JPS6229461B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to a polyamide resin composition comprising an aromatic polyether amide copolymer blended with a polyamide comprising an aromatic dibasic acid component and an aliphatic diamine component. Aromatic polyetheramides produced from aromatic dibasic acids or functional derivatives thereof and diamines containing ether bonds or functional derivatives thereof are known from JP-A-52-23198 and the like. Such aromatic polyetheramides have excellent electrical properties such as mechanical strength, arc resistance, and dielectric loss factor, as well as chemical resistance, flame retardance, abrasion resistance, and dimensional stability. ing. However, molding this resin requires a high temperature of around 350°C, which is close to its decomposition temperature, and the narrow allowable temperature range has been a problem in its application. Therefore, the inventors of the present invention have made extensive studies to improve this problem, and have completed the present invention. That is, it is an object of the present invention to provide an aromatic polyetheramide resin composition having excellent properties and improved moldability. Its characteristics are: [A] General formula () (In the 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. _{R 5} and R ₆ are hydrogen, a methyl group, , ethyl group, trifluoromethyl group, or trichloromethyl group, which 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 general formula () (In the formula, X is -CH ₂ -, -O-, or -SO ₂ -
, and is bonded to the benzene nucleus at the meta or para position to the nitrogen atom, and Ar has the above general formula ()
Same as Ar in . ) [B] General formula () (In the formula, Ar' represents a p-phenylene group, m-phenylene group, 4,4'-oxydiphenylene group, biphenylene group, sulfonyldiphenylene group, or naphthylene group, and Y represents a carbon number of 5 to 10. It is made by blending 1 to 100 parts by weight of a polyamide represented by (representing an alkylene group). The general formula () used in the present invention
Aromatic polyetheramides consisting of repeating units represented by and () are composed of aromatic dibasic acids or their functional derivatives and general formula ( (In the 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. _{R 5} and R ₆ are hydrogen, a methyl group, , represents an ethyl group, a trifluoromethyl group, or a trichloromethyl group, and may be the same or different.) and general formula () (In the formula, X is -O-, -CH ₂ -, or -SO ₂ -
and the amino group is bonded to the benzene nucleus at the meta or para position relative to X. ) and 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 and their dichlorides or dibromides and alkyls. or aryl esters. Further, as specific examples of diamines 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-bis[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,
Examples include 3-hexafluoro-2,2-bis[3-methyl-4-(4-aminophenoxy)phenyl]propane. Among these, 2,2-bis[4-(4-aminophenoxy)phenyl]propane is a representative example. Note that, if necessary, it is also possible to use two or more of the above diamines in combination. Further, specific examples of the diamines represented by the general formula () include 4,4'-diaminodiphenylmethane, 3,3'-diaminodiphenyl sulfone, 4,4'-diaminodiphenyl sulfone, 4,
4'-diaminophenyl ether, etc., but the commonly produced and representative ones are 4,4'-diaminodiphenyl methane and 4,4'-diaminodiphenyl ether, with the latter being more preferred in terms of heat resistance. It is preferably used in a proportion of 2 to 30 mol % based on the total diamines. When polycondensing the aromatic dibasic acids or their functional derivatives with the diamines represented by the general formulas () and (), a solution polymerization method, a melt polymerization method, or a method related to Japanese Patent Publication No. 54-21237 may be used. It can be by any method, such as the method shown. Next, the polyamide having repeating units represented by the above-mentioned general formula (), which is the other component of the resin composition of the present invention, can be molded without impairing the excellent properties of the aromatic polyether amide. It acts to improve workability. Such polyamides include, for example, poly(iminohexamethyleneiminoterephthaloyl), poly(iminotrimethylhexamethyleneiminoterephthaloyl), poly(iminotrimethylheptanediyliminoterephthaloyl), poly(iminohexamethyleneiminoisophthaloyl). poly(iminotrimethylhexamethyleneiminoisophthaloyl), poly(iminodimethylpentamethyleneimino(oxydibenzoyl)), poly[iminononanediylimino(oxydibenzoyl)], poly(iminodimethylpentamethyleneiminocarbonyl) biphenylenecarbonyl), poly(iminomethylbutaniminocarbonylnaphthylenecarbonyl), poly(iminodimethylpentamethyleneiminocarbonylnaphthylenecarbonyl), and the like. These polyamides are made of the corresponding diamines, that is, aliphatic diamines containing 5 to 10 carbon atoms in the molecule, and aromatic dibasic acids or their functional derivatives, which were mentioned earlier as raw materials for the synthesis of aromatic polyetheramides. can be produced by polycondensation reaction using a well-known method. In the present invention, the polyamide having repeating units represented by the general formula () is an aromatic polyether amide copolymer 100 comprising repeating units represented by the general formulas () and ().
It is blended in an amount of 1 to 100 parts by weight. When the amount of polyamide exceeds 100 parts by weight, the heat resistance of the resin composition decreases, and when it is less than 1 part by weight, the moldability of the composition is only slightly improved. From the viewpoint of moldability and heat resistance,
The polyamide is preferably used in an amount of 5 to 50 parts by weight based on 100 parts by weight of the aromatic polyetheramide copolymer. The method of mixing the aromatic polyetheramide copolymer and polyamide when producing the resin composition of the present invention is not limited in any way as long as both can be substantially uniformly dispersed, for example, mixing in solid form. or may be 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 in the form of powder, chips, or other shapes, and is molded using commonly known plastic molding methods such as press molding, injection molding, and extrusion molding. Molded under relaxed conditions. The molded product is
It 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. Synthesis Example 1 Production of aromatic polyetheramide copolymer 171.8 g of sodium hydroxide dissolved in 800 ml of water was charged into a reactor equipped with a stirrer, a thermometer, and a dropping funnel. Next, 2,2-bis [4-(4-
594 g of aminophenoxy)phenyl]propane and 66 g of 4,4'-diaminodiphenyl ether were 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 182 g of terephthalic acid dichloride and 182 g of isophthalic acid dichloride in 2.4 kg of cyclohexanone,
While keeping the liquid temperature in the container below 10℃,
Drip. Three hours after the start of the dropwise addition, 18.9 g of benzoyl chloride was dissolved in 500 g of cyclohexanone and added. After another 2 hours, the reaction solution was poured into methanol, the polymer was separated, and an aromatic polyetheramide copolymer was produced. Example 1 Trogamide T was added to the aromatic polyetheramide copolymer pellets obtained in Synthesis Example 1.
(manufactured by Daynamite Nobel. Acid component: terephthalic acid, amine component: 2,2,4-trimethylhexamethylenediamine and 2,4,4-trimethylhexamethylenediamine) pellets at the weight ratio shown in Table 1. The mixture was mixed and granulated using a 40 mmφ extruder at a die temperature of 300°C. Pellets of this resin composition were molded into predetermined test pieces using a 4.5 oz screw ^- type injection molding machine, and property tests were conducted. The obtained results are the first
Shown in the table. Note that the injection molding pressure was 1100 Kg/cm ² .

[Table] Example 2 Using a super mixer, powders of polyhexamethylene terephthalamide and poly(5-methyl-nonamethylene terephthalamide) were added to the aromatic polyetheramide copolymer powder obtained in the above reference example. After uniformly mixing the mixture, the mixture was granulated using a 40 mmφ extruder at a die temperature of 300°C. The obtained composition was injection molded to prepare test pieces, and physical property tests were conducted on the test pieces. The results obtained are shown in Table 2.

[Table] Synthesis Example 2 An aromatic polyetheramide copolymer was produced in the same manner as in Synthesis Example 1 using the raw materials having the following composition.

【table】

【table】

[Table] Example 3 80 parts of the polyetheramide copolymer obtained in Synthesis Example 2 was mixed with 20 parts of Trogamide T, and the mixture was granulated using a 40 mmφ extruder. Using this pellet,
Injection molding was performed at 330°C and 1100 kg/cm ² to prepare test pieces. Bending strength 1200Kg/cm ² , Izotsu impact strength 9.6
It was Kgcm/ ^cm2 . Synthesis Example 3 An aromatic polyetheramide copolymer was produced in the same manner as in Synthesis Example 1 using the raw materials having the following composition.

【table】

[Table] Example 4 80 parts of the polyetheramide copolymer obtained in Synthesis Example 3 was mixed with 20 parts of Trogamide T, and the mixture was granulated using a 40 mmφ extruder. Using this pellet,
Injection molding was performed at 330°C and 1100 kg/cm ² to prepare test pieces. Bending strength 1220Kg/cm ² , Izotsu impact strength 9.2
It was Kgcm/ ^cm2 . From the above, it is recognized that the present invention can provide a resin composition that has improved moldability and has properties substantially equivalent to those of aromatic polyetheramide.

Claims (1)

[Claims] 1 [A] General formula () (In the 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, a methyl group, an ethyl group, a trifluoromethyl group or a trichloromethyl group, and may be the same or different. Ar is p-
It represents a phenylene group, m-phenylene group, oxydiphenylene group, sulfonyldiphenylene group, biphenylene group, or naphthylene group. ) and general formula () (In the formula, X is -CH ₂ -, -O-, or -SO ₂ -
, and is bonded to the benzene nucleus at the meta or para position to the nitrogen atom, and Ar has the above general formula ()
Same as Ar in . ) [B] General formula () (In the formula, Ar' represents a p-phenylene group, m-phenylene group, sulfonyldiphenylene group, oxydiphenylene group, biphenylene group, or naphthylene group, and Y represents an alkylene group having 5 to 10 carbon atoms. ) A polyetheramide resin composition containing 1 to 100 parts by weight of a polyamide represented by: _{2 The} polyetheramide copolymer has _the formula ₍ ) and The polyetheramide resin composition according to claim 1, which is a polyetheramide copolymer represented by (). 3 In the polyetheramide copolymer, Ar is a p-phenylene group and/or m-phenylene group, X is -O-, and any imino group is bonded to the benzene nucleus at the para position. The polyetheramide resin composition according to claim 1 or 2, which is a polyetheramide copolymer represented by the formulas () and (). 4 The polyamide is represented by the formula () in which Ar' is a p-phenylene group and Y is a 2,2,4-trimethylhexamethylene group and/or a 2,4,4-trimethylhexamethylene group. The polyetheramide resin composition according to claim 1 or 2, which is a polyamide.