JPH06200141A - Resin composition containing polycarbonate and polyarylate - Google Patents

Abstract

PURPOSE:To provide a flame-retardant resin composition composed mainly of a polycarbonate and a polyarylate, excellent in heat deformation resistance and heat stability in melting, remarkably low in coloring during molding and improved in impact resistance, especially low-temperature impact resistance. CONSTITUTION:In a resin composition comprising (A) 95 to 5 pts.wt. polycarbonate and (B) 5 to 95 pts.wt. polyarylate, the polycarbonate is a melt polymerization product between an aromatic dihydroxy compound and a carbonic acid diester and has an equivalent ratio of the phenolic end groups (I) to the non- phenolic end groups (II) of >=1/19.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a resin composition containing a polycarbonate and a polyarylate having excellent thermal stability and excellent low temperature impact resistance.

[0002]

It is known that a resin composition having both heat distortion resistance and impact resistance (at room temperature) can be obtained by blending polycarbonate and polyarylate (for example, Japanese Patent Publication No. 50-27061). ). The polycarbonate specifically used there is produced by the phosgene method. Further, JP-A-58-176239 describes a resin composition comprising a polyarylate to which a phosphite ester is added in order to suppress a foaming phenomenon during melt processing, a polycarbonate and a phosphite ester. There is.

[0003]

However, the resin composition comprising polycarbonate and polyarylate is
The impact resistance, particularly the low temperature impact resistance, is considerably lower than that of polycarbonate alone, and has a drawback in that it is severely limited in practical use. In addition, there is a drawback that coloring is often caused during melt processing.

Therefore, the present invention retains the excellent heat distortion resistance of the conventional resin composition comprising polycarbonate and polyarylate, has good thermal stability during melt processing, has very little coloring, and has impact resistance. Another object of the present invention is to provide a resin composition containing a polycarbonate and a polyarylate, which has remarkably improved low temperature impact resistance.

[0005]

Means for Solving the Problems The present invention for achieving the above-mentioned object is to provide a resin composition containing A) 95 to 5 parts by weight of polycarbonate, and B) 5 to 95 parts by weight, wherein the polycarbonate is an aromatic dihydroxy compound. And a carbonic acid diester, which is a melt polymerization product, and has an equivalent ratio (I) between the phenolic end group (I) and the non-phenolic end group (II) in the polycarbonate.
/ (II) is 1/19 or more, which is a resin composition.

In the present invention, a melt polymerization product of an aromatic dihydroxy compound and a carbonic acid diester is used as the polycarbonate, and the equivalent ratio of the phenolic end group and the non-phenolic end group in the polycarbonate is adjusted. Is an important point. The resin composition of the present invention based on a polycarbonate and a polyarylate produced by a melting method is excellent in thermal stability during melt processing as compared with a system using a polycarbonate by a conventional phosgene method, and coloring during molding is extremely high. In addition, the heat distortion resistance of the molded product is maintained, and the impact resistance, especially the low temperature impact resistance, due to blending the polyarylate with the polycarbonate is very little deteriorated. Further, in the aromatic polycarbonates that have been generally used in the past, particularly in the aromatic polycarbonate produced by the phosgene method, the ratio of the phenolic end groups to the non-phenolic end groups is less than 1/19. There, a bisphenol A and phosgene are reacted to make a polycarbonate. By adding a small amount of phenol in the raw material or during the reaction, the polymer end is blocked with phenol (the hydroxyl group reacts).
is doing. When using a polycarbonate having an equivalent ratio (I) / (II) of less than 1/19, especially obtained by an interfacial method,
The compatibility with polyarylate is not good, the coloring during melting is remarkable, and the low temperature impact resistance is not satisfactory. On the other hand, when a polycarbonate having an equivalent ratio (I) / (II) of the phenolic terminal group (I) and the non-phenolic terminal group (II) is 1/19 or more, compatibility with polyarylate is obtained. It is possible to obtain a resin composition having significantly improved properties, less coloring during melting, and excellent heat resistance and low temperature impact resistance. These are totally unexpected.

The polycarbonate resin used as component A) in the present invention is a melt polymerization product of an aromatic dihydroxy compound and a carbonic acid diester, which comprises a phenolic end group (I) and a non-phenolic end group in the polycarbonate. The equivalent ratio (I) / (II) to the group (II) is 1/19 or more. The terminal group ratio can be easily adjusted by adjusting the molar ratio of the aromatic dihydroxy compound used as a raw material and the carbonic acid diester when a polycarbonate is produced by a melting method (transesterification method). For example, when bisphenol A is used as the aromatic dihydroxy compound and diphenyl carbonate is used as the carbonic acid diester, the terminal of the obtained polycarbonate is a phenolic residue derived from bisphenol A or a phenyl group derived from diphenyl carbonate. Therefore, if the molar ratio of bisphenol A is increased during the transesterification reaction, the terminal ratio of the phenolic residue in the polycarbonate produced will increase. More preferably, the end group equivalent ratio (I) of the polycarbonate used in the present invention
/ (II) is set to 1/10 or more, particularly 1/5 to 1/0.

The polycarbonate used in the present invention may be branched. Such branched polycarbonates are obtained as branched thermoplastic random branched polycarbonates by reacting polyfunctional aromatic compounds with diphenol and / or carbonate precursors.

In the polycarbonate used in the present invention, the phenolic terminal group (I) has the following formula:

[0010]

[Chemical 3] The non-phenolic terminal group (II) is represented by the following formula

[0011]

[Chemical 4] The group represented by is preferable.

The melting method itself is known, and is a method for synthesizing a polycarbonate by transesterification reaction of an aromatic dihydroxy compound and a carbonic acid diester in a molten state.

The aromatic dihydroxy compound is not particularly limited, and various known compounds can be used. As an example, the following formula

[0014]

[Chemical 5] (Wherein R ^a and R ^b are each independently a halogen or a monovalent unsubstituted or halogen-substituted hydrocarbon group, and X is —C (R ^c ) (R ^d ) —, —C (= R ^e )
-, - O -, - S -, - SO- or -SO ₂ - and and, R ^c and R ^d are each independently a hydrocarbon group of a hydrogen atom or a monovalent, R ^e is a divalent hydrocarbon Hydrogen group, p
And q each independently represent an integer of 0 to 4), for example, bis (4-hydroxyphenyl) methane, 1,1-bis (4-hydroxyphenyl) ethane, 2,2-bis ( 4-hydroxyphenyl) propane, 2,2-bis (4-hydroxyphenyl) butane, 2,2-bis (4-hydroxyphenyl) octane, bis (4-hydroxyphenyl) phenylmethane, 2,2-bis (4 -Hydroxy-1-methylphenyl) propane, 1,1-bis (4-hydroxy-t-butylphenyl) propane, 2,2-bis (4-hydroxy-3-bromophenyl) propane and other bis (hydroxyaryl) s Alkanes; 1,1-bis (4-hydroxyphenyl) cyclopentane, 1,1-bis (4-hydroxyphenyl) cyclohexane and other bis (hydroxyaryl) cycloalkanes; 4,4'-dihydroxydiphenyl ether, 4, Four '-Dihydroxy-3,3'-dimethylphenyl ether and other dihydroxyaryl ethers; 4,4'-dihydroxydiphenyl sulfide, 4,4'-dihydroxy-3,3'-dimethylphenyl sulfide and other dihydroxydiaryl sulfides; 4,4'-dihydroxydiphenyl sulfoxide, 4,4'-dihydroxy-3,3'-dimethyldiphenyl sulfoxide and other dihydroxydiaryl sulfoxides; 4,4'-dihydroxydiphenyl sulfone, 4,4'-dihydroxy-3,3 Examples thereof include, but are not limited to, dihydroxydiaryl sulfones such as'-dimethyldiphenyl sulfone. Among these, especially 2,2-
Bis (4-hydroxyphenyl) propane is preferably used. In addition to the above, as the aromatic dihydroxy compound, the following general formula

[0015]

[Chemical 6] (Wherein R ^f is each independently a hydrocarbon group having 1 to 20 carbon atoms or a halide thereof or a halogen atom, and m is an integer of 0 to 4), for example, Resorcin, 3-methylresorcin, 3-ethylresorcin, 3-propylresorcin, 3-butylresorcin, 3-t-butylresorcin, 3-phenylresorcin, 3-
Substituted resorcins such as cumylresorcin, 2,3,4,6-tetrafluororesorcin, 2,3,4,6-tetrabromoresorcin; catechol; hydroquinone and 3-methylhydroquinone, 3-ethylhydroquinone, 3-propyl Hydroquinone, 3-butylhydroquinone, 3-t-butylhydroquinone, 3-phenylhydroquinone, 3-cumylhydroquinone, 2,3,5,6-tetramethylhydroquinone, 2,
Substituted hydroquinone such as 3,5,6-tetra-t-butylhydroquinone, 2,3,5,6-tetrafluorohydroquinone, and 2,3,5,6-tetrabromohydroquinone, and the following formula

[0016]

[Chemical 7] 2,2,2 ', 2'- Tetrahydro-3,3,3', 3'- Tetramethyl-1,1'-spirobi- [1H-indene] -7,7'-
It is also possible to use a diol or the like.

These aromatic dihydroxy compounds may be used alone or in combination of two or more.

The carbonic acid diester is not particularly limited, and examples thereof include diphenyl carbonate, ditolyl carbonate, bis (chlorophenyl) carbonate, m-cresyl carbonate, dinaphthyl carbonate, bis (diphenyl) carbonate, diethyl carbonate, dimethyl carbonate, dibutyl. Examples include, but are not limited to, carbonates, dicyclohexyl carbonates, and the like. Diphenyl carbonate is preferably used.

These carbonic acid diesters may also be used alone or in combination of two or more kinds.

When a polycarbonate is produced from the above aromatic dihydroxy compound and carbonic acid diester, the molar ratio of the two is 100/95 to 100/107 in order to adjust the terminal group ratio of the obtained polycarbonate to 1/19 or more. Especially 100
It is preferably / 98 to 100/103. However,
When a polycarbonate other than the above, for example, a compound capable of introducing a phenolic terminal group is further used in the production of polycarbonate, the molar ratio of aromatic dihydroxy compound / carbonic acid diester may be set to a value outside the above range. it can.

For example, when a polycarbonate is produced, the polycarbonate produced has the following formula:

[0022]

[Chemical 8] (Here, the aromatic ring or chromanyl group may be substituted with halogen or an alkyl group having 1 to 9 carbon atoms) A compound capable of introducing one or more terminal groups can be further used. Examples of the compound capable of introducing the hydroxyl group represented by (1) include diol compounds such as bisphenol A. Further, as the compound capable of introducing the phenoxy group represented by (2), phenol, diphenyl carbonate and the like; as the compound capable of introducing the pt-butylphenoxy group represented by (3), pt-butylphenol, pt-butylphenyl Phenyl carbonate, pt-butylphenyl carbonate, etc .; p-cumylphenol, p-cumylphenylphenyl as a compound capable of introducing the p-cumylphenoxy group (p-phenylisopropylphenoxy group) represented by (4) Carbonate, p-cumylphenyl carbonate and the like can be mentioned respectively. As the chromanylphenoxy group represented by (5) in the above formula,

[0023]

[Chemical 9] Examples thereof include a chromanylphenoxy group and the like. As a compound capable of introducing a group represented by (5-1) 2,2,
4-trimethyl-4- (4-hydroxyphenyl) chroman, 2,
2,4,6-Tetramethyl-4- (3,5-dimethyl-4-hydroxyphenyl) chroman, 2,3,4-trimethyl-2-ethyl-4- (3-
Nonyl-4-hydroxyphenyl) -7-nonyl-chroman,
2,2,4-Trimethyl-4- (3,5-diethyl-4-hydroxyphenyl) -6-ethylchroman, 2,2,4,6,8-pentamethyl-4-
(3,5-dimethyl-4-hydroxyphenyl) chroman, 2,
2,4-triethyl-3-methyl-4- (4-hydroxyphenyl)
Chroman, 2,2,4-trimethyl-4- (3-bromo-4-hydroxyphenyl) chroman, 2,2,4-trimethyl-4- (3-bromo
-4-Hydroxyphenyl) -6-bromochroman, 2,2,4-trimethyl-4- (3,5-dibromo-4-hydroxyphenyl) -6-
Bromochroman, 2,2,4-trimethyl-4- (3,5-dibromo-4
-Hydroxyphenyl) -6,8-dibromochroman, etc., among which 2,2,4-trimethyl-4-
(4-hydroxyphenyl) chroman is preferred; (5-2)
2,2,3-trimethyl-3- (4-hydroxyphenyl) chroman, 2,2,3,6-tetramethyl-3- (3,5-dimethyl-4) as a compound capable of introducing a group represented by -Hydroxyphenyl) chroman, 2,3,4-trimethyl-2-ethyl-3- (3-nonyl-4)
-Hydroxyphenyl) -7-nonyl-chroman, 2,2,3-trimethyl-3- (3,5-diethyl-4-hydroxyphenyl)-
6-ethyl-chroman, 2,2,3,6,8-pentamethyl-3- (3,
5-Dimethyl-4-hydroxyphenyl) chroman, 2,2,3-
Triethyl-3-methyl-3- (4-hydroxyphenyl) chroman, 2,2,3-trimethyl-3- (3-bromo-4-hydroxyphenyl) -6-bromochroman, 2,2,3-trimethyl-3 -
(3,5-dibromo-4-hydroxyphenyl) -6-bromochroman, 2,2,3-trimethyl-3- (3,5-dibromo-4-hydroxyphenyl) -6,8-dibromochroman, etc. Of these, 2,2,3-trimethyl-3- (4-hydroxyphenyl) chroman is particularly preferable; as the compound capable of introducing the group represented by (5-3), 2,4,4-trimethyl -2- (2-hydroxyphenyl) chroman, 2,4,4,6-tetramethyl-2-
(3,5-dimethyl-2-hydroxyphenyl) chroman, 2,
3,4-Trimethyl-4-ethyl-2- (3,5-dimethyl-2-hydroxyphenyl) -7-nonyl-chroman, 2,4,4-trimethyl-2- (3,5-dimethyl-2- Hydroxyphenyl) -6-ethylchroman, 2,4,4,6,8-pentamethyl-2- (3,5-dimethyl
-2-Hydroxyphenyl) -6-ethylchroman, 2,4,4-trimethyl-2- (3-bromo-2-hydroxyphenyl) chroman, 2,4,4-trimethyl-2- (3-bromo-2 -Hydroxyphenyl) -6-bromochroman, 2,4,4-trimethyl-2- (3,5
-Dibromo-2-hydroxyphenyl) -6-bromochroman, 2,4,4-trimethyl-2- (3,5-dibromo-2-hydroxyphenyl) -6,8-dibromochroman, and the like. Of these, 2,2,4-trimethyl-2- (2-hydroxyphenyl) chroman is particularly preferable; as the compound capable of introducing the group represented by (5-4), 2,4,4-trimethyl-2- ( 4-hydroxyphenyl) chroman, 2,4,4,6-tetramethyl-2-
(3,5-dimethyl-4-hydroxyphenyl) chroman, 2,
4,4-triethyl-2- (4-hydroxyphenyl) chroman,
2,3,4-Trimethyl-4-ethyl-2- (3,5-dimethyl-4-hydroxyphenyl) -7-nonyl-chroman, 2,4,4-trimethyl-2- (3,5-diethyl- 4-hydroxyphenyl) -6-ethyl-chroman, 2,4,4,6,8-pentamethyl-2- (3,5-dimethyl
-4-Hydroxyphenyl) -6-ethylchroman, 2,4,4-trimethyl-2- (3-bromo-4-hydroxyphenyl) chroman, 2,4,4-trimethyl-2- (3-bromo-4) -Hydroxyphenyl) -6-bromochroman, 2,4,4-trimethyl-2- (3,5-dibromo-4-hydroxyphenyl) -6-bromochroman, 2,
4,4-trimethyl-2- (3,5-dibromo-4-hydroxyphenyl) -6,8-dibromochroman and the like can be mentioned, among which 2,4,4-trimethyl-2- (4 -Hydroxyphenyl) chroman is preferred. In the above, the aromatic ring or the aliphatic ring may be further substituted with halogen or an alkyl group having 1 to 9 carbon atoms. These compounds may be used alone or in combination of two or more. In the present invention, the proportion of phenolic terminal groups in the terminal groups is preferably 5% or more, and particularly preferably 20% or more.

Further, when producing polycarbonate,
1 with aromatic dihydroxy compound and carbonic acid diester
It is also possible to use a polyfunctional compound having three or more functional groups in the molecule. As these polyfunctional compounds,
A compound having a phenolic hydroxyl group or a carboxyl group is preferable, and a compound containing three phenolic hydroxyl groups is particularly preferable. Specific examples of preferable compounds include 1,
1,1-tris (4-hydroxyphenyl) ethane, 2,2 ', 2 "
-Tris (4-hydroxyphenyl) diisopropylbenzene, α-methyl-α, α ', α'-tris (4-hydroxyphenyl) -1,4-diethylbenzene, α, α', α ″-Tris (4-hydroxy Phenyl) -1,3,5-triisopropylbenzene, phloroglysin, 4,6-dimethyl-2,4,6-tri (4-hydroxyphenyl) -heptane-2,1,3,5-tri (4- (Hydroxyphenyl) benzene, 2,2-bis- [4,4-
(4,4'-dihydroxyphenyl) -cyclohexyl] -propane, trimellitic acid, 1,3,5-benzenetricarboxylic acid,
Examples include pyromellitic acid. Particularly preferably, 1,
1,1-tris (4-hydroxyphenyl) ethane, α, α ',
α ″ -tris (4-hydroxyphenyl) -1,3,5-triisopropylbenzene or the like is used. The polyfunctional compound is preferably 0.03 mol or less, more preferably 1 mol of the aromatic dihydroxy compound. 0.001-0.02 mol,
Particularly preferably, it is used in an amount of 0.001 to 0.01 mol.

Further, the carbonic acid diester may contain a dicarboxylic acid or a dicarboxylic acid ester. Examples of dicarboxylic acids and dicarboxylic acid esters include aromatic dicarboxylic acids such as terephthalic acid, isophthalic acid, diphenyl terephthalate, and diphenyl isophthalate; succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacine. Acids, decanedioic acid, dodecanedioic acid, diphenyl sebacate, diphenyl decanedioate, diphenyl dodecanedioate, and other aliphatic dicarboxylic acids; cyclopropanedicarboxylic acid, 1,2-cyclobutanedicarboxylic acid, 1,3-cyclobutanedicarboxylic acid ,
1,2-cyclopentanedicarboxylic acid, 1,3-cyclopentanedicarboxylic acid, 1,2-cyclohexanedicarboxylic acid, 1,3-
Cyclohexanedicarboxylic acid, 1,4-cyclohexanedicarboxylic acid, cyclopropanedicarboxylic acid diphenyl, 1,
2-Cyclobutanedicarboxylic acid diphenyl, 1,3-cyclobutanedicarboxylic acid diphenyl, 1,2-cyclopentanedicarboxylic acid diphenyl, 1,3-cyclopentanedicarboxylic acid diphenyl, 1,2-cyclohexane dicarboxylic acid diphenyl, 1,3-cyclohexane Diphenyl dicarboxylate, 1,4-
Examples thereof include alicyclic dicarboxylic acids such as diphenyl cyclohexanedicarboxylate. These dicarboxylic acids or dicarboxylic acid esters may be used alone or in combination of two or more.
The dicarboxylic acid or dicarboxylic acid ester is contained in the carbonic acid diester in an amount of preferably 50 mol% or less, more preferably 30 mol% or less.

When the polycarbonate used in the present invention is produced, the aromatic dihydroxy compound and the carbonic acid diester are preferably reacted in the presence of a catalyst.

As the catalyst, for example, the applicant of the present invention has a patent application
The compounds proposed in 2-85218 can be used. As an example, it is preferable to use (a) organic acid salts, inorganic acid salts, oxides, hydroxides, hydrides or alcoholates of metals such as alkali metals and alkaline earth metals. Specific examples of these compounds include sodium hydroxide, potassium hydroxide, lithium hydroxide, sodium hydrogen carbonate, potassium hydrogen carbonate, lithium hydrogen carbonate, sodium carbonate, potassium carbonate, lithium carbonate, sodium acetate, potassium acetate, lithium acetate, stearin. Sodium acid, potassium stearate, lithium stearate,
Sodium borohydride, lithium borohydride, sodium phenyl borohydride, sodium benzoate, potassium benzoate, lithium benzoate, disodium hydrogen phosphate, dipotassium hydrogen phosphate, dilithium hydrogen phosphate, disodium bisphenol A Salt, dipotassium salt, dilithium salt, sodium salt of phenol, potassium salt, lithium salt, etc .; calcium hydroxide, barium hydroxide, magnesium hydroxide, strontium hydroxide, calcium hydrogen carbonate, barium hydrogen carbonate, magnesium hydrogen carbonate, Strontium hydrogen carbonate, calcium carbonate, barium carbonate, magnesium carbonate, strontium carbonate, calcium acetate, barium acetate, magnesium acetate, strontium acetate, calcium stearate, barium stearate, stearic acid Magnesium, it can be mentioned strontium stearate, and the like. These compounds may be used alone,
You may use it in combination of 2 or more type. The amount of these alkali metal compounds and / or alkaline earth metal compounds is preferably 10 per mol of the aromatic dihydroxy compound.
^-8 to 10 ^-3 mol, more preferably 10 ^-7 to 10 ^-6 mol, and particularly preferably 10 ^-7 to 8 × 10 ^-7 mol.

As the catalyst, the basic compound (b) may be used together with the alkali metal compound and / or the alkaline earth metal compound. As an example of the basic compound,
For example, nitrogen compounds, specifically, tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrabutylammonium hydroxide, trimethylbenzylammonium hydroxide, and other ammonium hydroxides having an alkyl, aryl, or aryl group; trimethylamine, triethylamine ,
Tertiary amines such as dimethylbenzylamine and triphenylamine; secondary or primary amines having an alkyl group such as methyl group and ethyl group, aryl group such as phenyl group and toluyl group; ammonia; tetramethylammoniumboro Examples thereof include, but are not limited to, basic salts such as hydride, tetrabutylammonium borohydride, tetrabutylammonium tetraphenylborate, and tetramethylammonium tetraphenylborate. Of these, ammonium hydroxides are particularly preferable. These basic compounds may be used alone or in combination of two or more.

In the present invention, as the catalyst, the above-mentioned (a) alkali metal compound and / or alkaline earth metal compound,
By using the combination of (b) nitrogen-containing basic compound, a high-molecular weight polycarbonate can be obtained with high polymerization activity.

Alternatively, a combination of (a) an alkali metal compound and / or an alkaline earth metal compound as a catalyst, (b) a nitrogen-containing basic compound, and (c) at least one of boric acid and borate ester, etc. Can be used. When a catalyst composed of such a combination is used, (a) the alkali metal compound and / or the alkaline earth metal compound is used in the amount as described above, and (b) the nitrogen-containing basic compound is used in an amount of 1 mol of the aromatic dihydroxy compound. It is preferably used in an amount of 10 ^-6 to 10 ^-1 mol, especially 10 ^-5 to 10 ^-2 mol. (c) As boric acid or boric acid ester, the following general formula B (OR ^g ) _r (OH) _3-r (wherein R ^g is a hydrogen atom, an aliphatic hydrocarbon group, an alicyclic hydrocarbon group) Or an aromatic hydrocarbon group, and r is 1 to 3
Is an integer of), and examples thereof include boric acid, trimethyl borate, triethyl borate, tributyl borate, trihexyl borate, triheptyl borate, triphenyl borate, tritolyl borate, boric acid. Trinaphthyl etc. can be mentioned. Of these, triphenyl borate is particularly preferable. These (c) boric acid or boric acid ester of the above (a), when used as a catalyst with (b), the amount 10 ^-6 10 ^-1 mole relative to 1 mole of the aromatic dihydroxy compound, particularly 10 ^{- It} is preferably ⁵ to 10 ^-2 mol.

Conditions such as temperature and pressure at the time of the melt polymerization reaction are arbitrary, and known conventional conditions can be used.
Specifically, the reaction in the first step is preferably 80 to 250 ° C,
More preferably 100 to 230 ° C, particularly preferably 120 to 19 ° C.
It is carried out at a temperature of 0 ° C., preferably 0 to 5 hours, more preferably 0 to 4 hours, particularly preferably 0.25 to 3 hours, and atmospheric pressure. Next, the reaction temperature is raised while reducing the pressure of the reaction system to cause the reaction between the aromatic dihydroxy compound and the carbonic acid diester, and finally under a reduced pressure of 0.05 to 5 mmHg at 240 to 320 ° C.
It is preferable to carry out the reaction of the aromatic dihydroxy compound and the carbonic acid diester at the temperature of.

The reaction between the aromatic dihydroxy compound and the carbonic acid diester as described above may be carried out continuously or batchwise. Further, the reaction apparatus used when carrying out the above reaction may be of a tank type, a tube type, or a column type.

The polyarylate used in the present invention is obtained from an aromatic dicarboxylic acid or its derivative and a dihydric phenol or its derivative.

The aromatic dicarboxylic acid used for preparing the polyarylate may be any one as long as it reacts with a dihydric phenol to give a satisfactory polymer, and one kind or a mixture of two or more kinds is used. be able to. Preferable aromatic dicarboxylic acids include terephthalic acid and isophthalic acid, and a mixture thereof is particularly preferable in terms of melt processability and overall performance. In the case of such a mixture, its compounding ratio is not limited, but terephthalic acid / isophthalic acid = 9/1 to 1/9 (molar ratio) is preferable, and particularly, melt processability and other performance balance points. 7/3 to 3/7 (molar ratio), and more preferably 1/1 (molar ratio).

Examples of the dihydric phenol used for preparing the polyarylate include those represented by the following general formula (i), (ii) or (iii).

[0036]

[Chemical 10] In the above general formula, R ₁ , R ₂ , R ₃ , R ₄ , R _{1 ′} ,
R _{2 ′} , R _{3 ′} and R _{4 ′} are selected from the group consisting of a hydrogen atom, a halogen atom, a hydrocarbon group and a halogenated hydrocarbon group,
Y represents O, S, SO, CO, an alkylene group or an alkylidene group (if necessary, the alkylene group or the alkylidene group may be substituted with one or more halogen atoms). Specific examples of preferable dihydric phenols include 2,2-bis (4-hydroxyphenyl) propane, 2,2-bis (4-hydroxy-3,5-dibromophenyl) propane and 2,2-bis (4-hydroxy). -
3,5-dichlorophenyl) propane, 4,4'-dihydroxydiphenyl sulfone, 4,4'-dihydroxydiphenyl ether, 4,4'-dihydroxydiphenyl sulfide,
4,4'-dihydroxydiphenyl ketone, 4,4'-dihydroxydiphenylmethane, 2,2'-bis (4-hydroxy-3,
5-dimethylphenyl) propane, 1,1-bis (4-hydroxyphenyl) ethane, 1,1-bis (4-hydroxyphenyl) cyclohexane, 4,4′-dihydroxydiphenyl,
Examples thereof include benzoquinone. These may be used alone or in combination of two or more. Although the above-mentioned dihydric phenol is a para-substituted product, other isomers may be used, and ethylene glycol, propylene glycol or the like may be used in combination with these dihydric phenols. The most representative dihydric phenol is
2,2-bis (4-hydroxyphenyl) propane, which is usually called bisphenol A, is most preferable from the viewpoint of comprehensive physical properties.

Therefore, the most preferable polyarylate in the present invention is a mixture of terephthalic acid and isophthalic acid or their derivatives (provided that the molar ratio of terephthalic acid group to isophthalic acid group is 9: 1 to 1: 2).
9, particularly 7: 3 to 3: 7) and a dihydric phenol represented by the general formula (iii), particularly bisphenol A or a derivative thereof. In the present invention, polyarylate having a molecular weight of about 12,000 to about 30,000 is preferably used.

In the resin composition of the present invention, the blending ratio of the polycarbonate and the polyarylate is 95 to 5 parts by weight of the polycarbonate and 5 to 95 parts by weight of the polyarylate, and 80 to 10 parts by weight of the polycarbonate and the polyarylate. 20 to 90 parts by weight is preferred. When the amount of polycarbonate is less than 5 parts by weight, the moldability is lowered, and when it is more than 95 parts by weight, the high heat distortion temperature of the polycarbonate / polyarylate resin composition is impaired and the chemical resistance is also lowered. It is not preferable.

In addition, as a stabilizer, phosphorous acid; phosphorous metal salts, phosphorous acid esters, for example, phosphorous acid monoesters such as monophenyl hydrogen diene phosphite and monolauryl hydrogen diene phosphite, diphenyl hydrogen dienephos Phosphite diesters such as phyto and dilauryl hydrogen phosphite, and phosphite triesters such as triphenyl phosphite and tris (nonylphenyl) phosphite are preferably contained.

The resin composition of the present invention may contain other additives during resin mixing and molding as long as the physical properties of the resin composition are not impaired.
For example, pigments, dyes, reinforcing agents, fillers, impact modifiers, heat resistance agents, oxidative deterioration inhibitors, weathering agents, lubricants, mold release agents, crystal nucleating agents, plasticizers, flame retardants, fluidity improvers, antistatic agents. Agents and the like can be added.

There is no particular limitation on the method for producing the resin composition of the present invention, and ordinary methods can be satisfactorily used. However, melt mixing is generally preferred. Any melt mixing method can be used provided it can process the molten viscous mass. The method is used in a batch system or a continuous system. In particular, an extruder, a Banbury mixer, a roller, a kneader and the like can be mentioned as examples.

The present invention will be further described below with reference to examples, but the present invention is not limited to the examples.

[0043]

【Example】

[0044]

[Examples 1 to 4 and Comparative Examples 1 to 4] The following components were blended in the ratios (parts by weight) shown in Table 1 and were mixed in a 65 mm uniaxial extruder (L / D = 17.5) set at 300 ° C and 200 rpm. Extruded into pellets. PC (30): Polycarbonate obtained by synthesizing bisphenol A and diphenyl carbonate by a melting method (intrinsic viscosity in methylene chloride at 25 ° C. of 0.50 dl / g, molar ratio of bisphenol A and diphenyl carbonate adjusted. Then, the equivalent ratio of phenolic end group / non-phenolic end group was set to 3/7. PC (50): Polycarbonate obtained by synthesizing from bisphenol A and diphenyl carbonate by melting method (25 in methylene chloride) Intrinsic viscosity at ℃ 0.50 dl / g, the molar ratio of bisphenol A and diphenyl carbonate was adjusted to make the equivalent ratio of phenolic end groups / non-phenolic end groups 1/1) PC (1): Bisphenol Aromatic polycarbonate prepared by polymerizing A by the phosgene method and end-capping it with phenyl groups to make the ratio of phenolic end groups about 1/99. To (Lexan141
, Trademarks, General Electric Company, in methylene chloride 2
Intrinsic viscosity at 5 ° C 0.51 dl / g) PAR: polyarylate [molecular weight of about 20,000 obtained from dicarboxylic acid (mixture of terephthalic acid and isophthalic acid at a molar ratio of 1: 1) and bisphenol A] STB: stable Agent, tris (nonylphenyl) phosphite.

Using the obtained pellets, each test piece for the following evaluation was molded with a 150-ton molding machine at a cylinder temperature of 300 ° C. and a mold temperature of 80 ° C. * Izod impact strength: The impact strength at each temperature shown in Table 1 is calculated using a notched 1/8 inch bar.
Measured according to ASTM D256, * Heat distortion temperature: Measured according to ASTM D648.

From the pellets thus obtained, an injection-molded plate having a thickness of 3 mm was prepared at a cylinder temperature of 290 ° C. and an injection pressure of 1000 kg / cm.
^2. Molded at a mold temperature of 90 ° C. for one cycle of 45 seconds. * Yellowness (abbreviated as IY in Table 1): X of the above test piece,
The Y and Z values are Color and Color D manufactured by Nippon Denshoku Industries Co., Ltd.
Using the ifference Meter ND-1001 DP, the transmission method
YI was calculated by the following formula: YI = 100 × (1.277X-1.060Z) / Y. The evaluation results are shown in Table 1.

[0047]

[Table 1]

[0048]

As is apparent from the examples, the resin composition according to the present invention is a resin composition containing a polycarbonate obtained by the phosgene method and having a small equivalent ratio of phenolic end groups / non-phenolic end groups. Compared to, excellent thermal stability at the time of melting, very little coloration at the time of molding, and decrease in impact resistance by blending polycarbonate with polyarylate, especially decrease in impact resistance at low temperature, Very few.

Claims (2)

[Claims] 1. A resin composition comprising A) 95 to 5 parts by weight of polycarbonate and B) 5 to 95 parts by weight of polyarylate, wherein the polycarbonate is a melt polymerization product of an aromatic dihydroxy compound and a carbonic acid diester, A resin composition, wherein the equivalent ratio (I) / (II) of the phenolic terminal group (I) and the non-phenolic terminal group (II) in the polycarbonate is 1/19 or more. 2. A phenolic terminal group (I) is represented by the following formula: And a non-phenolic end group (I
I) is the following formula (Wherein R and R ′ may be the same or different and each is a hydrogen atom or an unsubstituted or halogen-substituted alkyl group having 20 or less carbon atoms). The resin composition according to 1.