JPS636111B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to a novel thermoplastic resin composition,
More specifically, the present invention relates to a novel resin composition containing a polyether amide and an aromatic polyester copolymer and having excellent moldability, chemical properties, mechanical properties, and heat resistance. A polyether amide produced from an aromatic dibasic acid or a functional derivative thereof and a diamine containing an ether bond or a functional derivative thereof is known from, for example, JP-A-52-23198. Such polyetheramides have various properties such as mechanical strength, arc resistance, electrical properties such as dielectric loss factor, chemical resistance, flame retardance, abrasion resistance, fatigue resistance, and dimensional stability. It is excellent. However, molding this resin requires high temperatures of around 350°C, which is close to its decomposition temperature, and one of its weaknesses is that the allowable working temperature range is narrow. On the other hand, aromatic polyester copolymers produced from terephthalic acid, isophthalic acid, or their functional derivatives, and dihydric phenols have excellent properties such as impact resistance and flame retardancy, but have poor water resistance. It was inferior, and its field of application was limited. Therefore, the inventors of the present invention have made extensive studies to improve these problems, and have completed the present invention. An object of the present invention is to provide a novel resin composition having excellent properties and improved moldability. That is, the present invention provides [A] General formula () (In formula (), R ₁ to _{R 4} represent hydrogen, a lower alkyl group, a lower alkoxy group, chlorine, or bromine, and may be the same or different from each other. _{R 5} and R ₆ are hydrogen , methyl group, ethyl group,
They are a trifluoromethyl group or a trichloromethyl group, and may be the same or different. Ar represents a p-phenylene group, m-phenylene group, oxydiphenylene group, sulfonyldiphenylene group, biphenylene group, or naphthylene group) and [B] terephthalic acid or A mixture of its functional derivative and isophthalic acid or its functional derivative (however, the molar ratio of terephthalic acid group to isophthalic acid group is 9:1 to 1:9) and the general formula () _{Bisphenols represented by _ _ _ _ _} The present invention relates to a resin composition containing an aromatic polyester copolymer obtained from lower alkyl or halogen, which may be the same or different. The polyether amide having a repeating unit represented by the general formula () used in the present invention is
Aromatic dibasic acids or their functional derivatives and general formula () (In the formula (), R ₁ to _{R 6} mean the same as in the formula ()) and are obtained by a polycondensation reaction. Aromatic dibasic acids and their functional derivatives used herein include terephthalic acid, isophthalic acid, oxydibenzoic acid, biphenyl dicarboxylic acid, naphthalene dicarboxylic acid, diphenyl sulfone dicarboxylic acid, their dichlorides, their These include dibromide, their alkyl esters, and their aryl esters. Further, as a specific example of the diamic acid represented by the general formula (), 2,2-bis[4-(4-
Aminophenoxy)phenyl]propane, 2.2
-bis[3-methyl-4-(4-aminophenoxy)phenyl]propane, 2,2-bis[3-chloro-4-(4-aminophenoxy)phenyl]
Propane, 2,2-bis[3-bromo-4-(4
-aminophenoxy)phenyl]propane, 2.
2-bis[3-ethyl-4-(4-aminophenoxy)phenyl]propane, 2,2-bis[3-
Propyl-4-(4-aminophenoxy)phenyl]propane, 2,2-bis[3-isopropyl-4-(4-aminophenoxy)phenyl]propane, 2,2-bis[3-butyl-4-(4-aminophenoxy) ) Phenyl]propane, 2,2-
Bis[3-sec-butyl-4-(4-aminophenoxy)phenyl]propane, 2,2-bis[3-
Methoxy-4-(4-aminophenoxy)phenyl]propane, 2,2-bis[3-ethoxy-4
-(4-aminophenoxy)phenyl]propane,
2,2-bis[3,5-dimethyl-4-(4-aminophenoxy)phenyl]propane, 2,2-
Bis[3,5-dichloro-4-(4-aminophenoxy)phenyl]propane, 2,2-bis[3,5-dibromo-4-(4-aminophenoxy)phenyl]propane, 2,2-bis[3. 5
-dimethoxy-4-(4-aminophenoxy)phenyl]propane, 2,2-bis[3-chloro-
4-(4-aminophenoxy)-5-methylphenyl]propane, 1,1-bis[4-(4-aminophenoxy)phenyl]ethane, 1,1-bis[3-methyl-4-(4-aminophenoxy)phenyl] Ethane, 1,1-bis[3-chloro-4-
(4-aminophenoxy)phenyl]ethane,
1,1-bis[3-bromo-4-(4-aminophenoxy)phenyl]ethane, 1,1-bis[3
-ethyl-4-(4-aminophenoxy)phenyl]ethane, 1,1-bis[3-propyl-4-
(4-aminophenoxy)phenyl]ethane,
1,1-bis[3-isopropyl-4-(4-aminophenoxy)phenyl]ethane, 1,1-bis[3-butyl-4-(4-aminophenoxy)
Phenyl]ethane, 1,1-bis(3-sec-butyl-4-(4-aminophenoxy)phenyl)
Ethane, 1,1-bis[3-methoxy-4-(4
-aminophenoxy)phenyl]ethane, 1.1
-bis[3-ethoxy-4-(4-aminophenoxy)phenyl]ethane, 1,1-bis[3,5
-dimethyl-4-(4-aminophenoxy)phenyl]ethane, 1,1-bis[3,5-dichloro-4-(4-aminophenoxy)phenyl]ethane, 1,1-bis[3,5-dibromo-4 -(4
-aminophenoxy)phenyl]ethane, 1.1
-bis[3,5-dimethoxy-4-(4-aminophenoxy)phenyl]ethane, 1,1-bis[3-chloro-4-(4-aminophenoxy)phenyl-5-methylphenyl]ethane, bis[4-
(4-aminophenoxy)phenyl]methane, bis[3-methyl-4-(4-aminophenoxy)
phenyl]methane, bis[3-chloro-4-(4
-aminophenoxy)phenyl]methane, bis[3-bromo-4-(4-aminophenoxy)phenyl]methane, bis[3-ethyl-4-(4-aminophenoxy)phenyl]methane, bis[3-
Propyl-4-(4-aminophenoxy)phenyl]methane, bis[3-isopropyl-4-(4
-aminophenoxy)phenyl]methane, bis[3-butyl-4-(4-aminophenoxy)phenyl]methane, bis[3-sec-butyl-4-(4
-aminophenoxy)phenyl]methane, bis[3-methoxy-4-(4-aminophenoxy)phenyl]methane, bis[3-ethoxy-4-(4
-aminophenoxy)phenyl]methane, bis[3,5-dimethyl-4-(4-aminophenoxy)phenyl]methane, bis[3,5-dichloro-4-(4-aminophenoxy)phenyl]methane, bis[3,5 -dibromo-4-(4-aminophenoxy)phenyl]methane, bis[3,5-
Dimethoxy-4-(4-aminophenoxy)phenyl]methane, bis[3-chloro-4-(4-aminophenoxy)-5-methylphenyl]methane,
1.1.1.3.3.3-hexafluoro-2.
2-bis[4-(4-aminophenoxy)phenyl]propane, 1,1,1,3,3,3-hexachloro-2,2-bis[4-(4-aminophenoxy)phenyl]propane, 3,3- Screw [4-
(4-aminophenoxy)phenyl]pentane,
1,1-bis[4-(4-aminophenoxy)phenyl]propane, 1,1,1,3,3,3-hexafluoro-2,2-bis[3,5-dimethyl-4-(4-aminophenoxy) ) phenyl] propane, 1, 1, 1, 3, 3, 3-hexachloro-
2,2-bis[3,5-dimethyl-4-(4-aminophenoxy)phenyl]propane, 3,3-
Bis[3,5-dimethyl-4-(4-aminophenoxy)phenyl]pentane, 1,1-bis[3,5-dimethyl-4-(4-aminophenoxy)phenyl]propane, 1,1,1,3, 3.
3-hexafluoro-2,2-bis[3,5-dibromo-4-(4-aminophenoxy)phenyl]
Propane 1,1,1,3,3,3-hexachloro-2,2-bis[3,5-dibromo-4-(4-
Aminophenoxy)phenyl]propane, 3.3
-bis[3,5-dibromo-4-(4-aminophenoxy)phenyl]pentane, 1,1-bis[3,5-dibromo-4-(4-aminophenoxy)phenyl]propane, 2,2-bis[4 −
(4-aminophenoxy)phenyl]butane,
2,2-bis[3-methyl-4-(4-aminophenoxy)phenyl]butane, 2,2-bis[3,5-dimethyl-4-(4-aminophenoxy)phenyl]butane, 2,2-bis[ 3.5-
Dibromo-4-(4-aminophenoxy)phenyl]butane 1,1,1,3,3,3-hexafluoro-2,2-bis[3-methyl-4-(4-aminophenoxy)phenyl]propane, etc. . Among these, 2,2-bis[4-(4-aminophenoxy)phenyl]propane is a representative example. If necessary, two or more of the above diamines can be used in combination, or other known aromatic diamines or aliphatic diamines can also be used in combination. Therefore, the polyether amide of component [A] may contain repeating units other than the repeating units represented by the general formula (). Examples of other aromatic diamines include m-phenylenediamine, p-phenylenediamine, 4,4'-diaminodiphenylmethane, and 4.
4'-diaminodiphenyl ether, 4,4'-diaminodiphenyl sulfone, 4,4'-diaminodiphenylpropane-2,2,4,4'-diaminodiphenyl sulfide, 1,5-diaminonaphthalene , 4,4'-diaminodiphenylethane, m-tolylenediamine, p-tolylenediamine,
3,4'-diaminobenzanilide, 1,4-diaminonaphthalene, 3,3'-dichloro-4,4'-diaminodiphenyl, benzidine, 4,4'-diaminodiphenylamine, 4,4'-diamino Diphenyl-N-methylamine, 4,4'-diaminodiphenyl-N-phenylamine, 3,3'-diaminodiphenyl sulfone, 4,4'-diaminodiphenyldiethylsilane, 4,4'-diaminodiphenyl Examples include silane, 4,4'-di(p-aminophenoxy)diphenylsulfone, and 4,4'-di(m-aminophenoxy)diphenylsulfone, and at least one of these is used. These are preferably used in an amount of 50 mol % or less in the aromatic diamine. If it exceeds 50 mol%, there is a risk that molding processability will deteriorate. In addition, known aliphatic diamines include piperazine, hexamethylene diamine, heptamethylene diamine, octamethylene diamine, nonamethylene diamine, decamethylene diamine, p-xylylene diamine, m-xylylene diamine, tetramethylene diamine, and dodecamethylene diamine. diamine,
4,4-dimethylheptamethylenediamine, 3-
Examples include methylheptamethylenediamine, 2,11-diaminododecane, and 1,12-diaminooctadecane. It is preferably used in an amount of not more than 30 mol %, particularly preferably not more than 10 mol %, of the total diamine component. When reacting the above diamine with an aromatic dibasic acid or its functional derivative, the method already used for the reaction between a publicly known amine and an acid can be directly adopted, and there are no particular limitations on the conditions. isn't it. For example, this can be achieved by an interfacial polycondensation method or a solution polycondensation method. When aromatic dicarboxylic acid dihalides are used, known water-soluble neutralizing agents described below are used in the interfacial polycondensation reaction, and known tertiary amines such as triethylamine, pyridine, tributylamine, and pyridine are used in the solution polymerization method. A neutralizing agent consisting of is used. A reaction solvent is used in the interfacial polycondensation method and the solution polymerization method, and this solvent may be a diamine whose main component is an aromatic diamine, an aromatic dibasic acid, or a functional derivative thereof (preferably an aromatic dicarboxylic acid dihalide). It must be possible to dissolve at least one of them, preferably both. A representative example of a particularly effective reaction solvent for use in the present invention is cyclohexanone. Some examples of other solvents that can be used include methylene chloride, trichlene,
Berkrene, ethane dichloride, nitrobenzene, chloroform, carbon tetrachloride, diisobutyl ketone,
Acetophenone, p-methylacetophenone,
N/N-dimethylformamide, N/N-dimethylacetamide, N/N-diethylformamide, N/N-diethylacetamide, N/N-dimethylmethoxyacetamide, dimethylsulfoxide, N-methyl-2-pyrrolidone, pyridine,
Examples include dimethylsulfone, hexamethylphosphoramide, tetramethylenesulfone, dimethyltetramethylenesulfone, and the like. Two or more reaction solvents may be used in combination, if necessary, to facilitate the dissolution operation. Furthermore, in order to obtain a product with as high a molecular weight as possible, it is preferable to use a highly dehydrated solvent for dissolving the aromatic dibasic acid or its functional derivative (preferably aromatic dicarboxylic acid dihalide). especially,
When carrying out solution polycondensation using a polar solvent such as N/N-dimethylformamide, N/N-dimethylacetamide, or N-methyl-2-pyrrolidone, 5 to 10% by weight of lithium chloride, calcium chloride, Synthesis by adding rhodan calcium or the like is advantageous because the solubility increases significantly. In addition to this co-solvent, all other known co-solvents as described below are effective. Further, according to research conducted by the present inventors, the following effective reaction method was discovered. That is, unlike the usual interfacial polycondensation method in which diamines are dissolved in an alkaline aqueous solution, the diamine is dispersed in an alkaline aqueous solution, and a solution of an aromatic dicarboxylic acid dihalide dissolved in an organic solvent is added thereto. This is a method of causing a reaction. By polymerizing in this method, the resulting halogenated aqueous solution is neutralized with a neutralizing agent and becomes water and the halogenated metal, which dissolves in water.If the polymer is precipitated from the organic phase, hydrochloric acid or a neutralizing agent Since no residue remains, this gives favorable results to various properties of the polymer. In this case, the amount of alkali used is at least 1.3 equivalents, preferably 1.0 to 1.1 equivalents, of the aromatic dicarboxylic acid dihalide. Examples of the neutralizing agent used here include, but are not limited to, sodium hydroxide, potassium hydroxide, sodium carbonate, sodium hydrogen carbonate, etc. that are soluble in water. Further, the amount of water is sufficient as long as the above-mentioned neutralizing agent is sufficiently dissolved at room temperature. Of course, using more than that will not affect the reaction. Further, the reaction temperature is in a state where water is a liquid, that is, in the range of 0 to 100°C, preferably 5 to 60°C. The above polycondensation method can be carried out, for example, by the following procedure. First, a neutralizing agent is dissolved in an appropriate amount of water, and an aromatic diamine is added thereto. Furthermore, a solution of aromatic dicarboxylic acid halide dissolved in an organic solvent is added and reacted. At this time, it is preferable to carry out the reaction in a state where the aromatic diamine is dispersed in the alkaline aqueous solution by stirring. Next, only the organic phase is separated and placed in an organic solvent that does not dissolve the polymer and is easily compatible with the reaction solvent to precipitate the polymer. By filtering this, an aromatic polyetheramide resin is obtained. In the present invention, the aforementioned various aromatic diamines and aliphatic diamines can be used as neutralizing agents. In this case, the amount may be increased at a rate of 1 equivalent or less (an amount not involved in the reaction). In addition, a known polyamide-forming reaction between an amide-forming derivative other than aromatic dicarboxylic acid dihalide and a diamine whose main component is an aromatic diamine represented by the general formula (), such as high-temperature polycondensation or transesterification using a phosphorus catalyst. An aromatic polyetheramide resin having a repeating unit represented by the general formula () can also be obtained by a method such as the following method. When producing polyetheramide, it is preferable to use the aromatic dibasic acid or its functional derivative in an amount of 0.9 to 1.2 equivalents per equivalent of diamine. Outside this range, it becomes difficult to obtain a high molecular weight product. Particularly preferably, the aromatic dibasic acid or its functional derivative is used in an amount of 0.97 to 1.03 equivalents per equivalent of the diamine. Next, the aromatic polyester copolymer described above, which is the other component of the resin composition of the present invention, is a mixture of terephthalic acid or its functional derivative and isophthalic acid or its functional derivative (however, the terephthalic acid group and the isophthalic acid group The molar ratio of the groups is 9:1 to 1:
9) and a bisphenol represented by the general formula (). Specific examples of such bisphenols represented by the general formula () include 4,4'-dihydroxydiphenyl ether, bis(4-hydroxy-
2-methylphenyl) ether, bis(4-hydroxy-3-chlorophenyl) ether, bis(4-hydroxyphenyl) sulfide, bis(4-hydroxyphenyl) sulfone, bis(4-hydroxyphenyl) ether
-hydroxyphenyl)ketone, bis(4-hydroxyphenyl)methane, bis(4-hydroxy-3,5-dibromophenyl)methane, bis(4-hydroxyphenyl)methane,
-Hydroxy-3,5-dichlorophenylmethane, 2,2-bis(4-hydroxy-3-methylphenyl)propane, 2,2-bis(4-hydroxy-3-chlorophenyl)propane, 2,2-
Bis(4-hydroxy-3,5-dichlorophenyl)propane, 2,2-bis(4-hydroxy-
Examples include 3,5-dibromophenyl)propane. Those having a bilaterally symmetrical structural formula are preferably used. The most commonly produced and representative ones are:
2,2-bis(4-hydroxyphenyl)propane or bisphenol A. If necessary, two or more of the above bisphenols can be used together, or a small amount of other dihydric phenols can also be used together. For example, 4,4'-dihydroxydiphenyl,
Mixtures of dihydroxynaphthalenes such as 2,6-dihydroxynaphthalene, hydroquinone, resorcinol, etc. can be used. In the present invention, the blending ratio of the polyether amide as the component [A] and the aromatic polyester copolymer as the component [B] can be freely selected within the range of 95/5 to 5/95 in terms of weight ratio. The range of /20 to 20/80 is more preferable. [A]/[B] has a weight ratio of 95/
If it exceeds 5, the effect of expanding the molding temperature range by using the aromatic polyester copolymer will be small, and if it is less than 5/95, the effect of improving the water resistance of the aromatic polyester copolymer will be small. The method of mixing the aromatic polyether amide and the aromatic polyester copolymer when producing the resin composition of the present invention is not limited in any way as long as it is a method that allows both to be substantially uniformly dispersed. The mixture may be mixed in a vacuum or melt-mixed. Incomplete or non-uniform dispersion of both components is undesirable because the mechanical performance of the molded article will be impaired. Furthermore, the resin composition of the present invention can contain a thermal decomposition inhibitor, an antioxidant, or an ultraviolet absorber in order to improve its heat resistance and weather resistance. In addition, plasticizers, pigments, lubricants, etc. may be added. The resin composition of the present invention is prepared into powder, chips, or other shapes, and is made into a resin composition that is more relaxed than aromatic polyether amide by a commonly known plastic molding method such as press molding, injection molding, or extrusion molding. Shaped according to conditions. The molded article has excellent impact strength, tensile strength, bending strength, abrasion resistance, and electrical properties, and is flame retardant. Therefore,
This resin composition is useful as an engineering plastic, and is used in the manufacture of various products that require high performance, such as gears, bearings, and electrical component containers. Next, the present invention will be specifically explained with reference to Examples. Example 1 (A) Production of aromatic polyetheramide In a reactor equipped with a stirrer, a thermometer, and a dropping funnel, 154.8 g of sodium hydroxide was added to 800 g of water.
Dissolve in ml and prepare. Next, 2.2-bis [4-
(4-aminophenoxy)phenyl]propane
656 g was dissolved in 3.4 Kg of cyclohexanone, added to the reactor, and cooled to -2°C. On the other hand, a solution prepared by dissolving 164 g of terephthalic acid dichloride and 164 g of isophthalic acid dichloride in 2.4 kg of cyclohexanone is added dropwise while maintaining the liquid temperature in the vessel not to exceed 10°C. Three hours after the start of the dropwise addition, 16.9 g of benzoyl chloride was dissolved in 500 g of cyclohexanone and added. After another two hours,
The reaction solution is poured into methanol to separate the polymer. (B) Add U polymer (aromatic polyester copolymer manufactured by Unitika Co., Ltd. U-1060) to the aromatic polyether amide pellets obtained in (A) above. The phenol component is bisphenol A, terephthalic acid group and The molar ratio of isophthalic acid groups is approximately 1:1) were mixed in the weight ratio shown in Table 1, and the mixture was kneaded using a 40 mmφ extruder at a die temperature of 300° C. to form granules. 4.5 ounces of pellets of this resin composition,
A predetermined test piece was molded using an in-line screw type injection molding machine, and a characteristic test was conducted. The results obtained are shown in Table 1. Note that the injection molding pressure was 1100 Kg/cm ² .

[Table] When the tensile test pieces No. 1 to 6 were left in an atmosphere of 60℃ and 98% RH or higher for one month, no decrease in strength was observed. When tested, the tensile strength was
It decreased to 500Kg/cm ² . Example 2 (A) Manufacturing method of aromatic polyetheramide copolymer 10 Set a stirrer, thermometer, and dropping funnel in a separable flask, and dissolve 171.8 g of NaOH in 800 ml of water and put it into the flask. next,
2,2-bis-[4-(4-aminophenoxy)
Phenyl] 594 g of propane and 66 g of 4,4'-diaminodiphenyl ether were mixed with cyclohexanone.
Dissolve it to 3.4Kg and pour it into the flask above.
Cool to -2°C. On the other hand, 182 g of terephthalic acid dichloride and isophthalic acid dichloride
Dissolve 182g in 2.4Kg of cyclohexanone. Pour this acid chloride solution through the dropping funnel, making sure that the reaction temperature does not exceed 10°C. 3 hours after the start of dropping, benzoyl chloride
Dissolve 18.9g in 500g of cyclohexanone and add. After another 2 hours, the reaction solution is poured into methanol to isolate the polymer. (B) The same U polymer as in Example 1 was mixed in the weight ratio shown in Table 2 to the aromatic polyetheramide pellets obtained in (A) above, and Example 1
Characteristic tests were conducted in the same manner as above.

[Table] Example 3 (A) Production of aromatic polyetheramide Using the raw materials with the following composition, the above Example 1 (A)
Aromatic polyetheramide powder was obtained in the same manner as in the above.

[Table] (B) Production of aromatic polyester copolymer A methylene chloride solution containing a mixture of 30% by weight of terephthalic acid dichloride and 70% by weight of isophthalic acid dichloride and bisphenol A.
An aromatic polyester copolymer powder was obtained by an interfacial polycondensation method using an alkaline aqueous solution of . This copolymer had a logarithmic viscosity of about 0.62. (C) After uniformly mixing the aromatic polyether amide powder obtained in the above (A) and the aromatic polyester copolymer powder obtained in the above (B) using a super mixer, the mixture was mixed using a 40 mmφ extruder. It was granulated using a die temperature of 300°C. The obtained composition was injection molded to prepare test pieces, and physical property tests were conducted. Table 3 shows the results obtained.
Shown below.

[Table] As is clear from the above, according to the present invention,
A resin composition having a wide molding temperature range (excellent molding processability) and excellent water resistance can be obtained, and the resin composition has other excellent mechanical properties.

Claims (1)

[Claims] 1 [A] General formula () (In formula (), R ₁ to _{R 4} represent hydrogen, a lower alkyl group, a lower alkoxy group, chlorine, or bromine, and may be the same or different from each other. _{R 5} and R ₆ are hydrogen , methyl group, ethyl group,
They are a trifluoromethyl group or a trichloromethyl group, and may be the same or different. Ar represents a p-phenylene group, m-phenylene group, oxydiphenylene group, sulfonyldiphenylene group, biphenylene group, or naphthylene group) and [B] terephthalic acid or A mixture of its functional derivative and isophthalic acid or its functional derivative (however, the molar ratio of terephthalic acid group to isophthalic acid group is 9:1 to 1:9) and the general formula () _{Bisphenols represented by _ _ _ _ _} A resin composition containing an aromatic polyester copolymer obtained by reacting hydrogen, lower alkyl, or halogen, which may be the same or different. 2. The resin composition according to claim 1, wherein the bisphenol represented by the general formula () is 2,2-bis(4-hydroxyphenyl)propane. 3 The polyetheramide has general formula () in which Ar is a p-phenylene group and/or m
- phenylene group, R ₁ to R ₄ are hydrogen,
3. The resin composition according to claim 1 or 2, which is a polyether amide having repeating units in which R ₅ and R ₆ are methyl groups.