JPH0241543B2 - - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a resin composition having excellent moldability, impact resistance, and heat resistance, which is obtained by blending a styrene resin with an aromatic polyetheramide obtained from a specific diamine. Although styrenic resins exhibit excellent moldability using the molding methods commonly used for plastics, they are insufficient in terms of heat resistance, which limits their uses. On the other hand, proposed by Japanese Patent Application Laid-open No. 52-23198,
Aromatic polyetheramides obtained from specific diamines containing ether bonds have mechanical properties such as tensile strength, flexural strength, and impact strength, thermal properties such as heat distortion temperature and pyrolysis temperature, arc resistance, dielectric constant, and Although it has excellent electrical properties such as dielectric loss, abrasion resistance, flame retardancy, and dimensional stability, it has the disadvantage of generally poor moldability in various molding methods. The present inventors have arrived at the present invention as a result of intensive studies aimed at improving the above-mentioned weaknesses of styrene resins and aromatic polyetheramides. That is, the present invention provides a styrene resin with the general formula Aromatic polyether amide having a repeating unit represented by (however, in formula (), R ₁ to _{R 4} are hydrogen,
It represents 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, methyl group, ethyl group,
They are a trifluoromethyl group or a trichloromethyl group, and may be the same or different. Ar represents p-phenylene, m-phenylene, diphenylene ether, diphenylene, or naphthylene group. ) is provided. The resin composition of the present invention is composed of 3 to 95% by weight of a styrene resin and 97 to 5% by weight of an aromatic polyetheramide, and when the aromatic polyetheramide content is 5% by weight or less, it has excellent heat resistance. No improvement was observed, and when the aromatic polyetheramide content exceeds 97% by weight (styrenic resin content is less than 3% by weight), the moldability of the composition is impaired. More preferred is a resin composition comprising 20 to 80% by weight of a styrene resin and 80 to 20% by weight of an aromatic polyetheramide, which has a good balance in terms of moldability, impact resistance, and heat resistance. The styrenic resin in the present invention includes polystyrene, styrene-butadiene block copolymer resin,
AS resin (acrylonitrile-styrene copolymer resin), impact-resistant polystyrene (butadiene-styrene copolymer resin, butyl acrylate-styrene copolymer resin, EPDM rubber-styrene copolymer resin),
ABS resin (acrylonitrile-butadiene-styrene copolymer resin), MBS resin (methyl methacrylate-butadiene-styrene copolymer resin), AAS
Resin (acrylonitrile-butyl acrylate-styrene copolymer resin) MAS resin (methyl methacrylate-butyl acrylate-styrene copolymer resin),
AES resin (acrylonitrile-EPDM rubber-styrene copolymer resin), etc. The aromatic polyether amide used in the present invention is composed of aromatic dicarboxylic acid or its functional derivative and the 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, ethyl group, trifluoromethyl group, or trichloromethyl group, which may be the same or different. It can be obtained by reacting with a known method for producing aromatic polyamides. Specific examples of diamines having an ether bond represented by the general formula () are 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, 1,1,1,3,3,3-hexane Fluoro-
Examples include 2,2-bis[3-methyl-4-(4-aminophenoxy)phenyl]propane. The styrenic resin and aromatic polyetheramide can be mixed using a known method such as a roll, Banbury mixer, or extruder. Furthermore, in order to improve the heat resistance and weather resistance of the resin composition of the present invention, a thermal decomposition inhibitor, an antioxidant, or an ultraviolet absorber may be present in the resin composition. In addition, plasticizers, colorants, lubricants, flame retardants, etc. may also be present. Next, the present invention will be explained in more detail using reference examples and examples. Reference example Production method of aromatic polyether amide 10 In a separable flask, add a stirring bar, a thermometer,
Set the dropping funnel and add 154.8g of NaOH to 800ml of water.
Dissolve it and put it in a flask. Next, 656 g of 2,2-bis-[4-(4-aminophenoxy)phenyl]propane is dissolved in 3.4 kg of cyclohexanone, poured into the flask, and cooled to -2°C. Meanwhile, 164 g of terephthalic acid dichloride and 164 g of isophthalic acid dichloride are dissolved in 2.4 kg 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, add 16.9g of benzoyl chloride to cyclohexanone.
Dissolve in 500g and add. After another 2 hours, the reaction solution is poured into methanol to isolate the polymer. Examples Impact-resistant polystyrene (styrene-butyl acrylate copolymer resin), AAS resin (acrylonitrile-butyl acrylate-styrene copolymer resin)
A predetermined amount of each powder of AES resin (acrylonitrile-EPDM rubber-styrene copolymer resin) and aromatic polyetheramide powder obtained in the above reference example were mixed uniformly in a super mixer, and
The extruder was used for granulation at a die temperature of 250°C. The obtained composition was injection molded into test pieces, and physical property tests were conducted. The results are shown in the table below. 【table】

Claims (1)

[Claims] 1. General formula for styrenic resin Aromatic polyether amide having a repeating unit represented by (however, in formula (), R ₁ to _{R 4} are hydrogen,
It represents 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, methyl group, ethyl group,
They are a trifluoromethyl group or a trichloromethyl group, and may be the same or different. Ar represents p-phenylene, m-phenylene, diphenylene ether, diphenylene, or naphthylene group. ). 2 The styrenic resin is polystyrene, impact-resistant polystyrene, styrene-butadiene block copolymer resin, acrylonitrile-styrene copolymer resin, acrylonitrile-butadiene-styrene copolymer resin, acrylonitrile-butyl acrylate-styrene copolymer resin, acrylonitrile-
The resin composition according to claim 1, which is selected from the group consisting of EPDM rubber-styrene copolymer resin. 3. The resin composition according to claim 1, comprising 3 to 95% by weight of a styrene resin and 97 to 5% by weight of the aromatic polyetheramide. 4 aromatic polyetheramide gaterephthalic acid and isophthalic acid as dicarboxylic acid components, 2,2
-bis[4-(4-aminophenoxy)phenyl]
The resin composition according to claim 1 or 2, which contains propane as a diamine component. 5 Styrenic resin is acrylonitrile-butadiene-styrene copolymer resin, acrylonitrile-
The resin composition according to claim 2, which is selected from the group consisting of butyl acrylate-styrene copolymer resin and acrylonitrile-EPDM rubber-styrene copolymer resin. 6 The following formula is added to the acrylonitrile-butyl acrylate-styrene copolymer resin. [However, the carbonyl groups are mutually bonded to the benzene nucleus at the para or meta position.] Claim 3 comprising an aromatic polyether amide having a repeating unit represented by the following:
The resin composition according to item 1 or 5.