JPS621421B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to a resin composition comprising an aromatic polyetheramide resin mixed with a modifier. General formula () (In the formula, R ₁ to _{R 4} represent hydrogen, a lower alkyl group, a lower alkoxy group, chlorine or bromine, and R ₅ and R ₆ represent hydrogen, a methyl group, an ethyl group, a trifluoromethyl group, or a trichloromethyl group. ,
They may be the same or different. ) The method of obtaining an aromatic polyamide from an aromatic diamine containing an ether bond and an aromatic dicarboxylic acid halide is disclosed in JP-A No. 50-98616 and
It is known from USP.3505288 etc. By the way, the aromatic polyether amide obtained using such a special diamine as a raw material has mechanical properties such as tensile strength, bending strength, and impact strength, thermal properties such as heat distortion temperature and thermal decomposition, arc resistance, It maintains excellent electrical properties such as dielectric constant and dielectric loss, flame resistance, and dimensional stability, and is therefore widely used in general molded products, films, etc. made by injection molding, extrusion molding, press molding, etc. It is expected to have many uses. However, a drawback of this type of aromatic polyether amide is that it has poor moldability. In general, evaluation of moldability is extremely important for plastics, and even if the plastic itself has excellent properties, if the moldability is poor, it will not be possible to economically manufacture the product. Therefore, the excellent properties cannot be fully demonstrated in the product. For example, when manufacturing products by injection molding using polymers with high softening and melting temperatures, high plasticizing temperatures, high injection pressures, and high mold temperatures are required, which only increases costs. However, high plasticization temperatures induce thermal decomposition of the polymer, and high injection pressures cause distortion in the product. In addition, if such strict conditions are not met,
This may cause external defects such as shots, sink marks, and flow marks, and may cause deterioration of mechanical properties. Therefore, it has been desired to improve the moldability of aromatic polyetheramides as well. The present inventors have conducted intensive studies to improve moldability and processability while maintaining the excellent properties of aromatic polyetheramide, and as a result, have arrived at the present invention. That is, an object of the present invention is to provide a resin composition that lowers the melt viscosity and molding temperature of an aromatic polyether amide while maintaining excellent properties such as mechanical properties. Therefore, the resin composition of the present invention has the general formula () (However, 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, metaphenylene, diphenylene ether, diphenylene sulfone, diphenylene, or naphthylene group. ) to an aromatic polyetheramide resin having repeating units represented by the general formula (), (In the formula, R ₇ is hydrogen or a lower alkyl group, R ₈
and R ₉ are hydrogen or a group selected from a hydroxyl group, a lower alkyl group, and a lower alkoxy group, and may be the same or different from each other. ), a carbazole compound represented by the general formula (), (In the formula, R ₁₀ , R ₁₁ and R ₁₂ are groups selected from hydrogen, hydroxyl group, lower alkyl group, amino group, nitro group and lower alkoxy group, and may be the same or different) good.)
Anthraquinone compound represented by the general formula (), (In the formula, Y is

[expression] or

[Formula]. It is characterized by containing at least one aromatic compound selected from polyphenyl compounds shown in ). Examples of the carbazole compound represented by the general formula () used in the present invention include carbazole, N-methylcarbazole, N-ethylcarbazole, N-hydroxymethylcarbazole,
Examples of anthraquinone compounds represented by the general formula () such as 2-methylcarbazole include anthraquinone, 2-methylanthraquinone, 2-
Ethylanthraquinone, 2,3-dimethylanthraquinone, 1,8-dihydroxyanthraquinone, 1,2,7-trihydroxyanthraquinone, 1-aminoanthraquinone, 2-aminoanthraquinone, 1-amino-4-hydroxyanthraquinone, 1,4- Examples of polyphenyl compounds represented by the general formula () such as diamino-5-nitroanthraquinone include metaterphenyl,
Paraterphenyl, orthoterphenyl, paratetraphenyl, etc. In the present invention, the above-mentioned aromatic compound () ~
() can be mixed with the aromatic polyetheramide resin by various known methods. (1) Direct addition to aromatic polyetheramide resin powder; (2) Dissolving or swelling immersion of aromatic polyetheramide resin powder in a low boiling point solvent such as alcohol, ketone, or saturated hydrocarbon; A method of impregnating or adhering the aromatic compound to aromatic polyetheramide resin powder by dissolving the compound, stirring and mixing, and distilling off the solvent, (3) manufacturing process of aromatic polyetheramide resin (4) In the manufacturing process, the aromatic compound is added to the aromatic polyetheramide resin solution after the completion of polymerization. The aromatic compound-containing aromatic polyetheramide resin powder can be obtained by a concentration solidification method, a solvent stripping method, or the like. If the amount of the aromatic compound added is too small, no effect will be observed, and if it is too large, moldability will be significantly improved, but mechanical strength such as tensile strength will be significantly reduced. Therefore, the amount of the aromatic compound added is practically 0.5 to 10 parts by weight per 100 parts by weight of the resin. The aromatic polyetheramide resin used in the present invention is, for example, an aromatic diamine represented by the above general formula (), an aromatic dicarboxylic acid dihalide represented by the following general formula (), XCO-Ar-COX...() ( However, Ar represents a p-phenylene group, m-phenylene group, diphenylene ether group, diphenylene sulfone group, diphenylene group, or naphthylene group, and X represents chlorine or bromine) using a known method, such as a solution. It can be obtained by reaction using a polymerization method or the method shown in JP-A No. 50-98616. Examples of the aromatic diamine represented by the general formula () include 2,2-bis[4-(4-aminophenoxy)phenyl]propane, bis[4-
(4-aminophenoxy)phenyl]methane,
2,2-bis[3,5-dimethyl-4-(4-aminophenoxy)phenyl]propane, 2,2-
Bis[3-methyl-4-(4-aminophenoxy)phenyl]propane, 2,2-bis[3,5
-dibromo-4-(4-aminophenoxy)phenyl]propane, and one or more of these may be used. Examples of the aromatic dicarboxylic acid dihalide represented by the general formula () include terephthalic acid dichloride, isophthalic acid dichloride, diphenyl ether dicarboxylic acid dichloride, diphenyldicarboxylic acid dichloride, naphthalene dicarboxylic acid dichloride, etc.
A mixture of terephthalic acid dichloride and isophthalic acid dichloride is particularly preferably used. It is also possible to use a known polyamide-forming reaction between an amide-forming derivative other than an aromatic dicarboxylic acid dihalide and an aromatic diamine represented by the general formula (), such as high-temperature polycondensation using a phosphorus catalyst or transesterification method. An aromatic polyetheramide resin represented by the formula () can be obtained. Furthermore, by blending other types of polymers into the resin composition of the present invention, its properties can be improved, and antioxidants, ultraviolet absorbers, lubricants,
By coexisting with additives such as flame retardants,
Its properties can also be improved. EXAMPLES Hereinafter, the present invention will be explained in more detail with reference to Examples, but the present invention is not limited thereto. Example 1 A 10% cyclohexanone solution of an acid chloride mixture with a mixing ratio of terephthalic acid dichloride and isophthalic acid dichloride of 1:1 (weight ratio) and 2,2-bis-[4-(4-aminophenoxy)]
20% cyclohexanone solution of phenylpropane
An aromatic polyether amide was produced by contacting and reacting in the presence of a 10% aqueous solution of caustic soda. However, the blending ratio of the acid chloride mixture and the aromatic diamine is equimolar. The reduced viscosity of this in dimethylformamide (0.2g/d) is
It was 0.94 dl/g. To 100 parts by weight of this aromatic polyetheramide resin powder, carbazole was added as shown in Table 1.
The amount shown was added and pelletized at 300 to 320°C using an extruder. Various test pieces were molded from the pellets using an injection molding machine. Table 1 shows the molding conditions and various properties of each pellet.

[Table] Example 2 A 10% cyclohexanone solution of an acid chloride mixture with a mixing ratio of terephthalic acid dichloride/isophthalic acid dichloride of 4:6 (weight ratio), and 2,
An aromatic polyetheramide resin was produced from 2-bis[4-4-(aminophenoxy)phenyl]propane in the same manner as in Example 1. After the polymerization was completed, the resulting polymer solution was separated from the aqueous phase and washed with water, and 5 parts by weight of carbazole was added to 100 parts by weight of the polymer. This was concentrated and solidified to obtain a carbazole-containing aromatic polyetheramide resin composition. I got something. The reduced viscosity was 0.88 d/g. This was pelletized at 300-310°C and molded into test pieces by injection molding, with a tensile strength of 987 Kg/cm ² .
The impact strength was 10.6 kgcm/cm ² and the heat distortion temperature was 175°C. Example 3 N-methylpyrrolidone was prepared from an acid chloride mixture with a mixing ratio of terephthalic acid dichloride/isophthalic acid dichloride of 1:1 (weight ratio) and 2,2-bis[4-(4-aminophenoxy)phenyl]propane. An aromatic polyetheramide resin having a reduced viscosity of 0.77 d/g was obtained using a solution polymerization method as a solvent. 3 parts by weight of carbazole was added to 100 parts by weight of this polymer, pelletized at 300-310°C, and a test piece was molded by injection molding. The tensile strength was 960 Kg/cm ² , the impact strength was 11.0 Kgcm/cm ² , and the heat distortion temperature was 180°C. Example 4 Anthraquinone was added in the amounts shown in Table 2 to aromatic polyetheramide resin powder obtained in exactly the same manner as in Example 1, and pelletized at 300 to 320°C using an extruder. Various test pieces were molded from the pellets using an injection molding machine. Table 2 shows the pellet molding conditions and various properties.

[Table] Example 5 A 10% cyclohexanone solution of an acid chloride mixture with a mixing ratio of terephthalic acid dichloride/isophthalic acid dichloride of 4:6 (weight ratio), and 2,
An aromatic polyetheramide resin was produced from 2-bis[4-4-(aminophenoxy)phenyl]propane in the same manner as in Example 1. After the polymerization was completed, the resulting polymer solution was separated from the aqueous phase and washed with water, and then 5 parts by weight of anthraquinone was added to 100 parts by weight of the polymer. This was concentrated and solidified to obtain an anthraquinone-containing aromatic polyetheramide resin composition. The reduced viscosity was 0.86 d/g.
This was pelletized at 300 to 310°C, and a test piece was molded by injection molding. Tensile strength 922Kg/
cm ² , impact strength 9.9 Kgcm/cm ² , and heat distortion temperature 177°C. Example 6 N-methylpyrrolidone was prepared from an acid chloride mixture with a mixing ratio of terephthalic acid dichloride/isophthalic acid dichloride of 1:1 (weight ratio) and 2,2-bis[4-(4-aminophenoxy)phenyl]propane. An aromatic polyetheramide resin having a reduced viscosity of 0.72 d/g was obtained using a solution polymerization method as a solvent. 3 parts by weight of anthraquinone was added to 100 parts by weight of this polymer, pelletized at 300-310°C, and a test piece was molded by injection molding.
Tensile strength 955Kg/cm ² , Impact strength 10.2Kgcm/cm ² ,
The heat distortion temperature was 178°C. Example 7 Paraterphenyl was added to the aromatic polyetheramide resin powder obtained in exactly the same manner as in Example 1 in Table 3.
The amount shown was added and pelletized at 300 to 320°C using an extruder. Various test pieces were molded from the pellets using an injection molding machine. Table 3 shows the pellet molding conditions and various properties.

[Table] Example 8 A 10% cyclohexanone solution of an acid chloride mixture with a mixing ratio of terephthalic acid dichloride/isophthalic acid dichloride of 4:6 (weight ratio), and 2,
An aromatic polyetheramide resin was produced from 2-bis[4-4-(aminophenoxy)phenyl]propane in the same manner as in Example 1. After polymerization,
After washing the polymer solution obtained by separating it from the aqueous phase with water,
5 parts by weight of metaterphenyl was added to 100 parts by weight of the polymer. This was concentrated and solidified to obtain a metaterphenyl-containing aromatic polyetheramide resin composition. The reduced viscosity was 0.83 d/g.
This was pelletized at 300-310°C and molded into test pieces by injection molding, with a tensile strength of 860 kg/
cm ² , impact strength 9.8 Kgcm/cm ² , heat distortion temperature 173℃
It was hot. Example 9 N-methylpyrrolidone was prepared from an acid chloride mixture with a mixing ratio of terephthalic acid dichloride/isophthalic acid dichloride of 1:1 (weight ratio) and 2,2-bis[4-(4-aminophenoxy)phenyl]propane. An aromatic polyether amide having a reduced viscosity of 0.72 d/g was obtained using a solution polymerization method as a solvent. 3 parts by weight of paraterphenyl was added to 100 parts by weight of this polymer, pelletized at 300-310°C, and a test piece was molded by injection molding. The tensile strength was 876 Kg/cm ² , the impact strength was 8.8 Kgcm/cm ² , and the heat distortion temperature was 172°C. Example 10 3 parts by weight of N-ethylcarbazole was added to 100 parts by weight of aromatic polyetheramide resin powder obtained in exactly the same manner as in Example 1, and 300 to 300 parts by weight was added using an extruder.
It was pelletized at 320°C. Various test pieces were molded from the pellets using an injection molding machine. Molding temperature
360-370℃. Injection pressure 1300Kg/cm ² . Tensile strength 980
Kg/ ^cm2 , elongation 16%, Izotsu impact strength 10.6Kg
cm/cm ² , and the heat distortion temperature was 175°C. Example 11 5 parts by weight of 2-ethylanthraquinone was added to 100 parts by weight of aromatic polyetheramide resin powder obtained in exactly the same manner as in Example 1, and 300 parts by weight was added using an extruder.
Pelletized at ~320°C. This pellet was molded using an injection molding machine at a molding temperature of 370°C and an injection pressure of 1300°C.
Various test pieces were molded at Kg/cm ² . tensile strength
960Kg/cm ² , elongation 15%, Izotsu impact strength 11.2
Kgcm/cm ² , and the heat distortion temperature was 176°C.

Claims (1)

[Claims] 1 General formula () (However, 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, metaphenylene, diphenylene ether, diphenylene sulfone, diphenylene, or naphthylene group. ) to an aromatic polyetheramide resin having repeating units represented by the general formula (), (In the formula, R ₇ is hydrogen or a lower alkyl group, R ₈
and R ₉ are hydrogen or a group selected from a hydroxyl group, a lower alkyl group, and a lower alkoxy group, and may be the same or different from each other. ), a carbazole compound represented by the general formula (), (In the formula, R ₁₀ to R ₁₂ are a group selected from hydrogen, a hydroxyl group, a lower alkyl group, an amino group, a nitro group, and a lower alkoxy group, and may be the same or different from each other.) Anthraquinone compound represented by the general formula (), (In the formula, Y is [Formula] or [Formula].) Aromatic polyetheramide resin characterized by being blended with at least one aromatic compound selected from polyphenyl compounds represented by [Formula] or [Formula]. Composition. 2. The aromatic polyetheramide resin composition according to claim 1, wherein the aromatic compound is a carbazole in which _R7 to _R9 in formula () are hydrogen. 3 Aromatic compounds are R ₁₀ , R ₁₁ and
The aromatic polyetheramide resin composition according to claim 1, characterized in that R ₁₂ is anthraquinone represented by hydrogen. 4. The aromatic polyetheramide resin composition according to claim 1, wherein the aromatic compound is paraterphenyl. 5. The aromatic polyetheramide resin composition according to claim 1, wherein the aromatic compound is blended in an amount of 0.5 to 10 parts by weight per 100 parts by weight of the aromatic polyetheramide resin. 6. The aromatic polyetheramide resin composition according to claim 2, wherein the amount of the aromatic compound blended is 0.5 to 10 parts by weight based on 100 parts by weight of the aromatic polyetheramide resin.