JP2002265771A - Thermoplastic resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a thermoplastic resin composition comprising a polycarbonate and a polyester and excellent in moist heat fatigue properties while retaining chemical resistance and other characteristics inherent in the polycarbonate and the polyester. SOLUTION: This thermoplastic resin composition comprises 5-95 pts.wt. of a polycarbonate and 95-5 pts.wt. of a specific polyester and has a melt viscosity stability of not higher than 2.5%.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a thermoplastic resin composition comprising polycarbonate and polyester having excellent chemical resistance and wet heat fatigue resistance. More specifically, the present invention relates to a thermoplastic resin composition having excellent chemical resistance and wet heat fatigue resistance by using a polyester and a polycarbonate containing specific amounts of specific components.

[0002]

2. Description of the Related Art A thermoplastic resin composition comprising a polycarbonate and a polyester (hereinafter sometimes abbreviated as polyethylene terephthalate or simply PET in connection with polyethylene terephthalate which is a typical polyester) has the inherent properties of polycarbonate. As a material having both impact resistance and chemical resistance of polyethylene terephthalates, it is widely used in the fields of automobiles, OA fields, and the like.

[0003] Polyethylene terephthalates are prepared by direct esterification from aliphatic glycol such as ethylene glycol and terephthalic acid which is an ester bond-forming precursor, or by transesterification from dimethyl terephthalate, or A method of producing from a terephthalic acid dichloride by an interfacial polymerization method, and a method of producing a relatively low-molecular-weight polyethylene terephthalate produced by the above method in a solid state by polycondensation under normal pressure or reduced pressure. Etc. are known.

[0004] As for polycarbonate, a method of directly reacting a dihydroxy compound with phosgene which is a carbonate bond-forming precursor (interfacial polymerization method) or a method of transesterifying a diester carbonate such as diphenyl carbonate in a molten state to polymerize ( Melting method) is known.

[0005] The thermoplastic resin composition made of polyethylene terephthalate and polycarbonate produced by these methods is expected to have excellent physical properties of both components, such as chemical resistance, impact resistance, and moldability. I have.

At the same time, many proposals have conventionally been made to further improve these physical properties.

[0007] Polycarbonates having excellent impact resistance also have disadvantages inferior in melt viscosity stability, wet heat fatigue resistance and chemical resistance. Therefore, a composition with polyethylene terephthalate having excellent chemical resistance and wet heat fatigue resistance. However, in the composition with polyethylene terephthalate using ethylene glycol as the aliphatic glycol, when exposed to high-temperature and high-humidity conditions for a long time, the crystal of polyethylene terephthalate Because of the progress of hydrolysis and hydrolysis of the polycarbonate, the hinge characteristics are significantly reduced, the resistance to wet heat fatigue in repeated bending is reduced, and there are cases where molded articles are broken.

[0008] For this reason, it satisfies the requirements for fields requiring mechanical strength, chemical resistance and wet heat fatigue, such as outer handles and inner door handles for automobile parts and mechanical parts such as power tool covers. At present, no material has been obtained yet.

[0009]

DISCLOSURE OF THE INVENTION The present invention is based on the present invention, which maintains excellent properties such as melt viscosity stability and wet heat fatigue resistance while maintaining the inherent properties such as impact resistance and chemical resistance of polycarbonate and polyalkylene terephthalates. An object of the present invention is to provide a plastic resin composition.

As a result of intensive studies on such a resin composition, the present inventors have found that a thermoplastic resin composition having specific properties of a polyester containing a specific amount of a specific component and a polycarbonate containing a specific amount of a specific component is excellent. It has been found that the composition has excellent heat and moisture fatigue resistance, and has reached the present invention.

[0011]

That is, according to the present invention, the main repeating unit is represented by the formula (2) based on 5 to 95 parts by weight of the polycarbonate (A) whose main repeating unit is represented by the formula (1). The present invention proposes a thermoplastic resin composition comprising 95 to 5 parts by weight of a polyester (P) having a melt viscosity stability of 2.5% or less.

[0012]

Embedded image (R ¹ , R ² , R ³ and R ⁴ are each independently a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an aralkyl group or an aryl group, W is an alkylidene group, an alkylene group, a cycloalkylidene group, a cycloalkylene group, A phenyl-substituted alkylene group, an oxygen atom, a sulfur atom, a sulfoxide group, or a sulfone group.)

[0013]

Embedded image (In the formula, A represents an arylene group.)

[0014] In the above description, the term "comprising thermoplastic resin composition" means that the thermoplastic resin composition is produced by blending or kneading materials containing the above-mentioned components.

That is, the present inventors use the polyester (P) as the polyester, and control the melt viscosity stability of the thermoplastic resin composition to 2.5% or less to thereby improve the chemical resistance of the thermoplastic resin composition. It has been found that it is possible to improve wet heat fatigue resistance and melt stability.

That is, in order to enhance the wet heat stability of the thermoplastic resin composition, the thermoplastic resin composition comprising the polycarbonate (A) and the polyester (P) has a melt viscosity stability of 2.5% or less. More preferably, the melt viscosity stability is in the range of 2% or less, more preferably 1.5%, particularly preferably 1.0% or less. Ideally, this value is 0.

(Range of Acid Value) In a further preferred embodiment of the present invention, the polyester (P) has an acid value of 10 to 10.
It is characterized by being 60 equivalents / 10 ⁶ g.

As the terminal structure of the polyester (P), there are an aliphatic hydroxyl group from the glycol component, a carboxyl group from the carboxylic acid component, and a methyl ester group when the polyester (P) is produced by a transesterification method. However, in the present invention, the acid value is 1 per 10 ⁶ g of the polyester (P) with respect to the amount of the carboxy terminal group.
The presence of 0 to 60 equivalents is preferable for improving the heat resistance and chemical resistance of the resin composition of the present invention. The range is more preferably selected from 20 to 50 equivalents, particularly preferably from 25 to 45 equivalents.

It is presumed that the terminal carboxy group causes a closer interaction between the polyester (P) component and the polycarbonate (A) component in the thermoplastic resin composition, thereby improving the resistance to wet heat aging. ing.

If the acid value exceeds the above range, undesirable phenomena such as air bubbles entering the thermoplastic resin composition may occur and must be avoided. Conversely, if the acid value is too small, the above effects are not expected.

(Amount of Branching Component) In order to increase the closer interaction between the polyester (P) component and the polycarbonate (A) component in the thermoplastic resin composition of the present invention, a further preferred embodiment is polycarbonate (A). Is the amount of the branched component (D) represented by the formula (3) -1 to 3 to 1 to 2.0 mol% with respect to 1 mol of the carbonate bond.
It is characterized by containing. The presence of such a structural unit has a favorable effect on improving the mechanical strength of the composition of the present invention, such as fatigue resistance and impact resistance.

The preferred range of such structural components in the polycarbonate (A) is 0.02 to 1.5 mol%. More preferably in the range of 0.05 to 1.0 mol%,
Particularly preferably, it is in the range of 0.05 to 0.8 mol%.

In the present invention, the branched component (D) has a more preferred structure represented by (6) -1 to (3) -3.

[0024]

Embedded image

Embedded image

Embedded image (In the formula, Ar ₁ and Ar ₃ represent a trivalent aromatic group having 6 to 50 carbon atoms, and Ar and Ar ₄ represent a divalent aromatic group having 6 to 50 carbon atoms.)

[0025]

Embedded image

Embedded image

Embedded image

The molar ratio (D) of the component (D) represented by (3) -1 to 3 contained in the polycarbonate (A) to the terminal carboxy group (C ′) of the polyester (P)
/ C ′) is preferably D / C ′ = 0.01 to 15. By the presence of the components (C ′) and (D) at such a ratio, the actions of both act synergistically, which is suitable for achieving the object of the present invention. A more preferred range is 0.0
A range of 2 to 10, particularly preferably 0.05 to 5, is selected.

In the present invention, the acid value of the polyester (P) is represented by (C), and the carboxy group is represented by (C ′).
It is represented by

In the present invention, more preferably, the polyester (P) is a polyester selected from polypropylene terephthalate and polypropylene 2,6-naphthalate.

The polycarbonate (A) referred to in the present invention
Is preferably a compound having a main repeating unit represented by the formula (1) produced by reacting a dihydroxy compound represented by the formula (4) with a carbonate bond-forming precursor by an interfacial polymerization method or a melting method.

[0030]

Embedded image

Embedded image (R ¹ , R ² , R ³ and R ⁴ are each independently a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an aralkyl group or an aryl group, and W is an alkylidene group, an alkylene group, a cycloalkylidene group, a cycloalkylene Group, phenyl group-substituted alkylene group, oxygen atom, sulfur atom, sulfoxide group,
Or a sulfone group. )

The polycarbonate preferably used in the present invention is obtained by reacting a dihydroxy compound, particularly an aromatic dihydroxy compound, with a carbonate bond-forming precursor by a melt polycondensation method. The effect of the present invention is particularly large when the polycarbonate (A) according to the present invention is an aromatic polycarbonate or the dihydroxy compound is an aromatic dihydroxy compound. In the specification of the present application, various addition amounts are specified as amounts based on the dihydroxy compound, but the amount relation in this case is particularly appropriate when the dihydroxy compound is an aromatic dihydroxy compound.

Among the polycarbonates produced by the melt method, in the presence of a transesterification catalyst, especially as a transesterification catalyst, a) a nitrogen-containing basic compound and / or a phosphorus-containing basic compound and / or a) an alkali metal compound are contained. Polycarbonate resins polycondensed in the presence of a transesterification catalyst are preferably used for the purpose of the present invention, that is, for stability during molding.

As the aromatic dihydroxy compound, specifically, bis (4-hydroxyphenyl) methane, 2,2
-Bis (4-hydroxyphenyl) propane, 2,2-
Bis (4-hydroxy-3-methylphenyl) propane, 1,1-bis (4-hydroxyphenyl) -1-phenylethane, 4,4 '-[1,3-phenylenebis (1-methylethylidene)] bisphenol , 4,4 '
Bis (1,4-phenylenebis (1-methylethylidene)] bisphenol such as 9,9-bis (4-hydroxyphenyl) fluorene, 9,9-bis (4-hydroxy-3-methylphenyl) fluorene; 4-hydroxyaryl) alkane, 1,1-bis (4-hydroxyphenyl) cyclohexane, 1,1-bis (4-
(Hydroxyphenyl) -3,3,5-trimethylcyclohexane, 4- [1- [3- (4-hydroxyphenyl) -4-methylcyclohexyl] -1-methylethyl] -phenol, 4,4 ′-[1- Methyl-4- (1
-Methylethyl) -1,3-cyclohexanediyl] bisphenol, 2,2,2 ′, 2′-tetrahydro-
Bis (hydroxyaryl) cycloalkanes such as 3,3,3 ′, 3′-tetramethyl-1,1′-spirobis- [1H-indene] -6,6′-diol, bis (4
-Hydroxyphenyl) ether, dihydroxyaryl ethers such as 4,4'-dihydroxy-3,3'-dimethylphenylether, 4,4'-dihydroxydiphenylsulfide, 4,4'-dihydroxy-3,
Dihydroxydiaryl sulfides such as 3′-dimethyldiphenyl sulfide, 4,4′-dihydroxydiphenyl sulphoxide, 4,4′-dihydroxy-3,
Dihydroxydiarylsulfoxides such as 3'-dimethyldiphenylsulfoxide, 4,4'-dihydroxydiphenylsulfone, 4,4'-dihydroxy-3,
Dihydroxydiarylsulfones such as 3′-dimethyldiphenylsulfone; and dihydroxydiarylisatins such as 4,4′-dihydroxydiphenyl-3,3′-isatin. Dihydroxydiarylxanthenes such as 3,6-dihydroxy-9,9-dimethylxanthene, resorcinol, hydroquinone, 2-t-butylhydroquinone, 2-phenylhydroquinone, 2-cumylhydroquinone, and dihydroxybenzenes such as 4,4-dihydroxydiphenyl Etc. are exemplified.

Among them, 2,2-bis (4-hydroxyphenyl) propane is more preferable because of its stability as a monomer, and furthermore, it is easy to obtain although the amount of impurities contained therein is small.

In the invention of the present application, various monomers may be added to a polycarbonate (A) as required for the purpose of controlling the glass transition temperature, improving the fluidity, increasing the refractive index or reducing the birefringence, and controlling the optical properties. )) May be used alone or in combination of two or more.

Specific examples of these include, for example, aliphatic dihydroxy compounds such as 1,4-butanediol,
1,4-cyclohexanedimethanol, 1,10-decanediol, 3,9-bis (1,1-dimethyl-2-hydroxyethyl) -2,4,8,10-tetraoxaspiro [5,5] undecane , Diethylene glycol, polytetramethylene glycol, tricyclodecane dimethanol or the like, or a dicarboxylic acid such as terephthalic acid, isophthalic acid, 2,6-naphthalenedicarboxylic acid, adipic acid, cyclohexanedicarboxylic acid, or an oxy acid such as p-hydroxybenzoic acid Acid, 6-hydroxy-2-naphthoic acid, lactic acid and the like.

The carbonate bond forming precursors include:
In the solution method, a carbonyl halide such as phosgene or a haloformate compound is used. In the melting method, an aromatic carbonate is used, and specifically, diphenyl carbonate, ditolyl carbonate or the like is used. In addition, dimethyl carbonate, dicyclohexyl carbonate and the like can be used if desired. Of these, diphenyl carbonate is preferred from the viewpoints of reactivity, stability against coloring of the obtained resin, and cost.

Polycarbonate oligomers having a low molecular weight produced by the above-mentioned interfacial polymerization method or melting method are crystallized by the solid-phase polymerization method, and the polycarbonate is polymerized in a solid state at a high temperature (optionally under reduced pressure). Can be preferably used.

In the production of polycarbonate, dicarboxylic acid, dicarboxylic dihalide,
The present invention can be effectively used for poly (ester carbonate) containing an ester bond, which is produced by using a dicarboxylic acid derivative such as a dicarboxylic acid diester in combination.

Examples of the dicarboxylic acid derivative which is an ester bond forming precursor include aromatic dicarboxylic acid derivatives such as terephthalic acid, terephthalic acid dichloride, isophthalic acid dichloride, terephthalic acid diphenyl and isophthalic acid diphenyl, succinic acid, dodecanoic acid, dimer Aliphatic dicarboxylic acid derivatives such as acid, adipic dichloride, diphenyl decane diacid, diphenyl dodecane diacid;
And alicyclic dicarboxylic acid derivatives such as -cyclohexanedicarboxylic acid, 1,3-cyclohexanedicarboxylic acid dichloride, cyclopropanedicarboxylic acid diphenyl, and 1,4-cyclohexanedicarboxylic acid diphenyl.

A polyfunctional compound having three or more functional groups in one molecule can be used together with the dihydroxy compound represented by the formula (4). As such a polyfunctional compound, a compound having a phenolic hydroxyl group or a carboxy group is preferably used.

Specifically, for example, 1,1,1-tris (4-hydroxyphenyl) ethane, α, α ′, α ″-
Tris (-hydroxyphenyl) -1,3,5-triisopropylbenzene, 4,6-dimethyl-2,4,6-
Tris (4-hydroxyphenyl) -heptane-2,
Examples thereof include 1,3,5-tris (4-hydroxyphenyl) benzene, trimellitic acid, and pyromellitic acid.

For example, when a polyfunctional compound is used in combination for the purpose of increasing the melt viscosity of the polycarbonate (A), it is preferably 0.03 mol or less, preferably 0.00005 to 0.02 mol, per mol of the dihydroxy compound. Preferably, a range of 0.0001 to 0.01 mol is selected.

In the method for producing a polycarbonate (A) having a repeating unit represented by the formula (1), in the above-mentioned interfacial polymerization method, a tertiary amine, a quaternary ammonium salt, a quaternary phosphonium salt, a nitrogen-containing heterocyclic ring are used as catalysts. Compounds and salts thereof, imino ethers and salts thereof, compounds having an amide group and the like are used.

In the interfacial polymerization method, a large amount of an alkali metal compound or an alkaline earth metal compound is used as a scavenger for hydrogen halide such as hydrochloric acid generated during the reaction.
It is preferable to carry out sufficient washing and purification so that such impurities do not remain in the polymer after production.

In the melting method and the solid phase polymerization method, as the catalyst system, a catalyst system containing an alkali metal compound is preferably used. However, the amount of the alkali metal used is 0.01 × 10 ⁻ to 1 mol of the dihydroxy compound. It is preferable to make ^{6 to} 2 × 10 ⁻⁶ equivalent. Outside the above range, there is a problem that adversely affects various physical properties of the obtained polycarbonate, or a case where a transesterification reaction does not sufficiently proceed and a high-molecular-weight polycarbonate may not be obtained. Many.

Examples of the alkali metal compound include a hydroxide, a hydrocarbon compound, a carbonate, a cyanate, a thiocyanate, an organic carboxylate, a boron hydride and a hydrogen phosphate of an alkali metal conventionally known as a transesterification catalyst. Compounds, bisphenols, phenol salts and the like.

Specific examples include sodium hydroxide, potassium lithium carbonate, rubidium nitrate, sodium nitrite, potassium sulfite, sodium cyanate, sodium thiocyanate, potassium thiocyanate, lithium stearate, sodium borohydride, and boron hydride. lithium,
Sodium phenylated, sodium benzoate, dica 4 hydrogen diphosphate, disodium salt of bisphenol A, monopotassium salt, sodium potassium salt, sodium salt of phenol and the like.

It is preferable to use a nitrogen-containing basic compound and / or a phosphorus-containing basic compound in combination as a cocatalyst.

Specific examples of the nitrogen-containing basic compound include, for example, quaternary ammonium hydroxides having an alkyl, aryl, alkylaryl group and the like such as tetramethylammonium hydroxide, tetrabutylammonium hydroxide and benzyltrimethylammonium hydroxide. , Tetramethylammonium acetate, tetraethylammonium phenoxide, tetrabutylammonium carbonate, alkyl such as hexadecyltrimethylammonium ethoxide, basic ammonium salts having an alkylaryl group and the like, tertiary amines such as triethylamine, or Bases such as tetramethylammonium borohydride, tetrabutylammonium borohydride, tetramethylammonium tetraphenylborate And the like salt.

Specific examples of the phosphorus-containing basic compound include, for example, alkyl such as tetrabutylphosphonium hydroxide, benzyltrimethylphosphonium hydroxide and hexadecyltrimethylphosphonium hydroxide.
Examples thereof include quaternary phosphonium hydroxides having an aryl or alkylaryl group, and basic salts such as tetrabutylphosphonium borohydride and tetrabutylphosphonium tetraphenylborate.

The nitrogen-containing basic compound and / or the phosphorus-containing basic compound may have a basic nitrogen atom or a basic phosphorus atom in an amount of 2 mol per mol of the aromatic dihydroxy compound.
It is preferably used in a ratio of 0 × 10 ^{−6 to} 1000 × 10 ⁻⁶ equivalent. A more preferable usage ratio is a ratio that is 30 × 10 ^{−6 to} 700 × 10 ⁻⁶ equivalents with respect to the same standard. A particularly desirable ratio is 50 × 10 ⁻⁶ to the same standard.
The ratio is 500 × 10 ⁻⁶ equivalent.

(Melt Viscosity Stability) In the present invention, the melt viscosity stability of the thermoplastic resin composition is defined as follows. The dry sample is measured by a rheometrics RAA-type flow analyzer under a nitrogen stream at a shear rate of 1 rad / sec. The absolute value of the change in the melt viscosity measured at 280 ° C. was measured for 30 minutes, and the change was determined as the rate of change per minute. In order for the short- and long-term stability of the resin composition of the present invention to be good, this value must not exceed 2.5%.

In order to make the melt viscosity stability of the resin composition of the present invention 2.5% or less, the polycarbonate (A) which is one component of the thermoplastic resin composition has a melt viscosity stability of 1.0%. %, And more preferably, the melt viscosity stability is 0.5% or less.

The polycarbonate has a melt viscosity stability of 0.1.
In order to reduce the content to 5% or less, it is preferable to add a specific amount of the melt viscosity stabilizer (E) to the polycarbonate after the polycarbonate polycondensation reaction and, if desired, after the end-capping reaction of the terminal hydroxyl groups. By using a polycarbonate having such a melt viscosity stability, the thermoplastic resin composition of the present invention can have a melt viscosity stability of 2.5% or less.

In a thermoplastic resin composition having inferior melt viscosity stability, in addition to poor stability at the time of molding processing, problems of poor mechanical property stability under high humidity conditions and long-term use of a molded product are posed. is there. In particular, the impact resistance is significantly deteriorated, that is, the impact resistance is remarkably reduced, so that it is often not practical.

Melt viscosity stabilizers used in the present invention include (E) -1; phosphonium salts and ammonium salts of sulfonic acids and / or (E) -2; sulfonic acids and / or lower esters of sulfonic acids.

Specific examples of the compound represented by the above formula (E) -1 include, for example, tetrabutylphosphonium benzenesulfonate, tetrabutylphosphonium dodecylbenzenesulfonate, tetramethylammonium decylsulfonate, dodecylsulfonate And benzenesulfonic acid tetrabutylammonium salt.

(E) -2 Sulfonic acid and lower ester of sulfonic acid include aromatic sulfonic acid such as p-toluenesulfonic acid, aliphatic sulfonic acid such as octadecylsulfonic acid, butyl benzenesulfonate and ethyl hexadecylsulfonate. And butyl decylsulfonate.

Preferably, an ester compound is used rather than the sulfonic acid itself. Such a melt viscosity stabilizer is effective for a polycarbonate produced by a phosgene method, but reduces the activity of a basic alkali metal compound remaining in a polycarbonate produced by a melt polymerization method or a solid phase polymerization method. It is effective for

With respect to the amount used, per chemical equivalent of the alkali metal element of the basic alkali metal compound catalyst,
In the compound of (E) -1, 0.7 to 50 chemical equivalents, preferably 0.8 to 20 chemical equivalents, more preferably 0.9 to 10 chemical equivalents, and in the compound of (E) -2, 0.7 to 20 chemical equivalents, preferably 0.8 to 1
By using 0 chemical equivalents, more preferably 0.9 to 5 chemical equivalents, the melt viscosity stability of the thermoplastic resin composition according to the present invention can be suppressed to 2.5% or less. In some cases, it can be suppressed to 0.5% or less.

When the melt viscosity stabilizer (E) -2 is used, it is preferable to apply a reduced pressure treatment to the melt viscosity stabilizer-treated polycarbonate. There is no particular limitation on the type of processing apparatus used for performing the decompression process. On the other hand, when the melt viscosity stabilizer (E) -1 is used, it is not necessary to perform such a decompression treatment. The decompression treatment is performed in a vertical tank reactor, a horizontal tank reactor, or a single shaft with a vent,
Or 6.7-8 × 10 ³ P in a twin screw extruder
a, preferably reduced pressure treatment under reduced pressure of 1.3 × 10 ⁴ Pa or less. The reduced pressure treatment is 5 minutes to 3 hours in a tank reactor, and 5 seconds to 5 seconds when a twin screw extruder is used.
It takes about 15 minutes. The processing temperature can be carried out at 240 ° C to 350 ° C. Further, the treatment can be carried out simultaneously with the pelletizing by an extruder. It is also a preferred method to add such a melt viscosity stabilizer to the polycarbonate in the form of a masterbatch previously blended in a high concentration in the polycarbonate.

Such a melt viscosity stabilizer is optionally added simultaneously when melt-mixing a polycarbonate and a polyester to which no melt viscosity stabilizer is added, so that the melt viscosity stability of the thermoplastic resin composition falls within a predetermined range. This is a preferable method from the viewpoint of production efficiency.

By performing the above-described vacuum treatment, there is an advantage that the raw material monomers remaining in the polycarbonate are reduced or completely removed.

In the present invention, the polycarbonate (A)
Is preferably substantially composed of an aryloxy group and a phenolic hydroxyl group, and has a phenolic terminal group concentration of 50 mol% or less.

The aryloxy group has 1 to 20 carbon atoms.
Is preferably selected from hydrocarbon-substituted or unsubstituted phenyloxy groups. From the viewpoint of thermal stability, the above-mentioned hydrocarbon group substitution is preferably a tertiary alkyl group, tertiary aralkyl group, aryl group or simply a hydrogen atom. A compound having a benzyl-type hydrogen atom can be used when it has a desired purpose such as improvement in stability of actinic radiation, but it is better to avoid it from the viewpoint of stability against heat aging and thermal decomposition. Specific examples of preferred aryloxy groups include a phenoxy group, a 4-t-butylphenyloxy group, a 4-t-amylphenyloxy group,
-Phenylphenyloxy group, 4-cumylphenyloxy group and the like.

In a further preferred embodiment, the polycarbonate (A) has a phenolic terminal group concentration of 5 to 50 mol%, more preferably 5 to 4 mol%, based on all terminal groups.
0 mol% is contained. Even if the phenolic terminal group concentration is reduced below 5 mol%, further improvement in physical properties is small. It is obvious from the above discussion that the introduction of a phenolic terminal group concentration exceeding 50 mol% is often undesirable for the purpose of the present invention.

In the interfacial polymerization method, the terminal hydroxyl group is suppressed to a low concentration by a monofunctional compound used as a molecular weight regulator, and the terminal hydroxyl group concentration is within the above range. The terminal hydroxyl group is 50
Since those having a molar percentage of about 1 are easily produced, it is necessary to positively reduce the number of terminal hydroxyl groups.

That is, the concentration of terminal hydroxyl groups within the above range can be achieved by the following known method 1) or 2).

1) Controlling the molar ratio of charged raw materials for polymerization DPC (diphenyl carbonate) at the time of charging for the polymerization reaction
/ BPA (bisphenol-A) molar ratio is increased. For example, it is set between 1.02 and 1.10.

2) End-capping method At the end of the polymerization reaction, for example, US Pat.
In accordance with the method described in the specification of JP-A-222, the terminal hydroxyl group is blocked with a salicylate-based compound described in the above document.

The amount of the salicylate compound used is 0.8 to 10 per chemical equivalent of the terminal hydroxyl group before the capping reaction.
Mol, more preferably 0.8 to 5 mol, particularly preferably 0.9 to 2 mol. By adding at such a ratio, 80% or more of the terminal hydroxyl groups can be suitably sealed. When the present sealing reaction is performed, it is preferable to use the catalyst described in the above patent. The reduction of the terminal hydroxyl group concentration is preferably performed at a stage before the polymerization catalyst is deactivated.

Specific examples of the salicylic acid ester compound include 2-methoxycarbonylphenyl-phenyl carbonate, 2-methoxycarbonylphenyl-aryl carbonate such as 2-methoxycarbonylphenyl-cumylphenyl carbonate, and (2-methoxycarbonylphenyl). (2'-methoxycarbonylphenyl) esters of aromatic carboxylic acids such as benzoate and 4- (O-ethoxycarbonylphenyl) oxycarbonylbenzoic acid (2'-methoxycarbonylphenyl) ester.

The polyester (P) used in the present invention is
It can be obtained by a polycondensation reaction containing arylenedicarboxylic acid or its ester-forming precursor and 1,3-propylene glycol or its ester-forming derivative as main components.

The aromatic dicarboxylic acids mentioned here include:
Terephthalic acid, isophthalic acid, orthophthalic acid, 1,4
-Naphthalenedicarboxylic acid, 1,5-naphthalenedicarboxylic acid, 2,6-naphthalenedicarboxylic acid, 2,7-naphthalenedicarboxylic acid, 4,4'-diphenyldicarboxylic acid, 4,4'-diphenyletherdicarboxylic acid,
4,4′-diphenylmethanedicarboxylic acid, 2,2-bis (4-carboxyphenyl) propane, 2,5-anthracenedicarboxylic acid, 2,6-anthracenedicarboxylic acid, 4,4′-P-terphenylenedicarboxylic acid,
Aromatic dicarboxylic acids such as 2,5-pyridinedicarboxylic acid are preferably used, and terephthalic acid and 2,6-naphthalenedicarboxylic acid are particularly preferred.

These aromatic dicarboxylic acids may be used as a mixture of two or more kinds. In addition, if it is a small amount, it is also possible to use one or more kinds of aliphatic dicarboxylic acids such as adipic acid, azelaic acid, sebacic acid and dodecane diacid, and alicyclic dicarboxylic acids such as cyclohexane dicarboxylic acid together with the dicarboxylic acid. .

The diol component of the polyester (P) of the present invention is mainly composed of 1,3-propylene glycol.

In addition, the glycols exemplified below can be used for desired purposes as long as they do not contradict the object of the present invention.

Examples of the glycols include aliphatic diols such as ethylene glycol, butylene glycol, hexylene glycol, neopentylene glycol and pentamethylene glycol; alicyclic diols such as 1,4-cyclohexanedimethanol; 2-bis (2-
Examples thereof include diols having an aromatic ring such as (hydroxyethoxyphenyl) propane, and mixtures thereof.

Further, as long as the object of the present invention is not impaired, a desired molecular weight can be achieved.
00 long chain diols, ie, polyethylene glycol, polypropylene glycol, polytetramethylene glycol, and the like can be used.

The polyester (P) of the present invention can be branched by introducing a branching agent in order to achieve a desired object, as long as the object of the present invention is not impaired. Examples of the branching agent include trimesic acid,
Examples include trimellitic acid, pyromellitic acid, trimethylolpropane, pentaerythritol and the like.

Specific examples of the polyester (P) include poly-1,3-propylene terephthalate and poly-1,3
-Propylene 2,6-naphthalate, poly-1,3-propylene 2,7-naphthalate, poly-1,3-propylene 4,4'-diphenyldicarboxylate, poly-
Examples thereof include 1,3-propylene-4,4'-diphenylmethane dicarboxylate and poly-1,3-propylene-1,2-diphenoxyethane-4,4'-dicarboxylate. In addition, copolymerized polyesters such as poly-1,3-propylene isophthalate / terephthalate and the like and mixtures thereof can be preferably used.

The polyester (P) used in the present invention can be produced using a conventionally known transesterification catalyst. Among them, preferred transesterification catalysts include compounds containing titanium, antimony, germanium and tin. Is preferably used. Among them, a compound containing an element selected from titanium, antimony, and germanium is preferably used. Further, a catalyst in which these are combined, for example, a composite catalyst in which a molar ratio of a magnesium compound to a titanium compound is 0.3 to 6 is preferable.

Examples of the titanium-based polymerization catalyst include titanium acid compounds, hydroxides, halides, alcoholates, phenolates, carboxylates and the like. More specifically, titanium oxide, titanium hydroxide, titanium tetrachloride, tetramethoxytitanium, tetrabutoxytitanium and the like can be exemplified.

In the polymerization of polyester, the transesterification catalyst is used in an amount of 5 × 10 ^{-5 to} 5 × 10 ^-3 mol per mol of arylenedicarboxylic acid.

According to a conventional method, the polyester is subjected to polycondensation of a dicarboxylic acid component and the diol component while heating in the presence of a catalyst, and the resulting diol component such as water or a lower alcohol or 1,3-propylene glycol is used. It can be manufactured by discharging to the outside.

In the present invention, compounds such as manganese, zinc, calcium, and magnesium used in a transesterification reaction which is a pre-stage of a conventionally known polyester polycondensation can be used together. It is also possible to deactivate such a catalyst with an acid or phosphorous acid compound or the like to perform polycondensation.

The polyester (P) of the present invention preferably has an acid value of 10 to 60 equivalents / 10 ⁶ g-polyester. The polyester is sampled during the production of the polyester, and the acid value is measured. By adding the above-mentioned arylenedicarboxylic acids or diols, an acid value in this range can be realized.

(Polyester Melt Viscosity Stability) In the polyester (P) of the present invention, with respect to the above-mentioned melt viscosity stability, it is important to keep the content at 3% or less for the wet heat stability of the thermoplastic resin composition with the polycarbonate (A). It is preferable to maintain the property at a good level.

To reduce the melt viscosity stability of the polyester to 3% or less, a melt viscosity stabilizer for polycarbonate can be suitably used. In the case of polyester (P), phosphoric acid, phosphoric acid acid ester, or phosphoric acid acid salt can also be suitably used in addition to (E) -1 and (2) described above.

Specific examples of such compounds include phosphoric acid,
Phosphorous acid, pyrophosphoric acid, metaphosphoric acid, or phenylphosphonic acid and their acid esters, dimethyl phosphate, phenyl dihydrogen phosphate, dihydrogen phosphate 2,4-di-
Examples include t-butylphenyl, monophenyl phosphite, octyl phenylphosphonate, tetrabutylphosphonium dihydrogen phosphate, tetramethylammonium dihydrogen phosphate and the like.

The amount and method of adding these melt viscosity stabilizers can be suitably carried out in accordance with those of polycarbonate.

The molecular weight of the polyester (P) is 0.6 or more, preferably 0.65 to 5, as the intrinsic viscosity measured at 25 ° C. using o-chlorophenol as a solvent.
1.6, more preferably 0.7 to 1.5.

The polyester (P) is liable to be colored when melted in the air, and a preferable measure is to use a phenol stabilizer and / or a phosphite stabilizer described below to prevent the polyester from being oxidized and degraded. Can be.

Regarding the terminal group of the polyester (P),
Keeping the amount of vinyl end groups at a low level is also a preferable means for suppressing coloring of the thermoplastic resin composition comprising the polyester (P) and the polycarbonate (A).

That is, the amount of the terminal vinyl group, as measured by NMR, is preferably 50 equivalents / (polymer 10 ⁶ g) or less, more preferably 40 equivalents / (polymer 10 ⁶ g) or less. More preferably, it is 20 equivalents / (polymer 10 ⁶ g) or less, ideally 0 equivalents / (polymer 10 ⁶ g).

The mixing ratio of the polycarbonate (A) and the polyester (P) in the thermoplastic resin composition of the present invention is such that the total amount of the polycarbonate (A) and the polyester (P) is 100 parts by weight. ) 5 to 95 parts by weight, 95 to 5 parts by weight of polyester (P), preferably 20 to 95 parts by weight of polycarbonate (A), 80 to 5 parts by weight of polyester (P), more preferably 30 to 95 parts by weight of polycarbonate (A) 70 to 5 parts by weight of polyester (P), particularly preferably 50 to 95 parts by weight of polycarbonate (A), polyester (P)
A range of 50 to 5 parts by weight is selected.

The compounding ratio of the polycarbonate (A) is less than 5 parts by weight, that is, the compounding ratio of the polyester (P) is 9
If the amount is more than 5 parts by weight, the impact resistance becomes insufficient, and the compounding ratio of the polycarbonate (A) becomes more than 95 parts by weight, that is, if the compounding ratio of the polyester (P) becomes less than 5 parts by weight, the chemical resistance becomes poor. It is not preferable because it is insufficient.

In addition, in the present invention, in order to maintain the wet heat fatigue resistance of the thermoplastic resin composition at a good level, it is necessary to maintain the melt viscosity stability at 2.5% or less.

That is, the polyester (P) generally has poor melt viscosity stability as compared with polycarbonate in general. Therefore, from the viewpoint of the melt viscosity stability of the composition, the blending of the polyester (P) is also difficult. Quantity may be limited.

Further, a rubber-like elastic body (F) can be added to the thermoplastic resin composition of the present invention for the purpose of further improving impact resistance. The rubber-like elastic material (F) usable in the present invention is a rubber component having a glass transition temperature of 10 ° C. or less, aromatic vinyl, vinyl cyanide, acrylate, methacrylate, and copolymerizable with these. And a graft copolymer obtained by copolymerizing one or more monomers selected from various vinyl compounds. On the other hand, various elastomers known as thermoplastic elastomers having no crosslinked structure, for example, polyurethane elastomers, polyester elastomers,
It is also possible to use styrene-ethylene propylene-styrene elastomers, polyetheramide elastomers and the like.

The rubber component having a glass transition temperature of 10 ° C. or lower includes butadiene rubber, butadiene-acryl composite rubber, acrylic rubber, acryl-silicon composite rubber, isoprene rubber, styrene-butadiene rubber, chloroprene rubber, ethylene- Examples thereof include propylene rubber, nitrile rubber, ethylene-acryl rubber, silicon rubber, epichlorohydrin rubber, fluorine rubber, and those obtained by adding hydrogen to unsaturated bond portions thereof.

Among the rubber-like elastic bodies (F), examples of the rubber-like elastic body containing a rubber component having a glass transition temperature of 10 ° C. or lower include butadiene rubber, butadiene-acryl composite rubber, acrylic rubber, and acrylic-silicon composite. A rubber-like elastic body using rubber is preferable. Butadiene-acrylic composite rubber is a rubber obtained by polymerizing a component of butadiene rubber and a component of acrylic rubber so as to have an IPN structure entangled with each other so as not to be copolymerized or separated. An acrylic rubber component and a silicone rubber component have an IPN structure in which they are entangled with each other so that they cannot be separated from each other, or are copolymerized with a functional group in the silicone rubber.

Examples of the aromatic vinyl include styrene, α-methylstyrene, p-methylstyrene, alkoxystyrene, halogenated styrene and the like, and styrene is particularly preferred. Also, as acrylates,
Examples thereof include methyl acrylate, ethyl acrylate, butyl acrylate, cyclohexyl acrylate, octyl acrylate, and the like. Examples of methacrylates include methyl methacrylate, ethyl methacrylate, butyl methacrylate, cyclohexyl methacrylate, and methacryl. Examples thereof include octyl acid, and methyl methacrylate is particularly preferable.

The rubber-like elastic body containing a rubber component having a glass transition temperature of 10 ° C. or less is used for bulk polymerization, solution polymerization,
Any of suspension polymerization and emulsion polymerization may be used, and the copolymerization may be a single-stage graft or a multi-stage graft. Further, it may be a mixture with a copolymer of only a graft component produced as a by-product at the time of production. Such a rubber-like elastic body is commercially available and can be easily obtained. For example, as a rubber component having a glass transition temperature of 10 ° C. or less, butadiene rubber or a butadiene-acrylic composite rubber is mainly used, for example, Kaneace B series of Kanebuchi Chemical Industry Co., Ltd. Series, EXL series, KIA series, BTA series, KCA series of Kureha Chemical Industry Co., Ltd.
As the rubber component having a temperature of 0 ° C. or lower, an acrylic-silicon composite rubber is mainly used, for example, those commercially available from Mitsubishi Rayon Co., Ltd. under the trade name of Metablen S-2001 or RK-200. When the total amount of the polycarbonate (A) and the polyester (P) is 100 parts by weight,
It is preferably 50 parts by weight, more preferably 3 to 40 parts by weight.

Further, the thermoplastic resin composition of the present invention is used in order to suppress the transesterification reaction between the polycarbonate (A) and the polyester (P) and to prevent a decrease in the molecular weight and deterioration of the hue during molding and the like. And a heat stabilizer.

Examples of such a heat stabilizer include phosphorous acid, phosphoric acid, phosphonous acid, phosphonic acid and esters thereof, and specific examples thereof include triphenyl phosphite, tris (nonylphenyl) phosphite, Tris (2,4-di-tert-butylphenyl) phosphite, tridecyl phosphite, trioctyl phosphite, trioctadecyl phosphite, didecyl monophenyl phosphite, dioctyl monophenyl phosphite, diisopropyl monophenyl phosphite, Monobutyldiphenylphosphite, monodecyldiphenylphosphite, monooctyldiphenylphosphite, bis (2,6-di-tert-butyl-4-methylphenyl) pentaerythritol diphosphite, 2,2-methylenebis (4,6 − -tert- butylphenyl)
Octyl phosphite, bis (nonylphenyl) pentaerythritol diphosphite, bis (2,4-di-t
tert-butylphenyl) pentaerythritol diphosphate, distearylpentaerythritol diphosphite, tributyl phosphate, triethyl phosphate, trimethyl phosphate, triphenyl phosphate, diphenyl monoorthoxenyl phosphate, dibutyl phosphate, dioctyl phosphate, diisopropyl phosphate, 4, Examples include tetrakis (2,4-di-tert-butylphenyl) 4'-biphenylenediphosphinate, dimethyl benzenephosphonate, diethyl benzenephosphonate, and dipropyl benzenephosphonate. Among them, trisnonylphenyl phosphite, trimethyl phosphate, tris (2,4-di-t
tert-Butylphenyl) phosphite and dimethyl benzenephosphonate are preferably used.

These heat stabilizers may be used alone or in combination of two or more. When the total amount of the polycarbonate (A) and the polyester (P) is 100 parts by weight, the amount of the heat stabilizer is preferably 0.0001 to 1 part by weight, more preferably 0.0005 to 0.5 part by weight. More preferably, 0.001 to 0.1 part by weight is further preferable.

Further, the thermoplastic resin composition of the present invention may contain a generally known antioxidant for the purpose of preventing oxidation. Such antioxidants include, for example, pentaerythritol tetrakis (3-mercaptopropionate), pentaerythritol tetrakis (3-laurylthiopropionate), glycerol-3-stearylthiopropionate, triethylene glycol-
Bis [3- (3-tert-butyl-5-methyl-4-
Hydroxyphenyl) propionate], 1,6-hexanediol-bis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate], pentaerythritol-tetrakis [3- (3,5-di-
tert-butyl-4-hydroxyphenyl) propionate], octadecyl-3- (3,5-di-tert)
-Butyl-4-hydroxyphenyl) propionate,
1,3,5-trimethyl-2,4,6-tris (3,5
-Di-tert-butyl-4-hydroxybenzyl) benzene, N, N-hexamethylenebis (3,5-di-t
tert-butyl-4-hydroxy-hydrocinnamide), 3,5-di-tert-butyl-4-hydroxy-benzylphosphonate-diethyl ester, tris (3,5-di-tert-butyl-4-hydroxybenzyl) Isocyanurate, tetrakis (4,4′-biphenylenediphosphinic acid) (2,4-di-tert-butylphenyl), 3,9-bis {1,1-dimethyl-2-
[Β- (3-tert-butyl-4-hydroxy-5-
Methylphenyl) propionyloxy] ethyl} -2,
4,8,10-tetraoxaspiro (5,5) undecane and the like. The compounding amount of these antioxidants is preferably 0.0001 to 0.5 parts by weight when the total amount of the polycarbonate (A) and the polyester (P) is 100 parts by weight.

Further, an inorganic filler can be added to the thermoplastic resin composition of the present invention in order to improve rigidity and the like within a range not to impair the object of the present invention. Such inorganic fillers include talc, mica, glass flake,
Examples thereof include plate-like or granular inorganic fillers such as glass beads, calcium carbonate, and titanium oxide, and fibrous fillers such as glass fiber, glass milled fiber, wollastonite, carbon fiber, and metal-based conductive fiber. When the total amount of the polycarbonate (A) and the polyester (P) is 100 parts by weight,
100 parts by weight is preferable, and 3 to 70 parts by weight is more preferable.

The inorganic filler usable in the present invention may be surface-treated with a silane coupling agent or the like.
By this surface treatment, degradation of the polycarbonate (A) is suppressed, and the wet heat fatigue property as an object of the present invention can be further improved. The silane coupling agent referred to herein is the following formula (5)

[0112]

Embedded image [Wherein Y is an amino group, an epoxy group, a carboxyl group, a vinyl group, a mercapto group, component reactive or affinity groups having the thermoplastic resin composition according to the present invention such as a halogen atom, Z ^1, Z ^2, Z ^3, Z ⁴ represents respectively a single bond or an alkylene group having 1 to 7 carbon atoms, in the alkylene molecular chain, an amide bond, an ester bond, may be an ether bond or an imino bond is interposed, X ¹ , X ² , X ³
Is an alkoxy group, preferably an alkoxy group having 1 to 4 carbon atoms or a halogen atom], specifically, vinyltrichlorosilane, vinyltriethoxysilane, vinyltrimethoxysilane, γ
-Methacryloxypropyltrimethoxysilane, β-
(3,4-epoxycyclohexyl) ethyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane, N-β (aminoethyl) γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, N-phenyl- γ-aminopropyltrimethoxysilane, γ-mercaptopropyltrimethoxysilane, γ-chloropropyltrimethoxysilane and the like.

In order to further improve the releasability from the mold during the melt molding, a releasing agent may be added to the thermoplastic resin composition of the present invention within a range that does not impair the object of the present invention. It is possible. Examples of the release agent include an olefin wax, an olefin wax containing a carboxy group and / or a carboxylic anhydride group, a silicone oil, an organopolysiloxane, a higher fatty acid ester of a monohydric or polyhydric alcohol, paraffin wax, and beeswax. And the like. The compounding amount of such a release agent is such that the total amount of the polycarbonate (A) and the polyester (P) is 10
When it is 0 parts by weight, 0.01 to 5 parts by weight is preferable.

As the olefin wax, use of a polyethylene wax and / or a 1-alkene polymer is particularly preferred, and a very good releasing effect can be obtained. As the polyethylene wax, those generally widely known at present can be used, and examples thereof include those obtained by polymerizing ethylene under high temperature and high pressure, those obtained by thermally decomposing polyethylene, and those obtained by separating and purifying a low molecular weight component from a polyethylene polymer. The molecular weight and the degree of branching are not particularly limited, but the number average molecular weight is preferably 1,000 or more.

The 1-alkene polymer may have 5 to 4 carbon atoms.
What polymerized 1-alkene of 0 can be used. The molecular weight of the 1-alkene polymer was 1,000 in number average molecular weight.
0 or more is preferable.

The olefin wax containing a carboxy group and / or a carboxylic anhydride group is a compound containing a carboxy group and / or a carboxylic anhydride group by post-treatment of an olefin wax, preferably maleic acid. And / or those modified by post-treatment with maleic anhydride. Further ethylene and / or
Or a compound containing a carboxy group and / or carboxylic anhydride group copolymerizable with such monomers when polymerizing or copolymerizing a 1-alkene, preferably a copolymer of maleic acid and / or maleic anhydride Such a copolymer is preferred because it contains a carboxy group and / or a carboxylic anhydride group in a high concentration and stably. The carboxy group or carboxylic anhydride group may be bonded to any part of the olefin wax, and the concentration thereof is not particularly limited, but is preferably in the range of 0.1 to 6 meq / g per gram of the olefin wax. . In addition, in this specification, eq means an equivalent.

Commercially available olefin waxes containing a carboxy group and / or a carboxylic acid anhydride group include, for example, Diacarna-PA30 (trade name of Mitsubishi Chemical Corporation), high wax acid treatment type 220.
3A and 1105A (trade names of Mitsui Petrochemical Co., Ltd.) and the like, and these are used alone or as a mixture of two or more.

In the case where an inorganic filler is blended in the present invention, the addition of an olefin-based wax containing a carboxyl group and / or a carboxylic anhydride group can improve the releasability from a mold during melt molding. Not only for further improvement, but also an effect of suppressing a decrease in impact strength due to the blending of the inorganic filler is exhibited and can be preferably used.

As the higher fatty acid esters, monohydric or polyhydric alcohols having 1 to 20 carbon atoms and 10 carbon atoms can be used.
Preference is given to partial or full esters with up to 30 saturated fatty acids. Examples of the partial or total ester of a monohydric or polyhydric alcohol and a saturated fatty acid include stearic acid monoglyceride, stearic acid diglyceride, stearic acid triglyceride, stearic acid monosorbitatate, behenic acid monoglyceride, pentaerythritol monostearate, and pentaerythritol Tetrastearate, pentaerythritol tetraperargonate, propylene glycol monostearate,
Examples include stearyl stearate, palmityl palmitate, butyl stearate, methyl laurate, isopropyl palmitate, biphenyl biphenate, sorbitan monostearate, 2-ethylhexyl stearate and the like.

Among them, stearic acid monoglyceride,
Triglyceride stearate and pentaerythritol tetrastearate are preferably used.

A light stabilizer can be added to the thermoplastic resin composition of the present invention as long as the object of the present invention is not impaired.

As such a light stabilizer, for example, 2-
(2'-hydroxy-5'-tert-octylphenyl) benzotriazole, 2- (3-tert-butyl-5-methyl-2-hydroxyphenyl) -5-chlorobenzotriazole, 2- (5-methyl-2 -Hydroxyphenyl) benzotriazole, 2- [2-hydroxy-3,5-bis (α, α-dimethylbenzyl) phenyl] -2H-benzotriazole, 2,2′-methylenebis (4-cumyl-6-benzotriazole Phenyl), 2,2′-p-phenylenebis (1,3-benzoxazin-4-one) and the like. When the total amount of the polycarbonate (A) and the polyester (P) is 100 parts by weight,
2 parts by weight are preferred.

The thermoplastic resin composition of the present invention may contain an antistatic agent as long as the object of the present invention is not impaired. Examples of such an antistatic agent include polyetheresteramide, glycerin monostearate, ammonium dodecylbenzenesulfonate, phosphonium dodecylbenzenesulfonate, sodium alkylsulfonate, monoglyceride maleic anhydride, diglyceride maleic anhydride and the like. Can be

The thermoplastic resin composition of the present invention may contain a flame retardant in an amount that does not impair the object of the present invention. As the flame retardant, halogenated bisphenol A
Polycarbonate flame retardant, organic salt-based flame retardant, aromatic phosphate ester-based flame retardant, or halogenated aromatic phosphate ester-based flame retardant, and one or more of them can be blended.

Specifically, the polycarbonate type flame retardant of halogenated bisphenol A includes a polycarbonate type flame retardant of tetrachlorobisphenol A, a copolymerized polycarbonate type flame retardant of tetrachlorobisphenol A and bisphenol A, and a polycarbonate type flame retardant of tetrabromobisphenol A. Flame retardants, such as polycarbonate-type flame retardants copolymerized with tetrabromobisphenol A and bisphenol A.

Specifically, organic salt-based flame retardants include dipotassium diphenylsulfone-3,3'-disulfonate, potassium diphenylsulfon-3-sulfonate, sodium 2,4,5-trichlorobenzenesulfonate, 2,4,4 5-
Potassium trichlorobenzenesulfonate, bis (2,6
Potassium dibromo-4-cumylphenyl) phosphate, sodium bis (4-cumylphenyl) phosphate, bis (p
-Potassium toluene-sulfone) imide, potassium bis (diphenylphosphate) imide, potassium bis (2,4,6-tribromophenyl) phosphate, potassium bis (2,4-dibromophenyl) phosphate, bis (4-bromo Potassium phenyl) phosphate, potassium diphenylphosphate, sodium diphenylphosphate, potassium perfluorobutanesulfonate, sodium or potassium lauryl sulfate, sodium or potassium hexadecyl sulfate, and the like.

Specifically, halogenated aromatic phosphate ester type flame retardants include tris (2,4,6-tribromophenyl) phosphate, tris (2,4-dibromophenyl) phosphate and tris (4-bromophenyl) Phosphate and the like.

Specifically, aromatic phosphate ester-based flame retardants include triphenyl phosphate, tris (2,6-xylyl) phosphate, tetrakis (2,6-xylyl)
Resorcinol diphosphate, tetrakis (2,6-xylyl) hydroquinone diphosphate, tetrakis (2
6-xylyl) -4,4'-biphenol diphosphate, tetraphenyl resorcin diphosphate, tetraphenyl hydroquinone diphosphate, tetraphenyl-4,4'-biphenol diphosphate, and the aromatic ring source is resorcin and phenol, and phenolic OH Aromatic polyphosphate containing no groups, aromatic polyphosphates containing resorcinol and phenol and containing aromatic phenolic OH groups, aromatic polyphosphates containing hydroquinone and phenol containing no phenolic OH groups, Similar aromatic polyphosphate containing phenolic OH group, aromatic polyphosphate whose aromatic ring source is bisphenol A and phenol, aromatic polyphosphate whose aromatic ring source is tetrabromobisphenol A and phenol, aromatic ring source Resorcinol and aromatic polyphosphate of 2,6-xylenol, aromatic polyphosphate of hydroquinone and aromatic polyphosphate of 2,6-xylenol, aromatic polyphosphate of aromatic ring source of bisphenol A and 2,6-xylenol And aromatic polyphosphates whose aromatic ring sources are tetrabromobisphenol A and 2,6-xylenol. In addition, of the above,
For compounds after "aromatic polyphosphate in which the aromatic ring source is bisphenol A and phenol", "aromatic polyphosphate" refers to both aromatic polyphosphate containing phenolic OH groups and aromatic polyphosphate not containing. Shall mean.

Among these flame retardants, polycarbonate-type flame retardants of halogenated bisphenol A, polycarbonate-type flame retardants of tetrabromobisphenol A,
A copolymerized polycarbonate of tetrabromobisphenol A and bisphenol A is preferable, and a polycarbonate type flame retardant of tetrabromobisphenol A is more preferable. As organic salt-based flame retardants, diphenyl sulfone-3,
3'-dipotassium disulfonic acid, diphenyl sulfone-
Potassium 3-sulfonate and sodium 2,4,5-trichlorobenzenesulfonate are preferred. As aromatic phosphate ester flame retardants, triphenyl phosphate,
Tricresyl phosphate, cresyl diphenyl phosphate, resorcinol bis (dixylenyl phosphate), bis (2,3 dibromopropyl) phosphate,
Tris (2,3 dibromopropyl) phosphate is preferred. Among these, triphenyl phosphate, which is an aromatic phosphate ester flame retardant that does not destroy the ozone layer,
Tricresyl phosphate, resorcinol bis (dixylenyl phosphate) is most preferred.

Other resins can be added to the thermoplastic resin composition of the present invention as long as the object of the present invention is not impaired.

As such other resins, for example, polyamide resins, polyimide resins, polyetherimide resins,
Polyurethane resin, polyphenylene ether resin, polyphenylene sulfide resin, polysulfone resin, polyolefin resin such as polyethylene and polypropylene, polystyrene resin, acrylonitrile / styrene copolymer (AS resin), acrylonitrile / butadiene / styrene copolymer (ABS resin), poly Methacrylate resin,
Resins such as phenolic resins and epoxy resins are exemplified.

For producing the thermoplastic resin composition of the present invention, any method is employed. For example, tumbler, V
Type blender, super mixer, Nauta mixer,
A method of mixing with a Banbury mixer, a kneading roll, an extruder or the like is appropriately used. The thermoplastic resin composition thus obtained can be used as it is or once in the form of a pellet by a melt extruder, and then formed into a molded product by a generally known method such as an injection molding method, an extrusion molding method, or a compression molding method. it can.
In order to enhance the miscibility of the thermoplastic resin composition of the present invention and obtain stable mold release properties and various physical properties, it is preferable to use a twin-screw extruder in melt extrusion. Furthermore, when compounding an inorganic filler, a method of directly charging the extruder from the hopper opening or in the middle of the extruder, a method of previously mixing with a polycarbonate resin or a polyester resin, a method of previously mixing with some polycarbonate resin or polyester resin and forming a master Either a method of preparing and charging, or a method of charging such a master from the middle of the extruder can be adopted.

The thus obtained thermoplastic resin composition of the present invention can be used for personal computers, word processors, fax machines, copiers,
OA equipment housings and chassis such as printers,
CD-ROM tray, chassis, turntable,
OA internal parts such as pickup chassis and various gears, housings and parts for home appliances such as TVs, videos, electric washing machines, electric dryers, and vacuum cleaners, electric tools such as electric saws and electric drills, telescope barrels, Optical device parts such as microscope lens barrel, camera body, camera housing, camera lens barrel,
It is useful for automotive parts such as door handles, pillars, bumpers, and instrument panels. Especially mechanical strength, chemical resistance,
It is useful for automotive parts (outer door handles, inner door handles, etc.) and mechanical parts (power tool covers, etc.) that require wet heat fatigue resistance.

[0134]

EXAMPLES Examples will be further described below with reference to examples. “Parts” or “%” in Examples has no meanings unless otherwise specified, or indicates parts by weight or% by weight, unless otherwise specified.
The symbols for the evaluation items and each component in the composition mean the following.

(I) Evaluation Items 1) Determination of Acid Value, That is, Determination of Terminal Carboxyl Group Approximately 1 g of a polyester sample was precisely weighed and dissolved in 100 mL of purified benzyl alcohol. Cool and purify chloroform 100
mL, add phenol red as indicator, 0.1N
It was titrated with a solution of sodium hydroxide in benzyl alcohol.

In this example, the same quantification method was used because there was no factor that substantially affects the acid value other than the terminal carboxy group. Needless to say, it needs to be quantified.

2) Determination of Branched Structure 0.1 g of a polycarbonate sample was precisely weighed, dissolved in 5 mL of tetrahydrofuran, added with 1 mL of a 5N methanolic sodium hydroxide solution, stirred at room temperature for 2 hours, and hydrolyzed. Subsequently, 0.6 mL of concentrated hydrochloric acid was added, and the mixture was quantified by reversed-phase liquid chromatography.

The conditions of use are as follows. UV detector; wavelength: 300 nm, column: Inertsil ODS-3 (manufactured by GL Sciences) Eluent: mixed eluent of methanol / 1% phosphoric acid aqueous solution Analysis conditions: column temperature 25 ° C., methanol / 1% aqueous solution of phosphoric acid 20 / A calibration curve was prepared with a standard substance having a structure obtained by hydrolyzing the structural units of formulas (3) -1 to 3 starting from 80 and under a gradient condition of 100/0 and quantified.

3) Melt Viscosity Stability A sample dried at 120 ° C. under a high vacuum of 10 Pa or less for 5 hours was subjected to a shear rate of 1 rad / sec under a nitrogen stream using a rheometrics RAA flow analyzer.
c, the absolute value of the change in melt viscosity measured at 270 ° C.
The measurement was performed for one minute, and the rate of change per minute was determined. In order for the thermoplastic resin composition according to the present invention to have good short-term and long-term stability, this value must not exceed 2.5%.

4) Wet Heat Fatigue Using a so-called C-type measurement sample,
% RH atmosphere, sinusoidal frequency 1Hz, maximum load 2
Using a fatigue tester [Shimadzu Servo Pulsar EHF-EC5 manufactured by Shimadzu Corporation] under the condition of kg, the number of times until the measurement sample was broken was measured.

The thermoplastic resin composition with poly-1,3-propylene terephthalate has a wet heat fatigue resistance of 2 × 1
If it is 000 times or more, it is determined that the wet heat fatigue resistance is acceptable.
It was judged to be good if the number was 1000 times or more, and to have excellent wet heat resistance if it was 3 × 1000 times or more.

FIG. 1 shows a front view of a so-called C-type sample used for evaluating wet heat fatigue resistance. The thickness of the sample is 3 mm. The test is performed by passing a jig of a test machine through the hole indicated by reference numeral 6 and applying a predetermined load in the vertical direction indicated by reference numeral 7.

5) Chemical Resistance A 1% strain was applied to a tensile test piece used in accordance with ASTM D638, and the test piece was immersed in Esso-regular gasoline at 30 ° C. for 3 minutes.
The retention was calculated by the following equation. Retention rate (%) = (strength of treated sample / strength of untreated sample) × 100 It was determined that the sample had good chemical resistance at a retention rate of 75% or more.

(II) Symbol of each component in the composition and its production method The following symbols were used. In addition, PPT-1 to 3 were produced by the direct esterification method as follows. That is,
According to a conventional method, 1300 of 1.3-propylene glycol
Parts by weight and 2000 parts by weight of terephthalic acid were charged into an autoclave, and the internal temperature was set at 180 ° C. Internal temperature 120 ° C
When the temperature reached 2, a catalyst of 2.0 parts by weight of tetrabutyl titanate and 2.0 parts by weight of monohydroxytin oxide was added, and polymerization was carried out. In some cases, the intrinsic viscosity is about 0.7-
At the time of 0.8, terephthalic acid and 10 parts by weight of PPT-2 and PPT-3 were added so as to obtain a predetermined acid value, and polymerization was continued until a predetermined intrinsic viscosity was reached. Further, at this time, 5 parts by weight of phosphonium benzenesulfonate BSP was added to PPT-3 as a stabilizer to finally produce polypropylene terephthalate having the following physical properties. The description following each symbol below is about physical properties.

PPT-1 intrinsic viscosity: 0.9, acid value: 35 eq. / Ton, melt viscosity stability; 1.3 PPT-2 intrinsic viscosity; 0.9, acid value; 80 eq. / Ton, melt viscosity stability; 2.0 PPT-3 intrinsic viscosity; 0.9, acid value; 80 eq. / Ton, melt viscosity stability; 1.7

PPT-4 was produced by the transesterification method as follows. To 1412 parts by weight of dimethyl terephthalate and 830 parts by weight of 1,3-propanediol, 0.247 parts by weight of tetrabutyl titanate was added,
The transesterification was performed at 150-220 ° C for 3 hours.
At the end of transesterification, 0.4 g of magnesium acetate tetrahydrate
66 parts by weight dissolved in 1.3-propanediol diol were added, followed by 0.49 parts of tetrabutyl titanate.
4 parts by weight were added to carry out a polycondensation reaction. The molar ratio between Mg and the Ti metal element was set to 1.0. Polycondensation reaction is normal pressure to 1 To
The pressure was gradually reduced to rr, and at the same time, the temperature was raised to 255 ° C. Thereafter, polymerization was carried out at 1 Torr and 255 ° C until a predetermined degree of polymerization was reached. At 255 ° C. after polymerization, 3.6 parts by weight of tetrabutylphosphonium benzenesulfonate was added. The description following each symbol below is about physical properties. PPT-4 intrinsic viscosity; 0.71, acid value; 10 eq. / Ton, melt viscosity stability; 0.8

PC-1 The production of this polycarbonate was carried out as follows. 137 parts by weight of purified BPA and 133 parts by weight of purified DPC as raw materials, and 4.1 × 10 ⁻⁵ parts by weight of bisphenol A disodium salt as a polymerization catalyst in a reaction vessel equipped with a stirrer, a rectification tower, and a decompression device. And 5 × 10 ⁻³ parts by weight of tetramethylammonium hydroxide were melted at 180 ° C. under a nitrogen atmosphere.

Under stirring, the inside of the reaction tank was kept at 13.33 kPa (1
The pressure was reduced to 00 mmHg, and the reaction was carried out for 20 minutes while distilling off the generated phenol. Next, after the temperature was raised to 200 ° C., the pressure was gradually reduced to 4.00 while phenol was distilled off.
The reaction was performed at 0 kPa (30 mmHg) for 20 minutes. The temperature was gradually increased, and the temperature was increased to 220 ° C for 20 minutes and 240 ° C for 20 minutes.
Reaction at 260 ° C. for 20 minutes, then 260 ° C.
, The reaction was continued at 2.666 kPa (20 mmHg) for 10 minutes and 1.333 kPa (10 mmHg) for 5 minutes, and finally 260 ° C./66.7 Pa (0.
The reaction was continued at 5 mmHg until the viscosity average molecular weight became 25,000.

With respect to 100 parts by weight of this polycarbonate,
0.003 parts by weight of tris (2,4-t-butylphenyl phosphite), 0.05 of trimethyl phosphate
The mixture was extruded at 280 ° C. with an extruder to obtain aromatic polycarbonate resin pellets.

Finally, the viscosity average molecular weight was 25,000,
A polycarbonate having a terminal OH group concentration of 43 (eq / ton-polycarbonate), a branch component content of 0.3 mol (% / carbonate bond), and a melt viscosity stability of 1.1 was obtained.

PC-2 The polymerization reaction was continued in the same manner as in PC-1, and the polymerization reaction was continued until the viscosity-average molecular weight became 25,000. The obtained polycarbonate was treated with tetrabutylphosphonium dodecylbenzenesulfonate (hereinafter abbreviated as DBSP). ) 3.6x
10 ^-4 parts by weight were added.

Then, 0.003 parts by weight of bis (2,4-di-tert-butylphenyl) pentaerythrityl diphosphite and 0.0005 parts by weight of phosphoric acid were mixed per 100 parts by weight of the polycarbonate, and the mixture was added to an extruder. 28
Extruded at 0 ° C., polycarbonate pellets were obtained.

The viscosity average molecular weights of the finally obtained polycarbonates were all 25,000, the content of branching components was 0.3 (mol% / carbonate bond), the terminal hydroxyl group concentration was 43 (eq / ton-polycarbonate), and the melt viscosity was The stability was 0.

PC-3 bisphenol A disodium salt 4.1 × 1 as a catalyst
Polymerization was carried out in the same manner as PC-2 except that 9.1 × 10 ^-4 parts by weight of bisphenol A2 potassium salt was used instead of 0 ^-5 parts by weight. DB on the obtained polycarbonate
7.0 × 10 ⁻³ parts by weight of SP was added to obtain polycarbonate pellets.

Finally, the viscosity average molecular weight was 25,000, the content of the branched component was 1.2 mol%, and the concentration of terminal hydroxyl groups was 38.
(Eq / ton-polycarbonate), a polycarbonate having a melt viscosity stability of 0.1 was obtained.

PC-4 In a reactor equipped with a thermometer, a stirrer and a reflux condenser, 3022 parts of ion-exchanged water and 251.6 parts of a 48% aqueous sodium hydroxide solution were put, and 0.8 parts of hydrosulfite and 267.8 parts of bisphenol A were added. After dissolution, and adding 136.5 parts of 48% aqueous sodium hydroxide solution, 176 of methylene chloride was added.
2.6 parts are added and phosgene 150 is added under stirring at 15-20 ° C.
The part was blown in for 60 minutes. After the injection of phosgene was completed, 5.28 parts of p-tert-butylphenol was dissolved in 40 parts of methylene chloride and added, and 48.6 parts of a 48% aqueous sodium hydroxide solution was added to emulsify. Then, 0.3 parts of triethylamine was added. The reaction was completed by stirring at 28 to 33 ° C. for about 1 hour. After completion of the reaction, the product was diluted with methylene chloride, washed with water, acidified with hydrochloric acid, and washed with water. When the conductivity of the aqueous phase became almost the same as that of ion-exchanged water, methylene chloride was evaporated to obtain a colorless polymer. 7 parts were obtained (98% yield). The viscosity average molecular weight of this polymer is 24
000, and the terminal hydroxyl group concentration was 10 (eq / ton-polycarbonate).

To this aromatic polycarbonate resin, 0.003% by weight of tris nonylphenyl phosphite and 0.05% by weight of trimethyl phosphate were added, and the mixture was extruded at 280 ° C. using an extruder.
Aromatic polycarbonate resin pellets having a branch component content of 0.01 (mol% / carbonate bond) or less, a terminal hydroxyl concentration of 10 (eq / ton-polycarbonate), and a melt viscosity stability of 0.1 were obtained. .

The rubbery elastic body (F) is as follows. E-1 Butadiene-alkyl acrylate-alkyl methacrylate copolymer (EXL-2602; manufactured by Kureha Chemical Industry Co., Ltd.). E-2 Composite rubber in which a polyorganosiloxane component and a polyalkyl (meth) acrylate rubber component have an interpenetrating network structure (S-2001; manufactured by Mitsubishi Rayon Co., Ltd.)
It is.

The inorganic filler is as follows. G Glass fiber (chopped strand ECS-03T-5)
11; manufactured by NEC Corporation, urethane convergence treatment, fiber diameter 13 μm). T talc (P-3; manufactured by Nippon Talc Co., Ltd.). WAX An olefin-based wax containing a carboxyl group and / or a carboxylic anhydride group (an olefin-based wax obtained by copolymerizing an α-olefin and maleic anhydride: Diacarna-PA30; manufactured by Mitsubishi Kasei Corporation (containing maleic anhydride Amount = 10 wt%)).

[Examples 1 to 9 and Comparative Examples 1 to 3] When the total amount of the above-mentioned polycarbonates and polyesters was 100 parts by weight, each component shown in Table 1 and a phosphorus-based stabilizer (pentaerythritylbis (octadecylphospho) were used. Fight): PEP-8 manufactured by Asahi Denka Kogyo Co., Ltd.) 0.1 part by weight, and in Examples 3 and 4, one more DBSP was added.
* 10 ^-3 parts by weight and 1.4 * 10 ^-1 parts by weight of BSP were uniformly mixed by using a tumbler, and then a twin screw extruder equipped with a 30 mmφ vent (KTX-30 manufactured by Kobe Steel Co., Ltd.) was used. The pellet was pelletized while devolatilizing at a cylinder temperature of 260 ° C. and a vacuum of 10 mmHg.
After drying at 0 ° C. for 5 hours, a molded piece for measurement was prepared at a cylinder temperature of 260 ° C. and a mold temperature of 70 ° C. using an injection molding machine (SG150U type manufactured by Sumitomo Heavy Industries, Ltd.).

As is clear from the respective comparisons, the thermoplastic resin composition comprising the polycarbonate (A) and the polyester (P) of the present invention has particularly a wet heat fatigue property as compared with the polycarbonate and polyester using the comparative examples. It turns out that it is excellent and also has excellent chemical resistance.

The results are shown in Table 1. <Table 1>

[Table 1]

From the above examination, it is found that the repeating unit represented by the formula (1), which is one embodiment of the present invention, has a content of 5 to 95%.
The repeating unit represented by the formula (2) is 95 to 100 parts by weight.
In a thermoplastic resin composition containing 5 parts by weight, the thermoplastic resin composition has a melt viscosity stability of 2.5 parts by weight.
% Of the thermoplastic resin composition having excellent properties.

[0164]

Embedded image (R ¹ , R ² , R ³ and R ⁴ are each independently a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an aralkyl group or an aryl group, W is an alkylidene group, an alkylene group, a cycloalkylidene group, a cycloalkylene group, A phenyl-substituted alkylene group, an oxygen atom, a sulfur atom, a sulfoxide group, or a sulfone group.)

[0165]

Embedded image (In the formula, A represents an arylene group.)

[0166]

Industrial Applicability According to the present invention, it is possible to provide a thermoplastic resin composition having excellent wet heat fatigue properties by making use of the inherent properties of polycarbonate and polyester, such as chemical resistance.

[Brief description of the drawings]

FIG. 1 is a front view of a so-called C-type sample used for evaluating wet heat fatigue resistance.

[Explanation of symbols]

1 Center of double circle of C shape 2 Radius of inner circle of double circle (20 mm) 3 Radius of outer circle of double circle (30 mm) 4 Central angle (60 °) indicating position of jig mounting hole 5 Gap between sample end faces (13 mm) 6 Jig mounting hole (circle 4 mm in diameter, located at center of sample width) 7 Direction of load imposed on sample during fatigue test

 ──────────────────────────────────────────────────続 き Continuing from the front page (72) Inventor Yuichi Kageyama 2-1 Hinodecho, Iwakuni-shi, Yamaguchi Prefecture Teijin Co., Ltd. Inside the Iwakuni Research Center (72) Inventor Katsuji Sasaki 2-1 Hinodecho, Iwakuni-shi, Yamaguchi Prefecture Teijin Shares 4J002 CF05X CF06X CF08X CG01W CG02W FD010 FD030 FD060 FD070

Claims (6)

[Claims] 1. A polyester (P) whose main repeating unit is represented by the formula (2) based on 5 to 95 parts by weight of the polycarbonate (A) whose main repeating unit is represented by the formula (1).
In a proportion of 95 to 5 parts by weight, and a melt viscosity stability of 2.5% or less. Embedded image (R ¹ , R ² , R ³ and R ⁴ are each independently a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an aralkyl group or an aryl group, W is an alkylidene group, an alkylene group, a cycloalkylidene group, a cycloalkylene group, A phenyl-substituted alkylene group, an oxygen atom, a sulfur atom, a sulfoxide group, or a sulfone group.) (In the formula, A represents an arylene group.) 2. The polyester (P) having an acid value (C) of 10
2. The composition according to claim 1, wherein the amount is from about 60 equivalents / 10 ⁶ g.
The thermoplastic resin composition according to the above. 3. The polycarbonate (A) is represented by the formula (3) -1
3. The thermoplastic resin composition according to claim 1, wherein the branching component (D) represented by (1) to (3) is contained in an amount of 0.01 to 2.0 mol% based on 1 mol of the carbonate bond. Embedded image Embedded image Embedded image (In the formula, Ar ₁ and Ar ₃ represent a trivalent aromatic group having 6 to 50 carbon atoms, and Ar and Ar ₄ represent a divalent aromatic group having 6 to 50 carbon atoms.) 4. The molar ratio (D / C ′) of the component (D) contained in the polycarbonate (A) to the terminal carboxy group (C ′) of the polyester (P) is D / C ′ =
The thermoplastic resin composition according to any one of claims 1 to 3, which is 0.01 to 15. 5. The thermoplastic resin composition according to claim 1, wherein the polyester (P) is a polyester selected from polypropylene terephthalate and polypropylene 2,6-naphthalate. 6. The repeating unit represented by the formula (1): 5 to 9
For 5 parts by weight, the repeating unit represented by the formula (2) is 95
５5 parts by weight, and the melt viscosity stability is 2.
A thermoplastic resin composition of not more than 5%. Embedded image (R ¹ , R ² , R ³ and R ⁴ are each independently a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an aralkyl group or an aryl group, W is an alkylidene group, an alkylene group, a cycloalkylidene group, a cycloalkylene group, A phenyl-substituted alkylene group, an oxygen atom, a sulfur atom, a sulfoxide group, or a sulfone group.) (In the formula, A represents an arylene group.)