatic vinyl compound, or an ethylene-propylene block copolymer. It is.

  (B) Particularly preferred as the block copolymer is a styrene compound-containing block copolymer. Here, the styrene compound-containing block copolymer is a block copolymer including at least one polymer block mainly composed of a styrene compound and at least one polymer block mainly composed of a conjugated diene compound, or A hydrogenated styrene compound-containing block copolymer obtained by hydrogenating an unsaturated bond in a polymer block mainly composed of a conjugated diene compound in such a block copolymer. Note that the styrene compound refers to styrene or a compound in which a hydrogen atom of styrene is substituted with an alkyl group, an acyl group, or a halogen element.

“Mainly” in the polymer block mainly composed of the styrene compound refers to a block in which at least 50% by mass or more is derived from the styrene compound in the block. More preferably, it is 70 mass% or more, More preferably, it is 80 mass% or more, Most preferably, it is 90 mass% or more. The same applies to “mainly” in a polymer block mainly composed of a conjugated diene compound, and at least 50% by mass or more refers to a block derived from a conjugated diene compound. More preferably, it is 70 mass% or more, More preferably, it is 80 mass% or more, Most preferably, it is 90 mass% or more.
In this case, for example, even in the case of a block in which a small amount of a conjugated diene compound or other compound is randomly bonded in the styrene compound block, if 50% by mass of the block is formed from the styrene compound, It is regarded as a block copolymer mainly composed of a styrene compound. The same applies to the case of a conjugated diene compound.

Specific examples of the styrene compound include styrene, α-methylstyrene, vinyltoluene and the like. One or more compounds selected from these can be used, and styrene is particularly preferable among them.
Specific examples of the conjugated diene compound include butadiene, isoprene, piperylene, 1,3-pentadiene, and one or more compounds selected from these can be used. Among them, butadiene, isoprene and these The combination of is preferable.

  The microstructure of the conjugated diene compound block portion of the styrene compound-containing block copolymer has a 1,2-vinyl content or a total amount of 1,2-vinyl content and 3,4-vinyl content of 5 to 80% by mass. It is preferable that it is 10-50 mass%, and it is most preferable that it is 15-40 mass%.

  In the styrene compound-containing block copolymer used in the present invention, a polymer block (a) mainly composed of a styrene compound and a polymer block (b) mainly composed of a conjugated diene compound are ab type, It is preferably a block copolymer that is bonded in any bond selected from the aba type and the abbab type. Among these, the aba type is more preferable. Of course, these may be a mixture.

The styrene compound-containing block copolymer used in the present invention is preferably a hydrogenated styrene compound-containing block copolymer.
A hydrogenated styrenic compound-containing block copolymer refers to a hydrogenated part of or all of the aliphatic double bonds of a polymer block mainly composed of a conjugated diene compound. Preferably, at least 50% or more of the group double bond is hydrogenated. More preferably 80% or more, and most preferably 98% or more hydrogenated.

  The number average molecular weight of the hydrogenated styrene compound-containing block copolymer used in the present invention is preferably 200,000 or more and 300,000 or less. Although it is possible to use a hydrogenated block copolymer outside this molecular weight range, it is possible to use a hydrogenated block copolymer in this range even in a small amount in order to develop a high impact with a small amount of addition. preferable.

In the present invention, the number average molecular weight is measured with an ultraviolet spectroscopic detector [UV-41: Showa Denko KK] using a gel permeation chromatography measuring apparatus [GPC SYSTEM21: Showa Denko KK]. And the number average molecular weight in terms of standard polystyrene. The measurement conditions can be as follows, for example. [Solvent: Chloroform, Temperature: 40 ° C., Column: Sample side (KG, K-800RL, K-800R), Reference side (K-805L × 2), Flow rate 10 ml / min, Measurement wavelength: 254 nm, Pressure 15-17 kg / cm < ² >]. In the measurement of the number average molecular weight, a low molecular weight component due to catalyst deactivation during polymerization may be detected, but such a low molecular weight component is not included in the molecular weight calculation. Usually, the calculated correct molecular weight distribution (weight average molecular weight / number average molecular weight) is in the range of 1.0 to 1.2.
The styrenic compound-containing block copolymer can be produced, for example, by a living anion polymerization method, and in this case, a copolymer having an extremely narrow molecular weight distribution (Mw / Mn = about 1.0 to 1.2) is obtained. It is done.

  Further, in the present invention, as the styrene compound-containing block copolymer, those having different bonding types, those having different styrene compound types, those having different conjugated diene compound types, 1,2-bonded vinyl content or 1,2 -You may mix and use multiple types, such as a thing with different bond vinyl content and 3, 4- bond vinyl content, a thing with different styrene-type compound component content, and a thing with a different hydrogenation rate. Of course, there is no problem in using a block copolymer other than the styrene compound-containing block copolymer.

Further, the styrene compound-containing block copolymer used in the present invention may be a styrene compound-containing block copolymer that has been modified in whole or in part. The modified styrene compound-containing block copolymer here means a styrene compound-containing block copolymer modified with (F) a compatibilizing agent.
As a method for producing a modified styrenic compound-containing block copolymer,
(1) A styrene compound-containing block copolymer and (F) at a temperature in the range of not less than the softening point of the styrene compound-containing block copolymer and not more than 250 ° C. in the presence or absence of a radical initiator. A method of reacting by melting and kneading a compatibilizing agent,
(2) The styrene compound-containing block copolymer and the (F) compatibilizer in the solution at a temperature below the softening point of the styrene compound-containing block copolymer in the presence or absence of a radical initiator. How to react,
(3) Melting the styrene compound-containing block copolymer and the (F) compatibilizer at a temperature below the softening point of the styrene compound-containing block copolymer in the presence or absence of a radical initiator. The method of making it react without mentioning is mentioned.
Any of these methods may be used, but the method (1) is preferable, and the method (1) performed in the presence of a radical initiator is most preferable.

  Moreover, in this invention, what mixed previously the oil which has a paraffin as a main component may be used as a styrene-type compound containing block copolymer. The processability of the thermoplastic resin composition can be improved by previously mixing oil mainly composed of paraffin.

In the present invention, the amount of the (B) block copolymer added is 0.1 to 100 parts by mass of the thermoplastic resin blend (A) composed of the thermoplastic resin a1 to 99% by weight and the thermoplastic resin b99 to 1% by weight. -100 mass parts.
In the present invention, the preferable addition amount of (B) block copolymer is 1 to 50 parts by mass with respect to 100 parts by mass of (A) thermoplastic resin blend.
In the present invention, the addition amount of the (B) block copolymer is more preferably 2 to 25 parts by mass with respect to 100 parts by mass of the (A) thermoplastic resin blend.
In the present invention, the addition amount of the (B) block copolymer is particularly preferably 5 to 15 parts by mass with respect to 100 parts by mass of the (A) thermoplastic resin blend.

3. (C) Polycarbodiimide represented by formula (1) In the present invention, (C) polycarbodiimide is a polycarbodiimide copolymer represented by formula (1).

Formula (1)

In the formula (1), k is an integer of 0 to 30, m is an integer of 2 to 100, n is an integer of 0 to 30, R ₁ is an alkylene group having 2 to 10 carbon atoms, and R ₂ is an aromatic diisocyanate residue. , R ₃ means an aromatic monoisocyanate residue.

Specific examples of R ₁ include ethylene, tetramethylene, hexamethylene, octamethylene groups and the like.
In addition, these alkylene groups may be used independently or may be used in mixture of 2 or more types.

Specific examples of R ₂ which is an aromatic diisocyanate residue include, for example, 4,4′-diphenylmethane diisocyanate, 2,6-tolylene diisocyanate, 2,4-tolylene diisocyanate, 1-methoxyphenyl-2,4- Diisocyanate, 3,3′-dimethoxy-4,4′-diphenylmethane diisocyanate, 4,4′-diphenyl ether diisocyanate, 3,3′-dimethyl-4,4′-diphenyl ether diisocyanate, 2,2 Aromatic diisocyanate residues such as -bis [4- (4-isocyanatotophenoxy) phenyl] hexafluoropropane, 2,2-bis [4- (4-isocyanatotophenoxy) phenyl] propane, and the like. Tolylene diisocyanate residues can be preferably used.
In addition, you may use these aromatic diisocyanate residues individually or in mixture of 2 or more types.

Specific examples of R ₃ which is an aromatic monoisocyanate residue include aromatic monoisocyanates such as phenyl isocyanate, p-nitrophenyl isocyanate, p- and m-tolyl isocyanate, p-formylphenyl isocyanate, and p-isopropylphenyl isocyanate. Residue, and p-isopropylphenyl isocyanate residue is particularly preferable.
In addition, you may use these aromatic monoisocyanate residues individually or in mixture of 2 or more types.

  k is preferably 2 to 20, m is preferably 5 to 80, and n is preferably 2 to 20.

  In the present invention, (C) as a polycarbodiimide that can be preferably used as the polycarbodiimide represented by the formula (1), a polyurethane obtained by reacting a polycarbonate diol and an aromatic diisocyanate in the presence of a carbodiimidization catalyst, Examples thereof include polycarbodiimide copolymers obtained by reacting a terminal isocyanate group with an aromatic diisocyanate to form a carbodiimide and then blocking the end with an aromatic monoisocyanate.

  Moreover, in this invention, what was obtained by making polycarbonate diol and excess aromatic diisocyanate react in presence of a carbodiimidization catalyst as a polycarbodiimide represented by (C) Formula (1) can also be used preferably.

In the present invention, (C) the presence of a carbodiimide group in the polycarbodiimide represented by the formula (1) can be confirmed by absorption (2140 cm ⁻¹ ) derived from a carbodiimide group by IR measurement.

Here, the polycarbonate diol may be a polycarbonate diol containing a carbonate group. Specific examples thereof include polyethylene carbonate diol, polytetramethylene carbonate diol, polyhexamethylene carbonate diol, and polyoctamethylene carbonate diol. And polydodecamethylene carbonate diol. Polyhexamethylene carbonate diol is particularly preferable.
In addition, these polycarbonate diols may be used independently and may be used in mixture of 2 or more types.

  As the polycarbonate diol, in particular, a polycarbonate diol represented by the following formula (7) can be preferably used.

Formula (7)

In formula (7), m represents an integer of 2 to 100, and R ₁ represents an alkylene group having 2 to 10 carbon atoms.

A phosphorus catalyst is preferably used as the carbodiimidization catalyst.
Specific examples of the phosphorus-based carbodiimidization catalyst include, for example, 1-phenyl-2-phospholene-1-oxide, 3-methyl-2-phospholene-1-oxide, 1-ethyl-2-phospholene-1-oxide, 3 -Methyl-1-phenyl-2-phospholene-1-oxide or phospholene oxides such as these 3-phospholene isomers.

In this invention, the addition amount of the polycarbodiimide represented by (C) Formula (1) is 0.1-50 mass parts with respect to 100 mass parts of (A) thermoplastic resin blend.
In this invention, the addition amount of the polycarbodiimide represented by preferable (C) Formula (1) is 1-30 mass parts with respect to 100 mass parts of (A) thermoplastic resin blend, More preferably, it is 2- 25 parts by mass, particularly preferably 5 to 15 parts by mass.

4). Thermoplastic resin composition The thermoplastic resin composition of the present invention has other additional components such as an impact resistance imparting agent, a plasticizer, a stabilizer, and an ultraviolet absorber as long as the characteristics and effects of the present invention are not impaired. Agent, flame retardant, mold release agent, antioxidant, polyolefin nucleating agent, slip agent, inorganic or organic filler or reinforcing agent (eg glass fiber, carbon fiber, whisker, mica, talc, calcium carbonate, Potassium titanate, wollastonite, etc.), various colorants, antistatic agents, conductivity improvers such as carbon black, etc. may be added.
The total content of these additional components is preferably 100 parts by mass or less with respect to a total of 100 parts by mass of (A), (B), and (C).

In the present invention, a preferred method for producing the thermoplastic resin composition is (A) a thermoplastic resin blend, (B) a block copolymer, (C) a polycarbodiimide represented by the formula (1), and, if necessary, the above-described method. In this method, the additional components are melt kneaded using a melt kneader such as a single screw extruder, a twin screw extruder, a kneader, or a Brabender.
In the present invention, a particularly preferable method for producing a thermoplastic resin composition is a method of melt kneading using a twin screw extruder or a kneader.

A preferable melt-kneading temperature when producing the thermoplastic resin composition of the present invention is 180 to 400 ° C. More preferably, it is 200-350 degreeC, Most preferably, it is 250-330 degreeC, Most preferably, it is 280-320 degreeC.
When producing the thermoplastic resin composition of the present invention, the components constituting the thermoplastic resin composition can be melt-kneaded together. Moreover, as a melt-kneading method, a well-known melt-kneading method is employable.

  In this invention, the order which melt-kneads the component which comprises a thermoplastic resin composition is not limited. For example, after melt-kneading thermoplastic resin a and thermoplastic resin b to prepare (A) a thermoplastic resin blend, (B) a block copolymer and (C) polycarbodiimide represented by formula (1) are added. Then, it may be further melt-kneaded to produce a thermoplastic resin composition, or a thermoplastic resin a, a thermoplastic resin b, (B) a block copolymer, (C) a polycrystal represented by the formula (1) Carbodiimide may be melt-kneaded at the same time, and (A) preparation of the thermoplastic resin blend and production of the thermoplastic resin composition may be performed simultaneously.

In the present invention, as a preferred method for producing a thermoplastic resin composition, at least a part of the thermoplastic resin a and / or the thermoplastic resin b and (C) polycarbodiimide represented by the formula (1) are previously melt-kneaded. Then, the method of adding the remaining components and melt-kneading can be mentioned.
In the present invention, as another preferred method for producing a thermoplastic resin composition, at least a part of the thermoplastic resin a and at least a part of the thermoplastic resin b are previously compatibilized and then melt kneaded with other components. The method of doing is mentioned.

  EXAMPLES Hereinafter, although an Example demonstrates this invention further in detail, this invention is not limited to this.

I. Preparation of raw materials In Examples and Comparative Examples, the following were used as the thermoplastic resin a, the thermoplastic resin b, the block copolymer, the polycarboimide, and the compatibilizer.
<Thermoplastic resin a>
The thermoplastic resin a has a reduced viscosity measured by the following method of 0.42 dl / g (0.5 g / dl, chloroform solution, measured using an Ubbelohde viscometer at 30 ° C.). 6-dimethyl-phenylene oxide) (hereinafter referred to as “PPE-a”).
(Measurement method of reduced viscosity)
A 0.5 (g / dl) chloroform solution was prepared, and the viscosity of the thermoplastic resin was measured at 30 ° C. using an Ubbelohde viscometer. From this result, the reduced viscosity was determined according to the following equation.
Reduced viscosity (η _{sp / C} ) = (ηr−1) / C
= (T / t ₀ -1) / C
Ηr (= t / t ₀ ): specific viscosity C: solution concentration (g / dl)
t: chloroform solution flow time t _0: chloroform flow time of

<Thermoplastic resin b>
As thermoplastic resin b, viscosity number: 129 (ml / g), amino group terminal: 30.9 (μmol / g), carboxyl group terminal: 93.1 (μmol / g), amino group terminal / carboxyl terminal ratio : Polyamide-6,6 (hereinafter referred to as “PA-b1”) of 0.30 was used.
As thermoplastic resin b, viscosity number: 129 (ml / g), amino group terminal: 24 (μmol / g), carboxyl group terminal: 100 (μmol / g), amino group terminal / carboxyl terminal ratio: 0.24 Polyamide-9, T (hereinafter referred to as “PA-b2”) was used.

<Compatibilizer>
Maleic anhydride was used as a compatibilizing agent.
<Block copolymer>
As the block copolymer, a polystyrene-polyethylene butylene-polystyrene block copolymer (manufactured by Kraton Polymer Japan, Kraton G1651 (trade name) (number average molecular weight: about 250,000)) (hereinafter referred to as “SEBS”) was used.

<Polycarbodiimide>
As the polycarbodiimide represented by the formula (1), aromatic polycarbodiimide (Stabaxol P manufactured by Bayer) (hereinafter referred to as “polycarbodiimide 1”) was used.

II. Production of Thermoplastic Resin Composition Thermoplastic resin compositions of Examples and Comparative Examples were produced as follows.
For melt kneading of the raw material, a ZSK-25 type co-rotating twin screw extruder of L / D = 44 manufactured by Coperion (Germany) was used. All cylinder temperatures were set to 300 ° C and the die temperature was set to 280 ° C. A quantitative feeder was installed at the main supply port of the twin screw extruder. In addition, when the total length of the screw is 1.0, vent port 1 is installed at a position of about 0.35 when viewed from the upstream side, and vent port 2 is installed at a position of about 0.80. Side feeder was installed.

Moreover, the master pellet of polycarbodiimide was manufactured as follows.
From the main supply port of the twin screw extruder, PA-b1 was supplied at a rate of 18 parts by mass / hour and polycarbodiimide 1 was supplied at a rate of 2 parts by mass / hour, and melt-kneaded to produce master pellets 1.
From the main supply port of the twin screw extruder, PA-b2 was quantitatively supplied at 18 parts by mass / hour and polycarbodiimide 1 was supplied at 2 parts by mass / hour, and melt-kneaded to produce master pellets 2.

[Example 1]
From the main supply port of the twin-screw extruder, PPE-a was quantitatively supplied at 35 parts by mass / hour, SEBS at 12 parts by mass / hour, and maleic anhydride at 0.5 parts by mass / hour. PA-b1 is quantitatively supplied at a rate of 35 parts by mass / hour, and at the same time, PA-b1 is quantitatively supplied from the side feeder 2 at a rate of 18 parts by mass / hour, and polycarbodiimide 1 is quantitatively supplied at a rate of 2 parts by mass / hour. Thus, a thermoplastic resin composition 1 was produced.

[Example 2]
From the main supply port of the twin-screw extruder, PPE-a was quantitatively supplied at 35 parts by mass / hour, SEBS at 12 parts by mass / hour, and maleic anhydride at 0.5 parts by mass / hour. PA-b1 is quantitatively supplied at 35 parts by mass / hour, and at the same time, master pellet 1 is quantitatively supplied from the side feeder 2 at 20 parts by mass / hour, and melt-kneaded to produce a thermoplastic resin composition 2. did.
[Example 3]
From the main supply port of the twin-screw extruder, PPE-a was quantitatively supplied at 35 parts by mass / hour, SEBS at 12 parts by mass / hour, and maleic anhydride at 0.5 parts by mass / hour. PA-b1 was supplied at a rate of 35 parts by mass / hour and master pellet 1 was supplied at a rate of 20 parts by mass / hour and melt-kneaded to produce a thermoplastic resin composition 3.
[Example 4]
From the main supply port of the twin-screw extruder, PPE-a was quantitatively supplied at 35 parts by mass / hour, SEBS at 12 parts by mass / hour, and maleic anhydride at 0.5 parts by mass / hour. PA-b2 is quantitatively supplied at a rate of 35 parts by mass / hour, and at the same time, PA-b2 is quantitatively supplied from the side feeder 2 at a rate of 18 parts by mass / hour, and polycarbodiimide 1 is quantitatively supplied at a rate of 2 parts by mass / hour. Thus, a thermoplastic resin composition 4 was produced.
[Example 5]
From the main supply port of the twin-screw extruder, PPE-a was quantitatively supplied at 35 parts by mass / hour, SEBS at 12 parts by mass / hour, and maleic anhydride at 0.5 parts by mass / hour. PA-b2 was quantitatively supplied at 35 parts by mass / hour and master pellet 2 was supplied at 20 parts by mass / hour and melt-kneaded to produce a thermoplastic resin composition 5.

[Comparative Example 1]
A thermoplastic resin composition 6 was produced in the same manner as in Example 1 except that the polycarboxylic diimide 1 was not supplied from the side feeder 2.
[Comparative Example 2]
A thermoplastic resin composition 7 was produced in the same manner as in Example 4 except that the polycarboxylic diimide 1 was not supplied from the side feeder 2.

III. Evaluation of thermoplastic resin composition <Evaluation of moldability>
About the thermoplastic resin composition of the present invention obtained in Examples 1 to 5 and Comparative Examples 1 and 2, using Toshiba Machine Co., Ltd. injection molding machine IS80EPN, the cylinder temperature was 280 ° C, and the mold temperature was 80 ° C. The injection molding was carried out while gradually increasing the injection pressure, and the pressure (SSP) (kg / cm ² ) at which the composition was almost filled in the mold was measured to evaluate the moldability.
<Measurement of tensile elongation>
About the thermoplastic resin composition of the present invention obtained in Examples 1 to 5 and Comparative Examples 1 and 2, cylinder temperature is 280 ° C., mold temperature is 80 ° C., using an injection molding machine IS80EPN manufactured by Toshiba Machine Co., Ltd. A multi-purpose test piece as defined in ISO 3167 was prepared according to the description of ISO 294 under the conditions of the injection speed. And using this multipurpose test piece, the tensile elongation was measured according to description of ISO527-1 and ISO527-2.
<Measurement of Izod impact strength>
Using the multi-purpose test piece, measurement was performed according to the description of ISO180 / 1A.
<Measurement of flexural modulus>
Using the multipurpose test piece, measurement was performed according to the description of ISO178.

The physical property measurement results of the thermoplastic resin compositions 1 to 7 of Examples 1 to 5 and Comparative Examples 1 and 2 are shown in Table 1.
From Table 1, the thermoplastic resin compositions 1-5 of Examples 1-5 corresponding to this invention are the same moldability as the thermoplastic resin compositions 6, 7 of Comparative Examples 1 and 2, which are conventional compositions. And excellent in tensile elongation, Izod impact strength, and flexural modulus.

  Since the thermoplastic resin composition of the present invention has a very high balance of moldability, tensile properties, impact resistance, and rigidity, various industrial parts are manufactured in the electric / electronic field, the automobile field, and the like. Can be used as a material.

Claims (8)

(A) 100 parts by mass of a thermoplastic resin blend consisting of thermoplastic resin a1 to 99% by mass and thermoplastic resin b99 to 1% by mass;
(B) 0.1-100 parts by mass of a block copolymer;
(C) 0.1 to 50 parts by mass of polycarbodiimide represented by the formula (1);
A thermoplastic resin composition comprising:
Formula (1)

(In Formula 1, k is an integer of 0 to 30, m is an integer of 2 to 100, n is an integer of 0 to 30, R ₁ is an alkylene group having 2 to 10 carbon atoms, R ₂ is an aromatic diisocyanate residue, R ₃ means an aromatic monoisocyanate residue.)   The thermoplastic resin composition according to claim 1, wherein the thermoplastic resin a is a polyphenylene ether resin and the thermoplastic resin b is a polystyrene resin.   The thermoplastic resin composition according to claim 1, wherein the thermoplastic resin a is a polyphenylene ether resin, and the thermoplastic resin b is a polyamide resin.   The thermoplastic resin composition according to claim 1, wherein the thermoplastic resin a is a polyphenylene ether resin, and the thermoplastic resin b is a polyphenylene sulfide resin.   The thermoplastic resin composition according to claim 1, wherein the thermoplastic resin a is a polyphenylene ether resin, and the thermoplastic resin b is an aromatic polyester.   The thermoplastic resin composition according to claim 3, wherein the thermoplastic resin b is polyamide 9T. The manufacturing method of the thermoplastic resin composition as described in any one of Claims 1-6 which contains the following processes a and a in this order:
(Step a) Step of melt-kneading at least a part of the thermoplastic resin a and / or the thermoplastic resin b and (C) the polycarbodiimide represented by the formula (1);
(Step a) Step of adding the remaining components to the melt-kneaded product obtained in step A and melt-kneading. The manufacturing method of the thermoplastic resin composition as described in any one of Claims 1-6 which contains the following processes c and d in this order:
(Process c) A step of compatibilizing at least a part of the thermoplastic resin a and at least a part of the thermoplastic resin b to obtain a thermoplastic resin blend in which the thermoplastic resin a and the thermoplastic resin b are compatible;
(Process d) The process of adding and kneading the remaining components to the thermoplastic resin blend obtained in Process C.