JPS6113493B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to an aromatic polyester polycarbonate resin composition with improved moldability and moist heat resistance. Aromatic polyester polycarbonate is a linear resin having an ester bond and a carbonate bond in the same molecule, for example, 2,2-bis(4
-Hydroxyphenyl)propane (bisphenol A), terephthaloyl chloride and phosgene, and has excellent mechanical properties, weather resistance, chemical resistance and transparency. Are known. (Unexamined Japanese Patent Publication No. 52-
128992) However, such aromatic polyester polycarbonates have a high softening temperature and high melt viscosity, so they have the disadvantage of poor moldability. For example, when manufacturing molded products by injection molding, high molding temperature, mold temperature, and injection pressure are required, but high temperatures cause thermal deterioration of the polymer, so high injection pressure is necessary. Since doing so has disadvantages such as causing distortion of the product and also increases costs, it has been desired to improve the moldability. As a result of intensive research to improve the above-mentioned drawbacks of aromatic polyester polycarbonate, the present inventors found that when a metal salt of an organic carboxylic acid is blended into aromatic polyester polycarbonate, its moldability can be greatly improved. The present invention was completed based on the knowledge that it is possible not only to improve heat and humidity resistance, that is, resistance in hot water, hot water, or steam. That is, the purpose of the present invention is to provide an aromatic polyester polycarbonate having improved moldability and moist heat resistance and having great industrial value. (In the formula, X represents a divalent group, and the aromatic nucleus may have a substituent.) A structural unit represented by the following and the general formula (In the formula, X and the aromatic nucleus have the same meanings as above.) Consisting of a structural unit represented by: dihydroxydiaryl compound residue: terephthalic acid residue:
The molar ratio of carbonate bonds is 1:0.33-0.75:
This is an aromatic polyester polycarbonate resin composition prepared by blending 0.01 to 3 parts by weight of a metal salt of an organic carboxylic acid having 2 to 30 carbon atoms to 100 parts by weight of an aromatic polyester polycarbonate having a carbon number of 0.67 to 0.25. The present invention will be explained in detail below. The aromatic polyester polycarbonate used in the present invention has, for example, the general formula (In the formula, X is

【formula】

[Formula] A divalent group such as -O-, -S-, -SO- or -SO ₂ -, R is
A hydrogen atom or a monovalent hydrocarbon group, R' represents a divalent hydrocarbon group, and the aromatic nucleus may have a halogen atom or a monovalent hydrocarbon group. ) and terephthaloyl chloride are reacted in the presence of an organic solvent such as methylene chloride and an acid binder such as pyridine, and then phosgene is introduced into the reaction mixture to Condensation solution polymerization method (JP-A-52-128992) or the general formula shown above []
An alkaline aqueous solution of a dihydroxydiaryl compound represented by the formula is reacted with a solution of terephthaloyl chloride in an organic solvent, and then phosgene is introduced into the reaction mixture to form an oligomer with a chloroformate group at the end. It can be produced by an interfacial polymerization method in which an alkaline aqueous solution of a dihydroxydiaryl compound represented by the general formula [] is added and polycondensed. Industrially, the interfacial polymerization method is advantageous in that it is not necessary to use pyridine, which has a large recovery loss and a strong odor. The amounts of the dihydroxydiaryl compound, terephthaloyl chloride, and phosgene to be used are such that the molar ratio of dihydroxydiaryl compound residue: terephthalic acid residue: carbonate bond in the resulting aromatic polyester polycarbonate is 1:0.33 or more.
0.75:0.67~~0.25, preferably 1:0.33~
0.49: Selected as appropriate to be 0.67 to 0.51. If the molar ratio of terephthalic acid residues is less than this, the improvement in the glass transition point is unsatisfactory, and on the other hand, if the molar ratio of carbonate bonds is too small, the inherent properties of polycarbonate will be impaired. However, this composition molar ratio was determined by infrared spectrum analysis.
COO− group 1740 cm ⁻¹ and −OCOO− group 1770 cm ⁻¹
This value is calculated from the peak ratio of Specific examples of the dihydroxydiaryl compound represented by the general formula [] include: 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-3-methylphenyl)propane, 1,1-bis(4-hydroxy-3-tert-butylphenyl)propane, 2,2-bis(4-hydroxy-3-promophenyl)propane, 2,2-bis( Bis(hydroxyaryl)alkanes such as 4-hydroxy-3,5-dibromophenyl)propane, 2,2-bis(4-hydroxy-3,5-dichlorophenyl)propane, 1,1-bis( 4-hydroxyphenyl)cyclopentane, bis(hydroxyaryl)cycloalkanes such as 1,1-bis(4-hydroxyphenyl)cyclohexane, 4,4'-dihydroxydiphenyl ether, 4,4'-dihydroxy -3,3'-dimethyldiphenyl ether, dihydroxydiarylethers such as 4,4'-dihydroxydiphenyl sulfide, 4,4'-dihydroxy-3,3'-dimethyldiphenyl sulfide dihydroxydiaryl sulfoxides such as 4,4'-dihydroxydiphenyl sulfoxide, dihydroxydiaryl sulfoxides such as 4,4'-dihydroxy-3,3'-dimethyldiphenyl sulfoxide, 4,4'-dihydroxydiphenyl sulfoxide; Examples include dihydroxydiarylsulfones such as enylsulfone and 4,4'-dihydroxy-3,3'-dimethyldiphenylsulfone. In addition to terephthaloyl chloride, terephthaloyl chloride has a halogen atom in its nucleus,
Terephthaloyl chloride having an alkyl group, such as 2,5-dichloroterephthaloyl chloride,
Examples include 2,5-dibromterephthaloyl chloride, chlorterephthaloyl chloride, methylterephthaloyl chloride, and 2,5-dimethylterephthaloyl chloride. In addition, small amounts of other dibasic acid chlorides, such as less than 20% isophthaloyl chloride, 2,6-naphthalene dicarboxylic acid dichloride, 4,4'-benzophenone dicarboxylic acid dichloride, etc., may be mixed and used. Good too. The aromatic polyester polycarbonate of the present invention produced in this manner has _{the following formula: SP /C=[η]+0.427[η} ] ² It is desirable that the intrinsic viscosity [η] calculated by C is 0.4 to 1.5, preferably 0.43 to 1.1. [η]
If it is too large, the moldability will be poor, and conversely, if it is too small, the mechanical properties will not be sufficient. Further, the glass transition point (Tg) of the aromatic polyester polycarbonate is usually 160 to 190°C, preferably 170 to 185°C. Furthermore, it is preferable that the aromatic polyester polycarbonate has a terminal carboxy group of 10 μequivalent/g resin or less. The metal salt of an organic carboxylic acid having 2 to 30 carbon atoms used in the present invention is an organic carboxylic acid having 2 to 30 carbon atoms and 1 to 4 carboxyl groups,
It is a metal salt with a group 4 metal. Specific examples of organic carboxylic acids include acetic propionic acid, n-butyric acid, isobutyric acid, n-valeric acid, trimethylacetic acid, caproic acid, enanthic acid,
Caprylic acid, pelargonic acid, capric acid, lauric acid, palmitic acid, stearic acid, behenic acid,
Aliphatic monoacids such as montanic acid, halogenated aliphatic monoacids such as fluoroacetic acid, chloroacetic acid, bromoacetic acid, dichloroacetic acid, trichloroacetic acid, chloropropionic acid, acrylic acid, methacrylic acid, oleic acid. unsaturated aliphatic monobasic acids such as benzoic acid, toluic acid, cinnamic acid, aromatic monobasic acids such as naphthalene monocarboxylic acid, halogenated aromatic monobasic acids such as chlorobenzoic acid, prombenzoic acid, aliphatic dibasic acids such as malonic acid, succinic acid, glutaric acid, adipic acid, suberic acid, azelaic acid, sebacic acid; aromatic dibasic acids such as terephthalic acid, isophthalic acid, phthalic acid, naphthalene dicarboxylic acid; Examples include tribasic acids such as trimellitic acid, tetrabasic acids such as pyromellitic acid, oxyacids such as glyoxylic acid, glycolic acid, lactic acid, and salicylic acid, as well as pyridinecarboxylic acid, quinolinecarboxylic acid, and cyclohexanedicarboxylic acid. Further, specific examples of metals constituting the metal salt of the organic carboxylic acid include lithium, sodium,
Examples include metals in group 1 of the periodic table such as potassium, metals in group 2 of the periodic table such as magnesium, calcium, barium, zinc, and cadmium, and other metals such as aluminum, tin, and lead. These may be used alone or in combination of two or more. The amount of the metal salt of an organic carboxylic acid having 2 to 30 carbon atoms is 0.01 to 3 parts by weight, preferably 0.1 to 2 parts by weight, per 100 parts by weight of the aromatic polyester polycarbonate.
Parts by weight. If the amount is too small, the effects of the present invention cannot be expected. On the other hand, if the amount is too large, moldability is improved, but impact resistance and other mechanical properties are deteriorated, which is not preferable. Various known methods can be used to blend the aromatic polyester polycarbonate and the metal salt of the organic carboxylic acid, for example,
From a method of dry blending both granular or powdered materials using a blender or mixer, a method of mixing both using an extruder, etc., a mixture of a metal salt of an organic carboxylic acid and a solution of an aromatic polyester polycarbonate, A method in which the solvent is evaporated or precipitated, or a method in which a metal salt of an organic carboxylic acid is added at any stage of producing the aromatic polyester polycarbonate can be adopted. The composition of the present invention may include other types of resins, such as polyethylene, to the extent that their properties are not impaired.
Polyolefin resins such as polypropylene, ethylene-vinyl acetate copolymer, polyacrylate resins such as polymethyl methacrylate, ethylene-methyl methacrylate copolymer, polymethacrylic acid, polystyrene, ABS,
Polystyrene resins such as AES, ACS, SAN, MBS, polyester resins such as polyethylene terephthalate, polybutylene terephthalate, polycaprolactone, polypivalolactone, nylon-6, nylon-66, nylon-610, nylon-11, nylon −12 polyamide resin,
Polycarbonate resin, polyacetal resin, etc. may be blended. In addition, stabilizers such as phosphoric acid, phosphorous acid, their esters or their metal salts, reinforcing agents such as glass fiber and carbon fiber, silica, alumina, silica-alumina, silica-magnesia, calcium compounds, etc. Fillers, other additives such as plasticizers, lubricants, ultraviolet absorbers, flame retardants, and dyes may also be added. The composition of the present invention has improved moldability and moist heat resistance without impairing the excellent properties inherent to aromatic polyester polycarbonate, so it can be used in a wide range of applications as an engineering plastic, and has industrial value. is large. EXAMPLES The present invention will be specifically explained below with reference to examples, but the present invention is not limited to the following examples unless it exceeds the gist thereof. In addition, "parts" in the examples indicate "parts by weight", and tensile strength and Izod impact strength are respectively
This is a value measured based on ASTM D638-68 and ASTM D256. In addition, heat and humidity resistance is determined by visually determining the presence or absence of crazes on a test piece that has been boiled in boiling water at 100°C for 20 hours. Production example of aromatic polyester polycarbonate A 3% methylene chloride solution of terephthaloyl chloride, a 13% aqueous solution of bisphenol A sodium salt prepared by dissolving bisphenol A in a 5% aqueous sodium hydroxide solution, and a 2% aqueous triethylamine solution, Flow rates of 44.2Kg/hr, 15.9Kg/hr and 0.2Kg/hr, respectively, are supplied to a column packed with glass bulbs with an inner diameter of 30mm and a length of 1.5m, and 0.75m from the supply port of the column.
A reaction was carried out by blowing 0.75 Kg/hr of phosgene from the position, and an oligomer having an ester bond and a chloroformate group at the end was produced. A methylene chloride solution of the above oligomer obtained by separating the reaction mixture 44.0 Kg/hr, a 13% aqueous solution of the same bisphenol A sodium salt as above 17.6 Kg/hr,
25% sodium hydroxide aqueous solution 1.1Kg/hr, 2% triethylamine aqueous solution 0.67Kg/hr and p-tertiarybutylphenol 27g/hr were fed into a stirring tank, and the mixture was heated so that the average residence time was 2 hours. A condensation reaction was performed. The methylene chloride solution of the polymer obtained by separating the reaction mixture was washed with water, an aqueous hydrochloric acid solution, and then water, and the methylene chloride was evaporated until [η] was 0.75.
An aromatic polyester polycarbonate having a bisphenol A residue: terephthalic acid residue: carbonate bond molar ratio of 1:0.46:0.54 was obtained. <Production example of wholly aromatic polyester> A methylene chloride solution of a 1:1 mixture of terephthalic acid dichloride and isophthalic acid dichloride and an alkaline aqueous solution of bisphenol A were polymerized by an interfacial polymerization method to obtain a total aromatic polyester with [η] of 0.63. An aromatic polyester was obtained. <Production Example of Aromatic Polycarbonate> An aqueous alkaline solution of bisphenol A and phosgene were polymerized by interfacial polymerization in the presence of methylene chloride to obtain an aromatic polycarbonate having a molecular weight of 30.000. <Production example of mixture of wholly aromatic polyester and aromatic polycarbonate> A mixture obtained by mixing the above-mentioned two resins in equal weights. Examples 1 to 7 and Comparative Example 1 100 parts of the aromatic polyester polycarbonate powder produced in the above production example was mixed with a metal salt of an organic carboxylic acid in the amount shown in Table 1 below, and the mixture was heated at 300°C using an extruder. It was melt mixed and extruded into pellets. These pellets are processed into an injection molding machine (Nissei Plastics Co., Ltd.).
TS-100 model) and a test piece mold specified by ASTM. The molding temperature, mold temperature and injection pressure at that time required the values shown in Table 1 below. The mechanical properties and moist heat resistance of the thus obtained test piece were as shown in Table 2 below. For comparison, the results obtained when no metal salt of organic carboxylic acid was blended are also shown.

【table】

[Table] Comparative Examples 2 to 4 In place of the aromatic polyester polycarbonate in Examples 1 to 7, 100 parts each of the fully aromatic polyester, aromatic polycarbonate, or a mixture of the same weight thereof produced in the above production example was used, and the other Sodium benzoate as in Example 6
0.2 part was blended and pelletized and continuously molded. The results were as shown in Table 3 below.

【table】

Claims (1)

[Claims] 1. General formula (In the formula, X represents a divalent group, and the aromatic nucleus may have a substituent.) A structural unit represented by the following and the general formula (In the formula, X and the aromatic nucleus have the same meanings as above.) Consisting of a structural unit represented by: dihydroxydiaryl compound residue: terephthalic acid residue:
The molar ratio of carbonate bonds is 1:0.33-0.75:
An aromatic polyester polycarbonate resin composition comprising 0.01 to 3 parts by weight of a metal salt of an organic carboxylic acid having 2 to 3 carbon atoms to 100 parts by weight of an aromatic polyester polycarbonate having a carbon number of 0.67 to 0.25. 2. The aromatic polyester polycarbonate resin composition according to claim 1, wherein the aromatic polyester polycarbonate has an intrinsic viscosity of 0.4 to 1.5. 3. The aromatic polyester polycarbonate resin composition according to claim 1, wherein the aromatic polyester polycarbonate has a glass transition point of 160 to 190°C. 4. The aromatic polyester polycarbonate resin composition according to claim 1, wherein the aromatic polyester polycarbonate has a terminal carboxy group of 10 μ equivalent/g resin or less.