JPH04306258A - Thermoplastic resin composition - Google Patents

Abstract

PURPOSE:To provide the subject thermoplastic resin composition composed of a hydroxyalkylated polyphenylene ether and a polycarbonate, excellent in compatibility thereof, excellent in moldability and mechanical strength and useful as an industrial material. CONSTITUTION:With (A) 5-95wt.% modified PPE of formula III synthesized by adding an alcoholic OH to a terminal phenolic OH of a polyphenylene ether (herein after abbreviated PPE) using a modifier and then reacting 1-50mol glycidol of formula II with 1mol terminal phenolic OH of the resultant hydroxyalkylated PPE, e.g. PPE represented by formula I (Q<1> is halogen, primary or secondary alkyl, etc.; Q<2> is H, halogen, primary or secondary alkyl, etc.; m is >=10) in the presence of a basic catalyst using or without using an organic solvent at 50-200 deg.C, (B) 95-5wt.% polycarbonate (Bisphenol A is preferably used as main raw material) and, as necessary, an impact strength improve and other additives are blended, thus giving the objective resin composition.

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a resin composition comprising hydroxyalkylated polyphenylene ether and polycarbonate, which has excellent moldability and mechanical strength.
The present invention relates to a thermoplastic resin composition useful as an industrial material. [Prior Art] Polyphenylene ether (hereinafter referred to as PPE)
) has excellent heat resistance, dimensional stability, non-hygroscopicity,
Although it is known as an engineering plastic with electrical properties, it has the drawbacks of poor melt flowability, difficulty in molding, and poor solvent resistance and impact strength. On the other hand, polycarbonate has excellent properties such as mechanical strength such as impact resistance, dimensional stability, and optical transparency, and is used as a molding material for various purposes. [0004] Various compositions have been proposed for the purpose of mixing these two materials and proposing a molding material that compensates for the drawbacks of each without impairing their respective advantages. For example, U.S. Pat.
No. 21080 discloses a resin mixture consisting of PPE and polycarbonate. However, P.P.
E and polycarbonate inherently have poor compatibility, and in such a simple resin mixture, the affinity at the interface is poor, phase separation occurs during molding, and a resin molded product with excellent mechanical strength cannot be obtained. [0005] Therefore, a method for improving the compatibility between the two is as follows.
Several proposals have been made so far. For example, a method of producing a block copolymer of polycarbonate and PPE obtained by coexisting a mixture of a diphenol compound, PPE, a solvent, water, and a tertiary amine with phosgene (Japanese Patent Laid-Open No. 60-42456
(Japanese Unexamined Patent Publication No. 1982-62555), a method of adding an acid imide compound as a compatibilizing agent for both (Japanese Unexamined Patent Publication No. 2-252757) (Japanese Unexamined Patent Publication No. 2-654), etc. are known. However, even if these methods are used,
The mechanical strength of the obtained composition was still not sufficient, and further improvement was desired. [0007] In order to solve the above-mentioned problems, the present invention further improves the compatibility of both PPE and polycarbonate, and has good moldability, impact resistance, The purpose of the present invention is to provide a thermoplastic resin composition with improved mechanical strength balance such as rigidity. [Means for Solving the Problems] As a result of extensive research, the present inventors have found that by using hydroxyalkylated PPE in which a hydroxyalkyl group is introduced into PPE, the PPE can be compatible with polycarbonate. The present invention has been completed based on the discovery that a thermoplastic resin composition with improved solubility and an excellent balance between moldability and mechanical strength can be obtained. That is, the present invention is a thermoplastic resin composition comprising the following components (a) and (b). (a) Hydroxyalkylated PPE
5-95% by weight (b)
polycarbonate
95-5 important% [
The present invention will be explained in detail below. <Hydroxyalkylated PPE> Hydroxyalkylated PPE (hereinafter referred to as modified PPE) used in the present invention
E) is a PPE in which an alcoholic hydroxyl group is added to the terminal phenolic hydroxyl group of PPE using a modifier. , PPE and modifier, P
It can be obtained by reaction at a temperature of 50 to 200°C using a basic catalyst in the presence or absence of an organic solvent capable of dissolving PE. (i) PPE The raw material PPE has the general formula: , represents a hydrocarbonoxy group or a halohydrocarbonoxy group, and Q2 each represents a hydrogen atom, a halogen atom, a primary or secondary alkyl group, a phenyl group, a haloalkyl group, a hydrocarbonoxy group, or a halohydrocarbonoxy group. m represents a number of 10 or more). Suitable examples of primary alkyl groups for Q1 and Q2 are methyl, ethyl, n-propyl, n-butyl, n-amyl, isoamyl, 2-methylbutyl, n-hexyl, 2,3-dimethylbutyl, 2-
, 3- or 4-methylpentyl or heptyl. Suitable examples of secondary alkyl groups are isopropyl, se
c-butyl or 1-ethylpropyl. In many cases, Q1 is an alkyl group or a phenyl group, especially a carbon number 1
~4 alkyl group, and Q2 is a hydrogen atom. A suitable PPE homopolymer is, for example, one consisting of 2,6-dimethyl-1,4-phenylene ether units. A suitable copolymer is a random copolymer consisting of a combination of the above units and 2,3,6-trimethyl-1,4-phenylene ether units. Many suitable homopolymers or random copolymers include
Described in patents and literature. PPE containing molecular moieties that improve properties such as, for example, molecular weight, melt viscosity and/or impact strength are also suitable. The molecular weight of PPE is usually 0.2 to 0.8 dl/g, which has an intrinsic viscosity at 30°C measured in chloroform.
It corresponds to the degree. PPE is usually produced by oxidative coupling of the monomers described above. A number of catalyst systems are known for the oxidative coupling polymerization of PPE. There are no particular restrictions on the selection of the catalyst, and any known catalyst can be used. For example, those containing at least one heavy metal compound such as copper, manganese, cobalt, etc., usually in combination with various other substances. (ii) The hydroxyalkylation modifier and the modified PPE obtained thereby can be produced, for example, by the methods shown in (A) to (E) below. (A) PPE (II) is reacted with glycidol represented by the formula: [Chemical formula 2] [0021] and m are the same as above; n represents a number from 1 to 10) (Japanese Patent Application No. 45653/1999). (B) PPE (II) has the general formula 002
5] [0026] (In the formula, X represents a halogen atom) An epihalohydrin, such as epichlorohydrin, is reacted, and the resulting glycidyl-terminated PPE is then hydrolyzed to form a compound of the general formula: ] [0028] A method for producing a modified PPE represented by the formula (wherein Q1, Q2 and m are the same as above)
45653 specification). (C) PPE (II) has the general formula
X-R1-OH
(III c) 0
A halogenated alkyl alcohol represented by the formula (wherein R1 represents an alkylene group having 1 to 10 carbon atoms and X is the same as above), such as 2-chloroethanol or 3-
By reacting chloro-1-propanol etc., the general formula 00
31 A method for producing a modified PPE represented by the formula (in which Q1, Q2 m and R1 are the same as above) (Japanese Patent Application No. 92998/1999). (D) PPE (II) has the general formula 003
4 [Chemical formula 7] (wherein, R2 is a hydrogen atom or a carbon number of 1 to
8 (representing an alkyl group), such as ethylene carbonate or propylene carbonate, is reacted with an alkylene carbonate represented by the general formula: A method for producing modified PPE shown in (the same) (Japanese Patent Application No. 45655/1999). (E) PPE (II) has the general formula:
] [Chemical formula 9] (wherein, R3 is a hydrogen atom or has 1 to 1 carbon atoms)
(representing an alkyl group of ) (Japanese Unexamined Patent Publication No. 128021/1983). The organic solvents used here include aromatic hydrocarbons such as benzene, toluene, and xylene; halogenated hydrocarbons such as chloroform and carbon tetrachloride; and halogenated aromatic hydrocarbons such as chlorobenzene and dichlorobenzene. Hydrogen; N-methyl-2-pyrrolidone, 1,3-dimethyl-2
-Heterocyclic compounds such as imidazolidinone, etc. As the basic catalyst, alcoholates such as sodium methoxide and sodium ethoxide; alkali metal hydroxides such as sodium hydroxide and potassium hydroxide; alkali metal carbonates such as sodium carbonate and potassium carbonate; Can be mentioned. The reaction amount ratio of the PPE and the modifier used in these reactions is 1 to 50 moles of the modifier per 1 mole of the terminal phenolic hydroxyl group of the PPE, and the amount of the basic catalyst used is 100 parts by weight of the PPE. 0.5 to 50 parts by weight. Among the modified PPE (IA) to (IE) obtained by the methods shown in (A) to (E) above, in the present invention, two or more alcoholic hydroxyl groups having different reaction activities and reactivities are used. (IA) or (IB) is preferred, and (IA) is particularly preferred. Modified P of component (a) used in the present invention
A portion of PE may be replaced with unmodified PPE. In that case, the unmodified PPE is 80%
Used in a proportion of % by weight or less. If the proportion of the modified PPE is less than 5% by weight based on the total composition, the effect of improving compatibility will be lowered, which is not preferable. <Polycarbonate> The polycarbonate used in the present invention is an optionally branched thermoplastic aromatic compound made by reacting an aromatic dihydroxy compound or a small amount of a polyhydroxy compound with a diester of phosgene or carbonic acid. Polycarbonate polymers. Examples of aromatic dihydroxy compounds are 2,2-bis(4-hydroxyphenyl)propane (bisphenol A), tetramethylbisphenol A, tetrabromobisphenol A, bis(4-hydroxyphenyl)-p
-diisopropylbenzene, hydroquinone, resorcinol, 4,4'-dihydroxydiphenyl, bis(4
-hydroxyphenyl)methane, bis(4-hydroxyphenyl)ether, bis(4-hydroxyphenyl)
Sulfone, bis(4-hydroxyphenyl) sulfoxide, bis(4-hydroxyphenyl) sulfide, bis(4-hydroxyphenyl)ketone, 1,1-bis(4
-hydroxyphenyl)ethane, 1,1-bis(4-hydroxyphenyl)cyclohexane, etc., especially,
Bisphenyl A is preferred. Further, in order to obtain a branched aromatic polycarbonate resin, phloroglucin, 4,6-dimethyl-2
,4,6-tri(4-hydroxyphenyl)heptene-
2,4,6-dimethyl-2,4,6-tri(4-hydroxyphenyl)heptane, 2,6-dimethyl-2,4,
6-tri(4-hydroxyphenyl)heptene-3,4
, 6-dimethyl-2,4,6-tri(4-hydroxyphenyl)heptane, 1,3,5-tri(4-hydroxyphenyl)benzene or 1,1,1-tri(4-hydroxyphenyl)ethane, etc. or 3,3-bis(4-hydroxyaryl)oxindole [isatin (bisphenol)]
, 5-chloroisatin, 5,7-dichloroisatin, 5-bromoisatin, or the like to replace a portion of the dihydroxy compound, for example, 0.1 to 2 mol %. Further monovalent aromatic hydroxy compounds suitable for adjusting the molecular weight are m- or p-methylphenol, m- or p-propylphenol, p-bromophenol, p-tert-butylphenol or p- Long-chain alkyl-substituted phenols and the like are preferred. A typical aromatic polycarbonate resin is bis(4
-Hydroxyphenyl)alkane compounds, especially polycarbonates whose main raw material is bisphenol A, polycarbonate copolymers obtained by using two or more aromatic dihydroxy compounds together, and small amounts of trivalent phenol compounds. Also mentioned are branched polycarbonates obtained by Aromatic polycarbonate resin is 2
It may be used as a mixture of more than one species. <Additional Components> Other additional components may be added to the thermoplastic resin composition according to the present invention. For example, using well-known additives such as antioxidants, weatherability modifiers, and flame retardants in polycarbonate; and using well-known antioxidants, weatherability modifiers, plasticizers, flowability modifiers, etc. as additional components in PPE. can. In addition, organic/inorganic fillers, reinforcing agents,
In particular, addition of glass fiber, mica, talc, wollastonite, potassium titanate, calcium carbonate, silica, etc. is effective in improving rigidity, heat resistance, dimensional accuracy, etc. For practical purposes, various known colorants and dispersants thereof can be used. Furthermore, the addition of impact strength improvers, particularly styrene-butadiene copolymer rubber and its hydrides, ethylene-propylene-(diene) copolymer rubber, and their α,β-unsaturated carboxylic acid anhydrides. Addition of modified products, modified products with unsaturated glycidyl esters or unsaturated glycidyl ethers, copolymers of unsaturated epoxy compounds and ethylene, unsaturated epoxy compounds, copolymers of ethylene and ethylenically unsaturated compounds, etc. It is particularly effective in improving the impact strength of the composition. The above impact strength improvers may be used alone or in combination of two or more. The amount of the impact strength improver varies depending on the target physical property values, but for example, in the case of improving the balance between the rigidity and impact strength of the composition, the resin component of the composition 100%
It is 5 to 30% by weight per part by weight. <Composition ratio of constituent components> Modified PPE as component (a) and component (b) in the thermoplastic resin composition of the present invention
The composition of the polycarbonate is such that (a) modified PPE is contained in an amount of 5 to 95% by weight, preferably 20 to 80% by weight, and unmodified PPE is contained in an amount of 0 to 8% by weight in view of the balance between heat resistance rigidity and moldability.
0% by weight, preferably 0-60% by weight, (b) polycarbonate 95-5% by weight, preferably 80-20% by weight
It is. If the polycarbonate content is less than 5% by weight, the molding processability will be poor, which is not preferable, and if it exceeds 95%, the heat-resistant rigidity will be insufficient, which is not preferable. In addition, hydroxyalkylated P
When PE is less than 5% by weight, the compatibility between PPE and polycarbonate is poor, and the strength of the resulting molded product is low. <Production method and molding method of mixed composition> As the melt-kneading method for obtaining the thermoplastic resin composition of the present invention, kneading methods generally used for thermoplastic resins can be applied. For example, each component in powder or granule form, if necessary, along with the additives etc. described in the section of additional components,
After uniformly mixing using a Henschel mixer, ribbon blender, V-type blender, etc., the mixture can be kneaded using a single-screw or multi-screw kneading extruder, roll, Banbury mixer, etc. The method of molding the thermoplastic resin composition of the present invention is not particularly limited, and may be any of the molding methods generally used for thermoplastic resin compositions, such as injection molding, blow molding, extrusion molding, and sheet molding. , thermoforming, rotational molding, lamination molding, press molding, and other molding methods can be applied. [Examples] The present invention will be explained in detail below with reference to Examples. The components used are as follows. PPE: Poly(2) prototyped by Nippon Polyether Co., Ltd.
, 6-dimethyl-1,4-phenylene ether) for 30
Intrinsic viscosity [η] measured in chloroform at °C
．． Using 31 dl/g, it was further modified by the following method. [0058] Modified PPE: 500g of the above PPE,
5 liters of toluene was added and stirred at 80°C under a nitrogen atmosphere to completely dissolve. In this solution, 75g of sodium ethoxide as a catalyst was dissolved in advance in ethanol5.
After adding 00 ml of glycidol, 250 g of glycidol was added dropwise. Furthermore, stirring was continued at 100°C for 5 hours. The reaction mixture was poured into 25 liters of methanol and the product modified PP
E was precipitated. The product was filtered, washed twice with methanol, and then dried under reduced pressure at 80°C. [0059] This modified PPE exhibited absorption derived from hydroxyl groups near 3,380 cm-1 in its infrared absorption spectrum. Furthermore, when the phenolic hydroxyl group of the terminal group was quantified, it was found that 74% had reacted. [0060] The reactivity rate of the terminal phenolic hydroxyl group of PPE is given in the Journal of Applied Polymers.
Science: Applied Polymer Symposium (J
Our own of Applied Polymer
Science Applied Polymer
Symposium), vol. 34, (1978), 10
The terminal phenolic hydroxyl groups before and after the reaction were quantitatively determined and calculated according to the method described on pages 3 to 117. Polycarbonate: Manufactured by Mitsubishi Gas Chemical Co., Ltd., trade name "Iupilon S2000" (viscosity average molecular weight 2
．． 5×104) was used. Examples 1, 2, and 3 and Comparative Examples 1, 2, and 3 According to the formulation shown in Table 1, predetermined amounts of each component were heated at a temperature of 280°C using a Laboplastomill manufactured by Toyo Seiki Co., Ltd. °C,
A thermoplastic resin composition was obtained by melt-kneading for 5 minutes at a rotor rotation speed of 60 rpm. [0063] [Table 1] [0064] This sample was pulverized using a pulverizer. A granular sample was molded using a compression molding machine manufactured by Toyo Seiki Co., Ltd. at a temperature of 280°C to a size of 75 mm long, 170 mm wide, and 2 m thick.
A sheet of m was molded, and a test piece for physical property evaluation was cut. [0065] In kneading and molding, the polycarbonate used had been vacuum-dried in advance at 100°C for 10 to 15 hours. Further, the test pieces for physical property evaluation were left in an atmosphere of 23° C. and 50% humidity for 2 to 6 days and then evaluated. The results are shown in Table 1. The evaluation method is as follows. (1) MFR In accordance with JIS K7210, using a melt indexer manufactured by Toyo Seiki Co., Ltd., at a temperature of 280°C and a load of 10 kg.
Measured under the following conditions. (2) Elastic Modulus A test piece with a length of 62 mm, a width of 12 mm, and a thickness of 2 mm was cut, and the storage modulus at a frequency of 1 Hz (
The temperature dependence of G') was measured, and the G' value at 23°C was determined. (3) Izod impact strength JIS K7
110, three test pieces with a thickness of 2 mm were stacked and fixed with cellophane tape, and the unnotched Izod impact strength at 23°C was measured using an Izod impact tester manufactured by Toyo Seiki Co., Ltd. (4) A part of the dispersion form molded product was cut out, melt-molded into a film on a slide glass, and then observed at a magnification of 250 to 500 times using a phase contrast microscope manufactured by Olympus Optical Industries, Ltd. . In addition, since the sample of Example 1 was finely dispersed, a part of the molded product was further stained with ruthenium tetroxide, and an ultrathin section was prepared using an ultramicrotome.
JEM-100SX transmission electron microscope with a magnification of 10.0
Observation was made at 00x magnification. Effect of the invention: As shown in the examples and comparative examples, hydroxyalkylated PPE (a) and polycarbonate (b)
), compared to the comparative example in which hydroxyalkylated PPE was not blended, the dispersed particle size of the composition was significantly reduced, and the compatibility of originally incompatible components was improved. , a thermoplastic resin composition with high fluidity and an excellent balance between rigidity and impact strength can be obtained.

Claims (1)

[Claims] 1. A thermoplastic resin composition comprising the following components (a) and (b). (a) Hydroxyalkylated polyphenylene ether 5-95% by weight (b) Polycarbonate
95-5% important