JPH0436346A - Aromatic polycarbonate resin composition - Google Patents

Abstract

PURPOSE:To obtain the title composition which is lowly yellowing and excellent in transparency and melt stability by mixing a specified aromatic polycarbonate resin with a phosphorus antioxidant, a phenol antioxidant or an epoxy stabilizer. CONSTITUTION:A resin composition comprising 100 pts.wt. aromatic polycarbonate resin (A) produced by transesterifying an aromatic dihydroxylic compound and a carbonic diester in a molten state in the presence of a catalyst system comprising a nitrogeneous basic compound (a) and an alkali metal compound or an alkaline earth metal compound (b) or comprising (a), (b) and boric acid or boric ester (c) and at least one member (B) selected from among a phosphorus antioxidant, a phenol antioxidant and an epoxy stabilizer. It is desirable that the aromatic polycarbonate used has a sodium content of 1ppm or below, a chlorine content of 20ppm or below, a terminal hydroxyl content of 30% or below based on the total terminals and an intrinsic viscosity [eta] of 0.3-1.0.

Description

Detailed Description of the Invention (Industrial Application Field) The present invention relates to an aromatic polycarbonate resin composition,
More specifically, the present invention relates to an aromatic polycarbonate resin composition that has little yellowing, excellent transparency, and excellent melt stability.

(Prior Art and Problems to be Solved by the Invention) Aromatic polycarbonates are resins with excellent mechanical strength and are therefore widely used as engineering plastics. Efforts are continuing to improve the properties of such aromatic polycarbonates. For example, in JP-A No. 2-124934, when produced using the melt polycondensation method, the color tone, heat resistance,
It is disclosed that water resistance is improved. Furthermore, in Japanese Patent Application No. 1-344041 filed by the present applicant, an attempt was made to improve the kneading properties and reactivity of aromatic polycarbonate with polyester resins and the like by adjusting the end group ratio of aromatic polycarbonate.

An object of the present invention is to provide an aromatic polycarbonate resin composition that has particularly improved transparency and melt stability among the excellent properties of aromatic polycarbonate resins.

(Means for Solving the Problem) As a result of intensive studies to achieve the above object, the present inventors have discovered that an aromatic polycarbonate resin produced by a melt polycondensation method using a specific catalyst, The present inventors have discovered that when combined with a stabilizer selected from a specific group, it is possible to provide an aromatic polycarbonate resin composition that has excellent melt stability, little yellowing, and excellent transparency, and has thus arrived at the present invention.

That is, the present invention combines (A) an aromatic organic dihydroxyl group compound and a carbonic acid diester, (a) a nitrogen-containing basic compound, and (b) an alkali metal compound or an alkaline earth metal compound, or (a) +( b) and (c) 100 parts by weight of an aromatic polycarbonate resin produced by transesterification in a molten state using a catalyst system containing boric acid or a boric acid ester, and (B) (a) An aromatic polycarbonate resin composition containing 0,005 to 0.5 parts by weight of one or more selected from phosphorus antioxidants, (1) phenolic antioxidants, and (3) epoxy stabilizers. It is something that provides something.

Aromatic polycarbonate-based resins usually have the formula (each R represents phenylene, halogen-substituted phenylene, or 01-2o alkyl-substituted phenylene, A and B are hydrogen atoms, 01-12 hydrocarbon groups containing no aliphatic unsaturation, or adjacent (Indicates a group that forms a cycloalkane group together with a carbon atom)
It mainly has repeating units shown in

The aromatic polycarbonate resin used in the present invention contains an aromatic organic dihydroxyl group compound and a carbonic acid diester, (a) a nitrogen-containing basic compound, and (b) an alkali metal compound or an alkaline earth metal compound, or ( It needs to be produced by transesterification in the melt (melt polycondensation method) using a catalyst system containing a) + (b) and (c) boric acid or a boric acid ester. This melt polycondensation method was developed by the applicant
The details are described in the No. 124934 publication.

Here, the aromatic organic dihydroxyl group compound is the following formula: (wherein, X is a divalent hydrocarbon group, 0, S, SO or S
02, and the aromatic ring may have a monovalent hydrocarbon group). Specifically, it is a compound represented by bis( hydroxyaryl) alkanes, 1,1-bis(4
-hydroxyphenyl)cyclopentane, 1,1-bis(4-hydroxyphenyl)cyclohexane, etc.
(hydroxyaryl) cycloalkanes, dihydroxyaryl ethers such as 4,4°-dihydroxy-3,3°-dimethylphenyl ether, dihydroxydiaryl sulfides such as 4,4-dihydroxydiphenyl sulfide, 4,4゛-dihydroxydif Dihydroxydiaryl sulfoxides such as enyl sulfoxide, 4
, 4-dihydroxydiphenylsulfone and the like. Among these, bisphenol A is particularly preferred.

Examples of diester carbonates include carbonate esters of aromatic diols such as diphenyl carbonate, tocresyl carbonate, and dinabutyl carbonate, carbonate esters of aliphatic diols such as diethyl carbonate and dibutyl carbonate, and fats such as dicyclohexyl dicarbonate. Examples include carbonate esters of cyclic diols. Among these, diethyl carbonate is particularly preferred.

The above carbonic acid diester is preferably 50 mol% or less,
More preferably, the dicarboxylic acid or dicarboxylic acid ester may be contained in an amount of 30 mol% or less. As such dicarboxylic acids or dicarboxylic acid esters, terephthalic acid, isophthalic acid, diphenyl terephthalate, and diphenyl isophthalate are used.

The carbonic acid diester is used in an amount of 1.01 to 1.30 mol, preferably 1.0 mol, per 1 mol of the aromatic organic dihydroxy compound.
2 to 1.20 mol is used.

In the catalyst system, (a) the nitrogen-containing basic compound is
Ammonium hydroxides having an alkyl, aryl or alkaryl group such as tetramethylammonium hydroxide and trimethylbenzylammonium hydroxide; tertiary amines represented by R3N (R is alkyl or aryl) such as trimethylamine and dimethylbenzylamine; , R, secondary amines represented by NH,
Examples include primary amines represented by RNH2, ammonia, basic salts such as tetramethylammonium borohydride, and tetrabutylammonium tetraphenylborate. Among these, tetraalkylammonium hydroxides are particularly preferred. (a) is 10-6 to 10-1 per mole of the aromatic organic dihydroxy compound.
It is used in a molar amount, preferably from 10@-5 to 10@-2.

(b) As the alkali metal compound or alkaline earth metal compound, organic acid salts of alkali metals or alkaline earth metals, such as acetates (e.g. magnesium acetate), stearates (e.g. potassium stearate), benzoic acid salts (e.g. sodium benzoate); inorganic acid salts such as carbonates (e.g. barium carbonate, sodium bicarbonate), phosphates (e.g. dipotassium hydrogen phosphate);
Hydrides such as sodium hydroxide, calcium hydroxide, strontium hydroxide; hydrides such as lithium borohydride; phenolates such as disodium bisphenol A, sodium boroborophenylate, and the like. (b) is 10-8 to 10-3 mol, preferably 10-7 to 10-3 mol, per mol of the aromatic organic dihydroxy compound.
Use in an amount of 10-4.

(c) As boric acid or boric acid ester, boric acid or the general formula B (OR> (OH) (formula % formula %), where R is alkyl such as methyl or ethyl, or aryl such as phenyl, and D is 1 .2 or 3) are used.

Examples of the boric acid ester include trimethyl ester, triphenyl ester, trinaphthyl ester, and the like. (c) is 10 to 10-1 mol, preferably 10-6 to 10-4 per mol of the aromatic organic dihydroxy compound.
Use in molar amounts.

The polycondensation reaction between the aromatic organic dihydroxy compound and the carbonic acid diester can be carried out under the same conditions as conventionally known polycondensation reaction conditions.

Further, in the above melt polycondensation method, phenols having 10 to 40 carbon atoms are present in the reaction system in an amount of 0.05 to 15 mol % based on 1 mol of the aromatic organic dihydroxy compound,
Preferably, 5 to 99 mol% of the phenolic ends are blocked. It is more preferable that the above phenols have 10 to 25 carbon atoms. In addition, as phenols,
pt-butylphenol, 2-phenyl-2-(4-
Dinuclear phenols such as hydroxyphenyl)propane and chromanylphenol are preferred. Chromanylphenol may or may not be substituted, and when substituted, the substituent is alkyl having 1 to 9 carbon atoms or halogen. Further, chromanylphenol is, for example, p-(4-chromanyl)phenol, Ell-
Examples include (2-chromanyl)phenol and p-(2-chromanyl)phenol.

Of the molecular terminals of the aromatic polycarbonate thus obtained, 5 to 99 mol% are blocked with chromanylphenoxy groups, and 1 to 95 mol% of the terminals are blocked with phenoxy groups, p-(2-(2-phenyl )Propyl)phenoxy group and pt-butylphenoxy group are preferred.

In addition, aromatic polycarbonate produced by the above-mentioned melt polycondensation method having a chromanylphenoxy group at the terminal group, phenoxy group, t-butylphenoxy group and p-(2-
A combination with an aromatic polycarbonate produced by the above melt polycondensation method to which a group selected from (2-phenyl)propyl)phenoxy groups is bonded can also be preferably used as the aromatic polycarbonate resin in the present invention.

The aromatic polycarbonate used in the present invention preferably has a sodium content of 1 ppm or less, more preferably 0.5 ppm or less, and a chlorine content of 20 ppm or less.
m or less, more preferably 10 ppm or less. Moreover, it is preferable that the hydroxyl group terminals account for 30 mol% or less of all the terminals, more preferably 5 to 30 mol%, particularly preferably 10 to 20 mol%. In addition, the intrinsic viscosity [
η] is preferably 0.3 to 1.0 (measured at 20° C. in methylene chloride).

Next, component (8) used in the resin composition of the present invention will be described. Ingredient (B) consists of (a) phosphorus antioxidant, (
selected from b) phenolic antioxidants, and (c) epoxy stabilizers.

(a) Phosphorous antioxidants include, for example, bis(2,
Aryl alkyl phosphites such as 4-di-t-butylphenyl) pentaerythrityl diphosphite, diphenyldecyl phosphite, diphenyl isooctyl phosphite, phenyl isooctyl phosphite, 2-ethylhexyl diphenyl phosphite; trimethyl phosphite; phyto, triethyl phosphite, tributyl phosphite, trioctyl phosphite, trinonyl phosphite, tridecyl phosphite, triotadecyl phosphite, distearyl pentaerythrityl diphosphite, tris(2-chloroethyl) phosphite, tris( Trialkyl phosphites such as 2,3-dichloropropyl) phosphite; tridiquaalkyl phosphites such as tricyclohexyl phosphite; triphenyl phosphite, tricresyl phosphite, tris(
ethyl phenyl) phosphite, tris(2,4-di-
t-butylphenyl) phosphite, tris(nonylphenyl) phosphite, tris(hydroxyphenyl)
Triarylphosphites such as phosphites; trimethyl phosphate, triethyl phosphate, tributyl phosphate, trioctyl phosphate, tridecyl phosphate, triotadecyl phosphate, distearyl pentaerythrityl diphosphate, tris(2
Tricycloalkyl phosphates such as nitricyclohexyl phosphate; triphenyl phosphate, tricresyl phosphate, tris(nonylphenyl) phosphate, 2- Examples include triaryl phosphates such as ethyl phenyl diphenyl phosphate, and these may be used alone or in combination of two or more.

(b) As the phenolic antioxidant, for example, n-
Octadecyl-3-(4-hydroxy:I,5-di-t-butylphenyl)propionate, tetrakis [
Methylene-3-(3-,5-di-t-butyl-4-hydroxyphenyl)propionate comethane, 1°1,3
- tris(2-methyl-4-hydroxy-5-t-butylphenyl)butane, distearyl(4-hydroxy-3-methyl-5-t-butyl)benzylmalonate,
Examples include 4-hydroxymethyl-2,6-di-t-butylphenol, which may be used alone or in combination of two or more.

(c) As the epoxy stabilizer, epoxidized soybean oil,
Epoxidized linseed oil, phenyl glycidyl ether, allyl glycidyl ether, t-butylphenyl glycidyl ether, 3,4-epoxycyclohexyl methyl 3
, 4-epoxycyclohexane carboxylate, 3.
4-Epoxy-6-methylcyclohexylmethyl 3.4
-Epoxy-6-methylcyclohexanecarboxylate, 2,3-epoxycyclohexylmethyl 3.4-epoxycyclohexanecarboxylate, 4-(3,4
-Epoxy-5-methylcyclohexyl)butyl 3,4
-Epoxycyclohexanecarboxylate, 3,4-
Epoxycyclohexylethylene oxide, cyclohexylmethyl 3,4-epoxycyclohexanecarboxylate, 3,4-epoxy-6-methylcyclohexylmethyl-6-methylcyclohexanecarboxylate,
Bisphenol-A diglycidyl ether, tetrabromobisphenol-heglycidyl ether, diglycidyl ester of phthalic acid, diglycidyl ester of hexahydrophthalic acid, bis-epoxy dicyclopentagenyl ether or ethylene glycol, bis-epoxycyclohexyl adipate , butadiene dieboxide,
Tetraphenylethylene epoxide, octyl eboxitalate, and epoxidized polybutadiene, 3,4-
Dimethyl-1,2-epoxycyclohexane, 3,5-
Dimethyl-1,2-epoxycyclohexane, 3-methyl-5-dobutyl-1,2-epoxycyclohexane,
Octadecyl-2,2-dimethyl-3,4-epoxycyclohexanecarboxylate, N-butyl-2,2-
Dimethyl-3,4-epoxycyclohexanecarboxylate, cyclohexyl-2-methyl-3,4-epoxycyclohexanecarboxylate, N-butyl-2-
Isopropyl-3,4-epoxy-5-methylcyclohexanecarboxylate, octadecyl-3,4-epoxycyclohexanecarboxylate, 2-ethylhexyl-3'.

4'-epoxycyclohexane carboxylate, 4.
6-dimethyl-2,3-epoxycyclohexyl-3'
.

4'-epoxycyclohexane carboxylate, 4.
5-Epoxytetrahydrophthalic anhydride, 3-t-butyl-4,5-epoxytetrahydrophthalic anhydride, diethyl 4,5-epoxy-cis-1,2-cyclohexanedicarboxylate, di-n-butyl-3- Examples include t-butyl-4,5-epoxy-cis-1,2-cyclohexanedicarboxylate, and these may be used alone or in combination of two or more.

Component (B) is preferably a combination of (a) and (c), a combination of (a) and (b), a combination of (b) and (c), and a combination of (a), (b) and (c). A combination is more preferred.

The above component (B) is used in an amount of 0.005 to 0.5 parts by weight, preferably 0.1 to 0.3 parts by weight, based on 100 parts by weight of the aromatic polycarbonate resin of component (A).

Furthermore, the resin composition of the present invention may not contain other resins or additives during mixing or molding as long as the physical properties are not impaired.
pigments, dyes, reinforcing agents and fillers (e.g. glass fillers, finely divided aluminium, metal oxides such as iron or nickel and non-metals, e.g. carbon filaments,
Silicates (e.g. mica, aluminum silicate (clay), talc, asbestos, titanium dioxide, wollastonite, tubaculite, potassium titanate and titanate whiskers, polymer fibers, etc.), heat resistant agents, oxidative deterioration inhibitors, weathering agents, lubricants , a mold release agent, a crystal nucleating agent, a plasticizer, a fluidity improver, an antistatic agent, etc. can be added.

When the resin composition of the present invention contains a polycarbonate consisting of brominated bisphenol, an inorganic or organic antimony compound may be further blended into the composition of the present invention in order to synergistically enhance the flame retardance achieved thereby. .

When producing the resin composition of the present invention, each component can be mixed by a conventionally known method. For example, after dispersing and mixing each component with a high-speed mixer such as a turn pull mixer, Henschel mixer, ribbon blender, or super mixer,
A method of melt-kneading using rolls or the like is appropriately selected.

(Example) Aromatic polycarbonate is diphenyl carbonate 1
03 parts by weight and 100 parts by weight of bisphenol A according to the melt polycondensation method disclosed in JP-A-2-124934.

In addition, as a catalyst system, 0.08 parts by weight of a 15% aqueous solution of tetramethylammonium hydroxide, 1.75 x 10' parts by weight of sodium hydroxide, and 6.8 x 1 part by weight of boric acid.
0-4 parts by weight were used. The intrinsic viscosity (in methylene chloride, 25°C) of this aromatic polycarbonate is 0.51
dl/g, and the ratio of phenolic to non-phenolic end groups was 2/8. In the following, this aromatic polycarbonate will be referred to as PC(A).

As component (B), Mark 2112 (trademark, phosphorus antioxidant, manufactured by Adeka Argus Co., Ltd., Tris (2,4
-Main component is di-t-butylphenyl phosphite)
, Mark AO-50 (trademark, phenolic antioxidant, manufactured by Adeka Argus, n-octadecyl-3-(
(based on 4-monohydroxy-3-,5-di-t-butylphenyl) propionate) and hepoxide 2021 P (trademark; epoxy acid stabilizer, manufactured by Daicel Chemical, Alicyclic Gepoxy Carboxylate) are used as main components) and are hereinafter referred to as St(a), St(b), and St(c), respectively.

Examples 1 to 7 and Comparative Examples Each component was mixed in the proportions (parts by weight) shown in the table below, and 1
After extruding with a axial extruder (65 mm), it was molded with a 150-ton molding machine to obtain a test piece. Molding temperature is 280℃
Then, the mixture was allowed to remain in the cylinder at 320°C for an additional 15 minutes. Furthermore, in order to check for yellowing,
It was left to stay for 00 hours.

The initial hue and the hue after retention were measured using Hitachi Analyzer C.
-2000 was measured using a spectrophotometer, and the value as yellow index (YI) was determined.

In addition, in order to evaluate the melt stability, the melt index (M I ) of the extruded pellet (initial stage) and molded product (after residence) was measured. In addition, Ml is ASTM
D1238, it was measured using a Melt Indexer HI machine (manufactured by Takara Kogyo ■).

The above results are shown in the table below.

(Effects of the Invention) According to the present invention, it is possible to provide an aromatic polycarbonate resin composition that has an excellent appearance with little yellowing and excellent transparency, and has excellent physical properties such as melt stability.

Claims (1)

[Scope of Claims] (A) an aromatic organic dihydroxy compound and a carbonic acid diester, (a) a nitrogen-containing basic compound, and (b) an alkali metal compound or an alkaline earth metal compound, or (a)+ (b) and (c) 100 parts by weight of an aromatic polycarbonate resin produced by transesterification in the molten state using a catalyst system containing boric acid or a boric acid ester; ) Aromatic polycarbonate resin containing 0.005 to 0.5 parts by weight of one or more selected from phosphorus antioxidants, (b) phenolic antioxidants, and (c) epoxy stabilizers. Composition.