JPS6234790B2 - - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a resin composition formed by blending a branched aromatic polyester and a polycarbonate. Aromatic polyesters obtained from aromatic dicarboxylic acids or their functional derivatives and bisphenols or their functional derivatives are transparent resins with high heat distortion temperatures and excellent mechanical and electrical properties, and their usefulness is widespread. However, due to the high flow start temperature and high viscosity when melted, the fluidity is insufficient when molding by methods such as injection molding, extrusion molding, and blow molding, making it difficult to mold multiple pieces or large molds. It is difficult to obtain products and their uses are limited. It has also been pointed out that molded products tend to crack (stress cracking) in the presence of residual stress or external stress, especially when they come into contact with chemicals such as carbon tetrachloride, xylene, and toluene. Regarding the improvement of such drawbacks, as described in Patent Application No. 26292 of 1978 (see Japanese Patent Publication No. 61-26567), which is an invention previously filed by the present applicant,
By using a specific amount of trihydric or higher alcohol or its functional derivative as a branching agent and giving the aromatic polyester a suitable branched structure, the melt viscosity has a large pressure dependence and exhibits high fluidity under high shear. Aromatic polyesters have also been obtained which exhibit excellent resistance to stress cracking. However, even in branched aromatic polyester (hereinafter referred to as APC), fluidity is insufficient for molds with small gates such as pin gates, and for injection molding of large molded products.
Further improvements are desired. On the other hand, polycarbonate (hereinafter referred to as PC)
is widely used as a transparent engineering plastic with excellent impact resistance and transparency, but the performance required of plastic is increasing year by year as society becomes more sophisticated, and even PC, which is considered to be an excellent resin, has even higher performance requirements. Heat deformation resistance is strongly desired in many fields. In general, in order to compensate for the drawbacks of resins, it is necessary to use resins with opposite properties, such as a resin with good processability for a resin with poor processability, and a resin with high heat distortion temperature for a resin with a low heat distortion temperature. A method of blending resins is used, but in this case, there is usually a significant sacrifice in mechanical properties or surface gloss of the molded product. In view of the above-mentioned circumstances, the present inventors have conducted extensive research and as a result, by blending APC and PC, the processability of APC is improved, the heat distortion temperature of PC is increased, and stress cracking resistance is improved. It has been found that it is possible to obtain a transparent thermoplastic resin with good surface gloss and good kingability and unexpectedly excellent mechanical properties. APC used in the present invention is a polyester obtained from an aromatic dicarboxylic acid or a functional derivative thereof and a bisphenol or a functional derivative thereof, and contains 0.01 to 5 mol of a trihydric or higher alcohol or a functional derivative thereof per 100 mol parts of the bisphenol. It is an aromatic polyester synthesized by adding a certain amount. Known polymerization methods are employed, such as interfacial polycondensation, solution polycondensation, and melt polycondensation, and the types of dicarboxylic acids, bisphenols, and functional derivatives thereof are selected appropriately according to each method. Ru. Specific examples of aromatic dicarboxylic acids or functional derivatives thereof used in the present invention include terephthalic acid, isophthalic acid, naphthalene dicarboxylic acid, and nuclear alkyl-substituted and nuclear halogenated derivatives thereof. Further, examples of these functional derivatives include acid chloride, phenyl ester, and alkyl ester. Preferred are terephthalic acid, isophthalic acid and functional derivatives thereof. More preferably, a mixture of terephthalic acid and isophthalic acid,
or a mixture of functional derivatives thereof. The bisphenols used in the present invention are represented by the following general formula. In the above formula, Ar ¹ represents an aromatic nucleus such as a phenylene nucleus, a biphenylene nucleus or a naphthylene nucleus, and R represents a hydrogen atom, an alkyl group (such as a methyl group and an ethyl group), a halogenated alkyl group, an aryl group (such as a phenyl group and (naphthyl group), halogenated aryl group, aralkyl group (e.g. benzyl group and phenylethyl group), halogenated aralkyl group, alkyl-substituted aryl group, halogenated alkyl-substituted aryl group, alicyclic group or halogenated alicyclic group, is an alkylene group or alkylidene group such as methylene group, ethylene group, propylene group, ethylidene group, propylidene group and isopropylidene group, aromatic group, tertiary amino group (-M(alk)
-), ether group (-O-), carbonyl group (-
CO-) or two or more alkylene or alkylidene groups interconnected by sulfur-containing groups, such as sulfide (-S-), sulfoxide (-SO-) or sulfonyl ( _-SO2- ) groups. show. X may also be an alicyclic group, or a sulfur-containing group, such as a sulfide, sulfoxide or sulfonyl group, an ether group, a carbonyl group or a tertiary amino group. Y is a halogen atom, a nitro group, or a group represented by R' or OR'(R' has the same meaning as R described above); m is the number of substitutable hydrogen atoms on O to X; n is an integer from 0 to the number of substitutable hydrogen atoms on aromatic Ar, p is at least 1
, q is an integer from 0 to 1, and r is an integer (however, when q is 0, r may be 0). In the diphenol shown in the above formula, when there is one or more substituents Y, these substituents may be the same or different. The same is true for R and R'. The substituent Y and the hydroxyl group on the aromatic nucleus may be in the ortho, meta or para position. A mixture of these may also be used. Examples of bisphenols having the general formula above and suitable for carrying out the process of the invention are as follows. Bis(4-hydroxyphenyl)-methane, bis(4-hydroxy-3-methylphenyl)-methane, bis(4-hydroxy-3,5-dichlorophenyl)-methane, bis(4-hydroxy-
3,5-dibromophenyl)-methane, bis(4
-Hydroxy-3,5-difluorophenyl)-
Methane, bis(4-hydroxyphenyl)-kent, bis(4-hydroxyphenyl)-sulfide, bis(4-hydroxyphenyl)-sulfone, 4,4'-dihydroxyphenyl ether,
1,1-bis(4-hydroxyphenyl)-ethane, 2,2-bis(4-hydroxyphenyl)-
Propane, 2,2-bis(4-hydroxy-3-
methylphenyl)propane, 2,2-bis(4-
Hydroxy-3,5-dimethylphenyl)-propane, 2,2-bis(4-hydroxy-3,5-
dibromophenyl)-propane, 2,2-bis(4-hydroxy-3-chlorophenyl)-propane, 2,2-bis(4-hydroxy-3,5-dichlorophenyl)-propane, 2,2-bis (4
-hydroxynaphthyl)propane, bis(4-hydroxyphenyl)-phenylmethane, bis(4-hydroxyphenyl)-phenylmethane,
-hydroxyphenyl)-diphenylmethane, bis(4-hydroxyphenyl)-4'-methylphenylmethane, 1,1-bis(4-hydroxyphenyl)2,2,2-trichloroethane, bis(4-hydroxyphenyl)-4'-diphenylmethane,
-hydroxyphenyl)-(4'-chlorophenyl)
-methane, 1,1-bis(4-hydroxyphenyl)-cyclohexane, bis(4-hydroxyphenyl)-cyclohexylmethane, 4,4'-dihydroxyphenyl, 2,2'-dihydroxyphenyl, 2, Dihydroxynaphthalenes such as 6-dihydroxynaphthalene, hydroquinone, resorcinol, 2,6-dihydroxytoluene, 2,6-
Dihydroxychlorobenzene, 3,6-dihydroxytoluene. Functional derivatives of bisphenols are diesters such as diacetate and dibenzoate. Preferred bisphenols are 2,2-bis(4-hydroxyphenyl)-propane and its nuclear halogen-substituted products and nuclear alkyl-substituted products. In the present invention, specific examples of trihydric or higher alcohols or functional derivatives thereof used as branching agents include glycerin, trimethylolethane, trimethylolpropane, trimethylolbutane, pentaerythritol, and 1,2,6-hexanetriol. , 1,3,6-hexanetriol, 1,2,5-pentanetriol, sorbitriol, tetrose, pentose, hexose, etc. 3
Typical examples thereof include aliphatic or alicyclic polyhydric alcohols of higher valences, trihydric or higher hydric alcohols of various saccharides, or functional derivatives thereof. 3
Functional derivatives of alcohols with higher valences are the reaction products of alcohols with higher valences than 3 and, for example, aliphatic or aromatic dicarboxylic acids (or functional derivatives thereof), or the reaction products of alcohols with 3 or more hydrides with phosgene (polychloro etc.). Examples include functional derivatives that can be esterified, such as (formate). The branching agent is used in an amount of 0.01 to 5 mol parts, preferably 0.1 to 3 mol parts, per 100 mol parts of the bisphenols. The PC used as a component of the composition of the present invention is a 4,4-dioxydiallylalkane polycarbonate, such as bis(4-hydroxyphenyl)methane, bis(4-hydroxyphenyl)ethane, 2,2- (4-hydroxyphenyl)propane, bis(4-hydroxy-3,5-
dichlorophenyl)methane, 2,2-(4-hydroxy-3,5-dimethylphenyl)propane,
It is a polycarbonate obtained from 4,4-dioxydiphenylalkane such as bis(4-hydroxyphenyl)phenylmethane and phosgene or diphenyl carbonate. The composition of the present invention has an APC of 1 to 99% based on the total amount of the composition.
% by weight and PC99 to 1% by weight. If the content of APC in the composition of the present invention is 99% by weight or more, the effect of improving processability is insufficient, and if the content of APC is less than 1% by weight, the effect of improving heat distortion temperature is not observed, and the effect of improving mechanical properties is also small. stomach. The compositions of this invention are particularly useful when the APC content is between 10 and 95% by weight. The compositions of the present invention can be homogeneously mixed by solution blending or by two roll, Banbury mixer, extruder or other mixing machines known in the art. The present invention will be explained below with reference to Examples, but these are illustrative and can be appropriately modified within the scope of the present invention. In the examples, the heat distortion temperature was measured at a load of 18.6 kg/cm ² in accordance with ASTM D569-59. Mechanical properties are
Shown as Izot impact strength (with V-notch) according to ASTM D256. Processing was performed using a Sumitomo Heavy Industries injection molding machine Neo Matsut 47/28, with an injection pressure of 1500 Kg/cm ² ,
Spiral flow length (width 8
mm, thickness 3 mm) is indicated by the injection molding temperature required to indicate 30 cm. Stress cracking was evaluated by the length (cm) of cracks generated when the 30 cm long spiral flow molded product was immersed in carbon tetrachloride for 1 minute at room temperature. Example 1 50.75 g of terephthalic acid chloride, 50.75 g of isophthalic acid chloride, and 0.6 g of trimethylolethane
Incubate at 80°C for 1 hour. After the reaction is complete, 1500 g of methylene chloride is added to form a solution. On the other hand, 2,2-bis-(4
114 g of -hydroxyphenyl)-propane, 2.82 g of phenol, 42 g of caustic soda, and 0.5 g of trimethylbenzylammonium chloride are dissolved in 2400 g of water. Next, the previously prepared methylene chloride solution is charged into the polymerization tank with vigorous stirring. Stirring was continued for 3 hours while adjusting the internal temperature to 20°C, and then stirring was stopped. After removing the aqueous layer separated into two layers, 2400 g of water and 10 g of concentrated hydrochloric acid are added to the polymer layer to wash the stirred polymer layer. Remove the water layer again and wash the polymer layer several times with water. After that, add 500 g of acetone to the polymer layer and continue stirring for a while to precipitate the polymer. The polymer is filtered and then dried. η of the branched aromatic polyester thus obtained measured at 25 °C at a concentration of 0.5% in chloroform
sp/c was 0.65 dl/g. The branched aromatic polyester (abbreviated as APC)
and PC (Mitsubishi Gas Chemical, Iupilon S2000) in the proportions shown in Table 1.
Supplied to a screw extruder (screw diameter 30 mmφ, L/D = 20) equipped with a die with mmφ diameter,
A strand was extruded at a screw rotation speed of 30 rpm and a processing temperature according to the mixing ratio shown in Table 1, and was cut into a length of 3 mm to obtain a granular sample. Using this sample, the processability and stress cracking property were evaluated by injection molding, and the 160 mm x 160 mm x 3
A sheet of mm was molded and subjected to physical property tests. The results are shown in Table 1. Comparative Example 1 Table 1 shows the physical properties and processability of APC used in Example 1 alone. Comparative Example 2 Table 1 shows the physical properties and processability of PC used in Example 1 alone. 【table】

Claims (1)

[Claims] 1 A polyester obtained from an aromatic dicarboxylic acid or its functional derivative and bisphenols or its functional derivative, which contains 100% of bisphenols.
A resin composition comprising 1 to 99% by weight of an aromatic polyester synthesized by adding 0.01 to 5 mol parts of a trihydric or higher alcohol or a functional derivative thereof per mol part, and 99 to 1% by weight of a polycarbonate.