JPH07310003A - Thermoplastic resin composition - Google Patents

Abstract

PURPOSE:To obtain a composition for providing a molded article having excellent molding fluidity, both improved transparency and excellent mechanical characteristics, improved resistance and surface properties, comprising a specific copolyester, a polycarbonate and a phenol-based stabilizer. CONSTITUTION:(A) A copolyester comprising a polymer main chain composed of a bisphenol-based compound (derivative) of formula I (X is O, S, SO2, CO, a 1-20C alkylene or a 3-20C alkylidene; R<1> to R<8> are each H, a halogen or a 1-20C monofunctional hydrocarbon group) and a dicarboxylic acid (derivative) containing 0.1-100mol% of an alicyclic dicarboxylic acid of formula II (two of R<9> to R<26> are each carboxyl group and the rest 16 groups are each H, a halogen, etc.) is blended with (B) a bis(4-hydroxyaryl)alkane-based polycarbonate and (C) a phenol-based stabilizer having steric hindrance in the weight ratio of the component A and the component B of 1/99 to 99/1 and in the ratio of 0.01-1.0 pt.wt. of the component C based on 100 pts.wt. of the components A+B.

Description

Detailed Description of the Invention

[0001]

The present invention has excellent molding fluidity,
The present invention relates to a novel thermoplastic resin composition that provides excellent transparency, heat resistance and mechanical properties when used as a molded product.

[0002]

2. Description of the Related Art General formula (I):

[0003]

[Chemical 5]

(In the formula, -X- is -O-, -S-, -SO.
₂ -, - CO-, an alkylene group or C ₃ to C ₁ -C ₂₀
To C ₂₀ alkylidene group, R ¹ , R ² , R ³ , R ⁴ and R
⁵ , R ⁶ , R ⁷ and R ⁸ are each independently a hydrogen atom, a halogen atom or a C _{1 to} C ₂₀ monovalent hydrocarbon group), a bisphenol compound or a derivative thereof, and a dicarboxylic acid or a derivative thereof. And 0.1 to 100 mol% of the dicarboxylic acid or its derivative is represented by the general formula (II):

[0005]

[Chemical 6]

(In the formula, two of R ^{9 to} R ²⁶ are carboxyl groups, and the remaining 16 are each independently a hydrogen atom, a halogen atom, a C _{1 to} C ₂₀ monovalent hydrocarbon group or The copolyester which is an alicyclic dicarboxylic acid or a derivative thereof represented by C _{1 to} C ₆ alkoxy group) has a high glass transition point and excellent heat resistance as compared with conventional copolyesters, and has a melt viscosity. It has been known that it has various excellent properties such as a low viscosity and excellent molding fluidity. Further, the copolyester as described above is excellent in mechanical properties such as tensile strength, flexural strength, flexural modulus, impact strength, recovery characteristics, thermal properties such as heat deformation temperature and thermal decomposition temperature, specific resistance value, It is also known to have excellent properties in electrical properties such as dielectric breakdown, arc resistance, dielectric constant and dielectric loss, flame retardancy, dimensional stability and chemical resistance.

Since the copolyester has many excellent properties as described above, it can be molded by injection molding, extrusion molding, press molding or other various molding methods.
It is used in various fields as general molded products, films, fibers, etc., and is expected to be used in a wider range of applications.

The method for producing the copolyester is as follows:
An interfacial polycondensation method in which an aromatic dicarboxylic acid chloride dissolved in an organic solvent that is incompatible with water and bisphenol dissolved in an alkaline aqueous solution are mixed and reacted (W. N. Earleks
on), Journal of Polymer Science (J. Poly. Sci.), XL, 399 (195).
9), JP-B-40-1959), a solution polycondensation method in which an aromatic dicarboxylic acid chloride and bisphenol and the like are reacted in an organic solvent (A. Conics (A. Co.
nix), Industrial and Engineering Chemistry (Ind. Eng. Chem., 5)
1, 147 (1959), Japanese Examined Patent Publication No. 37-5599), a melt polycondensation method of heating and polymerizing an aromatic dicarboxylic acid and bisphenol in the presence of acetic anhydride, a phenyl ester of aromatic dicarboxylic acid and bisphenol, etc. Melt polycondensation method of heat-polymerizing (Japanese Patent Publication No. 38-152
47), a melt polycondensation method in which an aromatic dicarboxylic acid and bisphenol and the like are heated and polymerized in the presence of a diaryl carbonate (Japanese Patent Publication No. 38-26299).

On the other hand, bis (4-hydroxyaryl) alkane-based polycarbonate (also known as 4,4'-dioxydiarylalkane-based polycarbonate) is already known as a resin having excellent transparency, impact strength, electrical characteristics and heat resistance. It is used in various fields.

As the method for producing the above-mentioned polycarbonate, a bis (4-hydroxyaryl) alkane as a dioxy compound is dispersed in an organic solvent and phosgene is blown thereinto, or a bis (4-hydroxyaryl) alkane and a carbonic acid diester are produced. There is a transesterification method in which and are transesterified in the presence of a catalyst.

[0011]

However, when the above-mentioned copolyester is actually used, there are some problems and its use range is limited.

First, the molded product of the copolyester is transparent but has a yellowish tint, which greatly restricts its use in fields requiring transparency.

Secondly, although the molding fluidity is improved as compared with the conventional copolyester, it is still insufficient, so that the copolyester itself has excellent properties. Nevertheless, not only cannot the product be economically produced, but it is difficult to produce a product in which its excellent properties are fully exhibited. Especially when molding large products, high resin temperature, high injection pressure, high mold temperature, etc. are required at the time of injection, which not only causes high cost, but also high resin temperature induces thermal decomposition of polymer. ,
High injection pressure causes distortion of the product, and when molding under such severe conditions, molding causes fatal defects such as short shots, sink marks, and flow marks.
Mechanical properties are also significantly reduced.

As described above, it is desired to improve transparency and molding fluidity of the copolymerized polyester.

On the other hand, bis (4-hydroxyaryl) alkane-based polycarbonate is superior in transparency, molding fluidity, impact strength, etc., but has heat resistance, weather resistance and chemical resistance when compared with the copolyester. Since its properties are inferior, its use is limited, and improvement is desired.

In order to solve such a problem, the applicant of the present invention has proposed that when the copolyester is mixed with polycarbonate, the molding fluidity is significantly improved.

However, although the composition comprising the copolyester and the polycarbonate certainly improves the molding fluidity as compared with the copolyester alone, the transparency of the molded article, particularly the yellowness, is It turns out that there is no significant improvement compared to the single case. It is considered that this is because when the composition is to be melt-mixed, the resin temperature must be about 330 to 350 ° C., so that the polycarbonate is thermally deteriorated. Further, in order to avoid the thermal deterioration of the polycarbonate, if the melt mixing is attempted at a resin temperature of 300 ° C. or lower, the molten resin becomes highly viscous and a realistic production amount cannot be secured, and the shear heat generation becomes large. It was found that deterioration occurred, resulting in loss of transparency.

On the other hand, when a small amount of the copolyester is melt-mixed with a large amount of the polycarbonate, since the copolyester and the polycarbonate have different flow start temperatures, the copolyester is melted and uniformly dispersed. Requires a temperature of 300 ° C. or higher, which is a relatively high temperature for polycarbonate and is easily yellowed.
For example, when kneading with an extruder, the polycarbonate flows first and has a low viscosity, so when the amount of the copolyester is small, the copolyester is not sufficiently kneaded and cannot be dispersed. For this reason, even when the amount of the copolyester is small, it is necessary to raise the temperature, and thus the yellowing is likely to occur.

[0019]

SUMMARY OF THE INVENTION In view of the above circumstances, the present invention has been earnestly studied to obtain a resin composition having improved molding fluidity and heat resistance and improved transparency during molding. As a result of stacking, a composition comprising a copolyester, a polycarbonate and a sterically hindered phenolic stabilizer is surprisingly excellent in molding fluidity and heat resistance, and the transparency of the molded product is significantly improved. This has led to the completion of the present invention.

That is, in the present invention, the main chain of the polymer (A) is represented by the general formula (I):

[0021]

[Chemical 7]

(In the formula, -X- is -O-, -S-, -SO.
₂ -, - CO-, an alkylene group or C ₃ to C ₁ -C ₂₀
To C ₂₀ alkylidene group, R ¹ , R ² , R ³ , R ⁴ and R
⁵ , R ⁶ , R ⁷ and R ⁸ are each independently a bisphenol compound represented by a hydrogen atom, a halogen atom or a C ₁ -C ₂₀ monovalent hydrocarbon group) or a derivative thereof and a dicarboxylic acid or a derivative thereof. 0.1-10 of said dicarboxylic acid or its derivative formed.
0 mol% is represented by the general formula (II):

[0023]

[Chemical 8]

(In the formula, two of R ^{9 to} R ²⁶ are carboxyl groups, and the remaining 16 are each independently a hydrogen atom, a halogen atom, a C _{1 to} C ₂₀ monovalent hydrocarbon group or Copolyester (hereinafter also referred to as copolyester (A)), which is an alicyclic dicarboxylic acid represented by C _{1 to} C ₆ alkoxy group) or a derivative thereof (B) Bis (4-hydroxyaryl) alkane-based polycarbonate (Hereinafter, also referred to as polycarbonate (B)) and (C) a sterically hindered phenolic stabilizer (hereinafter, also referred to as stabilizer (C)), and the use ratio of the component (A) and the component (B) is The weight ratio is 1/99 to 99/1,
The ratio of the component (C) to the total amount of the components (A) and (B) of 100 parts (parts by weight, the same applies hereinafter) is 0.01 to.
It relates to a thermoplastic resin composition which is 1.0 part.

[0025]

FUNCTION AND EXAMPLE The thermoplastic resin composition of the present invention comprises
(A) Copolymerized polyester (A), which is a component for imparting excellent heat resistance, weather resistance, chemical resistance and the like to a molded article from the thermoplastic resin composition, (B) of the composition Polycarbonate (A) and (C) which are components for imparting properties such as molding fluidity, transparency of a molded product from the composition, and impact strength, and transparency of a molded product from the thermoplastic resin composition. In particular, it is composed of a stabilizer (C) which is a component for improving.

The copolymerized polyester (A) which is the component (A) of the thermoplastic resin composition of the present invention has a polymer main chain represented by the general formula (I):

[0027]

[Chemical 9]

(In the formula, -X- is -O-, -S-, -SO.
₂ -, - CO-, an alkylene group or C ₃ to C ₁ -C ₂₀
To C ₂₀ alkylidene group, R ¹ , R ² , R ³ , R ⁴ and R
⁵ , R ⁶ , R ⁷ and R ⁸ are each independently a bisphenol compound represented by a hydrogen atom, a halogen atom or a C ₁ -C ₂₀ monovalent hydrocarbon group) or a derivative thereof and a dicarboxylic acid or a derivative thereof. 0.1-10 of said dicarboxylic acid or its derivative formed.
0 mol% is represented by the general formula (II):

[0029]

[Chemical 10]

(In the formula, two of R ^{9 to} R ²⁶ are carboxyl groups, and the remaining 16 are each independently a hydrogen atom, a halogen atom, a C _{1 to} C ₂₀ monovalent hydrocarbon group or It is a copolyester comprising an alicyclic dicarboxylic acid represented by a C _{1 to} C ₆ alkoxy group) or a derivative thereof.

The weight average molecular weight of the copolyester (A) measured by the GPC method is preferably about 10,000 to 150,000, and more preferably about 30,000 to 100,000 in order to provide sufficient strength. The solution viscosity (measured in a chloroform solution at 30 ° C.) is an intrinsic viscosity of 0.2 to 1.
5, more preferably in the range of 0.5 to 1.0.

The thermal behavior is that the glass transition temperature is 15
It is preferably in the range of 0 to 300 ° C, and more preferably 170 to 280 ° C.

The copolyester (A) has relatively high heat resistance and relatively good molding fluidity as compared with other copolyesters containing dihydric phenol and dicarboxylic acid, and has higher heat resistance than polycarbonate. , Has good weather resistance and chemical resistance.

However, it is inferior in molding fluidity, transparency and impact strength as compared with polycarbonate.

The bisphenol compound or its derivative (hereinafter, also referred to as bisphenol (I)) used as the diol component of the copolyester (A) is a bisphenol compound represented by the general formula (I) or its derivative as described above. It is a derivative. The alkylene group and alkylidene group in the general formula (I) include a substituted alkylene group and a substituted alkylidene group, and examples of the substituent include a phenyl group.

[0036] Specific examples of the alkylene group of the C ₁ -C _20, for example _{-CH 2 -, - C 2 H} 4 -, - CH
_{(C 2 H 5) -,} - (CH 2) 3 -, - C (CH 3) 2
_{-, - C (CH 3)} (C 2 H 5) - and the like, such as.
Among these, from the viewpoint of the heat resistance of the aromatic polyester formed by C _{1 to} C ₆ alkylene groups such as —CH ₂ — and —C (CH ₃ ) ₂ —, it is particularly preferable.

Specific examples of the C ₃ -C ₂₀ alkylidene group include, for example,

[0038]

[Chemical 11]

And the like. Of these

[0040]

[Chemical 12]

A C ₅ -C ₁₂ alkylidene group such as is particularly preferable from the viewpoint of the reactivity of the bisphenol compound or derivative with the dicarboxylic acid or its derivative.

Further, R ^{1 to} R ⁸ are each independently a hydrogen atom, a halogen atom such as Cl or Br, or CH _{3
-, C 2 H 5 -,} C 3 H 7 -, C 4 H 9 - C 1 such as -
Although it is a C ₂₀ monovalent hydrocarbon group, R is R from the viewpoint of workability.
Two or more of each of ^{1 to} R ⁴ and R ^{5 to} R ⁸ are preferably hydrogen atoms, and from the viewpoint of heat resistance of the polyester, R ² and R ^{3 of} R ^{1 to} R ⁸ are , R ⁶ and R ⁷
It is preferable that a substitution machine be present in the.

Specific examples of the bisphenol compound represented by the general formula (I) as described above include, for example,
X such as 2,2-bis (4'-hydroxyphenyl) propane (also referred to as bisphenol A), bis (4-hydroxyphenyl) methane, and 1,1-bis (4'-hydroxyphenyl) ethane is C ₁ -C. _A bisphenol compound in which R ^{1 to} R ⁸ are hydrogen atoms in ₂₀ alkylene groups,
1,1-bis (4-hydroxyphenyl) -3,3,5
-Trimethylcyclohexane (also referred to as bisphenol TMC), bis (4-hydroxyphenyl) cyclohexylmethane and the like, X is a C ₆ -C ₂₀ alkylidene group and R
^A bisphenol compound in which ^{1 to} R ⁸ are hydrogen atoms,
X such as 2,2-bis (4'-hydroxy-3,5'-dibromophenyl) propane (also referred to as tetrabromobisphenol A) and bis (4-hydroxy-3,5-dichlorophenyl) methane is C ₁ -C. _A bisphenol compound in which R ^{1 to} R ⁸ are hydrogen atoms and halogen atoms in ₂₀ alkylene groups, bis (4-hydroxy-3,5-dimethylphenyl) methane, 2,2-bis (4′-hydroxy-3 ′) , 5'-Dimethylphenyl) propane, etc., a bisphenol compound in which X is a C _{1 to} C ₂₀ alkylene group and R ^{1 to} R ⁸ are hydrogen atoms and a C _{1 to} C ₆ hydrocarbon group, 1,1-bis (4'-hydroxyphenyl)-
Bisphenol compounds in which X is an alkylene group substituted with a C _{1 to} C ₂₀ phenyl group such as 1-phenylethane and R ^{1 to} R ⁸ are hydrogen atoms, and X such as 4,4′-dihydroxydiphenyl ether is —O And bisphenol compounds in which R ^{1 to} R ⁸ are hydrogen atoms, bis (4-hydroxy-3,5-dimethylphenyl) ether and the like, X is —O—, R ^{1 to} R ⁸ are hydrogen atoms and C ₁ to bisphenolic compounds is a hydrocarbon group of C _6, bis (4-hydroxyphenyl) X, such as sulfone -SO ₂ - with R ¹
To R ⁸ are hydrogen atoms, bisphenol compounds such as bis (4-hydroxy-3,5-dimethylphenyl) sulfone, X is —SO ₂ —, R ^{1 to} R ⁸ are hydrogen atoms and C _{1 to} C ₆ A bisphenol-based compound which is a hydrocarbon group, X such as 4,4′-dihydroxybenzophenone is —CO— and bisphenol-based compounds in which R ^{1 to} R ⁸ are hydrogen atoms, and X such as bis (4-hydroxyphenyl) sulfide is Examples thereof include bisphenol-based compounds in which R _{1 to} R ₈ are —S— and are hydrogen atoms.

Examples of the bisphenol compound derivative include alkali metal (Na, K) salts and diacetates thereof.

These bisphenols (I) can be used alone or in combination of two or more.

Of these, bisphenol TMC or a derivative thereof (hereinafter also referred to as bisphenol TMCs) is preferable from the viewpoint of imparting heat resistance to the thermoplastic resin composition. When two or more kinds are used in combination, bisphenol TMCs and bisphenol A or a derivative thereof (hereinafter, also referred to as bisphenol A) are preferable from the viewpoint that heat resistance is not significantly impaired and good moldability is imparted.

When using bisphenol TMCs,
It is preferable to use 0.1 to 100 mol% of the bisphenol (I) from the viewpoint of heat resistance of the polyester. When the amount of the bisphenol TMCs used is less than 0.1 mol% with respect to the bisphenols (I), the heat resistance tends to be hardly improved.

The minimum amount of bisphenol TMC used is 1
When it is at least 10 mol%, more preferably at least 10 mol% (therefore, when the amount of the bisphenol (I) used in combination with the bisphenol TMC is 99 mol%, further 90 mol% or less), the heat resistance is low. It is more preferable in that it is provided. When the maximum amount of the bisphenol TMCs used is 99 mol% or more, or 90 mol% or less, it is more preferable from the viewpoint that the moldability is improved. In this case, bisphenol A is preferable as the bisphenol (I) used together.

In addition to a part of the bisphenol (I), if necessary, a small amount (10 mol% or less of the diol component) of 4,4'-biphenol, hydroquinone, resorcinol, 2,6-dihydroxynaphthalene, etc. You may use together the diol compound etc. of these. The combined use of these compounds has the advantage of improving chemical resistance and heat resistance.

Copolyester (A) used in the present invention
Is composed of dicarboxylic acid or a derivative thereof (hereinafter, also referred to as dicarboxylic acid (I)) together with the bisphenol (I).

The dicarboxylic acid (I) has 0.1
To 100 mol% of the alicyclic dicarboxylic acid represented by the general formula (II) or its derivative represented by the general formula (II) whose basic skeleton is bicyclo [4,4,0] decane (hereinafter, also referred to as decahydronaphthalene ring) (hereinafter, Alicyclic dicarboxylic acids (I).

Of R ^{9 to} R ²⁶ in the general formula (II), two are carboxyl groups, and the remaining 16 are each independently a hydrogen atom, a halogen atom such as Cl or Br, or CH _3- , _{C 2 H 5 -, C 3} H 7 -, C 4 H
₉ - a monovalent hydrocarbon group of C ₁ -C _20, such as, CH ₃ O
-, C ₂ H ₅ O-, C ₃ H ₇ O-, C ₄ H ₉ O-, etc. are C _{1 to} C ₆ alkoxy groups, but from the viewpoint of heat resistance and chemical resistance, each ring has It is preferable that one carboxyl group is present and 10 or more of the remaining 16 are hydrogen atoms.

Specific examples of the alicyclic dicarboxylic acid represented by the general formula (II) are decahydronaphthalene-2,6-dicarboxylic acid and decahydronaphthalene-1,5-dicarboxylic acid. To be

The dicarboxylic acid derivatives include diacid chlorides, alkyl ester compounds,
Examples include aryl ester compounds. These alicyclic dicarboxylic acids (I) can be used alone or in combination of two or more.

Among these, decahydronaphthalene-
2,6-dicarboxylic acid or its derivative (hereinafter, also referred to as decahydronaphthalene-2,6-dicarboxylic acid)
Is preferable from the viewpoint of heat resistance.

Examples of dicarboxylic acids other than the alicyclic dicarboxylic acids (I) include isophthalic acid, terephthalic acid,
Aromatic dicarboxylic acids or their derivatives such as phthalic acid, diphenyl ether-4,4'-dicarboxylic acid, benzophenone-4,4'-dicarboxylic acid, naphthalene-2,6-dicarboxylic acid, oxalic acid, malonic acid, succinic acid, Aliphatic dicarboxylic acids such as glutaric acid and adipic acid or derivatives thereof can be mentioned.

Examples of the dicarboxylic acid derivative include diacid chlorides, alkyl ester compounds and aryl ester compounds thereof. These dicarboxylic acids (I) can be used alone or in combination of two or more.

Among the dicarboxylic acids other than the alicyclic dicarboxylic acids (I), isophthalic acid or a derivative thereof (hereinafter also referred to as isophthalic acid), terephthalic acid or a derivative thereof (hereinafter also referred to as terephthalic acid) is used as a raw material. It is preferable from the viewpoint of low cost availability, and when two or more kinds are used in combination, the combined use of isophthalic acids and terephthalic acids is preferable from the viewpoint of imparting good moldability. When a mixture of the above isophthalic acids and terephthalic acids is used, the molar ratio of isophthalic acids / terephthalic acids is 9
It is preferably 9/1 to 1/99, more preferably 10/90 to 90/10 from the viewpoint of imparting a good balance between heat resistance and moldability.

The alicyclic dicarboxylic acid (I) is used in an amount of 0.1 to 100 mol% of the dicarboxylic acid (I) from the viewpoint of high glass transition temperature. When the amount of the alicyclic dicarboxylic acid (I) used is less than 0.1 mol% based on the dicarboxylic acid (I), the effect is low. The minimum amount of the alicyclic dicarboxylic acid (I) used is 1
When it is at least 10 mol%, it is preferable from the viewpoint that heat resistance is imparted and hydrolysis resistance is improved.

It is preferable that the maximum amount of the alicyclic dicarboxylic acid (I) used is 99 mol%, or more preferably 90 mol% or less, since the moldability is improved.

Copolyester (A) used in the present invention
Is produced by a polycondensation reaction using bisphenols (I) and dicarboxylic acids (I).

As the method of the polycondensation reaction, a known method as described in the section of the prior art can be used. Of these, the interfacial polycondensation method and the solution polycondensation method are preferable from the viewpoint of easily obtaining a high molecular weight product.

Specific examples of the copolyester (A) thus produced include bisphenol TMC.
(20 to 100 mol% of bisphenols), bisphenol A, decahydronaphthalene-2,6-dicarboxylic acid (20 to 100 mol% of dicarboxylic acid), polyesters composed of terephthalic acid and isophthalic acid. Among these, bisphenol TMC, decahydro-2,6-dicarboxylic acid (20 to 80 mol%), and polyester made of isophthalic acid (80 to 20 mol%) are preferable from the viewpoint of imparting high heat resistance,
Bisphenol TMC (20 to 80 mol%), bisphenol A (80 to 20 mol%), decahydro-2,6-
Polyesters composed of dicarboxylic acid (30 to 70 mol%) and terephthalic acid (30 to 70 mol%) and / or isophthalic acid (30 to 70 mol%) are preferable from the viewpoint of balance between heat resistance and moldability.

The thermoplastic resin composition of the present invention contains, together with the copolyester (A) which is the component (A),
Polycarbonate (B) is used as the component (B).

As described above, the polycarbonate (B) imparts excellent properties such as impact strength, electrical characteristics and transparency to the molded product from the thermoplastic resin composition of the present invention, and the molding flow of the composition. It is a component for improving the properties.

Polycarbonate (B) is composed of bis (4) and carbonic acid compounds such as phosgene and diphenyl carbonate.
-Hydroxyaryl) alkane.

The polycarbonate (B) has a viscosity-average molecular weight of about 10,000 to 60,000, more preferably 1
It is preferably about 5,000 to 40,000 from the viewpoint of heat resistance, moldability, mechanical properties and the like. If the molecular weight is lower than 10,000, the impact strength tends to decrease, and 60
If it is higher than 000, the moldability tends to deteriorate.

The polycarbonate (B) has a glass transition temperature of about 100 to 250 ° C., is colorless to pale yellow, and has a length of 3 m.
It is preferable that the molded product of about m has a total light transmittance of about 80% or more.

Specific examples of the polycarbonate (B) as described above include bis (4-hydroxyphenyl) methane, bis (4-hydroxyphenyl) ethane and 2,2-
Bis (4-hydroxyphenyl) propane (bisphenol A), bis (4-hydroxy-3,5-dichlorophenyl) propane, bis (4-hydroxy-3,5-dibromophenyl) propane, 2,2-bis (4- Hydroxy-3,5-dimethylphenyl) propane, 1,1-
Bis (4-hydroxyphenyl) ethane, 1,1-bis (4-hydroxyphenyl) cyclohexane, bis (4
-Hydroxyphenyl) phenylmethane, etc.
Examples thereof include those obtained from dioxydiphenylalkane and phosgene, or diphenylcarbonate. Among these, those obtained from bisphenol A and phosgene or diphenyl carbonate are preferable because they are inexpensive and easily available.

The polycarbonate (B) can be produced by a known polymerization method such as an interfacial polycondensation method, a solution polymerization method and a melt polymerization method.

In the thermoplastic resin composition of the present invention, a phenolic stabilizer having steric hindrance as the component (C) together with the components (A) and (B) (hereinafter also referred to as the stabilizer (C)). Is used.

The stabilizer (C) is a component for imparting thermal stability to the thermoplastic resin composition of the present invention when it is heated and melted, and imparting more excellent transparency to a molded article made from the composition. is there.

The stabilizer (C) is a phenolic stabilizer having steric hindrance and has the general formula (III):

[0074]

[Chemical 13]

(Wherein R ²⁷ is a C ₁ -C ₂₀ alkyl group,
R ^{28 to} R ³¹ are each independently a hydrogen atom, a C _{1 to} C ₃₀ alkyl group, a monovalent organic group), or a compound represented by the general formula (IV):

[0076]

[Chemical 14]

(Wherein R ³² is a C ₁ -C ₂₀ alkyl group,
Three of R ^{33 to} R ³⁶ are independently a hydrogen atom or C
_{1 to} C ₃₀ alkyl group, one is a bond, n is 2 to 4,
Z is a compound represented by an n-valent group.

Specific examples of the C ₁ -C ₂₀ alkyl group which is R ²⁷ in the above general formula (III) include, for example,-
_{CH 3, -C 2 H 5,} -C 3 H 7, -C (CH 3) 3,
Such as -C ₄ H ₉ and the like. Of these, -C
(CH ₃ ) ₃ is preferable from the viewpoint of imparting transparency.

Further, when R ^{28 to} R ³¹ are C _{1 to} C ₃₀ alkyl groups, specific examples thereof include —CH ₃ ,
_{-C 2 H 5, -C 3 H} 7, -C (CH 3) 3 and the like.

Further, specific examples of the monovalent organic group include, for example, —CH ₂ CH ₂ COO (CH ₂ ) ₁₇ CH ₃ , —C.
_{H 2 PO (OC 18 H 37} ) 2, -CH 2 PO (OCH 3)
_2, etc.

In particular, R ³¹ and R ³⁰ are-(CH ₃ ) ₃ and --C.
When it is H _3, it is preferable from the viewpoint of imparting transparency. R ²⁹ is a monovalent organic group such as —C ₂ H ₄ COOC ₁₈
When it is H _37, it is preferable from the viewpoint of imparting transparency.

R ³² in the general formula (IV) is the same as R ²⁷ in the general formula (III). Also, R ³³ ~
Specific examples in the case where R ³⁶ is a C _{1 to} C ₃₀ alkyl group also include C _{1 to} R ^{28 to} R ³¹ in the general formula (III).
Is the same as the alkyl _group -C30. In addition, as a preferable example, R ³² is preferably — (CH ₃ ) ₃ from the viewpoint of imparting transparency.

Further, Z represents an n-valent organic group or inorganic group, for example,

[0084]

[Chemical 15]

Preferred examples of the stabilizer (C) represented by the general formulas (III) and (IV) are 2,6-di-t-butyl-4-methylphenol and 4,4. ′ -Thio-bis (6-t-butyl-3-methyl) phenol, 2,2′-methylene-bis (6-t-
Butyl-4-methyl) phenol, 4,4'-butylidene-bis (6-t-butyl-3-methyl) phenol,
O, O-di-n-octadecyl-3,5-di-t-butyl-4-hydroxybenzylphosphonate, tetrakis [methylene (3,5-di-t-butyl-4-hydroxyhydrocinnamate)] Methane, octadecyl-3
-(3,5-Di-t-butyl-4-hydroxyphenyl) propionate, O, O-dimethyl-3,5-di-
t-butyl-4-hydroxybenzylphosphonate,
N, N'-hexamethylene-bis (3,5-di-t-butyl-4-hydroxy-hydrocinnamide), tris (2-methyl-4-hydroxy-5-t-butylphenyl) butane, 1, 6-hexanediol-bis (3,5
-Di-t-butyl-4-hydroxyphenyl) propionate, methylene-bis (3,5-di-t-butyl-4)
-Hydroxyphenol), 1,3,5-trimethyl-
2,4,6-Tris (3,5-di-t-butyl-4-hydroxyphenyl) benzene, 2,2'-thio-diethyl-bis [3- (3,5-di-t-butyl-4) -Hydroxyphenyl) propionate] and the like.

The stabilizer (C) can be used alone or in combination of two or more kinds.

The ratio of the component (A) to the component (B) used in the thermoplastic resin composition of the present invention is 1 / by weight.
It is 99-99 / 1. (A) in the thermoplastic resin composition
When the weight ratio of the component and the component (B) is less than 1/99, the heat resistance is insufficiently imparted to the component (B), and when it exceeds 99/1, the molding flow of the component (A) And the effect of improving transparency and transparency are reduced. The minimum use ratio of the component (A) and the component (B) is 5/95 or more in weight ratio, and further 10 /
90 or more is preferable from the viewpoint of heat resistance and weather resistance, and the maximum use ratio of the component (A) and the component (B) is 95/5 or less by weight ratio, and further 90/10 or less is molding flow. It is preferable from the viewpoints of transparency and transparency.

Further, the compounding ratio of the above-mentioned components (A), (B) and (C) constituting the thermoplastic resin composition of the present invention is such that the total amount of the components (A) and (B) is 10
The component (C) is 0.01 to 1.0 part with respect to 0 part.
When the compounding amount of the component (C) is less than 0.01 part,
The effect of improving transparency is not sufficient, and if it exceeds 1.0 part, the heat resistance and mechanical properties become poor. It is preferable that the minimum amount of the component (C) is 0.05 parts or more, more preferably 0.1 part or more from the viewpoint of imparting transparency. It is preferably 0.9 parts or less in terms of heat resistance and mechanical properties.

Particularly, when the weight ratio of the component (A) to the component (B) is 99/1 to 60/40, the heat resistance and weather resistance which are advantages of the copolyester (A). ,
It is possible to improve the drawbacks such as transparency and molding fluidity while strongly retaining the characteristics of flame retardancy and chemical resistance.

When the weight ratio of the component (A) to the component (B) is 40/60 to 1/99, the advantages of the polycarbonate (B) are transparency, molding fluidity,
While maintaining the feature of impact strength, it is possible to improve its heat resistance, which is a drawback thereof.

Further, when the weight ratio of the component (A) to the component (B) is 70/30 to 30/70,
A composition having the heat resistance and weather resistance characteristics of the copolyester (I) and the transparency, molding fluidity and impact strength characteristics of the polycarbonate (B) can be obtained.

The method for producing the thermoplastic resin composition of the present invention is not particularly limited, but it is preferable to use the melt mixing method using various blenders such as an extruder, a heat roll and a Banbury mixer from the viewpoint of productivity.

The method of blending the copolyester (A), the polycarbonate (B) and the phenolic stabilizer is not particularly limited, and for example, the three components of both resins constituting the composition and the phenolic stabilizer are added all at once. Alternatively, the copolyester (A) and / or the polycarbonate (B) may be melted in advance, and then the remaining components may be added and mixed.

In addition, polycarbonate (B) is added to a solution of copolyester (A) dissolved in methylene chloride or the like,
There is also a method of mixing the stabilizer (C) and then removing the solvent. In any case, an appropriate method can be adopted depending on the composition ratio of the resin composition and the desired shape and characteristics of the molded product.

The thermal behavior of the thermoplastic resin composition of the present invention obtained as described above has a glass transition temperature of 100.
It is preferably in the range of about 300 to 300 ° C, more preferably about 120 to 280 ° C.

Further, the transparency of the molded product produced by using the resin composition of the present invention is such that the yellow index is about 30 or less and the total light transmittance is about 60% or more in a molded product having a thickness of about 3 mm.

Further, in the thermoplastic resin composition of the present invention,
If necessary, a lubricant such as wax, an ultraviolet absorber, a pigment, a flame retardant, a plasticizer, an inorganic filler, a reinforcing fiber and the like can be added to impart a new function separately.

The composition of the present invention thus prepared has excellent fluidity at the time of molding and can be molded into various molded articles by molding methods such as injection molding, extrusion molding, blow molding and compression molding. . The obtained molded product has excellent transparency while maintaining heat resistance and mechanical properties, and is preferably used for automobile parts, mechanical parts, electric / electronic parts, and the like.

The copolymerized polyester (A) comprising bisphenols and dicarboxylic acids, the polycarbonate (B) and the stabilizer (C) and the thermoplastic resin composition of the present invention in which these are blended have been described above.
Among the compositions which have not been sufficiently explained yet, the combinations of the respective constituents of the main compositions and the effects thereof will be described below.

That is, as the bisphenols (A), 0.1 to 100 mol% of the bisphenols are bisphenol TMCs and dicarboxylic acids represented by the general formula (I
I) a copolymerized polyester (A) comprising a mixture of alicyclic dicarboxylic acids, isophthalic acids and terephthalic acids, (B) a polycarbonate (B) obtained from bisphenol A and phosgene, and (C) a general formula A composition comprising a phenolic stabilizer represented by (III) or (IV) is preferable from the viewpoint of providing a good balance of heat resistance, molding fluidity and transparency.

As (A) bisphenols, 0.1 to 100 mol% of bisphenols are bisphenol TMC, and as dicarboxylic acids, 0.1 to 100 mol% of dicarboxylic acids are decahydronaphthalene-2,6.
A copolymerized polyester (A) composed of dicarboxylic acids,
(B) Polycarbonate (B) obtained from bisphenol A and phosgene, and (C) general formula (II
A composition comprising a phenolic stabilizer represented by I) or (IV) is preferable from the viewpoint of imparting particularly high heat resistance and relatively good transparency.

Further, as (A) bisphenols, 0.1 to 100 mol% of bisphenols is bisphenol TMC, and as dicarboxylic acids, a mixture of decahydronaphthalene-2,6-carboxylic acids, isophthalic acids and terephthalic acids. A composition comprising a copolyester (A), a polycarbonate (B) obtained from bisphenol A and phosgene, and (C) a phenolic stabilizer represented by the general formula (III) or (IV) Is preferable in that it can impart relatively good transparency and molding fluidity in addition to high heat resistance.

Further, copolymerization of (A) a mixture of bisphenols with bisphenol TMCs and bisphenol A, and a mixture of dicarboxylic acids of alicyclic dicarboxylic acids represented by the general formula (II), isophthalic acids and terephthalic acids. Polyester (A), (B)
Polycarbonate (B) is a composition obtained from bisphenol A and phosgene and (C) a phenolic stabilizer represented by the general formula (III) or (IV). In addition, it is preferable in terms of impact strength.

As (A) bisphenols, a mixture of bisphenol TMCs and bisphenol A, and as dicarboxylic acids, 0.1 to 0.1% of dicarboxylic acids.
Copolyester (A) consisting of 100 mol% of decahydronaphthalene-2,6-dicarboxylic acids, (B) polycarbonate (B) obtained from bisphenol A and phosgene, and (C) general formula (III) or A composition comprising a phenolic stabilizer represented by (IV) is preferable from the viewpoint of providing high heat resistance and wet heat durability.

In addition, (A) bisphenols are a mixture of bisphenol TMCs and bisphenol A,
A copolymerized polyester (A) in which the dicarboxylic acid is a mixture of decahydronaphthalene-2,6-dicarboxylic acid, a mixture of isophthalic acid and terephthalic acid, (B) a polycarbonate (B) obtained from bisphenol A and phosgene, and (C) ) A composition comprising a phenolic stabilizer represented by the general formula (III) or (IV) is preferable from the viewpoint of good balance among heat resistance, moldability, transparency and impact strength.

Hereinafter, the composition of the present invention will be described in more detail with reference to Examples. However, the present invention is not limited to the following Examples, and various modifications can be made without departing from the scope of the invention. Is.

Production Example 1 Copolyester (A-1)
Preparation of 2,2-bis (4'-hydroxyphenyl) -propane 326.67 g (1.431 mol), 1,1-bis (4
-Hydroxyphenyl) -3,3,5-trimethylcyclohexane 147.85 g (0.477 mol), pt
-Butylphenol 13.9 g (0.0926 mol),
3.40 g (0.0195 mol) of sodium hyposulfite, 975.04 ml of 5N sodium hydroxide aqueous solution and 4152.22 ml of ion-exchanged water were mixed in a 5 liter flask under a nitrogen atmosphere and then heated to 5 ° C. After cooling, an alkaline aqueous solution of phenols was prepared.

On the other hand, 220.80 g of decahydronaphthalene-2,6-dicarboxylic acid was placed in another 5 liter flask.
(0.977 mol), isophthalic acid chloride 202.
64 g (0.998 mol) of methylene chloride 5000 ml
And was cooled to 5 ° C to prepare a liquid.

Then, another 15-liter separable flask was charged with 200 ml of ion-exchanged water and 6.67 g (0.0146 mol) of benzyltriethylammonium chloride as a phase transfer catalyst in a nitrogen atmosphere.
A liquid cooled to 5 ° C. was prepared.

While vigorously stirring the cooling liquid containing the phase transfer catalyst, the previously prepared alkaline aqueous solution of the phenols and the methylene chloride solution of the dicarboxylic acids were continuously treated with a pump for about 15 minutes at the same time. Was added to.

After 3 hours had passed after the completion of the addition, stirring was stopped, and two phases, a methylene chloride phase and an aqueous phase, were separated. After decanting the aqueous phase, the same amount of ion-exchanged water was added and the mixture was neutralized with a small amount of hydrochloric acid and acetic acid while stirring.
Further, after desalting by washing with water repeatedly, the same amount of acetone was added to the methylene chloride phase to precipitate a polymer, and a polymer powder (white powder) was obtained by filtration. The obtained polymer powder was dried at 120 ° C. for 15 hours using a vacuum dryer.

When the molecular weight was measured using the obtained polymer powder, the weight average molecular weight by GPC (gel permeation chromatography) was 62000 in terms of polystyrene.

Production Example 2 Copolyester (A-2)
Manufacture of 217.78 g (0.954 mol) of 2,2-bis (4′-hydroxyphenyl) -propane in Preparation Example 1, 1,1-bis (4-hydroxyphenyl) -3,
295.69 g of 3,5-trimethylcyclohexane
(0.954 mol) to 10 parts of isophthalic acid chloride
A copolyester was obtained in the same manner as in Production Example 1 except that the amount was changed to 1.32 g (0.463 mol) and 101.32 g (0.463 mol) of terephthaloyl chloride was newly added. The weight average molecular weight of the obtained copolyester was 61,000.

Examples 1-5 and Comparative Examples 1-5 Copolyester (A-1) 85 obtained in Production Example 1
Part and polycarbonate (trade name: Panlite L-
1250 W, Teijin Kasei Co., Ltd. 15 parts were dry-mixed and octadecyl-3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate (hereinafter,
C-1) or tetrakis [3- (3,5-di-
t-Butyl-4-hydroxyphenyl) propionate] (hereinafter referred to as C-2) was added in an amount shown in Table 1 and dry-mixed again. Then, it was melt-kneaded at 310 ° C. using a 30 mmφ same-direction twin-screw extruder to produce a pellet-shaped resin composition.

Properties such as molding fluidity, transparency, heat resistance and mechanical properties of the obtained resin composition were evaluated by the following methods. The results are shown in Table 1.

(Molding fluidity) Using a Capillograph PD-C manufactured by Toyo Seiki Co., Ltd., a cavity temperature of 330
℃, shear rate 1216S ^-1 , die size 1mmφ ×
The melt viscosity was measured under the measurement condition of 10 mm to evaluate the molding fluidity.

(Transparency) The resin composition in the form of pellets was dried at 140 ° C. for 4 hours and then tested with an injection molding machine at a resin temperature of 340 ° C. and a mold temperature of 130 ° C. to a thickness of 1/8 inch. A piece is molded, and Nippon Denshoku Industries Co., Ltd. Z-OPT
Using ICAL SENSOR, JIS-K 710
Yellow index according to 3 (hereinafter also referred to as YI)
The value was measured.

(Mechanical Properties-Tensile Yield Strength, Tensile Elongation at Break) ASTM No. 1 dumbbells were molded in the same manner as in the above-mentioned item of transparency, and subjected to a tensile test in accordance with ASTM D-638 to determine the yield strength and elongation at break The degree was measured.

(Heat resistance) A test piece having a thickness of 1/4 inch was molded in the same manner as described above, and was subjected to ASTM D648 (1.82).
The deflection temperature under load is measured according to
The heat resistance was evaluated.

[0120]

[Table 1]

Examples 6 to 8 and Comparative Examples 6 to 7 The amounts of the copolyester (A) shown in Table 2 shown in Table 2, the amounts of the polycarbonate (B) used in Example 1 shown in Table 2 and Table 2 are shown. A pelletized resin composition was produced in the same manner as in Example 1 using the amount of the stabilizer (C) shown in Table 2, and the transparency, heat resistance and molding fluidity were measured. The results are shown in Table 2.

[0122]

[Table 2]

From Tables 1 and 2, the copolymerized polyester (A)
The injection-molded product of the resin composition of the present invention obtained by adding a phenolic stabilizer having steric hindrance to the polycarbonate and the polycarbonate (B) has a low YI value, excellent transparency, and retains mechanical properties. Good heat resistance and molding fluidity.

On the other hand, when the stabilizer is not added (Comparative Examples 1 and 6.7) and when the added amount of the stabilizer is out of the range of the present invention (Comparative Examples 2 to 5). The obtained injection-molded product of the resin composition cannot satisfy both transparency, mechanical properties (tensile properties) and heat resistance.

As described above, the thermoplastic resin composition of the present invention obtained by adding the phenolic stabilizer having steric hindrance to the copolyester (A) and the polycarbonate (B) exhibits excellent properties. It's amazing.

[0126]

EFFECT OF THE INVENTION The thermoplastic resin composition of the present invention is excellent in molding fluidity, and using the composition as a molding material, it is possible to obtain a molded article which satisfies both transparency and mechanical properties and is further excellent in heat resistance. It is possible.

Claims (7)

[Claims] 1. The main chain of the polymer (A) has the general formula (I): (Wherein, -X- is -O -, - S -, - SO 2 -, - CO
-, alkylene or alkylidene radical of C ₃ -C ₂₀ in ^{_{C 1 ~C 20, R 1,}} R 2, R 3, R 4, R 5, R 6, R
⁷ and R ⁸ are each independently formed from a bisphenol compound represented by a hydrogen atom, a halogen atom or a C _{1 to} C ₂₀ monovalent hydrocarbon group) or a derivative thereof and a dicarboxylic acid or a derivative thereof, and the dicarboxylic acid Alternatively, 0.1 to 100 mol% of its derivative is represented by the general formula (II): (In the formula, two of R ^{9 to} R ²⁶ are carboxyl groups, and the remaining 16 are each independently a hydrogen atom, a halogen atom, a C _{1 to} C ₂₀ monovalent hydrocarbon group or C ₁ to (B) bis (4), which is a copolyester which is an alicyclic dicarboxylic acid represented by a C ₆ alkoxy group) or a derivative thereof.
-Hydroxyaryl) alkane-based polycarbonate and (C) a sterically hindered phenol-based stabilizer, and the ratio of components (A) and (B) used is 1 by weight.
/ 99 to 99/1, and the ratio of the (C) component to 100 parts by weight of the total amount of the (A) component and the (B) component is 0.
The thermoplastic resin composition is 01 to 1.0 part by weight. 2. The dicarboxylic acid or its derivative is
The thermoplastic resin composition according to claim 1, which is a mixture of an alicyclic dicarboxylic acid represented by the general formula (II) or a derivative thereof, isophthalic acid or a derivative thereof and terephthalic acid or a derivative thereof. 3. An alicyclic dicarboxylic acid represented by the general formula (II) or a derivative thereof is decahydronaphthalene-
A 2,6-dicarboxylic acid or its derivative.
Or the thermoplastic resin composition according to 2. 4. 0.1 to 100 mol% of the bisphenol compound represented by the general formula (I) or its derivative is 1,1-bis (4-hydroxyphenyl) -3,3,5.
-The thermoplastic resin composition according to claim 1, which is trimethylcyclohexane or a derivative thereof. 5. The bisphenol compound represented by the general formula (I) or its derivative is 1,1-bis (4-hydroxyphenyl) -3,3,5-trimethylcyclohexane or its derivative and 2,2-bis. The thermoplastic resin composition according to claim 1, which is a mixture of (4-hydroxyphenyl) propane or a derivative thereof. 6. The thermoplastic resin composition according to claim 1, wherein the bis (4-hydroxyaryl) alkane-based polycarbonate is a polycarbonate obtained from 2,2-bis (4-hydroxyphenyl) propane and phosgene. 7. A phenolic stabilizer having steric hindrance is represented by the general formula (III): (In the formula, R ²⁷ is a C _{1 to} C ₂₀ alkyl group, R ^{28 to} R ³¹ are each independently a hydrogen atom, a C _{1 to} C ₃₀ alkyl group,
A compound represented by a monovalent organic group) or the general formula (I
V): (In the formula, R ³² is a C _{1 to} C ₂₀ alkyl group, three of R ^{33 to} R ³⁶ are each independently a hydrogen atom, a C _{1 to} C ₃₀ alkyl group, one is a bond, and n is a bond. Is a compound represented by 2 to 4 and Z is an n-valent group), and the thermoplastic resin composition according to claim 1.